A Further Study of the Products of Sc and Dioxygen Reactions

NASA Technical Reports Server (NTRS)

Bauschlicher, Charles W., Jr.; Zhou, Mingfei; Andrews, Lester; Johnson, J. R. Tobias; Panas, Itai; Snis, Anders; Roos, Bjoern O.; Arnold, James O. (Technical Monitor)

1999-01-01

The products of the reaction of Sc and dioxygen have been reinvestigated. By adding the electron-trapping molecule CC14, additional information about the IR spectra has been obtained, as well as the observation of new bands. New ab initio calculations are also performed on possible products of the Sc plus O2 reaction. The previously observed band at 722.5 per cm is assigned as the b2 mode of ScO2(-). Bands arising from ScO(+), Sc(O2)(+), and(O2)ScO are also assigned. We are still unable to assign any bands to OScO. The problems associated with the computational study of ScO2 are discussed.

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

DOE R&D Accomplishments Database

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

1982-04-01

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

Fission product palladium-silicon carbide interaction in htgr fuel particles

NASA Astrophysics Data System (ADS)

Minato, Kazuo; Ogawa, Toru; Kashimura, Satoru; Fukuda, Kousaku; Shimizu, Michio; Tayama, Yoshinobu; Takahashi, Ishio

1990-07-01

Interaction of fission product palladium (Pd) with the silicon carbide (SiC) layer was observed in irradiated Triso-coated uranium dioxide particles for high temperature gas-cooled reactors (HTGR) with an optical microscope and electron probe microanalyzers. The SiC layers were attacked locally or the reaction product formed nodules at the attack site. Although the main element concerned with the reaction was palladium, rhodium and ruthenium were also detected at the corroded areas in some particles. Palladium was detected on both the hot and cold sides of the particles, but the corroded areas and the palladium accumulations were distributed particularly on the cold side of the particles. The observed Pd-SiC reaction depths were analyzed on the assumption that the release of palladium from the fuel kernel controls the whole Pd-SiC reaction.

Photoinduced ethane formation from reaction of ethene with matrix-isolated Ti, V, or Nb atoms.

PubMed

Thompson, Matthew G K; Parnis, J Mark

2005-10-27

The reactions of matrix-isolated Ti, V, or Nb atoms with ethene (C(2)H(4)) have been studied by FTIR absorption spectroscopy. Under conditions where the ethene dimer forms, metal atoms react with the ethene dimer to yield matrix-isolated ethane (C(2)H(6)) and methane. Under lower ethene concentration conditions ( approximately 1:70 ethene/Ar), hydridic intermediates of the types HMC(2)H(3) and H(2)MC(2)H(2) are also observed, and the relative yield of hydrocarbons is diminished. Reactions of these metals with perdeuterioethene, and equimolar mixtures of C(2)H(4) and C(2)D(4), yield products that are consistent with the production of ethane via a metal atom reaction involving at least two C(2)H(4) molecules. The absence of any other observed products suggests the mechanism also involves production of small, highly symmetric species such as molecular hydrogen and metal carbides. Evidence is presented suggesting that ethane production from the ethene dimer is a general photochemical process for the reaction of excited-state transition-metal atoms with ethene at high concentrations of ethene.

Crossed Molecular Beam Studies and Dynamics of Decomposition of Chemically Activated Radicals

DOE R&D Accomplishments Database

Lee, Y. T.

1973-09-01

The power of the crossed molecular beams method in the investigation of the dynamics of chemical reactions lies mainly in the direct observation of the consequences of single collisions of well controlled reactant molecules. The primary experimental observations which provide information on reaction dynamics are the measurements of angular and velocity distributions of reaction products.

Photochemical reactions of cyanoacetylene and dicyanoacetylene: Possible processes in Titan's atmosphere

NASA Technical Reports Server (NTRS)

Ferris, J. P.; Guillemin, J. C.

1991-01-01

Titan has an atmosphere which is subject to dramatic chemical evolution due mainly to the dramatic effect of the UV flux from the Sun. The energetic solar photons and other particles are converting the methane-nitrogen atmosphere into the unsaturated carbon compounds observed by the Voyager probes. These same solar photons are also converting some of these unsaturated reaction products into the aerosols observed in the atmosphere which obscure the view of the surface of Titan. In particular, the photochemical reactions of cyanoacetylene, dicyanoacetylene, acetylene and ethylene may result in the formation of the higher hydrocarbons and polymers which result in the aerosols observed in Titan's atmosphere. Polymers are the principal reaction products formed by irradiation of cyanoacetylene and dicyanoacetylene. Irradiation of cyanoacetylene with 185 nm of light also yields 1,3,5-tricyanobenzene while irradiation at 254 nm yields 1,2,4-tricyanobenzene and tetracyano cyclooctatetraenes. Photolyses of mixtures of cyanoacetylene and acetylene yields mono- and di- cyanobenzenes. The 1-Cyanocyclobutene is formed from the photochemical addition of cyanoacetylene with ethylene. The photolysis of dicyanoacetylene with acetylene yields 2,3-dicyano-1,3-butadiene and 1,2-dicyanobenzene. Tetracyano cyclooctatetraene products were also observed in the photolysis of mixtures of dicyanoacetylene and acetylene with 254 nm light. The 1,2-Dicyano cyclobutene is obtained from the photolysis dicyanoacetylene and ethylene. Reaction mechanisms will be proposed to explain the observed photoproducts.

The Effect of Temperature on Selectivity in the Oscillatory Mode of the Phenylacetylene Oxidative Carbonylation Reaction

PubMed Central

Novakovic, Katarina

2017-01-01

Abstract Reaction temperature plays a major role in product selectivity in the oscillatory mode of the palladium‐catalyzed phenylacetylene oxidative carbonylation reaction. At 40 °C, dimethyl (2Z)‐2‐phenyl‐2‐butenedioate is the major product whereas at 0 °C the major product is 5,5‐dimethoxy‐3‐phenyl‐2(5H)‐furanone. The occurrence of oscillations in pH coincides with an increase in the rate of phenylacetylene consumption and associated product formation. Experiments were performed isothermally in a reaction calorimeter to correlate reactant consumption and product formation with the occurrence of pH oscillations and the heat released by the reaction. An increase in the size of the pH drop in a single oscillation correlates with an increase in energy, indicating that this section of a single oscillation relates to reactant consumption. Based on these observations, a reaction pathway responsible for product formation is provided. PMID:28556572

The Effect of Temperature on Selectivity in the Oscillatory Mode of the Phenylacetylene Oxidative Carbonylation Reaction.

PubMed

Parker, Julie; Novakovic, Katarina

2017-08-05

Reaction temperature plays a major role in product selectivity in the oscillatory mode of the palladium-catalyzed phenylacetylene oxidative carbonylation reaction. At 40 °C, dimethyl (2Z)-2-phenyl-2-butenedioate is the major product whereas at 0 °C the major product is 5,5-dimethoxy-3-phenyl-2(5H)-furanone. The occurrence of oscillations in pH coincides with an increase in the rate of phenylacetylene consumption and associated product formation. Experiments were performed isothermally in a reaction calorimeter to correlate reactant consumption and product formation with the occurrence of pH oscillations and the heat released by the reaction. An increase in the size of the pH drop in a single oscillation correlates with an increase in energy, indicating that this section of a single oscillation relates to reactant consumption. Based on these observations, a reaction pathway responsible for product formation is provided. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

In situ alkali-silica reaction observed by x-ray microscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kurtis, K.E.; Monteiro, P.J.M.; Brown, J.T.

1997-04-01

In concrete, alkali metal ions and hydroxyl ions contributed by the cement and reactive silicates present in aggregate can participate in a destructive alkali-silica reaction (ASR). This reaction of the alkalis with the silicates produces a gel that tends to imbibe water found in the concrete pores, leading to swelling of the gel and eventual cracking of the affected concrete member. Over 104 cases of alkali-aggregate reaction in dams and spillways have been reported around the world. At present, no method exists to arrest the expansive chemical reaction which generates significant distress in the affected structures. Most existing techniques availablemore » for the examination of concrete microstructure, including ASR products, demand that samples be dried and exposed to high pressure during the observation period. These sample preparation requirements present a major disadvantage for the study of alkali-silica reaction. Given the nature of the reaction and the affect of water on its products, it is likely that the removal of water will affect the morphology, creating artifacts in the sample. The purpose of this research is to observe and characterize the alkali-silica reaction, including each of the specific reactions identified previously, in situ without introducing sample artifacts. For observation of unconditioned samples, x-ray microscopy offers an opportunity for such an examination of the alkali-silica reaction. Currently, this investigation is focusing on the effect of calcium ions on the alkali-silica reaction.« less

Formation kinetics of gemfibrozil chlorination reaction products: analysis and application.

PubMed

Krkosek, Wendy H; Peldszus, Sigrid; Huck, Peter M; Gagnon, Graham A

2014-07-01

Aqueous chlorination kinetics of the lipid regulator gemfibrozil and the formation of reaction products were investigated in deionized water over the pH range 3 to 9, and in two wastewater matrices. Chlorine oxidation of gemfibrozil was found to be highly dependent on pH. No statistically significant degradation of gemfibrozil was observed at pH values greater than 7. Gemfibrozil oxidation between pH 4 and 7 was best represented by first order kinetics. At pH 3, formation of three reaction products was observed. 4'-C1Gem was the only reaction product formed from pH 4-7 and was modeled with zero order kinetics. Chlorine oxidation of gemfibrozil in two wastewater matrices followed second order kinetics. 4'-C1Gem was only formed in wastewater with pH below 7. Deionized water rate kinetic models were applied to two wastewater effluents with gemfibrozil concentrations reported in literature in order to calculate potential mass loading rates of 4'C1Gem to the receiving water.

Single-molecule detection of dihydroazulene photo-thermal reaction using break junction technique

NASA Astrophysics Data System (ADS)

Huang, Cancan; Jevric, Martyn; Borges, Anders; Olsen, Stine T.; Hamill, Joseph M.; Zheng, Jue-Ting; Yang, Yang; Rudnev, Alexander; Baghernejad, Masoud; Broekmann, Peter; Petersen, Anne Ugleholdt; Wandlowski, Thomas; Mikkelsen, Kurt V.; Solomon, Gemma C.; Brøndsted Nielsen, Mogens; Hong, Wenjing

2017-05-01

Charge transport by tunnelling is one of the most ubiquitous elementary processes in nature. Small structural changes in a molecular junction can lead to significant difference in the single-molecule electronic properties, offering a tremendous opportunity to examine a reaction on the single-molecule scale by monitoring the conductance changes. Here, we explore the potential of the single-molecule break junction technique in the detection of photo-thermal reaction processes of a photochromic dihydroazulene/vinylheptafulvene system. Statistical analysis of the break junction experiments provides a quantitative approach for probing the reaction kinetics and reversibility, including the occurrence of isomerization during the reaction. The product ratios observed when switching the system in the junction does not follow those observed in solution studies (both experiment and theory), suggesting that the junction environment was perturbing the process significantly. This study opens the possibility of using nano-structured environments like molecular junctions to tailor product ratios in chemical reactions.

Observed side feeding in incomplete fusion dynamics in 16O + 160Gd reaction at energy ∼5.6 MeV/A: Spin distribution measurements

NASA Astrophysics Data System (ADS)

Ali, Rahbar; Afzal Ansari, M.; Singh, D.; Kumar, Rakesh; Singh, D. P.; Sharma, M. K.; Gupta, Unnati; Singh, B. P.; Shidling, P. D.; Negi, Dinesh; Muralithar, S.; Singh, R. P.; Bhowmik, R. K.

2017-12-01

Spin distributions of various residues populated via complete fusion (CF) and incomplete fusion (ICF) reactions in the interaction of 16O with 160Gd at the projectile energy Eproj ∼ 5.6 MeV/A have been studied. The experimentally measured spin distributions of the residues associated with the ICF reactions are found to be distinctly different from those populated via the CF reactions. An attempt has been made to extract the side-feeding pattern from the spin distributions of CF and ICF reaction products. It has been observed that the CF products are strongly fed over a broad spin range. But, no side-feeding takes place in the low observed spins as low partial waves are strongly hindered in the fast α-emission channels (associated with ICF) in the forward direction. It has also been observed that the mean input angular momentum for direct α-emitting (ICF) channels is relatively higher than evaporation α-emitting (CF) channels, and it increases with direct α-multiplicity in forward direction.

Measurement of the cross section of the residues from the 11B-induced reaction on 89Y and 93Nb: Production of 97Ru and Rhm101

NASA Astrophysics Data System (ADS)

Kumar, Deepak; Maiti, Moumita

2017-06-01

Background: The heavy-ion induced reactions on intermediate mass targets are complex in nature, even at the low energies. To understand those nuclear reaction phenomena in detail, more experimental studies are required in a wide range of energies. Purpose: Investigation of heavy-ion reactions by measuring production cross sections of the residues produced in the 11B-induced reactions on 89Y and 93Nb at low energies, near and above the barrier, and to check the effectiveness of the different nuclear models to explain them. Further, aim is also to optimize the production parameters of neutron deficient medically relevant 97Ru and Rhm101 radioisotopes produced in those reactions, respectively. Method: The 11B beam was allowed to impinge on 89Y and 93Nb foils supported by an aluminum (Al) catcher foil, arranged in a stack, in 27.5-58.7 and 30.6-62.3 MeV energy range, respectively. The off-line γ -ray spectrometry was carried out after the end of bombardment to measure the activity of the radionuclides produced in each foil and cross sections were calculated. Measured cross-sectional data were analyzed in terms of compound and precompound model calculations. Results: The measured cross sections of Ru,9597, 96,95,94Tc, Mom93, Ym90 radionuclides produced in the 11B+89Y reaction, and 101,100,99Pd, 101m,100,99mRh, 97Ru produced in the 11B+93Nb reaction showed good agreement with the model calculations based on the Hauser-Feshbach formulation and exciton model. Unlike theoretical estimation, consistent production of Ym90 was observed in the 11B+89Y reaction. Substantial pre-equilibrium contribution was noticed in the 3 n reaction channel in both reactions. Conclusions: Theoretical estimations confirmed that major production yields are mostly contributed by the compound reaction process. Pre-equilibrium emissions contributed at the high energy tail of the 3 n channel for both reactions. Moreover, an indirect signature of a direct reaction influence was also observed in the Ym90 production.

Incomplete mass transfer processes in 28Si +93Nb reaction

NASA Astrophysics Data System (ADS)

Tripathi, R.; Sodaye, S.; Ramachandran, K.; Sharma, S. K.; Pujari, P. K.

Cross sections of reaction products were measured in 28Si +93Nb reaction using recoil catcher technique involving by off-line gamma-ray spectrometry at beam energies of 105 and 155MeV. At Elab = 155MeV, the contribution from different incomplete mass transfer processes is investigated. Results of the present studies show the contribution from deep inelastic collision (DIC), massive transfer or incomplete fusion (ICF) and quasi-elastic transfer (QET). The contribution from massive transfer reactions was confirmed from the fractional yield of the reaction products in the forward catcher foil. The present results are different from those from the reactions with comparatively higher entrance channel mass asymmetry with lighter projectiles, for which dominant transfer processes are ICF and QET which involve mass transfer predominantly from projectile to target. The N/Z values of the products close to the target mass were observed to be in a wide range, starting from N/Z of the target (93Nb) and extending slightly below the N/Z of the composite system, consistent with the contribution from DIC and QET reactions. At Elab = 105MeV, a small contribution from QET was observed in addition to complete fusion.

Use of Helium Production to Screen Glow Discharges for Low Energy Nuclear Reactions (LENR)

NASA Astrophysics Data System (ADS)

Passell, Thomas O.

2011-03-01

My working hypothesis of the conditions required to observe low energy nuclear reactions (LENR) follows: 1) High fluxes of deuterium atoms through interfaces of grains of metals that readily accommodate movement of hydrogen atoms interstitially is the driving variable that produces the widely observed episodes of excess heat above the total of all input energy. 2) This deuterium atom flux has been most often achieved at high electrochemical current densities on highly deuterium-loaded palladium cathodes but is clearly possible in other experimental arrangements in which the metal is interfacing gaseous deuterium, as in an electrical glow discharge. 3) Since the excess heat episodes must be producing the product(s) of some nuclear fusion reaction(s) screening of options may be easier with measurement of those ``ashes'' than the observance of the excess heat. 4) All but a few of the exothermic fusion reactions known among the first 5 elements produce He-4. Hence helium-4 appearance in an experiment may be the most efficient indicator of some fusion reaction without commitment on which reaction is occurring. This set of hypotheses led me to produce a series of sealed tubes of wire electrodes of metals known to absorb hydrogen and operate them for 100 days at the 1 watt power level using deuterium gas pressures of ~ 100 torr powered by 40 Khz AC power supplies. Observation of helium will be by measurement of helium optical emission lines through the glass envelope surrounding the discharge. The results of the first 18 months of this effort will be described.

Bifurcations on Potential Energy Surfaces of Organic Reactions

PubMed Central

Ess, Daniel H.; Wheeler, Steven E.; Iafe, Robert G.; Xu, Lai; Çelebi-Ölçüm, Nihan; Houk, K. N.

2009-01-01

A single transition state may lead to multiple intermediates or products if there is a post-transition state reaction path bifurcation. These bifurcations arise when there are sequential transition states with no intervening energy minimum. For such systems, the shape of the potential energy surface and dynamic effects control selectivity rather than transition state energetics. This minireview covers recent investigations of organic reactions exhibiting reaction pathway bifurcations. Such phenomena are surprisingly general and affect experimental observables such as kinetic isotope effects and product distributions. PMID:18767086

Study of proton- and deuteron-induced spallation reactions on the long-lived fission product 93Zr at 105 MeV/nucleon in inverse kinematics

NASA Astrophysics Data System (ADS)

Kawase, Shoichiro; Nakano, Keita; Watanabe, Yukinobu; Wang, He; Otsu, Hideaki; Sakurai, Hiroyoshi; Ahn, Deuk Soon; Aikawa, Masayuki; Ando, Takashi; Araki, Shouhei; Chen, Sidong; Chiga, Nobuyuki; Doornenbal, Pieter; Fukuda, Naoki; Isobe, Tadaaki; Kawakami, Shunsuke; Kin, Tadahiro; Kondo, Yosuke; Koyama, Shunpei; Kubono, Shigeru; Maeda, Yukie; Makinaga, Ayano; Matsushita, Masafumi; Matsuzaki, Teiichiro; Michimasa, Shin'ichiro; Momiyama, Satoru; Nagamine, Shunsuke; Nakamura, Takashi; Niikura, Megumi; Ozaki, Tomoyuki; Saito, Atsumi; Saito, Takeshi; Shiga, Yoshiaki; Shikata, Mizuki; Shimizu, Yohei; Shimoura, Susumu; Sumikama, Toshiyuki; Söderström, Pär-Anders; Suzuki, Hiroshi; Takeda, Hiroyuki; Takeuchi, Satoshi; Taniuchi, Ryo; Togano, Yasuhiro; Tsubota, Jun'ichi; Uesaka, Meiko; Watanabe, Yasushi; Wimmer, Kathrin; Yamamoto, Tatsuya; Yoshida, Koichi

2017-09-01

Spallation reactions for the long-lived fission product ^{93}Zr have been studied in order to provide basic data necessary for nuclear waste transmutation. Isotopic-production cross sections via proton- and deuteron-induced spallation reactions on ^{93}Zr at 105 MeV/nucleon were measured in inverse kinematics at the RIKEN Radioactive Isotope Beam Factory. Remarkable jumps in isotopic production originating from the neutron magic number N=50 were observed in Zr and Y isotopes. The experimental results were compared to the PHITS calculations considering both the intranuclear cascade and evaporation processes, and the calculations greatly overestimated the measured production yield, corresponding to few-nucleon-removal reactions. The present data suggest that the spallation reaction is a potential candidate for the treatment of ^{93}Zr in spent nuclear fuel.

Dynamics of surface-migration: Electron-induced reaction of 1,2-dihaloethanes on Si(100)

NASA Astrophysics Data System (ADS)

Huang, Kai; MacLean, Oliver; Guo, Si Yue; McNab, Iain R.; Ning, Zhanyu; Wang, Chen-Guang; Ji, Wei; Polanyi, John C.

2016-10-01

Scanning Tunneling Microscopy was used to investigate the electron-induced reaction of 1,2-dibromoethane (DBE) and 1,2-dichloroethane (DCE) on Si(100).We observed a long-lived physisorbed molecular state of DBE at 75 K and of DCE at 110 K. As a result we were able to characterize by experiment and also by ab initio theory the dynamics of ethylene production in the electron-induced surface-reaction of these physisorbed species. For both DBE and DCE the ethylene product was observed to migrate across the surface. In the case of DBE the recoil of the ethylene favored the silicon rows, migrating by an average distance of 22 Å, and up to 100 Å. Trajectory calculations were performed for this electron-induced reaction, using an 'Impulsive Two-State' model involving an anionic excited state and a neutral ground-potential. The model agreed with experiment in reproducing both migration and desorption of the ethylene product. The computed migration exhibited a 'ballistic' launch and subsequent 'bounces', thereby accounting for the observed long-range migratory dynamics.

State-To Chemical Dynamics of the Hydrogen Atom Plus Hydrogen R Groups/deuterium R Groups Goes to Hydrogen/hydrogen Deuteride Plus R Group Hydrogen Abstraction Reactions

NASA Astrophysics Data System (ADS)

Germann, Geoffrey James

1990-01-01

The rotational and vibrational quantum state population distributions of the H_2/HD products of the H + HR/DR to H_2 /HD + R reactions (HD/DR = CD_4, C_2H_6, C _3H_8) have been measured using CARS spectroscopy. Very little of the available energy is partitioned to the H_2 /HD products of these reactions, although more rotational energy is found in the hydrogen product molecule as the size of the R radical increases, f_{ rm int}/f_{rm v}/f_{rm r} is 0.15/0.06/0.09, 0.18/0.06/0.12 and 0.20/0.06/0.14 for the H + CD_4, C_2 H_6, and C_3 H_8 reactions, respectively. Some anomalous behavior is exhibited in the rotational distributions of the reactions. The quantum state distributions show that more rotational energy is partitioned to those molecules formed in v^' = 1, the vibrationally excited state, than is partitioned to the product molecules formed in v^' = 0, the vibrational ground state. Of the energy that is available to produce product rotation 8(15), 11(22) and 12(27)% is partitioned to rotationally excite the H _2/HD product molecules formed in the v^' = 0(v ^' = 1) quantum states in the H + CD_4, C_2H _6, and C_3H _8 reactions, respectively. Finally, the H_2 product quantum state population distributions of the H + C_2H _6 and H + C_3H _8 reactions are observed to become less energetic, both vibrationally and rotationally, more rapidly than the HD product of the H + CD_4 reaction as the H atom reactant is allowed to undergo a greater number of collisions. This final observation could be the result of the differences in structure of the C _2H_6, and C_3H_8 and the CD_4 molecules and/or the differences in the barriers to reaction in each of the reactions.

Spectroscopic diagnostics of organic chemistry in the protostellar environment

NASA Technical Reports Server (NTRS)

Charnley, S. B.; Ehrenfreund, P.; Kuan, Y. J.

2001-01-01

A combination of astronomical observations, laboratory studies, and theoretical modelling is necessary to determine the organic chemistry of dense molecular clouds. We present spectroscopic evidence for the composition and evolution of organic molecules in protostellar environments. The principal reaction pathways to complex molecule formation by catalysis on dust grains and by reactions in the interstellar gas are described. Protostellar cores, where warming of dust has induced evaporation of icy grain mantles, are excellent sites in which to study the interaction between gas phase and grain-surface chemistries. We investigate the link between organics that are observed as direct products of grain surface reactions and those which are formed by secondary gas phase reactions of evaporated surface products. Theory predicts observable correlations between specific interstellar molecules, and also which new organics are viable for detection. We discuss recent infrared observations obtained with the Infrared Space Observatory, laboratory studies of organic molecules, theories of molecule formation, and summarise recent radioastronomical searches for various complex molecules such as ethers, azaheterocyclic compounds, and amino acids.

TEM and TED investigation of Ag/PbTe thin film bilayers.

NASA Astrophysics Data System (ADS)

Mandrino, Đorđe; Marinković, V.

Morphology and phase structure of Ag/PbTe thin film bilayers were investigated. This system was of particular interest because of interfacial reaction observed previously in an analogous Ag/SnTe system. Reaction products due to the interdiffusion of Ag with the substrate were determined as well as their orientations. They were discussed in view of the reaction products' structural relations to the PbTe.

Molecular Beam Studies of the Dynamics of Reactions Involving the Azide Radical and Hydrazoic Acid

NASA Astrophysics Data System (ADS)

Chen, Jing

1992-01-01

Several elementary reactions of atoms with N _3, HN_3, or halogens have been studied by laser fluorescence detection in a molecular beam-gas scattering arrangement approaching single -collision conditions. In the H + N_3, NCO to NH(X^3Sigma^ {-}, a^1Delta, b^1Sigma^{+}) + N_2, CO reactions, the NH product was detected. It was found in the N_3 reaction that product NH(a^1Delta ) carries considerable amount of vibrational energy (35% of the total available energy) while the NH(X ^3Sigma^{-}) product was vibrationally cold. An electronic state branching ratio of 3.2 +/- 1.3 was obtained for the X^3Sigma^{-} to a^1Delta electronic states. Comparison was made to the HN_3 (X ^1rm A^' ) photodissociation experiments and to our expectations based on our fragmentary knowledge of HN_3 potential energy surfaces. The corresponding NCO reaction was found to produce almost exclusively NH(X ^3Sigma^{-}) product due to the slight endothermicity of the NH(a^1 Delta) + CO channel. The total reaction cross section for H + NCO vs that for H + N_3 was estimated to be 1.2 +/- 0.3: 1. In the system of Ca, Sr + HN_3 , emission from electronically excited M( ^1P, ^3P), the MH(A ^2Pi, B^2Sigma ^{+}), and MOH(A^2 Pi, B^2Sigma^ {+}) was observed. The formation of MOH* was found due to a secondary reaction involving O _2 impurity in the HN_3 samples. Ground state MOH and MN_3 were detected but the search for CaNH was unsuccessful. All of the observed emissions can be explained as arising from secondary reactions of the metal imide (MNH) forced in the M + HN_3 primary reaction. A kinetic model shows that the M + HN_3 reaction proceeds mainly by formation of MNH, rather than MN_3. In the reactions of Pb + F_2 and Cl_2, the PbX products were detected. The PbCl product was observed in 18 vibrational levels of the ground electronic state with an average vibrational excitation of 21% of the total available energy. The PbF product was found to be characterized by a 300 K Boltzmann distribution for all the detected rovibrational states and proven to be an artifact. The radiative lifetimes of the PbF(A,B) and PbCl(A) states were also measured.

Aromatic fluorine compounds. VI. Displacement of aryl fluorine in diazonium salts

USGS Publications Warehouse

Finger, G.C.; Oesterling, R.E.

1956-01-01

Several chlorofluorobenzenes have been isolated from the Schiemann synthesis of fluorobenzenes. These have been shown to be the products of two side reactions occurring during thermal decomposition of the dry benzenediazonium fluoborate salt containing coprecipitated sodium chloride, an unavoidable contaminant in large preparations involving the use of hydrochloric acid and sodium fluoborate. The major side reaction and its chloro product were unexpected; a unique displacement of fluorine ortho to the diazonium group was observed. Replacement of the diazo group with chlorine was the predicted side reaction which proved to be minor. Conditions causing the side reactions and the isolation and identification of the products are described.

Identification and Characterization of Visible Absorption Components in Aqueous Methylglyoxal-Ammonium Sulfate Mixtures

NASA Astrophysics Data System (ADS)

McGivern, W. S.; Allison, T. C.; Radney, J. G.; Zangmeister, C. D.

2014-12-01

The aqueous reaction of methylglyoxal (MG) with ammonium sulfate has been suggested as a source of atmospheric ``brown carbon.'' We have utilized high-performance liquid chromatography coupled to ultraviolet-visible spectroscopy and tandem mass spectrometry to study the products of this reaction at high concentrations. The overall product spectrum shows a large number of distinct components; however, the visible absorption from this mixture is derived a very small number of components. The largest contributor is an imine-substituted (C=N-H) product of aldol condensation/facile dehydration reaction between the parent MG and a hydrated product of the MG + ammonia reaction. The asymmetric nature of this compound relative to the aldol condensation of two MG results in a sufficiently large redshift of the UV absorption spectrum that absorption of visible radiation can occur in the long-wavelength tail. The simplicity of the imine products is a result of a strong bias toward ketimine products due to the extensive hydration of the aldehydic moiety in the parent in aqueous solution. In addition, a strong pH dependence of the absorption cross section was observed with significantly greater absorption under more basic conditions. We have performed time-dependent density functional theory calculations to evaluate the absorption spectra of all of the possible condensation products and their respective ions, and the results are consistent with the experimental observations. We have also observed smaller concentrations of other condensation products of the imine-substituted parent species that do not contribute significantly to the visible absorption but have not been previously discussed.

Modeling the optimal central carbon metabolic pathways under feedback inhibition using flux balance analysis.

PubMed

De, Rajat K; Tomar, Namrata

2012-12-01

Metabolism is a complex process for energy production for cellular activity. It consists of a cascade of reactions that form a highly branched network in which the product of one reaction is the reactant of the next reaction. Metabolic pathways efficiently produce maximal amount of biomass while maintaining a steady-state behavior. The steady-state activity of such biochemical pathways necessarily incorporates feedback inhibition of the enzymes. This observation motivates us to incorporate feedback inhibition for modeling the optimal activity of metabolic pathways using flux balance analysis (FBA). We demonstrate the effectiveness of the methodology on a synthetic pathway with and without feedback inhibition. Similarly, for the first time, the Central Carbon Metabolic (CCM) pathways of Saccharomyces cerevisiae and Homo sapiens have been modeled and compared based on the above understanding. The optimal pathway, which maximizes the amount of the target product(s), is selected from all those obtained by the proposed method. For this, we have observed the concentration of the product inhibited enzymes of CCM pathway and its influence on its corresponding metabolite/substrate. We have also studied the concentration of the enzymes which are responsible for the synthesis of target products. We further hypothesize that an optimal pathway would opt for higher flux rate reactions. In light of these observations, we can say that an optimal pathway should have lower enzyme concentration and higher flux rates. Finally, we demonstrate the superiority of the proposed method by comparing it with the extreme pathway analysis.

Reactions of sulphur mustard on impregnated carbons.

PubMed

Prasad, G K; Singh, Beer

2004-12-31

Activated carbon of surface area 1100 m2/gm is impregnated with 4% sodium hydroxide plus 3% Cr(VI) as CrO3 with and without 5% ethylene diamine (EDA), 4% magnesium nitrate and 5% ruthenium chloride by using their aqueous solutions. These carbons are characterized for surface area analysis by BET conventional method and exposed to the vapours of sulphur mustard (HD) at room temperature (30 degrees C). After 24 h, the reaction products are extracted in dichloromethane and analyzed using gas chromatography and mass spectrometry (GC-MS). Hemisulphur mustard, thiodiglycol, 1,4-oxathiane are observed to be the products of reaction between sulphur mustard and NaOH/CrO3/C system, whereas on NaOH/CrO3/EDA/C system HD reacted to give 1,4-thiazane. On Mg(NO3)2/C system it gave hemisulphur mustard and thiodiglycol. On RuCl3/C system it degraded to divinyl sulphone. Residual sulphur mustard is observed along with reaction products in all systems studied. Reaction mechanisms are also proposed for these interesting surface reactions. Above-mentioned carbons can be used in filtration systems for protection against hazardous gases such as sulphur mustard.

Experimental survey of the production of α -decaying heavy elements in 238U+232Th reactions at 7.5-6.1 MeV/nucleon

NASA Astrophysics Data System (ADS)

Wuenschel, S.; Hagel, K.; Barbui, M.; Gauthier, J.; Cao, X. G.; Wada, R.; Kim, E. J.; Majka, Z.; Płaneta, R.; Sosin, Z.; Wieloch, A.; Zelga, K.; Kowalski, S.; Schmidt, K.; Ma, C.; Zhang, G.; Natowitz, J. B.

2018-06-01

The production of α -particle decaying heavy nuclei in reactions of 7.5-6.1 MeV/nucleon 238U +232Th was explored using an in-beam detection array composed of YAP scintillators and gas ionization chamber-Si telescopes. Comparisons of α energies and half-lives for the observed products with those of the previously known isotopes and with theoretically predicted values indicate the observation of a number of previously unreported α emitters. α -particle decay energies reaching as high as 12 MeV are observed. Many of these are expected to be from decay of previously unseen relatively neutron rich products. While the contributions of isomeric states require further exploration and specific isotope identifications need to be made, the production of heavy isotopes with quite high atomic numbers is suggested by the data.

Advanced Maillard reaction end products are associated with Alzheimer disease pathology.

PubMed Central

Smith, M A; Taneda, S; Richey, P L; Miyata, S; Yan, S D; Stern, D; Sayre, L M; Monnier, V M; Perry, G

1994-01-01

During aging long-lived proteins accumulate specific post-translational modifications. One family of modifications, termed Maillard reaction products, are initiated by the condensation between amino groups of proteins and reducing sugars. Protein modification by the Maillard reaction is associated with crosslink formation, decreased protein solubility, and increased protease resistance. Here, we present evidence that the characteristic pathological structures associated with Alzheimer disease contain modifications typical of advanced Maillard reaction end products. Specifically, antibodies against two Maillard end products, pyrraline and pentosidine, immunocytochemically label neurofibrillary tangles and senile plaques in brain tissue from patients with Alzheimer disease. In contrast, little or no staining is observed in apparently healthy neurons of the same brain. The Maillard-reaction-related modifications described herein could account for the biochemical and insolubility properties of the lesions of Alzheimer disease through the formation of protein crosslinks. Images PMID:8202552

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

NASA Astrophysics Data System (ADS)

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

2018-03-01

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

Enhanced hydroxyl radical production by dihydroxybenzene-driven Fenton reactions: implications for wood biodegradation.

PubMed

Contreras, David; Rodríguez, Jaime; Freer, Juanita; Schwederski, Brigitte; Kaim, Wolfgang

2007-09-01

Brown rot fungi degrade wood, in initial stages, mainly through hydroxyl radicals (.OH) produced by Fenton reactions. These Fenton reactions can be promoted by dihydroxybenzenes (DHBs), which can chelate and reduce Fe(III), increasing the reactivity for different substrates. This mechanism allows the extensive degradation of carbohydrates and the oxidation of lignin during wood biodegradation by brown rot fungi. To understand the enhanced reactivity in these systems, kinetics experiments were carried out, measuring .OH formation by the spin-trapping technique of electron paramagnetic resonance spectroscopy. As models of the fungal DHBs, 1,2-dihydroxybenzene (catechol), 2,3-dihydroxybenzoic acid and 3,4-dihydroxybenzoic acid were utilized as well as 1,2-dihydroxy-3,5-benzenedisulfonate as a non-Fe(III)-reducing substance for comparison. Higher amounts and maintained concentrations of .OH were observed in the driven Fenton reactions versus the unmodified Fenton process. A linear correlation between the logarithms of complex stability constants and the .OH production was observed, suggesting participation of such complexes in the radical production.

Association Reactions at Low Pressure: 5. The CH(sub 3)+/HCN System. A Final Word?

NASA Technical Reports Server (NTRS)

Anicich, V.; Sen, A.; Huntress, W.; McEwan, M.

1994-01-01

The reaction of the methyl cation with hydrogen cyanide is revisited. We have confidence that we have resolved a long standing apparent contradiction of experimental results. A literature history is presented along with one new experiment and a reexamination of an old experiment. In this present work it is shown that all of the previous studies had made consistent observations. Yet, each of the previous studies failed to observe all of the information present. The methyl cation does react with HCN by radiative association, a fact which had been in doubt. The product ions formed in the two-body and three-body processes react differently with HCN. The collisionally stabilized association product formed by a three-body mechanism does not react with HCN and is readily detected in the experiments. The radiatively stabilized association product, formed by a slow two-body reaction, is not detected because it reacts with HCN by a fast proton transfer reaction forming the protonated HCN ion.

Complex Chemical Reaction Networks from Heuristics-Aided Quantum Chemistry.

PubMed

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

2014-03-11

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

Controlling reactivity of nanoporous catalyst materials by tuning reaction product-pore interior interactions: Statistical mechanical modeling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Jing; Ackerman, David M.; Lin, Victor S.-Y.

2013-04-02

Statistical mechanical modeling is performed of a catalytic conversion reaction within a functionalized nanoporous material to assess the effect of varying the reaction product-pore interior interaction from attractive to repulsive. A strong enhancement in reactivity is observed not just due to the shift in reaction equilibrium towards completion but also due to enhanced transport within the pore resulting from reduced loading. The latter effect is strongest for highly restricted transport (single-file diffusion), and applies even for irreversible reactions. The analysis is performed utilizing a generalized hydrodynamic formulation of the reaction-diffusion equations which can reliably capture the complex interplay between reactionmore » and restricted transport.« less

Reaction of a chemotherapeutic agent, 6-mercaptopurine, with a direct-acting, electrophilic carcinogen, benzo[a]pyrene-7,8-diol 9,10-epoxide.

PubMed

MacLeod, M C; Stewart, E; Daylong, A; Lew, L K; Evans, F E

1991-01-01

The chemotherapeutic agent 6-mercaptopurine (6-MP) has been shown to react covalently with the ultimate carcinogenic metabolite of benzo[a]pyrene, 7-r,8-t-dihydroxy-9-t,10-t-oxy-7,8,9,10-tetrahydrobenzo[a]pyrene (BPDE), in aqueous solution, forming a single adduct. NMR studies of the HPLC-purified product were consistent with its identification as 10(S)-(6'-mercaptopurinyl)-7,8,9-trihydroxy-7,8,9,10- tetrahydrobenzo[a]pyrene. Reaction kinetics were analyzed by using both HPLC separation of the products formed and a spectrophotometric assay for adduct formation. A simple model in which direct reaction between 6-MP and BPDE takes place without formation of a physical complex was found to adequately predict the dependence of product ratios on 6-MP concentration. Variations in the observed rate constant for this reaction with changes in temperature, pH, and buffer concentration were determined and compared to the effects of these variables on the observed rate constant for BPDE hydrolysis. In each case, the processes were affected quite differently, suggesting that different rate-determining steps are involved. The data suggest that the reaction mechanism involves SN2 attack of the anion of 6-MP, formed by ionization of the sulfhydryl group, on carbon 10 of BPDE, resulting in a trans-9,10 reaction product.

Gas-phase hydrogen atom abstraction reactions of S- with H2, CH4, and C2H6

NASA Astrophysics Data System (ADS)

Angel, Laurence A.; Dogbevia, Moses K.; Rempala, Katarzyna M.; Ervin, Kent M.

2003-11-01

Reaction cross sections, product axial velocity distributions, and potential energy surfaces are presented for the hydrogen atom abstraction reactions S-+RH→R+HS- (R=H, CH3, C2H5) as a function of collision energy. The observed threshold energy, E0, for S-+H2→H+HS- agrees with the reaction endothermicity, ΔrH0. At low collision energies, the H+HS- products exhibit symmetric, low-recoil-velocity scattering, consistent with statistical reaction behavior. The S-+CH4→CH3+HS- and S-+C2H6→C2H5+HS reactions, in contrast, show large excess threshold energies when compared to ΔrH0. The excess energies are partly explained by a potential energy barrier separating products from reactants. However, additional dynamical constraints must account for more than half of the excess threshold energy. The observed behavior seems to be general for collisional activation of anion-molecule reactions that proceed through a tight, late transition state. For RH=CH4 and C2H6, the HS- velocity distributions show anisotropic backward scattering at low collision energies indicating small impact parameters and a direct rebound reaction mechanism. At higher collision energies, there is a transition to HS- forward scattering and high velocities consistent with grazing collisions and a stripping mechanism.

Measuring protection of aromatic wine thiols from oxidation by competitive reactions vs wine preservatives with ortho-quinones.

PubMed

Nikolantonaki, Maria; Magiatis, Prokopios; Waterhouse, Andrew L

2014-11-15

Quinones are central intermediates in wine oxidation that can degrade the quality of wine by reactions with varietal thiols, such as 3-sulfanylhexanol, decreasing desirable aroma. Protection by wine preservatives (sulphur dioxide, glutathione, ascorbic acid and model tannin, phloroglucinol) was assessed by competitive sacrificial reactions with 4-methyl-1,2-benzoquinone, quantifying products and ratios by HPLC-UV-MS. Regioselectivity was assessed by product isolation and identification by NMR spectroscopy. Nucleophilic addition reactions compete with two electron reduction of quinones by sulphur dioxide or ascorbic acid, and both routes serve as effective quenching pathways, but minor secondary products from coupled redox reactions between the products and reactants are also observed. The wine preservatives were all highly reactive and thus all very protective against 3-sulfanylhexanol loss to the quinone, but showed only additive antioxidant effects. Confirmation of these reaction rates and pathways in wine is needed to assess the actual protective action of each tested preservative. Copyright © 2014 Elsevier Ltd. All rights reserved.

High-energy γ rays resulting from low-energy nuclear reactions in light nuclei

NASA Astrophysics Data System (ADS)

Rose, Paul B.; Erickson, Anna S.

2018-06-01

Products resulting from 3.02 MeV deuterons incident on a natural boron target have been investigated by way of γ -ray spectroscopy and activation analysis. This study uses observed γ rays and cascades to deduce the populated states from the reaction products. Die-away measurements are included to investigate the built-up activation from the target and compared with tabulated half-lives to further understand the plethora of reactions taking place. Many of the observed γ rays, such as 15.1 MeV, result from the formation of excited states of 12C, while others are secondary and tertiary processes from α breakup resulting in 8Be.

An observational assessment of the influence of mesoscale and submesoscale heterogeneity on ocean biogeochemical reactions

NASA Astrophysics Data System (ADS)

Martin, Adrian P.; Lévy, Marina; van Gennip, Simon; Pardo, Silvia; Srokosz, Meric; Allen, John; Painter, Stuart C.; Pidcock, Roz

2015-09-01

Numerous observations demonstrate that considerable spatial variability exists in components of the marine planktonic ecosystem at the mesoscale and submesoscale (100 km-1 km). The causes and consequences of physical processes at these scales ("eddy advection") influencing biogeochemistry have received much attention. Less studied, the nonlinear nature of most ecological and biogeochemical interactions means that such spatial variability has consequences for regional estimates of processes including primary production and grazing, independent of the physical processes. This effect has been termed "eddy reactions." Models remain our most powerful tools for extrapolating hypotheses for biogeochemistry to global scales and to permit future projections. The spatial resolution of most climate and global biogeochemical models means that processes at the mesoscale and submesoscale are poorly resolved. Modeling work has previously suggested that the neglected eddy reactions may be almost as large as the mean field estimates in some cases. This study seeks to quantify the relative size of eddy and mean reactions observationally, using in situ and satellite data. For primary production, grazing, and zooplankton mortality the eddy reactions are between 7% and 15% of the mean reactions. These should be regarded as preliminary estimates to encourage further observational estimates and not taken as a justification for ignoring eddy reactions. Compared to modeling estimates, there are inconsistencies in the relative magnitude of eddy reactions and in correlations which are a major control on their magnitude. One possibility is that models exhibit much stronger spatial correlations than are found in reality, effectively amplifying the magnitude of eddy reactions.

Micromechanics investigation of expansive reactions in chemoelastic concrete.

PubMed

Lemarchand, Eric; Dormieux, Luc; Ulm, Franz-Josef

2005-11-15

Expansive reactions damage porous materials through the formation of reaction products of a volume in excess of the available space left by the reactants and the natural porosity of the material. This leads to pressurizing the pore space accessible to the reaction products, which differs when the chemical reaction is through-solution or topochemical or both in nature. This paper investigates expansive reactions from a micromechanical point of view, which allows bridging the scale from the local chemo-mechanical mechanisms to the macroscopically observable stress-free expansion. In particular, the study of the effect of morphology of the pore space, in which the chemical expansion occurs locally, on the macroscopically observable expansion is the main focus of this paper. The first part revisits the through-solution and the topochemical reaction mechanism within the framework of micro-macro-homogenization theories, and the effect of the microscopic geometry of pores and microcracks in the solid matrix on the macroscopic chemical expansion is examined. The second part deals with the transition from a topochemical to a through-solution-like mechanism that occurs in a solid matrix with inclusions (cracks, pores) of different morphology.

Synthesis of mucoadhesive thiolated gelatin using a two-step reaction process.

PubMed

Duggan, Sarah; O'Donovan, Orla; Owens, Eleanor; Cummins, Wayne; Hughes, Helen

2015-04-01

Using a novel two-step approach, the thiolation of gelatin for mucoadhesive drug delivery has been achieved. The initial step involved the amination of native gelatin via an amine to carboxylic acid coupling reaction with ethylene diamine, followed by thiolation with Traut's reagent. The resulting thiolated product showed an increase in thiol content of up to 10-fold in comparison with control gelatin samples. Improved cohesion and mucoadhesion in comparison with unmodified and control gelatin samples was also observed. This reaction process was observed to be influenced by both the temperature and the pH of the amination reaction, affecting both amine content and product yield. Swelling ability, cohesion and mucoadhesion were all observed to be strongly dependent on the thiol content of the samples but also, importantly, the molecular weight (MW) of the gelatin used. Gelatin with a MW of 20-25 kDa proved to be optimal in creating this novel mucoadhesive gelatin material. Copyright © 2015 Elsevier B.V. All rights reserved.

C=C bond cleavage on neutral VO3(V2O5)n clusters.

PubMed

Dong, Feng; Heinbuch, Scott; Xie, Yan; Bernstein, Elliot R; Rocca, Jorge J; Wang, Zhe-Chen; Ding, Xun-Lei; He, Sheng-Gui

2009-01-28

The reactions of neutral vanadium oxide clusters with alkenes (ethylene, propylene, 1-butene, and 1,3-butadiene) are investigated by experiments and density function theory (DFT) calculations. Single photon ionization through extreme ultraviolet radiation (EUV, 46.9 nm, 26.5 eV) is used to detect neutral cluster distributions and reaction products. In the experiments, we observe products (V(2)O(5))(n)VO(2)CH(2), (V(2)O(5))(n)VO(2)C(2)H(4), (V(2)O(5))(n)VO(2)C(3)H(4), and (V(2)O(5))(n)VO(2)C(3)H(6), for neural V(m)O(n) clusters in reactions with C(2)H(4), C(3)H(6), C(4)H(6), and C(4)H(8), respectively. The observation of these products indicates that the C=C bonds of alkenes can be broken on neutral oxygen rich vanadium oxide clusters with the general structure VO(3)(V(2)O(5))(n=0,1,2...). DFT calculations demonstrate that the reaction VO(3) + C(3)H(6) --> VO(2)C(2)H(4) + H(2)CO is thermodynamically favorable and overall barrierless at room temperature. They also provide a mechanistic explanation for the general reaction in which the C=C double bond of alkenes is broken on VO(3)(V(2)O(5))(n=0,1,2...) clusters. A catalytic cycle for alkene oxidation on vanadium oxide is suggested based on our experimental and theoretical investigations. The reactions of V(m)O(n) with C(6)H(6) and C(2)F(4) are also investigated by experiments. The products VO(2)(V(2)O(5))(n)C(6)H(4) are observed for dehydration reactions between V(m)O(n) clusters and C(6)H(6). No product is detected for V(m)O(n) clusters reacting with C(2)F(4). The mechanisms of the reactions between VO(3) and C(2)F(4)/C(6)H(6) are also investigated by calculations at the B3LYP/TZVP level.

Abiotic hydrogen production in fresh and altered MSWI-residues: texture and microstructure investigation.

PubMed

Heuss-Assbichler, S; Magel, G; Fehr, K T

2010-10-01

Long-term hydrogen generation was observed in a Bavarian mono-landfill for municipal solid waste incineration (MSWI) residues. Hydration reactions of non-noble metals, especially aluminum, predominantly produce hydrogen at alkaline reaction conditions. Microscopic investigations show that aluminum metal may occur in different forms: as larger single grains, as small particles embedded in a vitrified matrix or less frequently in blowholes together with metallic silica. Four types of corrosion texture were observed, indicating different reaction mechanisms: aluminum hydroxide rims caused by hydration reactions at alkaline reaction conditions (reaction type 1) and multiphase rims with ettringite and hydrocalumite due to the reaction of aluminum hydroxide with sulfate and chloride ions which are solved in the pore water (reaction type 2). Galvanic corrosion textures due to the electric potential difference between aluminum and embedded intermetallic Fe- or Cu-rich exsolution phases lead to two further corrosion textures: Strong hydration effects of aluminum except a border of aluminum remnant directly beside the Fe- or Cu-rich segregations were only observed in fresh samples (reaction type 3). The reaction type 4 shows a network of Al-hydroxide veins occurring along the embedded intermetallic Fe- or Cu-rich exsolution segregation pattern within the metallic aluminum grain. Metal particles enclosed in vitrified particles offers the potential for future corrosion processes. The occurrence of corrosion types 1, 2 and 3 in fresh bottom ashes indicates that these reaction mechanisms predominate during the first reaction period in the presence of chlorine in an alkaline solution. Corrosion type 4, however, was additionally observed in aged samples. Here aluminum acts as sacrificed anode implying electrochemical reaction due to electrolytic pore water. Chloride in the system keeps the reaction alive as Al-hydroxide is solved which normally builds a protection shield around the aluminum metal particles. Due to field observations and experimental results we have reasonable indications that after an initial strong formation of hydrogen the reaction time for hydrogen production in the landfill is lengthened for several decades by the presence of chloride in the alkaline pore water. (c) 2010 Elsevier Ltd. All rights reserved.

Structural basis for Diels-Alder ribozyme-catalyzed carbon-carbon bond formation

PubMed Central

Serganov, Alexander; Keiper, Sonja; Malinina, Lucy; Tereshko, Valentina; Skripkin, Eugene; Höbartner, Claudia; Polonskaia, Anna; Phan, Anh Tuân; Wombacher, Richard; Micura, Ronald; Dauter, Zbigniew; Jäschke, Andres; Patel, Dinshaw J

2015-01-01

The majority of structural efforts addressing RNA’s catalytic function have focused on natural ribozymes, which catalyze phosphodiester transfer reactions. By contrast, little is known about how RNA catalyzes other types of chemical reactions. We report here the crystal structures of a ribozyme that catalyzes enantioselective carbon-carbon bond formation by the Diels-Alder reaction in the unbound state and in complex with a reaction product. The RNA adopts a λ-shaped nested pseudoknot architecture whose preformed hydrophobic pocket is precisely complementary in shape to the reaction product. RNA folding and product binding are dictated by extensive stacking and hydrogen bonding, whereas stereoselection is governed by the shape of the catalytic pocket. Catalysis is apparently achieved by a combination of proximity, complementarity and electronic effects. We observe structural parallels in the independently evolved catalytic pocket architectures for ribozyme- and antibody-catalyzed Diels-Alder carbon-carbon bond-forming reactions. PMID:15723077

Evaluation of the Deuterium Isotope Effect in the Detonation of Aluminum Containing Explosives

DOE PAGES

Tappan, Bryce C.; Bowden, Patrick R.; Manner, Virginia W.; ...

2017-12-04

During or shortly after a detonation in condensed explosives, the reaction rates and the physical mechanism controlling aluminum reaction is poorly understood. We utilize the kinetic isotope effect to probe Al reactions in detonation product gases in aluminized, protonated and deuterated high explosives using high-fidelity detonation velocity and cylinder wall expansion velocity measurements. By observation of the profile of cylinder wall velocity versus time, we are able to determine the timing of aluminum contribution to energy release in product gases and observe the presence or absence of rate changes isotopic substitution. By comparison of the Al oxidation with lithium fluoridemore » (LiF), data indicate that Al oxidation occurs on an extremely fast time scale, with post-detonation kinetic isotope effects observed in carbon containing formulations.« less

Evaluation of the Deuterium Isotope Effect in the Detonation of Aluminum Containing Explosives

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tappan, Bryce C.; Bowden, Patrick R.; Manner, Virginia W.

During or shortly after a detonation in condensed explosives, the reaction rates and the physical mechanism controlling aluminum reaction is poorly understood. We utilize the kinetic isotope effect to probe Al reactions in detonation product gases in aluminized, protonated and deuterated high explosives using high-fidelity detonation velocity and cylinder wall expansion velocity measurements. By observation of the profile of cylinder wall velocity versus time, we are able to determine the timing of aluminum contribution to energy release in product gases and observe the presence or absence of rate changes isotopic substitution. By comparison of the Al oxidation with lithium fluoridemore » (LiF), data indicate that Al oxidation occurs on an extremely fast time scale, with post-detonation kinetic isotope effects observed in carbon containing formulations.« less

Products and mechanism of the reaction of OH radicals with 2,2,4-trimethylpentane in the presence of NO.

PubMed

Aschmann, Sara M; Arey, Janet; Atkinson, Roger

2002-02-15

Alkanes are important constituents of gasoline fuel and vehicle exhaust, with branched alkanes comprising a significant fraction of the total alkanes observed in urban areas. Products of the gas-phase reactions of OH radicals with 2,2,4-trimethylpentane and 2,2,4-trimethylpentane-d18 in the presence of NO at 298+/-2 K and atmospheric pressure of air have been investigated using gas chromatography with flame ionization detection (GC-FID), combined gas chromatography-mass spectrometry (GC-MS), and in situ atmospheric pressure ionization tandem mass spectrometry (API-MS). Acetone, 2-methylpropanal, and 4-hydroxy-4-methyl-2-pentanone were identified and quantified by GC-FID from 2,2,4-trimethylpentane with molar formation yields of 54+/-7%, 26+/-3%, and 5.1+/-0.6%, respectively; upper limits to the formation yields of acetaldehyde, 2,2-dimethylpropanal, and 4,4-dimethyl-2-pentanone were obtained. Additional products observed from 2,2,4-trimethylpentane by API-MS and API-MS/MS analyses using positive and negative ion modes were hydroxy products of molecular weight 130 and 144, a product of molecular weight 128 (attributed to a C8-carbonyl), and hydroxynitrates of molecular weight 135, 177, and 191 (attributed to HOC4H8ONO2, HOC7H14ONO2, and HOC8H16-ONO2, respectively). Formation of HOC8H16ONO2 and HOC7H14-ONO2 is consistent with the observation of products of molecular weight 207 (HOC8D16ONO2) and 191 (HOC7D14-ONO2), respectively, in the API-MS analyses of the 2,2,4-trimethylpentane-d18 reaction (-OD groups rapidly exchange to -OH groups under our experimental conditions). These product data allow the reaction pathways to be delineated to a reasonable extent, and the reaction mechanism is discussed.

Reactions of gas phase H atoms with ethylene, acetylene and ethane adsorbed on Ni( 1 1 1 )

NASA Astrophysics Data System (ADS)

Bürgi, T.; Trautman, T. R.; Gostein, M.; Lahr, D. L.; Haug, K. L.; Ceyer, S. T.

2002-03-01

The products of the reaction of the most energetic form of hydrogen, gas phase H atoms, with ethylene, acetylene and ethane adsorbed on a Ni(1 1 1) surface at 60 K are probed. Adsorbed ethylidyne (CCH 3) is identified by high resolution electron energy loss spectroscopy to be the major product (30% yield) in all three cases. Adsorbed acetylene is a minor product (3% yield) and arises as a consequence of a dynamic equilibrium between CCH 3 and C 2H 2 in the presence of gas phase H atoms. The observation of the same product for the reaction of H atoms with all three hydrocarbons implies that CCH 3 is the most stable C 2 species in the presence of coadsorbed hydrogen. The rates of CCH 3 production are measured as a function of the time of exposure of H atoms to each hydrocarbon. A simple kinetic model treating each reaction as a pseudo-first order reaction in the hydrocarbon coverage is fit to these data. A mechanism for the formation of CCH 3 via a CHCH 2 intermediate common to all three reactants is proposed to describe this model. The observed instability of the CH 2CH 3 species relative to C 2H 4 plays a role in the formulation of this mechanism as does the observed stability of CHCH 2 species in the presence of coadsorbed hydrogen. The CH 2CH 3 and the CHCH 2 species are produced by the translational activation of ethane and the dissociative ionization of ethane and ethylene, respectively. In addition, the binding energy and the vibrational spectrum of ethane adsorbed on Ni(1 1 1) are determined and exceptionally high resolution vibrational spectra of adsorbed ethylene and acetylene are presented.

Infrared matrix-isolation and theoretical studies of the reactions of ferrocene with ozone.

PubMed

Kugel, Roger W; Pinelo, Laura F; Ault, Bruce S

2015-03-19

The reactions between ferrocene (Cp2Fe) (2a) and ozone (O3) were studied using low-temperature matrix-isolation techniques coupled with theoretical density functional theory (DFT) calculations. Co-deposition of Ar/Cp2Fe and Ar/O3 gas mixtures onto a cryogenically cooled CsI window produced a dark-green charge-transfer complex, Cp2Fe-O3, that photodecomposed upon red (λ ≥ 600 nm) and infrared (λ ≥ 1000 nm) irradiation but was stable to green or blue irradiation. Products of photodecomposition were characterized by FT-IR, oxygen-18 labeling, and DFT calculations using the B3LYP functionals and the 6-311G++(d,2p) basis set. Likely, photochemical products included four structures having the molecular formula C10H10FeO, identified by DFT calculations based on their calculated infrared spectra and (18)O isotope shifts. Each of these calculated molecules had one intact and fully coordinated η(5)-C5H5 cyclopentadienyl (Cp) ring and (1) an η(5)-C5H5O cyclic ether (pyran ring) (2b), (2) an η(4)-C5H5O linear aldehyde (2c), (3) a bidentate cyclic aldehyde with a seven-membered ring including the iron atom (2d), or (4) an Fe-O bond and an η(2)-C5H5 (Cp) ring (2e). No conclusive evidence for a gas-phase thermal reaction between ferrocene and ozone was observed under the conditions of these experiments. However, strong evidence for a surface-catalyzed thermal reaction was observed in merged-jet experiments wherein the gases were premixed before deposition. Surface-catalyzed ferrocene-ozone reaction products included a thin film of Fe2O3 observed on the walls of the merged tube as well as cyclopentadiene (C5H6), cyclopentadienone (C5H4O), and further oxidation products observed in the matrix. Possible mechanisms for both the photochemical and the thermal reactions are discussed.

Preparation of Low Molecular Weight Heparin by Microwave Discharge Electrodeless Lamp/TiO2 Photo-Catalytic Reaction.

PubMed

Lee, Do-Jin; Kim, Byung Hoon; Kim, Sun-Jae; Kim, Jung-Sik; Lee, Heon; Jung, Sang-Chul

2015-01-01

An MDEL/TiO2 photo-catalyst hybrid system was applied, for the first time, for the production of low molecular weight heparin. The molecular weight of produed heparin decreased with increasing microwave intensity and treatment time. The abscission of the chemical bonds between the constituents of heparin by photo-catalytic reaction did not alter the characteristics of heparin. Formation of by-products due to side reaction was not observed. It is suggested that heparin was depolymerized by active oxygen radicals produced during the MDEL/TiO2 photo-chemical reaction.

Nitrogen-Containing Low Volatile Compounds from Pinonaldehyde-Dimethylamine Reaction in the Atmosphere: A Laboratory and Field Study.

PubMed

Duporté, Geoffroy; Parshintsev, Jevgeni; Barreira, Luís M F; Hartonen, Kari; Kulmala, Markku; Riekkola, Marja-Liisa

2016-05-03

Pinonaldehyde, which is among the most abundant oxidation products of α-pinene, and dimethylamine were selected to study the formation of N-containing low volatile compounds from aldehyde-amine reactions in the atmosphere. Gas phase reactions took place in a Tedlar bag, which was connected to a mass spectrometer ionization source via a short deactivated fused silica column. In addition to on-line analysis, abundance of gaseous precursors and reaction products were monitored off-line. Condensable products were extracted from the bag's walls with a suitable solvent and analyzed by gas chromatography coupled to chemical ionization high-resolution quadrupole time-of-flight mass spectrometry and by ultra-high-performance liquid chromatography coupled to electrospray ionization Orbitrap mass spectrometry. The reactions carried out resulted in several mid-low vapor pressure nitrogen-containing compounds that are potentially important for the formation of secondary organic aerosols in the atmosphere. Further, the presence of brown carbon, confirmed by liquid chromatography-UV-vis-mass spectrometry, was observed. Some of the compounds identified in the laboratory study were also observed in aerosol samples collected at SMEAR II station (Hyytiälä, Finland) in August 2015 suggesting the importance of aldehyde-amine reactions for the aerosol formation and growth.

Nitration of particle-associated PAHs and their derivatives (nitro-, oxy-, and hydroxy-PAHs) with NO 3 radicals

NASA Astrophysics Data System (ADS)

Zhang, Yang; Yang, Bo; Gan, Jie; Liu, Changgeng; Shu, Xi; Shu, Jinian

2011-05-01

The heterogeneous reactions of typical polycyclic aromatic hydrocarbons (PAHs) and their derivatives (nitro-, oxy-, and hydroxy-PAHs) adsorbed on azelaic acid particles with NO 3 radicals are investigated using a flow-tube reactor coupled to a vacuum ultraviolet photoionization aerosol time-of-flight mass spectrometer (VUV-ATOFMS). The mono-nitro-, di-nitro-, and poly-nitro-products from successive nitro-substitution reactions of PAHs and their derivatives are observed in real time with VUV-ATOFMS. 9-Nitroanthracene, anthraquinone, anthrone, 9,10-dinitroanthracene, 2-, 4-, and 9-nitrophenanthrene, 1-nitropyrene, 1,3-, 1,6-, and 1,8-dinitropyrene, 7-nitrobenzo[ a]anthracene, and benzo[ a]anthracene-7,12-dione are identified by GC/MS analysis of the reaction products of PAHs and their derivatives coated on the inner bottom surface of the conical flasks with NO 3 radicals. Other oxygenated products are tentatively assigned. 1-Nitropyrene is the only mono-nitrated product detected in the reaction of surface-bound pyrene with gas-phase NO 3 radicals. This phenomenon is different from what has been observed in previous studies of the gas-phase pyrene nitration, showing that 2-nitropyrene is the sole nitration product. The experimental results may reveal the discrepancies between the heterogeneous and homogeneous nitrations of pyrene.

Gas-Phase Anionic σ-Adduct (Trans)formations in Heteroaromatic Systems1

NASA Astrophysics Data System (ADS)

Zimnicka, Magdalena; Danikiewicz, Witold

2015-07-01

Anions of nitroderivatives of thiophene and furan were subjected to the reactions with selected C-H acids in the gas phase. Various structures and reaction pathways were proposed for the observed ionic products. In general, the reactions of heteroaromatic anions with C-H acids may be divided into three groups, depending on the proton affinity difference between C-H acid's conjugate base and heteroaromatic anion (ΔPA). The proton transfer from C-H acid to heteroaromatic anion is a dominant process in the reactions for which ΔPA < 0 kcal mol-1, whereas the reactions with high ΔPA (ΔPA > 16 kcal mol-1) do not lead to any ionic products. The formation of σ-adducts and products of their further transformations according to the VNS, SNAr, cine, and tele substitution mechanisms have been proposed for reactions with moderate ΔPA. The other possible mechanisms as SN2 reaction, nucleophilic addition to the cyano group, ring-opening pathway, and halogenophilic reaction have also been discussed to contribute in the reactions between heteroaromatic anions and C-H acids.

Stochastic surface walking reaction sampling for resolving heterogeneous catalytic reaction network: A revisit to the mechanism of water-gas shift reaction on Cu

NASA Astrophysics Data System (ADS)

Zhang, Xiao-Jie; Shang, Cheng; Liu, Zhi-Pan

2017-10-01

Heterogeneous catalytic reactions on surface and interfaces are renowned for ample intermediate adsorbates and complex reaction networks. The common practice to reveal the reaction mechanism is via theoretical computation, which locates all likely transition states based on the pre-guessed reaction mechanism. Here we develop a new theoretical method, namely, stochastic surface walking (SSW)-Cat method, to resolve the lowest energy reaction pathway of heterogeneous catalytic reactions, which combines our recently developed SSW global structure optimization and SSW reaction sampling. The SSW-Cat is automated and massively parallel, taking a rough reaction pattern as input to guide reaction search. We present the detailed algorithm, discuss the key features, and demonstrate the efficiency in a model catalytic reaction, water-gas shift reaction on Cu(111) (CO + H2O → CO2 + H2). The SSW-Cat simulation shows that water dissociation is the rate-determining step and formic acid (HCOOH) is the kinetically favorable product, instead of the observed final products, CO2 and H2. It implies that CO2 and H2 are secondary products from further decomposition of HCOOH at high temperatures. Being a general purpose tool for reaction prediction, the SSW-Cat may be utilized for rational catalyst design via large-scale computations.

Dominant Overall Chemical Reaction in a Chlorine Trifluoride Silicon Nitrogen System at Atmospheric Pressure

NASA Astrophysics Data System (ADS)

Habuka, Hitoshi; Otsuka, Toru; Qu, Wei-Feng

1999-11-01

This study evaluates the overall chemical reaction in a chlorine trifluoride silicon nitrogen system at atmospheric pressure, based on the observation of the dominant chemical species in the gas phase using a quadrupole mass spectra analyzer coupled with a horizontal cold-wall single-wafer epitaxial reactor. Chlorine trifluoride gas etches the silicon surface, producing two major products, silicon tetrafluoride gas and chlorine gas, at room temperature and 530 K. The production of chlorosilanes was not observed in this study. The results obtained in this study indicate that the dominant overall chemical reaction in a chlorine trifluoride silicon nitrogen system is 3Si + 4ClF3 →3SiF4 ↑+ 2Cl2 ↑.

Glycerol electro-oxidation on a carbon-supported platinum catalyst at intermediate temperatures

NASA Astrophysics Data System (ADS)

Ishiyama, Keisuke; Kosaka, Fumihiko; Shimada, Iori; Oshima, Yoshito; Otomo, Junichiro

2013-03-01

The electro-oxidation of glycerol on a carbon-supported platinum catalyst (Pt/C) in combination with a reaction products analysis was investigated at intermediate temperatures (235-260 °C) using a single cell with a CsH2PO4 proton conducting solid electrolyte. A high current density was achieved. The main products were H2, CO2 and CO but the formation of C2 compounds, such as glycolic acid and ethane, was also observed. In addition, several C3 compounds were detected as minor products. A reaction products analysis revealed that the C-C bond dissociation ratio of glycerol was 70-80% at both low and high potentials (>200 mV vs. reversible hydrogen electrode) at 250 °C, suggesting that rapid dissociation occurs on Pt/C. The reaction products analysis also suggested that hydrogen production via thermal decomposition and/or steam reforming of glycerol (indirect path) and direct electro-oxidation of glycerol (direct path) proceed in parallel. More detailed reaction paths involving C1, C2 and C3 reaction products are discussed as well as the possible rate-determining step in glycerol electro-oxidation at intermediate temperatures.

Low temperature hydrogen production during experimental hydration of partially-serpentinized dunite

NASA Astrophysics Data System (ADS)

Miller, Hannah M.; Mayhew, Lisa E.; Ellison, Eric T.; Kelemen, Peter; Kubo, Mike; Templeton, Alexis S.

2017-07-01

Dissolved hydrogen is common in mafic and ultramafic aquifers; however, the water/rock reactions that give rise to hydrogen production at near-surface temperatures are enigmatic. Similarly, mineral hydration experiments have not yet unequivocally demonstrated whether H2 can be produced at low-temperatures at significant rates from reaction of aqueous fluids with basalts and peridotites for prolonged amounts of time. We conducted laboratory-based water/rock reactions between partially serpentinized Oman dunite and a simulated Oman rainwater (RW) media, as well as a simulated seawater (SW) media, to quantify H2 generation rates at 100 °C. Throughout more than 9 months of water/rock reaction, extensive hydrogen production and consumption were observed in RW and SW media. In the first 24 h of reaction in anoxic fluids containing only dissolved N2 and CO2, the room-temperature pH in both RW and SW media increased from 6.5 to ∼9, and the average pH then remained relatively constant at pH 8.5 (±0.5 pH) for the duration of the experiments. We also measured some of the highest hydrogen concentrations observed in experimental low-temperature serpentinization reactions. The maximum measured H2 concentrations in SW media were 470 nmol H2 per g mineral after ∼3 months, while RW media H2 concentrations reached 280 nmol/g H2 after ∼3 months. After reaching micromolar dissolved H2(aq), the H2 concentrations notably declined, and CO2 was almost fully consumed. We measured the formation of formate (up to 98 μM) and acetate (up to 91 μM) associated with a drawdown of H2 and CO2 in the experiments. No CH4 or carbonate formation was observed. To identify reactions giving rise to low-temperature hydrogen production, the mineralogy and oxidation state of the Fe-bearing species in the dunite were extensively characterized before and after reaction using Raman spectroscopy, Quantitative Evaluation of Minerals by SCANing electron microscopy (QEMSCAN), powder X-ray diffraction (XRD), magnetic susceptibility, scanning electron microscopy (SEM), and Fe K-edge X-ray absorption near edge structure (XANES) spectroscopic techniques. The mineralogy of the solid starting material was dominated by olivine and serpentine with minor brucite, pyroxene and spinel. After reaction, additional serpentine and magnetite could be detected as reaction products, and pre-existing brucite was consumed. No changes were observed in the abundance or grain sizes of olivine or pyroxene. Thus, we propose that the destabilization of Fe(II)-bearing brucite and the subsequent oxidation of the aqueous Fe(II) to form magnetite and Fe(III)-rich serpentine give rise to H2 production at 100 °C. This work demonstrates that dissolved hydrogen and low molecular weight organic acids can be produced by the reaction of labile Fe(II)-bearing minerals generated during a prior stage of water/rock reactions. In particular, progressive alteration of partially-serpentinized peridotites containing brucite may generate sufficient electron donors to fuel in-situ subsurface microbial activity.

Use of hydrostatic pressure for modulation of protein chemical modification and enzymatic selectivity.

PubMed

Makarov, Alexey A; Helmy, Roy; Joyce, Leo; Reibarkh, Mikhail; Maust, Mathew; Ren, Sumei; Mergelsberg, Ingrid; Welch, Christopher J

2016-05-11

Using hydrostatic pressure to induce protein conformational changes can be a powerful tool for altering the availability of protein reactive sites and for changing the selectivity of enzymatic reactions. Using a pressure apparatus, it has been demonstrated that hydrostatic pressure can be used to modulate the reactivity of lysine residues of the protein ubiquitin with a water-soluble amine-specific homobifunctional coupling agent. Fewer reactive lysine residues were observed when the reaction was carried out under elevated pressure of 3 kbar, consistent with a pressure-induced conformational change of ubiquitin that results in fewer exposed lysine residues. Additionally, modulation of the stereoselectivity of an enzymatic transamination reaction was observed at elevated hydrostatic pressure. In one case, the minor diasteromeric product formed at atmospheric pressure became the major product at elevated pressure. Such pressure-induced alterations of protein reactivity may provide an important new tool for enzymatic reactions and the chemical modification of proteins.

The oleic acid-ozone heterogeneous reaction system: products, kinetics, secondary chemistry, and atmospheric implications of a model system - a review

NASA Astrophysics Data System (ADS)

Zahardis, J.; Petrucci, G. A.

2007-02-01

The heterogeneous processing of organic aerosols by trace oxidants has many implications to atmospheric chemistry and climate regulation. This review covers a model heterogeneous reaction system (HRS): the oleic acid-ozone HRS and other reaction systems featuring fatty acids, and their derivatives. The analysis of the commonly observed aldehyde and organic acid products of ozonolysis (azelaic acid, nonanoic acid, 9-oxononanoic acid, nonanal) is described. The relative product yields are noted and explained by the observation of secondary chemical reactions. The secondary reaction products arising from reactive Criegee intermediates are mainly peroxidic, notably secondary ozonides and α-acyloxyalkyl hydroperoxide oligomers and polymers, and their formation is in accord with solution and liquid-phase ozonolysis. These highly oxygenated products are of low volatility and hydrophilic which may enhance the ability of particles to act as cloud condensation nuclei (CCN). The kinetic description of this HRS is critically reviewed. Most kinetic studies suggest this oxidative processing is either a near surface reaction that is limited by the diffusion of ozone or a surface based reaction. Internally mixed particles and coatings represent the next stage in the progression towards more realistic proxies of tropospheric organic aerosols and a description of the products and the kinetics resulting from the ozonolysis of these proxies, which are based on fatty acids or their derivatives, is presented. Finally, the main atmospheric implications of oxidative processing of particulate containing fatty acids are presented. These implications include the extended lifetime of unsaturated species in the troposphere facilitated by the presence of solids, semi-solids or viscous phases, and an enhanced rate of ozone uptake by particulate unsaturates compared to corresponding gas-phase organics. Ozonolysis of oleic acid enhances its CCN activity, which implies that oxidatively processed particulate may contribute to indirect forcing of radiation.

UV-Photochemistry of the Disulfide Bond: Evolution of Early Photoproducts from Picosecond X-ray Absorption Spectroscopy at the Sulfur K-Edge.

PubMed

Ochmann, Miguel; Hussain, Abid; von Ahnen, Inga; Cordones, Amy A; Hong, Kiryong; Lee, Jae Hyuk; Ma, Rory; Adamczyk, Katrin; Kim, Tae Kyu; Schoenlein, Robert W; Vendrell, Oriol; Huse, Nils

2018-05-30

We have investigated dimethyl disulfide as the basic moiety for understanding the photochemistry of disulfide bonds, which are central to a broad range of biochemical processes. Picosecond time-resolved X-ray absorption spectroscopy at the sulfur K-edge provides unique element-specific insight into the photochemistry of the disulfide bond initiated by 267 nm femtosecond pulses. We observe a broad but distinct transient induced absorption spectrum which recovers on at least two time scales in the nanosecond range. We employed RASSCF electronic structure calculations to simulate the sulfur-1s transitions of multiple possible chemical species, and identified the methylthiyl and methylperthiyl radicals as the primary reaction products. In addition, we identify disulfur and the CH 2 S thione as the secondary reaction products of the perthiyl radical that are most likely to explain the observed spectral and kinetic signatures of our experiment. Our study underscores the importance of elemental specificity and the potential of time-resolved X-ray spectroscopy to identify short-lived reaction products in complex reaction schemes that underlie the rich photochemistry of disulfide systems.

Nitromethane decomposition under high static pressure.

PubMed

Citroni, Margherita; Bini, Roberto; Pagliai, Marco; Cardini, Gianni; Schettino, Vincenzo

2010-07-29

The room-temperature pressure-induced reaction of nitromethane has been studied by means of infrared spectroscopy in conjunction with ab initio molecular dynamics simulations. The evolution of the IR spectrum during the reaction has been monitored at 32.2 and 35.5 GPa performing the measurements in a diamond anvil cell. The simulations allowed the characterization of the onset of the high-pressure reaction, showing that its mechanism has a complex bimolecular character and involves the formation of the aci-ion of nitromethane. The growth of a three-dimensional disordered polymer has been evidenced both in the experiments and in the simulations. On decompression of the sample, after the reaction, a continuous evolution of the product is observed with a decomposition into smaller molecules. This behavior has been confirmed by the simulations and represents an important novelty in the scene of the known high-pressure reactions of molecular systems. The major reaction product on decompression is N-methylformamide, the smallest molecule containing the peptide bond. The high-pressure reaction of crystalline nitromethane under irradiation at 458 nm was also experimentally studied. The reaction threshold pressure is significantly lowered by the electronic excitation through two-photon absorption, and methanol, not detected in the purely pressure-induced reaction, is formed. The presence of ammonium carbonate is also observed.

A New Design Strategy for Observing Lithium Oxide Growth-Evolution Interactions Using Geometric Catalyst Positioning.

PubMed

Ryu, Won-Hee; Gittleson, Forrest S; Li, Jinyang; Tong, Xiao; Taylor, André D

2016-08-10

Understanding the catalyzed formation and evolution of lithium-oxide products in Li-O2 batteries is central to the development of next-generation energy storage technology. Catalytic sites, while effective in lowering reaction barriers, often become deactivated when placed on the surface of an oxygen electrode due to passivation by solid products. Here we investigate a mechanism for alleviating catalyst deactivation by dispersing Pd catalytic sites away from the oxygen electrode surface in a well-structured anodic aluminum oxide (AAO) porous membrane interlayer. We observe the cross-sectional product growth and evolution in Li-O2 cells by characterizing products that grow from the electrode surface. Morphological and structural details of the products in both catalyzed and uncatalyzed cells are investigated independently from the influence of the oxygen electrode. We find that the geometric decoration of catalysts far from the conductive electrode surface significantly improves the reaction reversibility by chemically facilitating the oxidation reaction through local coordination with PdO surfaces. The influence of the catalyst position on product composition is further verified by ex situ X-ray photoelectron spectroscopy and Raman spectroscopy in addition to morphological studies.

A new design strategy for observing lithium oxide growth-evolution interactions using geometric catalyst positioning

DOE PAGES

Ryu, Won -Hee; Gittleson, Forrest S.; Li, Jinyang; ...

2016-06-21

Understanding the catalyzed formation and evolution of lithium-oxide products in Li-O 2 batteries is central to the development of next-generation energy storage technology. Catalytic sites, while effective in lowering reaction barriers, often become deactivated when placed on the surface of an oxygen electrode due to passivation by solid products. Here we investigate a mechanism for alleviating catalyst deactivation by dispersing Pd catalytic sites away from the oxygen electrode surface in a well-structured anodic aluminum oxide (AAO) porous membrane interlayer. We observe the cross-sectional product growth and evolution in Li-O 2 cells by characterizing products that grow from the electrode surface.more » Morphological and structural details of the products in both catalyzed and uncatalyzed cells are investigated independently from the influence of the oxygen electrode. We find that the geometric decoration of catalysts far from the conductive electrode surface significantly improves the reaction reversibility by chemically facilitating the oxidation reaction through local coordination with PdO surfaces. Lastly, the influence of the catalyst position on product composition is further verified by ex situ Xray photoelectron spectroscopy and Raman spectroscopy in addition to morphological studies.« less

Confirmation of the Decay of 283112 and First Indication for Hg-like Behavior of Element 112

NASA Astrophysics Data System (ADS)

Eichler, R.; Aksenov, N. V.; Belozerov, A. V.; Bozhikov, G. A.; Chepigin, V. I.; Dressler, R.; Dmitriev, S. N.; Gäggeler, H. W.; Gorshkov, V. A.; Haenssler, F.; Itkis, M. G.; Lebedev, V. Ya.; Laube, A.; Malyshev, O. N.; Oganessian, Yu. Ts.; Petruschkin, O. V.; Piguet, D.; Rasmussen, P.; Shishkin, S. V.; Shutov, A. V.; Svirikhin, A. I.; Tereshatov, E. E.; Vostokin, G. K.; Wegrzecki, M.; Yeremin, A. V.

2007-05-01

Two gas phase adsorption chemistry experiments aimed at the chemical characterization of element 112 using its isotope 283112 have been performed at the Flerov Laboratory for Nuclear Reactions (FLNR) Dubna, Russia. The applied Insitu-Volatilization and On-line Detection (IVO) technique is a thermochromatographic system combining the determination of the deposition temperature of volatile elements on a surface along a temperature gradient with an efficient detection of the deposited species by event-by-event alpha and SF-fragment spectroscopy. Two possibilities to produce the isotope 283112 were used: 1.) the direct production reaction 238U( 48Ca,3n) 283112; 2.) the reaction 242Pu( 48Ca,3n), where the primary product 287114, decays via alpha emission to 283112 with a half-life of 0.5 s. The chemistry experiments were aimed at a chemical identification of 283112 and an independent confirmation of its decay properties. In the direct reaction no decays related to 283112 were observed. However, two decay chains unambiguously attributed to the decay of 283112 were observed using the second production path. Previously reported observation of 283112 and 279Ds and their decay properties were confirmed. From its thermochromatorgaphic deposition first thermochemical data were deduced for element 112, unveiling it as a typical group 12 element.

In situ measurement of magnesium carbonate formation from CO2 using static high-pressure and -temperature 13C NMR.

PubMed

Surface, J Andrew; Skemer, Philip; Hayes, Sophia E; Conradi, Mark S

2013-01-02

We explore a new in situ NMR spectroscopy method that possesses the ability to monitor the chemical evolution of supercritical CO(2) in relevant conditions for geological CO(2) sequestration. As a model, we use the fast reaction of the mineral brucite, Mg(OH)(2), with supercritical CO(2) (88 bar) in aqueous conditions at 80 °C. The in situ conversion of CO(2) into metastable and stable carbonates is observed throughout the reaction. After more than 58 h of reaction, the sample was depressurized and analyzed using in situ Raman spectroscopy, where the laser was focused on the undisturbed products through the glass reaction tube. Postreaction, ex situ analysis was performed on the extracted and dried products using Raman spectroscopy, powder X-ray diffraction, and magic-angle spinning (1)H-decoupled (13)C NMR. These separate methods of analysis confirmed a spatial dependence of products, possibly caused by a gradient of reactant availability, pH, and/or a reaction mechanism that involves first forming hydroxy-hydrated (basic, hydrated) carbonates that convert to the end-product, anhydrous magnesite. This carbonation reaction illustrates the importance of static (unmixed) reaction systems at sequestration-like conditions.

The photochemical formation and gas-particle partitioning of oxidation products of decamethyl cyclopentasiloxane and decamethyl tetrasiloxane in the atmosphere

NASA Astrophysics Data System (ADS)

Chandramouli, Bharadwaj; Kamens, Richard M.

Decamethyl cyclopentasiloxane (D 5) and decamethyl tetrasiloxane (MD 2M) were injected into a smog chamber containing fine Arizona road dust particles (95% surface area <2.6 μM) and an urban smog atmosphere in the daytime. A photochemical reaction - gas-particle partitioning reaction scheme, was implemented to simulate the formation and gas-particle partitioning of hydroxyl oxidation products of D 5 and MD 2M. This scheme incorporated the reactions of D 5 and MD 2M into an existing urban smog chemical mechanism carbon bond IV and partitioned the products between gas and particle phase by treating gas-particle partitioning as a kinetic process and specifying an uptake and off-gassing rate. A photochemical model PKSS was used to simulate this set of reactions. A Langmuirian partitioning model was used to convert the measured and estimated mass-based partitioning coefficients ( KP) to a molar or volume-based form. The model simulations indicated that >99% of all product silanol formed in the gas-phase partition immediately to particle phase and the experimental data agreed with model predictions. One product, D 4TOH was observed and confirmed for the D 5 reaction and this system was modeled successfully. Experimental data was inadequate for MD 2M reaction products and it is likely that more than one product formed. The model set up a framework into which more reaction and partitioning steps can be easily added.

Entropic factors provide unusual reactivity and selectivity in epoxide-opening reactions promoted by water

PubMed Central

Byers, Jeffery A.; Jamison, Timothy F.

2013-01-01

Despite the myriad of selective enzymatic reactions that occur in water, chemists have rarely capitalized on the unique properties of this medium to govern selectivity in reactions. Here we report detailed mechanistic investigations of a water-promoted reaction that displays high selectivity for what is generally a disfavored product. A combination of structural and kinetic data indicates not only that synergy between substrate and water suppresses undesired pathways but also that water promotes the desired pathway by stabilizing charge in the transition state, facilitating proton transfer, doubly activating the substrate for reaction, and perhaps most remarkably, reorganizing the substrate into a reactive conformation that leads to the observed product. This approach serves as an outline for a general strategy of exploiting solvent-solute interactions to achieve unusual reactivity in chemical reactions. These findings may also have implications in the biosynthesis of the ladder polyether natural products, such as the brevetoxins and ciguatoxins. PMID:24046369

Product distribution study of the Cl-atom initiated oxidation of ethyl methyl sulfide and diethyl sulfide

NASA Astrophysics Data System (ADS)

Oksdath-Mansilla, Gabriela; Peñéñory, Alicia B.; Barnes, Ian; Wiesen, Peter; Teruel, Mariano A.

2014-03-01

The products formed in the gas-phase reactions of Cl atoms with (CH3CH2)2S and CH3CH2SCH3 have been investigated in a large volume reactor in NOx-free air at atmospheric pressure and (298 ± 2) K using long path “in situ” FTIR spectroscopy for the analysis. HCl, SO2 and CH3CHO were identified as the major products for both reactions. For the Cl + CH3CH2SCH3 reaction HCHO was also identified as a major product. The yields of the products obtained for the reaction of Cl with (CH3CH2)2S were (59 ± 2) %, (52 ± 5) % and (103 ± 4) % for HCl, SO2 and CH3CHO, respectively. For the reaction of Cl with CH3CH2SCH3 yields of (43 ± 5) %, (55 ± 3) %, (58 ± 3) % and (53 ± 5) % were obtained for HCl, SO2, CH3CHO and HCHO, respectively. This is the first products and mechanistic study for the gas-phase Cl-initiated oxidation of non-CH3SCH3 alkyl sulfides. Comparison with previous results for the reaction of Cl with dimethyl sulfide is made and simple atmospheric degradation mechanisms are postulated to explain the formation of the observed products.

Brown Carbon Production in Aldehyde + Ammonium Sulfate Mixtures: Effects of Formaldehyde and Amines

NASA Astrophysics Data System (ADS)

Powelson, M.; De Haan, D. O.

2012-12-01

The formation of light-absorbing 'brown carbon,' or HULIS (humic- like substances), in atmospheric aerosol has an important impact on climate. However, the precursors responsible for brown carbon formation have not been identified. Several aldehydes present in clouds (methylglyoxal, glycolaldehyde, hydroxyacetone, glyoxal, and acetaldehyde) have the potential to create brown products when reacted with ammonium sulfate or primary amines such as methylamine or glycine. The formation of light-absorbing products from these reactions was characterized as a function of cloud-relevant pH (from 3- 6) using UV-Visible spectroscopy. Of the different aldehydes teste, the largest production rates of light-absorbing compounds were observed in reactions of glycolaldehyde and methylglyoxal. Primary amines produced more light- absorbing products than ammonium sulfate at lower concentrations. The addition of formaldehyde to any reaction with other aldehydes decreased the formation of light-absorbing products, while the addition of a small amount (1:5 mole ratio) of glycine to aldehyde + ammonium sulfate reactions can increase the production of light-absorbing products. These results suggest that the presence of primary amines significantly influence atmospheric brown carbon production by aldehydes even when much greater quantities of ammonium sulfate are present.

Catalysis of Nuclear Reactions by Electrons

NASA Astrophysics Data System (ADS)

Lipoglavšek, Matej

2018-01-01

Electron screening enhances nuclear reaction cross sections at low energies. We studied the nuclear reaction 1H(19F,αγ)16O in inverse kinematics in different solid hydrogen targets. Measured resonance strengths differed by up to a factor of 10 in different targets. We also studied the 2H(p,γ)3He fusion reaction and observed electrons emitted as reaction products instead of γ rays. In this case electron screening greatly enhances internal conversion probability.

The reactions of cobalt, iron and nickel in SO2 atmospheres Similarities and differences

NASA Technical Reports Server (NTRS)

Jacobson, N. S.; Worrell, W. L.

1985-01-01

The reactions of cobalt, iron and nickel in SO2 atmospheres are reviewed and compared. A mixed oxide-sulfide product layer is observed in all cases. Cobalt and nickel exhibit similar behavior. The observed rates are near the sulfidation rates, and the reaction rate is strongly influenced by the outward diffusion of metal through an interconnected sulfide network. A continuous interconnected sulfide is not observed in the oxide-sulfide scales formed on iron, and the reaction rates are more difficult to summarize. The differences and similarities among the three metals are explained in terms of the absence of scale-gas equilibrium and the ratio of the metal diffusivity in the corresponding oxide and sulfide.

The reactions of cobalt, iron and nickel in SO-2 atmospheres: Similarities and differences

NASA Technical Reports Server (NTRS)

Jacobson, N. S.; Worrell, W. L.

1984-01-01

The reactions of cobalt, iron and nickel in SO2 atmospheres are reviewed and compared. A mixed oxide-sulfide product layer is observed in all cases. Cobalt and nickel exhibits similar behavior. The observed rates are near the sulfidation rates, and the reaction rate is strongly influenced by the outward diffusion of metal through an interconnected sulfide network. A continuous interconnected sulfide is not observed in the oxide-sulfide scales formed on iron, and the reaction rates are more difficult to summarize. The differences and similarities among the three metals are explained in terms of the absence of scale-gas equilibrium and the ratio of the metal diffusivity in the corresponding oxide and sulfide.

Rate Constant and RRKM Product Study for the Reaction Between CH3 and C2H3 at T = 298K

NASA Technical Reports Server (NTRS)

Thorn, R. Peyton, Jr.; Payne, Walter A., Jr.; Chillier, Xavier D. F.; Stief, Louis J.; Nesbitt, Fred L.; Tardy, D. C.

2000-01-01

The total rate constant k1 has been determined at P = 1 Torr nominal pressure (He) and at T = 298 K for the vinyl-methyl cross-radical reaction CH3 + C2H3 yields products. The measurements were performed in a discharge flow system coupled with collision-free sampling to a mass spectrometer operated at low electron energies. Vinyl and methyl radicals were generated by the reactions of F with C2H4 and CH4, respectively. The kinetic studies were performed by monitoring the decay of C2H3 with methyl in excess, 6 < |CH3|(sub 0)/|C2H3|(sub 0) < 21. The overall rate coefficient was determined to be k1(298 K) = (1.02 +/- 0.53)x10(exp -10) cubic cm/molecule/s with the quoted uncertainty representing total errors. Numerical modeling was required to correct for secondary vinyl consumption by reactions such as C2H3 + H and C2H3 + C2H3. The present result for k1 at T = 298 K is compared to two previous studies at high pressure (100-300 Torr He) and to a very recent study at low pressure (0.9-3.7 Torr He). Comparison is also made with the rate constant for the similar reaction CH3 + C2H5 and with a value for k1 estimated by the geometric mean rule employing values for k(CH3 + CH3) and k(C2H3 + C2H3). Qualitative product studies at T = 298 K and 200 K indicated formation of C3H6, C2H2, and C2H5 as products of the combination-stabilization, disproportionation, and combination-decomposition channels, respectively, of the CH3 + C2H3 reaction. We also observed the secondary C4H8 product of the subsequent reaction of C3H5 with excess CH3; this observation provides convincing evidence for the combination-decomposition channel yielding C3H5 + H. RRKM calculations with helium as the deactivator support the present and very recent experimental observations that allylic C-H bond rupture is an important path in the combination reaction. The pressure and temperature dependencies of the branching fractions are also predicted.

Association reactions at low pressure. 5: The CH3(+)/HCN system. A final word?

NASA Technical Reports Server (NTRS)

Anicich, Vincent G.; Sen, Atish D.; Huntress, Wesley, Jr.; McEwan, Murray J.

1995-01-01

The reaction of the methyl cation with hydrogen cyanide is revisited. We have confidence that we have resolved a long standing apparent contradiction of experimental results. A literature history is presented along with one new experiment and a re-examination of an old experiment. In this present work it is shown that all of the previous studies had made consistent observations. Yet, each of the previous studies failed to observe all of the information present. The methyl cation does react with HCN by radiative association, a fact which had been in doubt. The product ions formed in the two-body and three-body processes react differently with HCN. The collisionally stabilized association product formed by a three-body mechanism, does not react with HCN and is readily detected in the experiments. The radiatively stabilized association product, formed by a slow two-body reaction, is not detected because it reacts with HCN by a fast proton transfer reaction forming the protonated HCN ion. Previous studies either 'lost' this product in the extremely large protonated HCN signal that is always present when HCN is used, or discounted it for various reasons. We have been able to show by ion cyclotron resonance (ICR) techniques (both FT-ICR and tandem ICR-dempster-ICR) that the radiative association product does react with the HCN to form the protonated HCN ion.

The Role of Oxygen in the Formation of TNT Product Ions in Ion Mobility Spectrometry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Daum, Keith Alvin; Atkinson, David Alan; Ewing, Robert Gordon

2002-03-01

The atmospheric pressure ionization of 2,4,6-trinitrotoluene (TNT) in air yields the (TNT-H)- product ion. It is generally accepted that this product ion is formed by the direct proton abstraction of neutral TNT by O2- reactant ions. Data presented here demonstrate the reaction involves the formation of an intermediate (TNT·O2)-, from the association of either TNT+O2- or TNT-+O2. This intermediate has two subsequent reaction branches. One of these branches involves simple dissociation of the intermediate to TNT-; the other branch is a terminal reaction that forms the typically observed (TNT-H)- ion via proton abstraction. The dissociation reaction involving electron transfer tomore » TNT- appeared to be kinetically favored and prevailed at low concentrations of oxygen (less than 2%). The presence of significant amounts of oxygen, however, resulted in the predominant formation of the (TNT-H)- ion by the terminal reaction branch. With TNT- in the system, either from direct electron attachment or by simple dissociation of the intermediate, increasing levels of oxygen in the system will continue to reform the intermediate, allowing the cycle to continue until proton abstraction occurs. Key to understanding this complex reaction pathway is that O2- was observed to transfer an electron directly to neutral TNT to form the TNT-. At oxygen levels of less than 2%, the TNT- ion intensity increased with increasing levels of oxygen (and O2-) and was larger than the (TNT-H)- ion intensity. As the oxygen level increased from 2 to 10%, the (TNT-H)- product ion became predominant. The potential reaction mechanisms were investigated with an ion mobility spectrometer, which was configured to independently evaluate the ionization pathways.« less

Morphology and phase evolution in microwave synthesized Al/FeO4 system.

PubMed

Chuan, Lee Chang; Yoshikawaa, Noboru; Taniguchia, Shoji

2011-01-01

Thermite reaction between Al/Fe3O4 raised by microwave (MW) heating under N2 atmosphere has been investigated, and compared with that by the electric furnace. In addition to the stoichiometric ratio for the production of metallic iron and alumina, mixture with slightly Lower in Al content is also studied. As thermite reaction is highly exothermic, melting of reaction product and destruction of microstructure may occur, which corresponds to the enthalpy and adiabatic temperature of the reaction. Hence, to avoid this problem, reaction coupled with a smaller driving force by controlling the MW ignition condition at low temperature exotherm has been investigated. The phase and microstructure evolution during the reaction were analyzed by differential thermal analysis (DTA), X-ray diffraction (XRD), and scanning electron microscopy (SEM). Thermogram of the DTA analysis, irrespective of their mole ratio, recorded two exothermic peaks, one at - 1310 degrees C and another one at - 1370 degrees C. When heated by microwave at 955 degrees C, the main products were identified as Al, FeO and Fe, minor amount of Fe3O4 and some Fe and alumina were detected. When heating to 1155 degrees C, Al and Fe3O4 peaks disappeared, formation of Fe-Al alloy was observed. For sample heated at 1265 degrees C, a porous body was obtained. Micron sized metal particles with complex morphology, irregular in size and shapes were formed, uniformly distributed within the spinel hercynite and/or alumina matrix. In contrast, conventional heating produced no porous products. Formation of alumina is also observed around the metal particles. Controlling of the reaction progress was possible while heating the sample by MW around the low temperature exotherm region, whereas the combustion wave could not be self-propagated.

Mineral-assisted production of benzene under hydrothermal conditions: Insights from experimental studies on C6 cyclic hydrocarbons

NASA Astrophysics Data System (ADS)

Venturi, Stefania; Tassi, Franco; Gould, Ian R.; Shock, Everett L.; Hartnett, Hilairy E.; Lorance, Edward D.; Bockisch, Christiana; Fecteau, Kristopher M.; Capecchiacci, Francesco; Vaselli, Orlando

2017-10-01

Volatile Organic Compounds (VOCs) are ubiquitously present at low but detectable concentrations in hydrothermal fluids from volcanic and geothermal systems. Although their behavior is strictly controlled by physical and chemical parameters, the mechanisms responsible for the production of most VOCs in natural environments are poorly understood. Among them, benzene, whose abundances were found to be relatively high in hydrothermal gases, can theoretically be originated from reversible catalytic reforming processes, i.e. multi-step dehydrogenation reactions, involving saturated hydrocarbons. However, this hypothesis and other hypotheses are difficult to definitively prove on the basis of compositional data obtained by natural gas discharges only. In this study, therefore, laboratory experiments were carried out to investigate the production of benzene from cyclic hydrocarbons at hydrothermal conditions, specifically 300 °C and 85 bar. The results of experiments carried out in the presence of water and selected powdered minerals, suggest that cyclohexane undergoes dehydrogenation to form benzene, with cyclohexene and cyclohexadiene as by-products, and also as likely reaction intermediates. This reaction is slow when carried out in water alone and competes with isomerization and hydration pathways. However, benzene formation was increased compared to these competing reactions in the presence of sulfide (sphalerite and pyrite) and iron oxide (magnetite and hematite) minerals, whereas no enhancement of any reaction products was observed in the presence of quartz. The production of thiols was observed in experiments involving sphalerite and pyrite, suggesting that sulfide minerals may act both to enhance reactivity and also as reactants after dissolution. These experiments demonstrate that benzene can be effectively produced at hydrothermal conditions through dehydrogenation of saturated cyclic organic structures and highlight the crucial role played by minerals in this process.

Spectral Rate Theory for Two-State Kinetics

NASA Astrophysics Data System (ADS)

Prinz, Jan-Hendrik; Chodera, John D.; Noé, Frank

2014-02-01

Classical rate theories often fail in cases where the observable(s) or order parameter(s) used is a poor reaction coordinate or the observed signal is deteriorated by noise, such that no clear separation between reactants and products is possible. Here, we present a general spectral two-state rate theory for ergodic dynamical systems in thermal equilibrium that explicitly takes into account how the system is observed. The theory allows the systematic estimation errors made by standard rate theories to be understood and quantified. We also elucidate the connection of spectral rate theory with the popular Markov state modeling approach for molecular simulation studies. An optimal rate estimator is formulated that gives robust and unbiased results even for poor reaction coordinates and can be applied to both computer simulations and single-molecule experiments. No definition of a dividing surface is required. Another result of the theory is a model-free definition of the reaction coordinate quality. The reaction coordinate quality can be bounded from below by the directly computable observation quality, thus providing a measure allowing the reaction coordinate quality to be optimized by tuning the experimental setup. Additionally, the respective partial probability distributions can be obtained for the reactant and product states along the observed order parameter, even when these strongly overlap. The effects of both filtering (averaging) and uncorrelated noise are also examined. The approach is demonstrated on numerical examples and experimental single-molecule force-probe data of the p5ab RNA hairpin and the apo-myoglobin protein at low pH, focusing here on the case of two-state kinetics.

Meson production in relativistic heavy-ion collisions at AGS energies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Steadman, S.G.; E802 Collaboration

1993-07-01

Single particle inclusive spectra are presented for pion and kaon production in Si+Au reactions at an incident momentum of 14.6 A {center_dot} GeV/c and Au+Au reactions at an incident momentum of 11.6 A {center_dot} GeV/c. A simple geometric scaling of the pion production for central collisions as A{sub proj}{sup 1/3} and A{sub targ}{sup 2/3} results from the observed production of about one pion per participant. Kaon yields are shown to be proportional to the number of excited participants and consistent with RQMD and ARC calculations.

Meson production in relativistic heavy-ion collisions at AGS energies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Steadman, S.G.

1993-01-01

Single particle inclusive spectra are presented for pion and kaon production in Si + Au reactions at an incident momentum of 14.6 A [center dot] GeV/c and Au + Au reactions at an incident momentum of 11.6 A [center dot] GeV/c. A simple geometric scaling of the pion production for central collisions as A[sub proj][sup 1/3] and A[sub targ][sup 2/3] results from the observed production of about one pion per participant. Kaon yields are shown to be proportional to the number of excited participants and consistent with RQMD and ARC calculations.

Studying Reaction Intermediates Formed at Graphenic Surfaces

NASA Astrophysics Data System (ADS)

Sarkar, Depanjan; Sen Gupta, Soujit; Narayanan, Rahul; Pradeep, Thalappil

2014-03-01

We report in-situ production and detection of intermediates at graphenic surfaces, especially during alcohol oxidation. Alcohol oxidation to acid occurs on graphene oxide-coated paper surface, driven by an electrical potential, in a paper spray mass spectrometry experiment. As paper spray ionization is a fast process and the time scale matches with the reaction time scale, we were able to detect the intermediate, acetal. This is the first observation of acetal formed in surface oxidation. The process is not limited to alcohols and the reaction has been extended to aldehydes, amines, phosphenes, sugars, etc., where reaction products were detected instantaneously. By combining surface reactions with ambient ionization and mass spectrometry, we show that new insights into chemical reactions become feasible. We suggest that several other chemical transformations may be studied this way. This work opens up a new pathway for different industrially and energetically important reactions using different metal catalysts and modified substrate.

Monoterpene SOA - Contribution of first-generation oxidation products to formation and chemical composition

NASA Astrophysics Data System (ADS)

Mutzel, Anke; Rodigast, Maria; Iinuma, Yoshiteru; Böge, Olaf; Herrmann, Hartmut

2016-04-01

Investigation of the consecutive reactions of first-generation terpene oxidation products provides insight into the formation of secondary organic aerosol (SOA). To this end, OH radical reactions with α-pinene, β-pinene, and limonene were examined along with the OH-oxidation of nopinone as a β-pinene oxidation product and pinonaldehyde and myrtenal as α-pinene oxidation products. The SOA yield of β-pinene (0.50) was much higher than that of α-pinene (0.35) and the limonene/OH system (0.30). This is opposite to the ozonolysis SOA yields described in the literature. The growth curve of SOA from β-pinene shows the contribution of secondary reactions, such as further reaction of nopinone. This contribution (17%) and the high SOA yield of nopinone (0.24) might lead to the high SOA formation potential observed for β-pinene. The majority of the C9 oxidation products observed from β-pinene can be attributed to the consecutive reaction of nopinone, whereas in the case of pinonaldehyde, only a few α-pinene oxidation products were identified. Nopinone contributes significantly to the formation of pinic acid (51%), homoterpenylic acid (74%), and 3-methyl-1,2,3-butane-tricarboxylic acid (MBTCA, 88%) during β-pinene oxidation. The oxidation of pinonaldehyde was expected to produce important SOA markers, but only negligible amounts were identified. This indicates that their formation by oxidation of α-pinene must proceed via different pathways from the further oxidation of pinonaldehyde. Only pinonic acid and MBTCA were found in considerable amounts and were formed in α-pinene oxidation with 57% yield, while that for the pinonaldehyde/OH reaction was 33%. The lack of important SOA marker compounds might cause the low SOA yield (0.07) observed for pinonaldehyde. Based on the low SOA yield, pinonaldehyde contributes only 4.5% to α-pinene SOA. Myrtenal was identified among the gas-phase products of α-pinene oxidation. A majority of α-pinene SOA marker compounds was indeed formed by myrtenal oxidation, especially terebic acid (84%), pinic acid (76%), and diaterpenylic acid acetate (DTAA; 40%). In general, the contribution of myrtenal to α-pinene SOA is estimated to be as high as 23%. Among the detected compounds, homoterpenylic acid was positively identified as a new SOA marker compound, which was formed from β-pinene/OH and nopinone/OH but not from α-pinene/OH. A new reaction pathway yielding MBTCA was also identified in the β-pinene/OH system formed by the oxidation of nopinone, while in the case of α-pinene, the oxidation of pinonaldehyde yielded MBTCA.

Surface reaction modification: The effect of structured overlayers of sulfur on the kinetics and mechanism of the decomposition of formic acid on Pt(111)

NASA Astrophysics Data System (ADS)

Abbas, N.; Madix, R. J.

The reaction of formic acid (DCOOH) on Pt(111), Pt(111)-(2×2)S and Pt(111)-(√3×√3)R30°S surfaces was examined by temperature programmed reaction spectroscopy. On the clean surface formic acid decomposed to yield primarily carbon dioxide and the hydrogenic species (H 2, HD and D 2) at low coverages. Although the formation of water and carbon monoxide via a dehydration reaction was observed at these coverages, the yield of these products was small when compared to the other products of reaction. The evolution of CO 2 at low temperature was ascribed to the decomposition of the formate intermediate. In the presence of sulfur the amount of molecularly adsorbed formic acid decreased up to a factor of three on the (√3×√3)R30°S surface, and a decline in the reactivity of over an order of magnitude was also observed. The only products formed were the hydrogenic species and carbon dioxide. The absence of carbon monoxide indicated that the dehydration pathway was blocked by sulfur. In addition to the low temperature CO 2 peak a high temperature CO 2-producing path was also evident. It was inferred from both the stoichiometry and the coincident evolution of D 2 and CO 2 in the high temperature states that these products also evolved due to the decomposition of the formate intermediate. On increasing the sulfur coverage to one-third monolayer this intermediate was further stabilized, and a predominance of the decomposition via the high temperature path was observed. Stability of the formate intermediate was attributed to inhibition of the decomposition reaction by sulfur atoms. The activation energy for formate decomposition increased from 15 kcal/gmole on the clean surface to 24.3 kcal/gmol on the (√3×√3)R30°S overlayer.

Comparison of sulfuric and hydrochloric acids as catalysts in hydrolysis of Kappaphycus alvarezii (cottonii).

PubMed

Meinita, Maria Dyah Nur; Hong, Yong-Ki; Jeong, Gwi-Taek

2012-01-01

In this study, hydrolysis of marine algal biomass Kappaphhycus alvarezii using two different acid catalysts was examined with the goal of identifying optimal reaction conditions for the formation of sugars and by-products. K. alvarezii were hydrolyzed by autoclave using sulfuric acid or hydrochloric acid as catalyst with different acid concentrations (0.1-1.0 M), substrate concentrations (1.0-13.5%), hydrolysis time (10-90 min) and hydrolysis temperatures (100-130 (°)C). A difference in galactose, glucose, reducing sugar and total sugar content was observed under the different hydrolysis conditions. Different by-product compounds such as 5-hydroxymethylfurfural and levulinic acid were also observed under the different reaction conditions. The optimal conditions for hydrolysis were achieved at a sulfuric acid concentration, temperature and reaction time of 0.2 M, 130 °C and 15 min, respectively. These results may provide useful information for the development of more efficient systems for biofuel production from marine biomass.

Modeling the Reaction of Fe Atoms with CCl4

DOE Office of Scientific and Technical Information (OSTI.GOV)

Camaioni, Donald M.; Ginovska, Bojana; Dupuis, Michel

2009-01-05

The reaction of zero-valent iron with carbon tetrachloride (CCl4) in gas phase was studied using density functional theory. Temperature programmed desorption experiments over a range of Fe and CCl4 coverages on a FeO(111) surface, demonstrate a rich surface chemistry with several reaction products (C2Cl4, C2Cl6, OCCl2, CO, FeCl2, FeCl3) observed. The reactivity of Fe and CCl4 was studied under three stoichiometries, one Fe with one CCl4, one Fe with two CCl4 molecules and two Fe with one CCl4, modeling the environment of the experimental work. The electronic structure calculations give insight into the reactions leading to the experimentally observed productsmore » and suggest that novel Fe-C-Cl containing species are important intermediates in these reactions. The intermediate complexes are formed in highly exothermic reactions, in agreement with the experimentally observed reactivity with the surface at low temperature (30 K). This initial survey of the reactivity of Fe with CCl4 identifies some potential reaction pathways that are important in the effort to use Fe nano-particles to differentiate harmful pathways that lead to the formation of contaminants like chloroform (CHCl3) from harmless pathways that lead to products such as formate (HCO2-) or carbon oxides in water and soil. The Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.« less

Surface chemistry reactions of alpha-terpineol [(R)-2-(4-methyl-3-cyclohexenyl)isopropanol] with ozone and air on a glass and a vinyl tile.

PubMed

Ham, J E; Wells, J R

2008-10-01

The surface-phase reaction products of alpha-terpineol [(R)-2-(4-methyl-3-cyclohexenyl)isopropanol] with ozone (O(3)), air or nitrogen (N(2)) on both a glass and vinyl flooring tile were investigated using the recently published FLEC Automation and Control System (FACS). The FACS was used to deliver O(3) (100 ppb), air or N(2) to the surface at a specified flow rate (300 ml/min) and relative humidity (50%) after application of a 1.6%alpha-terpineol solution in methanol. Oxidation products were detected using the derivatization agents: O-(2,3,4,5,6-pentafluorobenzyl) hydroxylamine and N,O-bis(trimethysilyl)trifluoroacetamide. The positively identified reaction products were glyoxal, methylglyoxal and 4-oxopentanal. The proposed oxidation products based on previously published VOC/O(3) reaction mechanisms were: 4-methylcyclohex-3-en-1-one, 6-hydroxyhept-en-2-one, 3-(1-hydroxy-1-methylethyl)-6-methylcyclohex-2-en-1-one) and one surface-enhanced reaction product: 5-(1-hydroxy-1-methylethyl)-2-methylcyclohex-2-en-1-one. Though similar products were observed in gas-phase alpha-terpineol/O(3) reactions, the ratio of the reaction products were different suggesting stabilization of larger molecular weight species by the surface. Emission profiles of these oxidation products over 72 h are also reported. Volatile organic compounds (VOCs) can interact with indoor initiators [such as hydroxyl radicals (OH*), ozone and nitrate radicals (NO(3)*)] to form a number of oxygenated by-products in the gas-phase. However, when VOCs are applied to or are present on the surface, heterogeneous chemistry with indoor initiators can also occur. The surface can influence the reaction mechanism to produce new surface reaction products. The work, described here, shows the interaction of alpha-terpineol (major component of pine oil) with ozone and air on both glass and vinyl flooring. These results demonstrated emissions of oxygenated organic compounds as a result of reaction and that further investigations of this chemistry are required to accurately estimate indoor occupant exposures.

Enhanced nucleon transfer in tip collisions of 238U+124Sn

NASA Astrophysics Data System (ADS)

Sekizawa, Kazuyuki

2017-10-01

Multinucleon transfer processes in low-energy heavy ion reactions have attracted increasing interest in recent years aiming at the production of new neutron-rich isotopes. Clearly, it is an imperative task to further develop understanding of underlying reaction mechanisms to lead experiments to success. In this paper, from systematic time-dependent Hartree-Fock calculations for the 238U+124Sn reaction, it is demonstrated that transfer dynamics depend strongly on the orientations of 238U, quantum shells, and collision energies. Two important conclusions are obtained: (i) Experimentally observed many-proton transfer from 238U to 124Sn can be explained by a multinucleon transfer mechanism governed by enhanced neck evolution in tip collisions; (ii) novel reaction dynamics are observed in tip collisions at energies substantially above the Coulomb barrier, where a number of nucleons are transferred from 124Sn to 238U, producing transuranium nuclei as primary reaction products, which could be a means to synthesize superheavy nuclei. Both results indicate the importance of the neck (shape) evolution dynamics, which are sensitive to orientations, shell effects, and collision energies, for exploring possible pathways to produce new unstable nuclei.

Chemiluminescence of metastable tin with fluorine, chlorine, and nitrogen trifluoride utilizing a beam-gas configuration

NASA Astrophysics Data System (ADS)

Rosano, W. J.; Parson, J. M.

1986-09-01

This paper reports the observation of electronic chemiluminescence (CL) from the reaction of metastable Sn with F2, Cl2, and NF3. All three reactions produced CL which was identified as emission from the A 2Σ+-X 2Π system of the tin monohalides and was first order with respect to the scattering gas. All spectra were highly congested suggesting that the product monohalides are produced with a large degree of internal excitation. Attenuation studies of various electronic states of metastable Sn in the beam with H2 show the 1D state to be the major contributor to CL product formation. Absolute CL cross sections were determined for Sn(1D) with F2, Cl2, and NF3 to be 67, >0.07, and 0.006 Å2, respectively, with uncertainties of ˜±60%. The cross section for the F2 reaction is approximately 35 times larger than the corresponding reaction for Sn(3P). The prior model, based on product state densities, predicts an increase of only about 6.5. We propose, in light of recent alignment experiments of Ca p orbitals, that the difference in reactivity of 1D and 3P states is a result of the symmetry of the second p orbital on Sn relative to the F2 molecule. Also, the production of the observed CL states requires a nonadiabatic process. Finally, the CL cross sections for the title reactions were found to increase with increasing collision energy.

Photoproduction of Λ and Σ0 hyperons off protons with linearly polarized photons at Eγ=1.5 -3.0 GeV

NASA Astrophysics Data System (ADS)

Shiu, S. H.; Kohri, H.; Chang, W. C.; Ahn, D. S.; Ahn, J. K.; Chen, J. Y.; Daté, S.; Ejiri, H.; Fujimura, H.; Fujiwara, M.; Fukui, S.; Gohn, W.; Hicks, K.; Hotta, T.; Hwang, S. H.; Imai, K.; Ishikawa, T.; Joo, K.; Kato, Y.; Kon, Y.; Lee, H. S.; Maeda, Y.; Mibe, T.; Miyabe, M.; Mizutani, K.; Morino, Y.; Muramatsu, N.; Nakano, T.; Nakatsugawa, Y.; Niiyama, M.; Noumi, H.; Ohashi, Y.; Ohta, T.; Oka, M.; Parker, J. D.; Rangacharyulu, C.; Ryu, S. Y.; Sawada, T.; Shimizu, H.; Sugaya, Y.; Sumihama, M.; Tsunemi, T.; Uchida, M.; Ungaro, M.; Yosoi, M.; LEPS Collaboration

2018-01-01

We report the measurement of the γ p →K+Λ and γ p →K+Σ0 reactions at SPring-8. The differential cross sections and photon-beam asymmetries are measured at forward K+ production angles using linearly polarized tagged-photon beams in the range of Eγ=1.5 -3.0 GeV. With increasing photon energy, the cross sections for both γ p →K+Λ and γ p →K+Σ0 reactions decrease slowly. Distinct narrow structures in the production cross section have not been found at Eγ=1.5 -3.0 GeV. The forward peaking in the angular distributions of cross sections, a characteristic feature of t -channel exchange, is observed for the production of Λ in the whole observed energy range. A lack of similar feature for Σ0 production reflects a less dominant role of t -channel contribution in this channel. The photon-beam asymmetries remain positive for both reactions, suggesting the dominance of K* exchange in the t channel. These asymmetries increase gradually with the photon energy, and have a maximum value of +0.6 for both reactions. Comparison with theoretical predictions based on the Regge trajectory in the t channel and the contributions of nucleon resonances indicates the major role of t -channel contributions as well as non-negligible effects of nucleon resonances in accounting for the reaction mechanism of hyperon photoproduction in this photon energy regime.

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…

Selective recovery of uranium from Ca-Mg uranates by chlorination

NASA Astrophysics Data System (ADS)

Pomiro, Federico J.; Gaviría, Juan P.; Quinteros, Raúl D.; Bohé, Ana E.

2017-07-01

A chlorination process is proposed for the uranium extraction and separation using Calciumsbnd Magnesium uranates such as starting reactants which were obtained by precipitation from uranyl nitrate solutions with calcium hydroxide. The study is based on thermodynamic and reaction analysis using chlorine gas as chlorination agent. The results showed that the chlorination reaction of Ca uranate is more feasible to occur than the Mg uranate. The products obtained after chlorination reactions were washed with deionized water to remove the chlorides produced and analyzed. The XRD patterns of the washed products indicated that the chlorination between 400 and 500 °C result in a single phase of calcium uranate (CaUO4) as reaction product. The formation of U3O8 and MgU3O10 was observed at temperatures between 600 °C and 700 °C for 8 hs. The optimal conditions to recover uranium were 3 l h-1 of chlorine and 10 hs of reaction at 700 °C being U3O8 the single uranium product obtained.

Preparation of Low Molecular Weight Gelatin Using Microwave Discharge Electrodeless Lamp/TiO2 Photocatalyst Hybrid System.

PubMed

Lee, Do-Jin; Kim, Hangun; Park, Young-Kwon; Kim, Byung Hoon; Lee, Heon; Jungf, Sana-Chul

2016-02-01

In this study, an MDEL/TiO2 photocatalyst hybrid system was applied to the production of low molecular weight gelatin. The molecular weight of produed gelatin decreased with increasing microwave intensity and increasing treatment time. The abscission of the chemical bonds between the con- stituents of gelatin by photocatalytic reaction did not alter the characteristics of gelatin. Formation of any by-products due to side reaction was not observed. It is suggested that gelatin was depolymerized by hydroxyl radicals produced during the MDEL/TiO2 photochemical reaction.

Assessing hydrodynamic effects on jarosite dissolution rates, reaction products, and preservation on Mars

NASA Astrophysics Data System (ADS)

Dixon, Emily M.; Elwood Madden, Andrew S.; Hausrath, Elisabeth M.; Elwood Madden, Megan E.

2015-04-01

Jarosite flow-through dissolution experiments were conducted in ultrapure water (UPW), pH 2 sulfuric acid, and saturated NaCl and CaCl2 brines at 295-298 K to investigate how hydrologic variables may affect jarosite preservation and reaction products on Mars. K+-based dissolution rates in flowing UPW did not vary significantly with flow rate, indicating that mineral surface reactions control dissolution rates over the range of flow rates investigated. In all of the solutions tested, hydrologic variables do not significantly affect extent of jarosite alteration; therefore, jarosite is equally likely to be preserved in flowing or stagnant waters on Mars. However, increasing flow rate did affect the mineralogy and accumulation of secondary reaction products. Iron release rates in dilute solutions increased as the flow rate increased, likely due to nanoscale iron (hydr)oxide transport in flowing water. Anhydrite formed in CaCl2 brine flow-through experiments despite low temperatures, while metastable gypsum and bassanite were observed in batch experiments. Therefore, observations of the hydration state of calcium sulfate minerals on Mars may provide clues to unravel past salinity and hydrologic conditions as well as temperatures and vapor pressures.

Separation of Betti Reaction Product Enantiomers: Absolute Configuration and Inhibition of Botulinum Neurotoxin A

DTIC Science & Technology

2011-03-01

of Betti Reaction Product Enantiomers : Absolute Configuration and Inhibition of Botulinum Neurotoxin A John H. Cardellina II,† Rebecca C. Vieira...observing sufficient resolution of the two enantiomers on a Chiralcel OD column to permit semipreparative purification of adequate quantities of (þ)-1...comparison of the botulinum neurotoxin serotype A (BoNT/A) inhibitory activity of the (þ) and () enantiomers of 1 was accomplished via an HPLC-based assay

Aerobic oxidations catalyzed by chromium corroles.

PubMed

Mahammed, Atif; Gray, Harry B; Meier-Callahan, Alexandre E; Gross, Zeev

2003-02-05

Oxochromium(V) complexes of 5,10,15-tris(pentafluorophenyl)corrole and brominated derivatives oxygenate substrates (triphenylphosphine and norbornene) with concomitant production of chromium(III). Regeneration of CrVO by reaction of dioxygen with CrIII completes an aerobic catalytic cycle, with very large solvent effects; in acetonitrile, rapid initial turnovers observed initially are shut down by formation of CrIVO, while in toluene, THF, and methanol, relatively slow reactions are further inhibited by product formation.

Kinetics of exciplex formation/dissipation in reaction following Weller Scheme II

NASA Astrophysics Data System (ADS)

Fedorenko, S. G.; Burshtein, A. I.

2014-09-01

Creation of exciplexes from the charged products of photoionization is considered by means of Integral Encounter Theory. The general kinetic equations of such a reaction following the Weller scheme II are developed. The special attention is given to the particular case of irreversible remote ionization of primary excited electron donor. Kinetics of exciplex formation is considered at fast biexponential geminate transformation of exciplexes in cage that gives way to subsequent bulk reaction of equilibrated reaction products controlled by power law recombination of ions. It is shown that the initial geminate stage of exciplex kinetics is observed only in diffusion controlled regime of the reaction and disappears with increasing mobility of ions in passing to kinetic regime. The quantum yield of exciplexes is studied along with their kinetics.

Kinetics of exciplex formation/dissipation in reaction following Weller Scheme II.

PubMed

Fedorenko, S G; Burshtein, A I

2014-09-21

Creation of exciplexes from the charged products of photoionization is considered by means of Integral Encounter Theory. The general kinetic equations of such a reaction following the Weller scheme II are developed. The special attention is given to the particular case of irreversible remote ionization of primary excited electron donor. Kinetics of exciplex formation is considered at fast biexponential geminate transformation of exciplexes in cage that gives way to subsequent bulk reaction of equilibrated reaction products controlled by power law recombination of ions. It is shown that the initial geminate stage of exciplex kinetics is observed only in diffusion controlled regime of the reaction and disappears with increasing mobility of ions in passing to kinetic regime. The quantum yield of exciplexes is studied along with their kinetics.

Oxygen atom reaction with shuttle materials at orbital altitudes

NASA Technical Reports Server (NTRS)

Leger, L. J.

1983-01-01

Significant effects of the environment on payload bay materials observed on all flights are discussed. The STS 5 experiment is described. Increased outgassing rates resulting in possible localized effects on experiments, changes in optical control surfaces, and photoemission from reaction products are considered.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Luo, Langli; Liu, Bin; Song, Shidong

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

Gas-phase reactions of glycine, alanine, valine and their N-methyl derivatives with the nitrosonium ion, NO+.

PubMed

Freitas, M A; O'Hair, R A; Schmidt, J A; Tichy, S E; Plashko, B E; Williams, T D

1996-10-01

The gas-phase reactions of the nitrosonium ion, NO+ with the amino acids glycine, alanine and valine and their N-methyl derivatives were investigated under chemical ionization mass spectrometric (CIMS) conditions. Two products were observed in all cases: the formation of the iminium ion and the formation of an [M-H]+ ion. The latter product is consistent with a reaction channel involving hydride abstraction by NO+, and was confirmed by (i) examining the Ar+CI mass spectra of the same amino acids under similar source conditions and (ii) examining the unimolecular fragmentation reactions of the [M + H]+ ions of the N-nitroso-N-methyl derivatives of each of the amino acids in a tandem mass spectrometer. Further insights into the reaction of glycine with NO+ were obtained by performing ab initio calculations (at the MP2/6-31G* parallel HF/6-31G* level). These results indicate that four reactions are thermodynamically viable for glycine: (i) hydride abstraction; (ii) iminium ion formation (with concomitant loss of HONO and CO); (iii) diazonium ion formation; and (iv) diazonium ion formation followed by loss of N2. Possible reasons why reactions (iii) and (iv) are not observed are discussed, and comparisons with solution reactivity and the gas-phase reactivity of NO+ are also made.

The reaction of C5N- with acetylene as a possible intermediate step to produce large anions in Titan's ionosphere.

PubMed

Lindén, Carl Fredrik; Žabka, Ján; Polášek, Miroslav; Zymak, Illia; Geppert, Wolf D

2018-02-21

A theoretical and experimental investigation of the reaction C 5 N - + C 2 H 2 has been carried out. This reaction is of astrophysical interest since the growth mechanism of large anions that have been detected in Titan's upper atmosphere by the Cassini plasma spectrometer are still largely unknown. The experimental studies have been performed using a tandem quadrupole mass spectrometer which allows identification of the different reaction channels and assessment of their reaction thresholds. Results of these investigations were compared with the predictions of ab initio calculations, which identified possible pathways leading to the observed products and their thermodynamical properties. These computations yielded that the majority of these products are only accessible via energy barriers situated more than 1 eV above the reactant energies. In many cases, the thresholds predicted by the ab initio calculations are in good agreement with the experimentally observed ones. For example, the chain elongation reaction leading to C 7 N - , although being slightly exoergic, possesses an energy barrier of 1.91 eV. Therefore, the title reaction can be regarded to be somewhat unlikely to be responsible for the formation of large anions in cold environments such as interstellar medium or planetary ionospheres.

Limonene ozonolysis in the presence of nitric oxide: Gas-phase reaction products and yields

NASA Astrophysics Data System (ADS)

Ham, Jason E.; Harrison, Joel C.; Jackson, Stephen R.; Wells, J. R.

2016-05-01

The reaction products from limonene ozonolysis were investigated using the new carbonyl derivatization agent, O-tert-butylhydroxylamine hydrochloride (TBOX). With ozone (O3) as the limiting reagent, five carbonyl compounds were detected. The yields of the carbonyl compounds are discussed with and without the presence of a hydroxyl radical (OHrad) scavenger, giving insight into the influence secondary OH radicals have on limonene ozonolysis products. The observed reaction product yields for limonaketone (LimaKet), 7-hydroxyl-6-oxo-3-(prop-1-en-2-yl)heptanal (7H6O), and 2-acetyl-5-oxohexanal (2A5O) were unchanged suggesting OHrad generated by the limonene + O3 reaction does not contribute to their formation. The molar yields of 3-isopropenyl-6-oxo-heptanal (IPOH) and 3-acetyl-6-oxoheptanal (3A6O) decreased by 68% and >95%; respectively, when OHrad was removed. This suggests that OHrad radicals significantly impact the formation of these products. Nitric oxide (NO) did not significantly affect the molar yields of limonaketone or IPOH. However, NO (20 ppb) considerably decreased the molar reaction product yields of 7H6O (62%), 2A5O (63%), and 3A6O (47%), suggesting NO reacted with peroxyl intermediates, generated during limonene ozonolysis, to form other carbonyls (not detected) or organic nitrates. These studies give insight into the transformation of limonene and its reaction products that can lead to indoor exposures.

Product study of oleic acid ozonolysis as function of humidity

NASA Astrophysics Data System (ADS)

Vesna, O.; Sax, M.; Kalberer, M.; Gaschen, A.; Ammann, M.

The heterogeneous reaction of ozone with oleic acid (OA) aerosol particles was studied as function of humidity and reaction time in an aerosol flow reactor using an off-line gas chromatography mass spectrometry (GC-MS) technique. We report quantitative yields of the major C9 ozonolysis products in both gas and condensed phases and the effect of relative humidity on the product distribution. The measurements were carried out with OA aerosol particles at room temperature. The results indicate that the product yields are increasing with increasing relative humidity during the reaction. Nonanal (NN) was detected as the major gas-phase product (55.6 ± 2.3%), with 94.5 ± 2.4% of the NN yield in the gas, and 5.5 ± 2.7% in the particulate phase, whereas nonanoic, oxononanoic and azelaic acids were detected exclusively in the particulate phase. Using UV-spectrometry, we observed that peroxides make up the largest fraction of products, about half of the product aerosol mass, and their concentration decreased with increasing humidity.

The price had better be right: women's reactions to sexual stimuli vary with market factors.

PubMed

Vohs, Kathleen D; Sengupta, Jaideep; Dahl, Darren W

2014-01-01

Two experiments tested when and why women's typically negative, spontaneous reactions to sexual imagery would soften. Sexual economics theory predicts that women want sex to be seen as rare and special. We reasoned that this outlook would translate to women tolerating sexual images more when those images are linked to high worth as opposed to low worth. We manipulated whether an ad promoted an expensive or a cheap product using a sexually charged or a neutral scene. As predicted, women found sexual imagery distasteful when it was used to promote a cheap product, but this reaction to sexual imagery was mitigated if the product promoted was expensive. This pattern was not observed among men. Furthermore, we predicted and found that sexual ads promoting cheap products heightened feelings of being upset and angry among women. These findings suggest that women's reactions to sexual images can reveal deep-seated preferences about how sex should be used and understood.

Comparing Positively and Negatively Charged Distonic Radical Ions in Phenylperoxyl Forming Reactions.

PubMed

Williams, Peggy E; Marshall, David L; Poad, Berwyck L J; Narreddula, Venkateswara R; Kirk, Benjamin B; Trevitt, Adam J; Blanksby, Stephen J

2018-06-04

In the gas phase, arylperoxyl forming reactions play a significant role in low-temperature combustion and atmospheric processing of volatile organic compounds. We have previously demonstrated the application of charge-tagged phenyl radicals to explore the outcomes of these reactions using ion trap mass spectrometry. Here, we present a side-by-side comparison of rates and product distributions from the reaction of positively and negatively charge tagged phenyl radicals with dioxygen. The negatively charged distonic radical ions are found to react with significantly greater efficiency than their positively charged analogues. The product distributions of the anion reactions favor products of phenylperoxyl radical decomposition (e.g., phenoxyl radicals and cyclopentadienone), while the comparable fixed-charge cations yield the stabilized phenylperoxyl radical. Electronic structure calculations rationalize these differences as arising from the influence of the charged moiety on the energetics of rate-determining transition states and reaction intermediates within the phenylperoxyl reaction manifold and predict that this influence could extend to intra-molecular charge-radical separations of up to 14.5 Å. Experimental observations of reactions of the novel 4-(1-carboxylatoadamantyl)phenyl radical anion confirm that the influence of the charge on both rate and product distribution can be modulated by increasing the rigidly imposed separation between charge and radical sites. These findings provide a generalizable framework for predicting the influence of charged groups on polarizable radicals in gas phase distonic radical ions. Graphical Abstract.

Comparing Positively and Negatively Charged Distonic Radical Ions in Phenylperoxyl Forming Reactions

NASA Astrophysics Data System (ADS)

Williams, Peggy E.; Marshall, David L.; Poad, Berwyck L. J.; Narreddula, Venkateswara R.; Kirk, Benjamin B.; Trevitt, Adam J.; Blanksby, Stephen J.

2018-06-01

In the gas phase, arylperoxyl forming reactions play a significant role in low-temperature combustion and atmospheric processing of volatile organic compounds. We have previously demonstrated the application of charge-tagged phenyl radicals to explore the outcomes of these reactions using ion trap mass spectrometry. Here, we present a side-by-side comparison of rates and product distributions from the reaction of positively and negatively charge tagged phenyl radicals with dioxygen. The negatively charged distonic radical ions are found to react with significantly greater efficiency than their positively charged analogues. The product distributions of the anion reactions favor products of phenylperoxyl radical decomposition (e.g., phenoxyl radicals and cyclopentadienone), while the comparable fixed-charge cations yield the stabilized phenylperoxyl radical. Electronic structure calculations rationalize these differences as arising from the influence of the charged moiety on the energetics of rate-determining transition states and reaction intermediates within the phenylperoxyl reaction manifold and predict that this influence could extend to intra-molecular charge-radical separations of up to 14.5 Å. Experimental observations of reactions of the novel 4-(1-carboxylatoadamantyl)phenyl radical anion confirm that the influence of the charge on both rate and product distribution can be modulated by increasing the rigidly imposed separation between charge and radical sites. These findings provide a generalizable framework for predicting the influence of charged groups on polarizable radicals in gas phase distonic radical ions.

Nuclear processes in solar flares

NASA Technical Reports Server (NTRS)

Ramaty, R.

1982-01-01

The theory of solar gamma-ray line production is reviewed and new calculations of line production yields are presented. Observations, carried out with gamma-ray spectrometers on OSO-7, HEAO-1, HEAO-3 and SMM are reviewed and compared with theory. These observations provide direct evidence for nuclear reactions in flares and furnish unique information on particle acceleration and flare mechanisms.

A Nitration Reaction Puzzle for the Organic Chemistry Laboratory

ERIC Educational Resources Information Center

Wieder, Milton J.; Barrows, Russell

2008-01-01

Treatment of phenylacetic acid with 90% HNO[subscript 3] yields a product, I, whose observed melting point is 175-179 degrees C and whose equivalent weight is approximately 226 grams. Treatment of phenylacetic acid with 70% HNO[subscript 3] yields a product, II, whose observed melting point is 106-111 degrees C and whose equivalent weight is…

Abrasion-ablation model for neutron production in heavy ion reactions

NASA Technical Reports Server (NTRS)

Cucinotta, Francis A.; Wilson, John W.; Townsend, Lawrence W.

1995-01-01

In heavy ion reactions, neutron production at forward angles is observed to occur with a Gaussian shape that is centered near the beam energy and extends to energies well above that of the beam. This paper presents an abrasion-ablation model for making quantitative predictions of the neutron spectrum. To describe neutrons produced from the abrasion step of the reaction where the projectile and target overlap, the authors use the Glauber model and include effects of final-state interactions. They then use the prefragment mass distribution from abrasion with a statistical evaporation model to estimate the neutron spectrum resulting from ablation. Measurements of neutron production from Ne and Nb beams are compared with calculations, and good agreement is found.

A green chemical approach for synthesis of shape anisotropic gold nanoparticles

NASA Astrophysics Data System (ADS)

Kalyan Kamal, S. S.; Vimala, J.; Sahoo, P. K.; Ghosal, P.; Ram, S.; Durai, L.

2014-06-01

A complete green chemical reaction between aurochloric acid and tea polyphenols resulted in the reduction of Au3+ → Au0. The reaction was carried out in a Teflon-coated bomb digestion vessel at 200 °C. It was observed that with increasing the reaction time from 1 to 5 h, the shape of the nanoparticles changed from spherical- to rod-like structures. The reaction was followed with the help of UV-vis spectrometer, which showed a single absorption peak at 548 nm for 1-h reaction product and two peaks for a 5-h reaction product at 533 and 745 nm corresponding to the transverse and longitudinal surface plasmon resonance bands. Microstructures obtained from transmission electron microscope revealed that the samples obtained after 1-h reaction are predominantly spherical in shape with an average size of 15 nm. Whereas samples obtained after 5 h of reaction exhibited rod-like structures with an average size of 45 nm.

Dynamics of the reaction of atomic oxygen with ethene: Observation of all carbon-containing products by single-photon ionization

NASA Astrophysics Data System (ADS)

Lee, Shih-Huang; Huang, Wen-Jian; Chen, Wei-Kan

2007-10-01

We measured time-of-flight (TOF) spectra of products from the reaction O( 3P/ 1D) + C 2H 4 at collision energy 6.4 kcal mol -1 using a quadrupole mass filter and tunable vacuum-ultraviolet light for ionization. All carbon-containing products from five exit channels - CH 2CHO + H, CH 2CO + H 2, CH 3 + HCO, CH 2 + HCHO, and CH 2CO + 2H - were identified. Product channels CH 2CHO + H and CH 2CO + 2H associate with 3P and 1D atomic oxygen reactants, respectively. Both 3P and 1D oxygen reactants might be responsible for the other reactions. The ionization threshold of nascent vinoxy radicals is 9.3 ± 0.1 eV.

Kinetics and products of the OH radical-initiated reaction of 3-methyl-2-butenal.

PubMed

Tuazon, Ernesto C; Aschmann, Sara M; Nishino, Noriko; Arey, Janet; Atkinson, Roger

2005-06-07

Kinetics and products of the gas-phase reaction of OH radicals with 3-methyl-2-butenal [(CH3)2C=CHCHO] have been investigated at room temperature and atmospheric pressure of air. Using a relative rate method with methacrolein as the reference compound, a rate constant for the reaction of OH radicals with 3-methyl-2-butenal of (6.21 +/- 0.18) x 10(-11) cm3 molecule(-1) s(-1) at 296 +/- 2 K was measured, where the indicated error does not include the uncertainty in the rate constant for the methacrolein reference compound. Products of this reaction were investigated using in situ Fourier transform infrared (FT-IR) spectroscopy and solid phase microextraction (SPME) fibers coated with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine for on-fiber derivatization of carbonyl compounds, with subsequent thermal desorption and analysis by gas chromatography. The products observed and the molar formation yields were: glyoxal, 40 +/- 3%; acetone, 74 +/- 6%; 2-hydroxy-2-methylpropanal, 4.6 +/- 0.7%; CO2, 39% initially, decreasing to 30% at greater extents of reaction; peroxyacyl nitrate(s) [RC(O)OONO2], 5-8%, increasing with the extent of reaction and with the sum of the CO2 and RC(O)OONO2 yields being 38 +/- 6%; and organic nitrates [RONO2], 8.5 +/- 2.3%. The formation of these products is readily explained by a reaction mechanism based on those previously formulated for the corresponding reactions of the alpha,beta-unsaturated aldehydes acrolein, crotonaldehyde and methacrolein. Based on the mechanism proposed, at room temperature H-atom abstraction from the CHO group accounts for 40 +/- 6% of the overall reaction, and OH radical addition to the carbon atoms of the C=C bond accounts for 53 +/- 4% of the overall reaction. Hence 93 +/- 8% of the reaction products and pathways are accounted for.

Optimization of Maillard Reaction between Glucosamine and Other Precursors by Measuring Browning with a Spectrophotometer.

PubMed

Ogutu, Benrick; Kim, Ye-Joo; Kim, Dae-Wook; Oh, Sang-Chul; Hong, Dong-Lee; Lee, Yang-Bong

2017-09-01

The individual Maillard reactions of glucose, glucosamine, cyclohexylamine, and benzylamine were studied at a fixed temperature of 120°C under different durations by monitoring the absorbance of the final products at 425 nm. Glucosamine was the most individually reactive compound, whereas the reactions of glucose, cyclohexylamine, and benzylamine were not significantly different from each other. Maillard reactions of reaction mixtures consisting of glucosamine-cyclohexylamine, glucosamine-benzylamine, glucose-cyclohexylamine, and glucose-benzylamine were also studied using different concentration ratios under different durations at a fixed temperature of 120°C and pH 9. Maillard reactions in the pairs involving glucosamine were observed to be more intense than those of the pairs involving glucose. Finally, with respect to the concentration ratios, it was observed that in most instances, optimal activity was realized, when the reaction mixtures were in the ratio of 1:1.

Optimization of Maillard Reaction between Glucosamine and Other Precursors by Measuring Browning with a Spectrophotometer

PubMed Central

Ogutu, Benrick; Kim, Ye-Joo; Kim, Dae-Wook; Oh, Sang-Chul; Hong, Dong-Lee; Lee, Yang-Bong

2017-01-01

The individual Maillard reactions of glucose, glucosamine, cyclohexylamine, and benzylamine were studied at a fixed temperature of 120°C under different durations by monitoring the absorbance of the final products at 425 nm. Glucosamine was the most individually reactive compound, whereas the reactions of glucose, cyclohexylamine, and benzylamine were not significantly different from each other. Maillard reactions of reaction mixtures consisting of glucosamine-cyclohexylamine, glucosamine-benzylamine, glucose-cyclohexylamine, and glucose-benzylamine were also studied using different concentration ratios under different durations at a fixed temperature of 120°C and pH 9. Maillard reactions in the pairs involving glucosamine were observed to be more intense than those of the pairs involving glucose. Finally, with respect to the concentration ratios, it was observed that in most instances, optimal activity was realized, when the reaction mixtures were in the ratio of 1:1. PMID:29043219

Solventless synthesis, morphology, structure and magnetic properties of iron oxide nanoparticles

NASA Astrophysics Data System (ADS)

Das, Bratati; Kusz, Joachim; Reddy, V. Raghavendra; Zubko, Maciej; Bhattacharjee, Ashis

2017-12-01

In this study we report the solventless synthesis of iron oxide through thermal decomposition of acetyl ferrocene as well as its mixtures with maliec anhydride and characterization of the synthesized product by various comprehensive physical techniques. Morphology, size and structure of the reaction products were investigated by scanning electron microscopy, transmission electron microscopy and X-ray powder diffraction technique, respectively. Physical characterization techniques like FT-IR spectroscopy, dc magnetization study as well as 57Fe Mössbauer spectroscopy were employed to characterize the magnetic property of the product. The results observed from these studies unequivocally established that the synthesized materials are hematite. Thermal decomposition has been studied with the help of thermogravimetry. Reaction pathway for synthesis of hematite has been proposed. It is noted that maliec anhydride in the solid reaction environment as well as the gaseous reaction atmosphere strongly affect the reaction yield as well as the particle size. In general, a method of preparing hematite nanoparticles through solventless thermal decomposition technique using organometallic compounds and the possible use of reaction promoter have been discussed in detail.

Production of edible carbohydrates from formaldehyde in a spacecraft. pH variations in the calcium hydroxide catalyzed formose reaction. Final Report, 1 Jul. 1973 - 30 Jun. 1974. M.S. Thesis

NASA Technical Reports Server (NTRS)

Weiss, A. H.; Kohler, J. T.; John, T.

1974-01-01

The study of the calcium hydroxide catalyzed condensation of formaldehyde was extended to a batch reactor system. Decreases in pH were observed, often in the acid regime, when using this basic catalyst. This observation was shown to be similar to results obtained by others using less basic catalysts in the batch mode. The relative rates of these reactions are different in a batch reactor than in a continuous stirred tank reactor. This difference in relative rates is due to the fact that at any degree of advancement in the batch system, the products have a history of previous products, pH, and dissolved catalyst. The relative rate differences can be expected to yield a different nature of product sugars for the two types of reactors.

Peculiarity of methoxy group-substituted phenylhydrazones in Fischer indole synthesis

PubMed Central

MURAKAMI, Yasuoki

2012-01-01

We found that the Fischer indole synthesis of ethyl pyruvate 2-methoxyphenylhydrazone (5) with HCl/EtOH gave an abnormal product, ethyl 6-chloroindole-2-carboxylate (7), as the main product, with a smaller amount of ethyl 7-methoxyindole-2-carboxylate (6) as the normal product. This abnormal reaction was the result of a cyclization on the side with the substituent (methoxy group) of a benzene ring on phenylhydrazone, which was not previously observed. In this initial investigation, we focused on 1) the application of the above-mentioned abnormal Fischer indole synthesis, 2) the details of this reaction of phenylhydrazone with other kinds of substituents, 3) the mechanism of the first step of the Fischer indole synthesis, 4) the abnormal reaction in methoxydiphenylhydrazones, and 5) a synthetic device to avoid an abnormal reaction. The results of these studies are summarized herein. PMID:22241067

U-238 fission and Pu-239 production in subcritical assembly

NASA Astrophysics Data System (ADS)

Grab, Magdalena; Wojciechowski, Andrzej

2018-04-01

The project touches upon an issue of U-238 fission reactions and Pu-239 production reactions in subcritical assembly. The experiment took place in November 2014 at the Dzhelepov Laboratory of Nuclear Problems (JINR, Dubna) using PHASOTRON.Data of this experiment were analyzed in Laboratory of Information Technologies (LIT). Four MCNPX models were considered for simulation: Bertini/Dresnen, Bertini/Abla, INCL4/Drensnen, INCL4/Abla. The main goal of the project was to compare the experimental data and simulation results. We obtain a good agreement of experimental data and computation results especially for detectors placed besides the assembly axis. In addition, the U-238 fission reactions are more probable to be observed in the region of a higher particle energy spectrum, located closer to the assembly axis and the particle beam as well and vice versa Pu-239 production reactions were dominant in the peripheral region of geometry.

Okara promoted acrylamide and carboxymethyl-lysine formation in bakery products.

PubMed

Palermo, Mariantonella; Fiore, Alberto; Fogliano, Vincenzo

2012-10-10

Soybeans are widely used in bakery products because of their technological advantages and, recently, soybean-containing products have been marketed as functional foods thanks to several health benefits. Okara is a soybean-based ingredient obtained after elimination of the water-soluble component from ground soybeans. In this paper the effect of okara addition to bakery products on the formation of some potentially harmful Maillard reaction products was evaluated. Cookies obtained by replacing 15% of wheat flour with okara showed a visible browning increase and a more intense Maillard reaction development as shown by higher concentrations of 5-hydroxymethyl-2-furaldehyde (HMF) (+100%), acrylamide (+60%), and carboxymethyl-lysine (CML) (+400%) with respect to the control. This phenomenon could be related to the presence in okara of about 50% of insoluble dietary fiber: the fiber reduces water activity during cooking, thus promoting Maillard reaction. To confirm this hypothesis, cookies obtained by replacing 7% of wheat flour with three different types of dietary fiber (cellulose, chitosan, and pea fiber) were prepared: these experimental cookies showed higher Maillard reaction product concentration with respect to the control and, in particular, HMF and CML values were directly related to the fiber water-holding capacity (WHC). To extend the observation to the food market, a sampling of soybean-containing commercial bakery products was analyzed by comparing the concentrations of Maillard reaction products with those of similar bakery products without soy. Soybean-containing samples showed higher concentrations of acrylamide and CML than corresponding controls.

Metabolic network reconstruction and genome-scale model of butanol-producing strain Clostridium beijerinckii NCIMB 8052

PubMed Central

2011-01-01

Background Solventogenic clostridia offer a sustainable alternative to petroleum-based production of butanol--an important chemical feedstock and potential fuel additive or replacement. C. beijerinckii is an attractive microorganism for strain design to improve butanol production because it (i) naturally produces the highest recorded butanol concentrations as a byproduct of fermentation; and (ii) can co-ferment pentose and hexose sugars (the primary products from lignocellulosic hydrolysis). Interrogating C. beijerinckii metabolism from a systems viewpoint using constraint-based modeling allows for simulation of the global effect of genetic modifications. Results We present the first genome-scale metabolic model (iCM925) for C. beijerinckii, containing 925 genes, 938 reactions, and 881 metabolites. To build the model we employed a semi-automated procedure that integrated genome annotation information from KEGG, BioCyc, and The SEED, and utilized computational algorithms with manual curation to improve model completeness. Interestingly, we found only a 34% overlap in reactions collected from the three databases--highlighting the importance of evaluating the predictive accuracy of the resulting genome-scale model. To validate iCM925, we conducted fermentation experiments using the NCIMB 8052 strain, and evaluated the ability of the model to simulate measured substrate uptake and product production rates. Experimentally observed fermentation profiles were found to lie within the solution space of the model; however, under an optimal growth objective, additional constraints were needed to reproduce the observed profiles--suggesting the existence of selective pressures other than optimal growth. Notably, a significantly enriched fraction of actively utilized reactions in simulations--constrained to reflect experimental rates--originated from the set of reactions that overlapped between all three databases (P = 3.52 × 10-9, Fisher's exact test). Inhibition of the hydrogenase reaction was found to have a strong effect on butanol formation--as experimentally observed. Conclusions Microbial production of butanol by C. beijerinckii offers a promising, sustainable, method for generation of this important chemical and potential biofuel. iCM925 is a predictive model that can accurately reproduce physiological behavior and provide insight into the underlying mechanisms of microbial butanol production. As such, the model will be instrumental in efforts to better understand, and metabolically engineer, this microorganism for improved butanol production. PMID:21846360

Methyl salicylate: a reactive chemical warfare agent surrogate to detect reaction with hypochlorite.

PubMed

Salter, W Bruce; Owens, Jeffery R; Wander, Joseph D

2011-11-01

Methyl salicylate (MeS) has a rich history as an inert physical simulant for the chemical warfare agents sulfur mustard and soman, where it is used extensively for liquid- and vapor-permeation testing. Here we demonstrate possible utility of MeS as a reactivity simulant for chlorine-based decontaminants. In these experiments MeS was reacted with sodium hypochlorite varying stoichiometry, temperature, reaction time, and pH. No colored oxidation products were observed; however, chlorination of the aromatic ring occurred ortho (methyl 3-chlorosalicylate) and para (methyl 5-chlorosalicylate) to the position bearing the -OH group in both the mono- and disubstituted forms. The monosubstituted para product accumulated initially, and the ortho and 3,5-dichloro products formed over the next several hours. Yields from reactions conducted below pH 11 declined rapidly with decreasing pH. Reactions run at 40 °C produced predominantly para substitution, while those run at 0 °C produced lower yields of ortho- and para-substituted products. Reactions were also carried out on textile substrates of cotton, 50/50 nylon-cotton, and a meta aramid. The textile data broadly reproduced reaction times and stoichiometry observed in the liquid phase, but are complicated by physical and possibly chemical interactions with the fabric. These data indicate that, for hypochlorite-containing neutralizing agents operating at strongly alkaline pH, one can expect MeS to react stoichiometrically with the hypochlorite it encounters. This suggests utility of MeS in lieu of such highly hazardous surrogates as monochloroalkyl sulfides as a simulant for threat scenarios involving the stoichiometric decomposition of sulfur mustard. Specifically, the extent of coverage of the simulant on a fabric by the neutralizing agent can be directly measured. Similar reactivity toward other halogen oxidizing agents is likely but remains to be demonstrated.

Theoretical investigation of the gas-phase reactions of CrO(+) with ethylene.

PubMed

Scupp, Thomas M; Dudley, Timothy J

2010-01-21

The potential energy surfaces associated with the reactions of chromium oxide cation (CrO(+)) with ethylene have been characterized using density functional, coupled-cluster, and multireference methods. Our calculations show that the most probable reaction involves the formation of acetaldehyde and Cr(+) via a hydride transfer involving the metal center. Our calculations support previous experimental hypotheses that a four-membered ring intermediate plays an important role in the reactivity of the system. We have also characterized a number of viable reaction pathways that lead to other products, including ethylene oxide. Due to the experimental observation that CrO(+) can activate carbon-carbon bonds, a reaction pathway involving C-C bond cleavage has also been characterized. Since many of the reactions involve a change in the spin state in going from reactants to products, locations of these spin surface crossings are presented and discussed. The applicability of methods based on Hartree-Fock orbitals is also discussed.

Patch test results with patients' own perfumes, deodorants and shaving lotions: results of the IVDK 1998-2002.

PubMed

Uter, W; Geier, J; Schnuch, A; Frosch, P J

2007-03-01

Assessment of the value of patch testing patients' own perfumes, eau de toilette, deodorants and shaving lotions with regard to diagnosing contact allergy to fragrances, and an analysis of the spectrum of concurrent patch test reactions to single fragrance allergens. Data of the Information Network of Departments of Dermatology (IVDK; http://www.ivdk.org) regarding patch test results with above products brought in by the patient, considered as possible cause of contact dermatitis, were retrospectively analysed. Between 1998 and 2002, 1468 patients were patch tested with 2557 single products (deodorants, n = 1094; eau de toilette, n = 598; perfume, n = 530; and pre- or after-shave, n = 325; remainder not classifiable), mostly 'as is'. Positive reactions were observed in 129 patients (to 191 products). In 58 of these patients, no further patch test reactions to the fragrance mix (FM-I), Myroxylon pereirae resin (balsam of Peru) or 4-(4-hydroxy-4-methyl-pentyl)-3-cyclohexencarboxaldehyde (e.g. Lyral(R)) were found. A strong association between contact sensitivity to the above commercial allergens and positive reactions to products was observed. Some single compounds such as ylang-ylang oil, propolis and especially oak moss absolute are important allergens in the 'perfume-positive' subgroup, but less in a subgroup positive to own deodorants. Patch testing this scope of products, brought in by the patient, can be regarded as a simple, safe and effective method to diagnose clinically relevant contact sensitization - the more so, as the composition of such products is ever-changing, and the sensitivity of established 'screening allergens' is thus insufficient.

Secondary organic aerosol formation through fog processing of VOCs

NASA Astrophysics Data System (ADS)

Herckes, P.; Hutchings, J. W.

2010-07-01

Volatile Organic Compounds (VOCs) including benzene, toluene, ethylbenzene and xylenes (BTEX) have been determined in highly concentrated amounts (>1 ug/L) in intercepted clouds in northern Arizona (USA). These VOCs are found in concentrations much higher than predicted by partitioning alone. The reactivity of BTEX in the fog/cloud aqueous phase was investigated through laboratory studies. BTEX species showed fast degradation in the aqueous phase in the presence of peroxides and light. Observed half-lives ranged from three and six hours, substantially shorter than the respective gas phase half-lives (several days). The observed reaction rates were on the order of 1 ppb/min but decreased substantially with increasing concentrations of organic matter (TOC). The products of BTEX oxidation reactions were analyzed using HPLC-UV and LCMS. The first generation of products identified included phenol and cresols which correspond to the hydroxyl-addition reaction to benzene and toluene. Upon investigating of multi-generational products, smaller, less volatile species are predominant although a large variety of products is found. Most reaction products have substantially lower vapor pressure and will remain in the particle phase upon droplet evaporation. The SOA generation potential of cloud and fog processing of BTEX was evaluated using simple calculations and showed that in ideal situations these reactions could add up to 9% of the ambient aerosol mass. In more conservative scenarios, the contribution of the processing of BTEX was around 1% of ambient aerosol concentrations. Overall, cloud processing of VOC has the potential to contribute to the atmospheric aerosol mass. However, the contribution will depend upon many factors such as the irradiation, organic matter content in the droplets and droplet lifetime.

Probing Metal Carbonation Reactions of CO2 in a Model System Containing Forsterite and H2O Using Si-29, C-13 Magic Angle Sample Spinning NMR Spectroscopy

NASA Astrophysics Data System (ADS)

Hu, J.; Kwak, J.; Hoyt, D. W.; Sears, J. A.; Rosso, K. M.; Felmy, A. R.

2009-12-01

Ex situ solid state NMR have been used for the first time to study fundamental mineral carbonation processes and reaction extent relevant to geologic carbon sequestration using a model silicate mineral forsterite (Mg2SiO4)+scCO2 with and without H2O. Run conditions were 80C and 96 bar. Si-29 NMR clearly shows that in the absence of CO2, the role of H2O is to hydrolyze surface Mg-O-Si bonds to produce Mg2+, and mono- and oligomeric hydroxylated silica species. The surface hydrolysis products contain only Q0 (Si(OH)4) and Q1 (Si(OH)3OSi) species. An equilibrium between Q0, Q1 and Mg2+ with a saturated concentration equivalent to less than 3.2% of the Mg2SiO4 conversion is obtained at a reaction time of up to 7 days. Using scCO2 without H2O, no reaction is observed within 7 days. Using both scCO2 and H2O, the surface reaction products for silica are mainly Q3 (SiOH(OSi)3) species accompanied by a lesser amount of Q2 (Si(OH)2(OSi)2) and Q4 (Si(OSi)4). However, no Q0 and Q1 were detected, indicating the carbonic acid formation/deprotonation and magnesite (MgCO3) precipitation reactions are faster than the forsterite hydrolysis process. Thus it can be concluded that the Mg2SiO4 hydrolysis process is the rate limiting step of the overall mineral carbonation process. Si-29 NMR combined with XRD, TEM, SAED and EDX further reveal that the reaction is a surface reaction with the Mg2SiO4 crystallite in the core and with condensed Q2-Q4 species forming amorphous surface layers. C-13 MAS NMR identified a possible reaction intermediates as (MgCO3)4*Mg(OH)2*5H2O. However, at long reaction times only crystallite magnesite MgCO3 products are observed. This research is part of a broader effort at PNNL to develop experimental tools and fundamental insights into chemical transformations affecting subsurface CO2 reactive transport. Si-29 (left) and C-13 (right) MAS NMR spectra of Mg2SiO4 under various reaction conditions. Si-29 NMR reveals that in scCO2 without H2O, no reaction is observed (b). In H2O without scCO2, only surface hydrolysis products Q0 and Q1 are present (c). In a mixture of both H2O and scCO2, the products are Q2, Q3 and Q4 (d). C-13 NMR (e-f) reveals the formation of MgCO3 at long reaction times with (MgCO3)4*Mg(OH)2*5H2O as a possible reaction intermediate.

Yields of O2(b 1 Sigma g +) from reactions of HO2. [in planetary atmospheres

NASA Technical Reports Server (NTRS)

Keyser, L. F.; Choo, K. Y.; Leu, M. T.

1985-01-01

The production of O2(b 1 Sigma g +) has been monitored for several reactions of the HO2 radical at 300 K using a discharge-flow apparatus with resonance fluorescence and chemiluminescence detection. In all cases, the resulting quantum efficiencies were found to be less than 0.03. O2(b) was observed when F atoms were added to H2O2 in the gas phase. The signal strengths of O2(b) were proportional to initial concentrations of HO2 formed by the F + H2O2 reaction. Observed /O2(b)/, /HO2/, and /OH/ vs /F/0 were analyzed using a simple three-step mechanism and a more complete computer simulation with 22 reaction steps. The results indicate that the F + HO2 reaction yields O2(b) with an efficiency of (3.6 + or - 1.4) x 10 to the -3rd. Yields from the O + OH2 reaction were less than 0.02, indicating that this reaction cannot be a major source of the O2(b) emission observed in the earth's nightglow.

Products and mechanism of the reaction of OH radicals with 2,3,4-trimethylpentane in the presence of NO.

PubMed

Aschmann, Sara M; Arey, Janet; Atkinson, Roger

2004-10-01

Alkanes are important constituents of gasoline fuel and vehicle exhaust, with branched alkanes comprising a significant fraction of the total alkanes observed in urban areas. Using a relative rate method, a rate constant for the reaction of OH radicals with 2,3,4-trimethylpentane of (6.84+/-0.12) x 10(-12) cm3 molecule(-1) s(-1) at 298+/-2 K was measured, where the indicated error is two least-squares standard deviations and does not include the uncertainty in the rate constant for the n-octane reference compound. Products of the gas-phase reaction of OH radicals with 2,3,4-trimethylpentane in the presence of NO at 298+/-2 K and atmospheric pressure of air have been investigated using gas chromatography with flame ionization detection (GC-FID), combined gas chromatographymass spectrometry (GC-MS), and in situ atmospheric pressure ionization tandem mass spectrometry (API-MS). Products identified and quantified by GC-FID and GC-MS were (molar yields given in parentheses): acetaldehyde (47+/-6%), acetone (76+/-11%), 3-methyl-2-butanone (41+/-5%), 3-methyl-2-butyl nitrate (1.6+/-0.2%), and 2-propyl nitrate (6.2+/-0.8%). These compounds account for 69+/-6% of the reaction products, as carbon. Additional products observed by API-MS analyses using positive and negative ion modes were C5- and C8-hydroxynitrates and a C8-hydroxycarbonyl, which, together with the predicted formation of octyl nitrates, account for some or all of the remaining products. The product distribution is compared to those for the linear and branched C8-alkanes n-octane and 2,2,4-trimethylpentane.

The Effect of Ambient Ozone on Unsaturated Tear Film Wax Esters.

PubMed

Paananen, Riku O; Rantamäki, Antti H; Parshintsev, Jevgeni; Holopainen, Juha M

2015-12-01

Tear film lipid layer (TFLL) is constantly exposed to reactive ozone in the surrounding air, which may have detrimental effects on ocular health. Behenyl oleate (BO), a representative tear film wax ester, was used to study the reaction with ozone at the air-water interface. Time-dependent changes in mean molecular area of BO monolayers were measured at different ozone concentrations and surface pressures. In addition, the effect of ascorbic acid on the reaction rate was determined. Reaction was followed using thin-layer chromatography and reaction products were identified using liquid chromatography-electrospray ionization mass spectrometry (LC-MS). Tear fluid samples from healthy subjects were analyzed with LC-MS for any ozonolysis reaction products. Behenyl oleate was found to undergo rapid ozonolysis at the air-water interface at normal indoor ozone concentrations. The reaction was observed as an initial expansion followed by a contraction of the film area. Ascorbic acid was found to decrease the rate of ozonolysis. Main reaction products were identified as behenyl 9-oxononanoate and behenyl 8-(5-octyl-1,2,4-trioxolan-3-yl)octanoate. Similar ozonolysis products were not detected in the tear fluid samples. At the air-water interface, unsaturated wax esters react readily with ozone in ambient air. However, no signs of ozonolysis products were found in the tear fluid. This is most likely due to the antioxidant systems present in tear fluid. Last, the results show that ozonolysis needs to be controlled in future surface chemistry studies on tear film lipids.

Fourier Transform Infrared Absorption Spectroscopy of Gas-Phase and Surface Reaction Products during Si Etching in Inductively Coupled Cl2 Plasmas

NASA Astrophysics Data System (ADS)

Miyata, Hiroki; Tsuda, Hirotaka; Fukushima, Daisuke; Takao, Yoshinori; Eriguchi, Koji; Ono, Kouichi

2011-10-01

A better understanding of plasma-surface interactions is indispensable during etching, including the behavior of reaction or etch products, because the products on surfaces and in the plasma are important in passivation layer formation through their redeposition on surfaces. In practice, the nanometer-scale control of plasma etching would still rely largely on such passivation layer formation as well as ion-enhanced etching on feature surfaces. This paper presents in situ Fourier transform infrared (FTIR) absorption spectroscopy of gas-phase and surface reaction products during inductively coupled plasma (ICP) etching of Si in Cl2. The observation was made in the gas phase by transmission absorption spectroscopy (TAS), and also on the substrate surface by reflection absorption spectroscopy (RAS). The quantum chemical calculation was also made of the vibrational frequency of silicon chloride molecules. The deconvolution of the TAS spectrum revealed absorption features of Si2Cl6 and SiClx (x = 1-3) as well as SiCl4, while that of the RAS spectrum revealed relatively increased absorption features of unsaturated silicon chlorides. A different behavior was also observed in bias power dependence between the TAS and RAS spectra.

Erosion of stereochemical control with increasing nucleophilicity: O-glycosylation at the diffusion limit.

PubMed

Beaver, Matthew G; Woerpel, K A

2010-02-19

Nucleophilic substitution reactions of 2-deoxyglycosyl donors indicated that the reactivity of the oxygen nucleophile has a significant impact on stereoselectivity. Employing ethanol as the nucleophile resulted in a 1:1 (alpha:beta) ratio of diastereomers under S(N)1-like reaction conditions. Stereoselective formation of the 2-deoxy-alpha-O-glycoside was only observed when weaker nucleophiles, such as trifluoroethanol, were employed. The lack of stereoselectivity observed in reactions of common oxygen nucleophiles can be attributed to reaction rates of the stereochemistry-determining step that approach the diffusion limit. In this scenario, both faces of the prochiral oxocarbenium ion are subject to nucleophilic addition to afford a statistical mixture of diastereomeric products. Control experiments confirmed that all nucleophilic substitution reactions were performed under kinetic control.

Enzymatic network for production of ether amines from alcohols.

PubMed

Palacio, Cyntia M; Crismaru, Ciprian G; Bartsch, Sebastian; Navickas, Vaidotas; Ditrich, Klaus; Breuer, Michael; Abu, Rohana; Woodley, John M; Baldenius, Kai; Wu, Bian; Janssen, Dick B

2016-09-01

We constructed an enzymatic network composed of three different enzymes for the synthesis of valuable ether amines. The enzymatic reactions are interconnected to catalyze the oxidation and subsequent transamination of the substrate and to provide cofactor recycling. This allows production of the desired ether amines from the corresponding ether alcohols with inorganic ammonium as the only additional substrate. To examine conversion, individual and overall reaction equilibria were established. Using these data, it was found that the experimentally observed conversions of up to 60% observed for reactions containing 10 mM alcohol and up to 280 mM ammonia corresponded well to predicted conversions. The results indicate that efficient amination can be driven by high concentrations of ammonia and may require improving enzyme robustness for scale-up. Biotechnol. Bioeng. 2016;113: 1853-1861. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

Determination of moxifloxacin and its oxidation products with kinetic evaluation under potassium permanganate treatment in acidic solution by ultra-performance liquid chromatography/tandem mass spectrometry.

PubMed

Hubicka, Urszula; Zmudzki, Paweł; Zajdel, Paweł; Krzek, Jan

2013-01-01

A simple, sensitive, and reproducible ultra-performance LC method for the determination of moxifloxacin (MOXI) oxidation stability under permanganate treatment in acidic conditions (pH 3.0-6.0) was developed. Besides the MOXI peak [retention time (RT) = 2.58], four additional products (RT = 0.86, 0.91, 1.42, and 1.89) were observed in all conditions tested. The oxidation process followed second-order reaction kinetics and depended upon solution acidity. The highest reaction rate constant was observed at pH 3.0, and this value decreased as the pH was increased to 6.0. The oxidation products were characterized, and their fragmentation pathways, derived from MS/MS data, were proposed. Two of these products were identified as hydroxyl derivatives of MOXI and two others as their oxidation product analogs with molecular ions of 418.4 and 416.4 m/z, respectively.

Aqueous-phase photooxidation of levoglucosan - a mechanistic study using aerosol time-of-flight chemical ionization mass spectrometry (Aerosol ToF-CIMS)

NASA Astrophysics Data System (ADS)

Zhao, R.; Mungall, E. L.; Lee, A. K. Y.; Aljawhary, D.; Abbatt, J. P. D.

2014-09-01

Levoglucosan (LG) is a widely employed tracer for biomass burning (BB). Recent studies have shown that LG can react rapidly with hydroxyl (OH) radicals in the aqueous phase despite many mass balance receptor models assuming it to be inert during atmospheric transport. In the current study, aqueous-phase photooxidation of LG by OH radicals was performed in the laboratory. The reaction kinetics and products were monitored by aerosol time-of-flight chemical ionization mass spectrometry (Aerosol ToF-CIMS). Approximately 50 reaction products were detected by the Aerosol ToF-CIMS during the photooxidation experiments, representing one of the most detailed product studies yet performed. By following the evolution of mass defects of product peaks, unique trends of adding oxygen (+O) and removing hydrogen (-2H) were observed among the products detected, providing useful information for determining potential reaction mechanisms and sequences. Additionally, bond-scission reactions take place, leading to reaction intermediates with lower carbon numbers. We introduce a data analysis framework where the average oxidation state (OSc) is plotted against a novel molecular property: double-bond-equivalence-to-carbon ratio (DBE/#C). The trajectory of LG photooxidation on this plot suggests formation of polycarbonyl intermediates and their subsequent conversion to carboxylic acids as a general reaction trend. We also determined the rate constant of LG with OH radicals at room temperature to be 1.08 ± 0.16 × 109 M-1 s-1. By coupling an aerosol mass spectrometer (AMS) to the system, we observed a rapid decay of the mass fraction of organic signals at mass-to-charge ratio 60 (f60), corresponding closely to the LG decay monitored by the Aerosol ToF-CIMS. The trajectory of LG photooxidation on a f44-f60 correlation plot matched closely to literature field measurement data. This implies that aqueous-phase photooxidation might be partially contributing to aging of BB particles in the ambient atmosphere.

Scope and Mechanistic Investigations on the Solvent-Controlled Regio- and Stereoselective Formation of Enol Esters from the Ruthenium-Catalyzed Coupling Reaction of Terminal Alkynes and Carboxylic Acids

PubMed Central

Yi, Chae S.; Gao, Ruili

2009-01-01

The ruthenium-hydride complex (PCy3)2(CO)RuHCl was found to be a highly effective catalyst for the alkyne-to-carboxylic acid coupling reaction to give synthetically useful enol ester products. Strong solvent effect was observed for the ruthenium catalyst in modulating the activity and selectivity; the coupling reaction in CH2Cl2 led to the regioselective formation of gem-enol ester products, while the stereoselective formation of (Z)-enol esters was obtained in THF. The coupling reaction was found to be strongly inhibited by PCy3. The coupling reaction of both PhCO2H/PhC≡CD and PhCO2D/PhC≡CH led to the extensive deuterium incorporation on the vinyl positions of the enol ester products. An opposite Hammett value was observed when the correlation of a series of para-substituted p-X-C6H4CO2H (X = OMe, CH3, H, CF3, CN) with phenylacetylene was examined in CDCl3 (ρ = +0.30) and THF (ρ = −0.68). Catalytically relevant Ru-carboxylate and –vinylidene-carboxylate complexes, (PCy3)2(CO)(Cl)Ru(κ2-O2CC6H4-p-OMe) and (PCy3)2(CO)(Cl)RuC(=CHPh)O2CC6H4-p-OMe, were isolated, and the structure of both complexes was completely established by X-ray crystallography. A detailed mechanism of the coupling reaction involving a rate-limiting C-O bond formation step was proposed on the basis of these kinetic and structural studies. The regioselective formation of the gem-enol ester products in CH2Cl2 was rationalized by a direct migratory insertion of the terminal alkyne via a Ru-carboxylate species, whereas the stereoselective formation of (Z)-enol ester products in THF was explained by invoking a Ru-vinylidene species. PMID:20161379

Product interactions and feedback in diffusion-controlled reactions

NASA Astrophysics Data System (ADS)

Roa, Rafael; Siegl, Toni; Kim, Won Kyu; Dzubiella, Joachim

2018-02-01

Steric or attractive interactions among reactants or between reactants and inert crowders can substantially influence the total rate of a diffusion-influenced reaction in the liquid phase. However, the role of the product species, which has typically different physical properties than the reactant species, has been disregarded so far. Here we study the effects of reactant-product and product-product interactions as well as asymmetric diffusion properties on the rate of diffusion-controlled reactions in the classical Smoluchowski-setup for chemical transformations at a perfect catalytic sphere. For this, we solve the diffusion equation with appropriate boundary conditions coupled by a mean-field approach on the second virial level to account for the particle interactions. We find that all particle spatial distributions and the total rate can change significantly, depending on the diffusion and interaction properties of the accumulated products. Complex competing and self-regulating (homeostatic) or self-amplifying effects are observed for the system, leading to both decrease and increase in the rates, as the presence of interacting products feeds back to the reactant flux and thus the rate with which the products are generated.

Intermediate mass fragment emission and iso-scaling in dissipative Ca+Sn reactions at 45 AMeV

NASA Astrophysics Data System (ADS)

Singh, H.; Quinlan, M. J.; Tõke, J.; Pawelczak, I.; Henry, E.; Schröder, W. U.; Amorini, F.; Anzalone, A.; Maiolino, C.; Auditore, L.; Loria, D.; Trifiro, A.; Trimarchi, M.; Cardella, G.; De Filippo, E.; Pagano, A.; Chatterjee, M. B.; Cavallaro, S.; Geraci, E.; Papa, M.; Pirrone, S.; Verde, G.; Grzeszczuk, A.; Guazzoni, P.; Zetta, L.; La Guidara, E.; Lanzalone, G.; Lo Nigro, S.; Politi, G.; Loria, D.; Porto, F.; Rizzo, F.; Russotto, P.; Vigilante, M.

2013-04-01

The production mechanism of intermediate-mass fragments (IMFs) with atomic numbers Z = 3 - 7 is explored in the intermediate energy regime, studying dissipative 48Ca+112Sn and 48Ca+124Sn reactions at E/A = 45MeV. Various aspects of IMF emission patterns point to an inelastic break-up type production mechanism involving excited projectile-like fragment from dissipative interactions. Isotopic yield ratios of identical IMFs from the above two dissipative reactions have been analysed using the "isoscaling" method. Observed trends are correlated with ground-state binding energy systematics and their relevance for an evaluation of the symmetry energy is discussed.

Theoretical investigation on the mechanism of NO3 radical-initiated atmospheric reactions of phenanthrene

NASA Astrophysics Data System (ADS)

Zhao, Nan; Shi, Xiangli; Xu, Fei; Zhang, Qingzhu; Wang, Wenxing

2017-07-01

Phenanthrene is a polycyclic aromatic hydrocarbon from fossil fuel combustion with toxic properties. The products arising from atmospheric reaction can be more mutagenic and carcinogenic compared to unmodified phenanthrene, and are therefore important to be studied. The products of the specific NO3-radical reactions with phenanthrene where therefore investigated in this study by means of Density Functional Theory (DFT). The results show that the main products are proposed to be 10-(nitrooxy)-10-hydro-phenanthrene-9-one, 2,2‧-diformylbiphenyl, 9,10-phenanthrenequinone, 9-fluorenone and dibenzopyranone. 10-(nitrooxy)-10-hydro-phenanthrene-9-one and 2,2‧-diformylbiphenyl are classified as first-generation products which are subject to secondary reactions to produce 9,10-phenanthrenequinone, 9-fluorenone and dibenzopyranone. The rate constants of elementary reactions were assessed by Rice-Ramsperger-Kassel-Marcus (RRKM) theory. The atmospheric lifetime of Phe determined by the gas-phase reaction with NO3 is estimated to be 1.8 h, based on the calculated overall rate constant of 3.04 × 10-13 cm3 molecule-1 s-1 at 298 K and 1 atm. Combined with available experimental observation, this work should help to clarify the transformation and potential health risk of Phe in the atmosphere.

Reaction of atomic hydrogen with formic acid.

PubMed

Cao, Qian; Berski, Slawomir; Latajka, Zdzislaw; Räsänen, Markku; Khriachtchev, Leonid

2014-04-07

We study the reaction of atomic hydrogen with formic acid and characterize the radical products using IR spectroscopy in a Kr matrix and quantum chemical calculations. The reaction first leads to the formation of an intermediate radical trans-H2COOH, which converts to the more stable radical trans-cis-HC(OH)2via hydrogen atom tunneling on a timescale of hours at 4.3 K. These open-shell species are observed for the first time as well as a reaction between atomic hydrogen and formic acid. The structural assignment is aided by extensive deuteration experiments and ab initio calculations at the UMP2 and UCCSD(T) levels of theory. The simplest geminal diol radical trans-cis-HC(OH)2 identified in the present work as the final product of the reaction should be very reactive, and further reaction channels are of particular interest. These reactions and species may constitute new channels for the initiation and propagation of more complex organic species in the interstellar clouds.

The Role of H2O in the Carbonation of Forsterite in Supercritical CO2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kwak, Ja Hun; Hu, Jian Z.; Turcu, Romulus VF

2011-07-01

The water concentration dependence of forsterite carbonation in supercritical CO2 (scCO2) at 80°C and 76 bars was investigated by a combination of NMR, XRD, TEM and XPS. Reaction products were not detected using scCO2 alone without added H2O. When trace amounts of water were included, limited reaction was observed. Below saturation, reaction products were a mixture of partially hydrated/hydroxylated magnesium carbonates and hydroxylated silica species that were mainly in an amorphous state, forming a non-resolved layer on the forsterite surface. At water concentrations above saturation, where forsterite was in contact with both a CO2-saturated aqueous fluid and a water-saturated scCO2more » fluid, solid reaction products were magnesite (MgCO3) and an amorphous polymerized SiO2 dominated by Q4, and to a lesser extent by Q3 silica coordination. Formation of these phases implies H2O initially bound in precursor hydrated/hydroxylated reaction products was liberated, inducing further reaction. Hence, for a given fluid/mineral ratio there is a water threshold above which a significant portion of the water serves in a catalytic role where more extensive carbonation reaction occurs. Defining the role of water, even in low water content environments, is therefore critical to determining the long term impact of CO2 reactivity in the subsurface.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tan Lin; Liu Fuyi; Armentrout, P.B.

The kinetic energy dependences of the reactions of Fe{sub n}{sup +} (n=1-19) with N{sub 2} are studied in a guided ion beam tandem mass spectrometer over the energy range of 0-15 eV. In addition to collision-induced dissociation forming Fe{sub m}{sup +} ions, which dominate the product spectra, a variety of Fe{sub m}N{sub 2}{sup +} and Fe{sub m}N{sup +} product ions, where m{<=}n, is observed. All processes are observed to exhibit thresholds. Fe{sub m}{sup +}-N and Fe{sub m}{sup +}-2N bond energies as a function of cluster size are derived from the threshold analysis of the kinetic energy dependences of the endothermicmore » reactions. The trends in this thermochemistry are compared to the isoelectronic D{sub 0}(Fe{sub n}{sup +}-CH), and to bulk phase values. A fairly uniform barrier of 0.48{+-}0.03 eV at 0 K is observed for formation of the Fe{sub n}N{sub 2}{sup +} product ions (n=12, 15-19) and can be related to the rate-limiting step in the Haber process for catalytic ammonia production.« less

In Situ Formation of Humic-like Substances In Model Cloud Water

NASA Astrophysics Data System (ADS)

Gelencsér, A.; Hoffer, A.; Kiss, G.; Tombácz, E.; Blazsó, M.; Bencze, L.

It is now widely established that humic-like substances (HULIS) are ubiquitous con- stituents in continental fine aerosol. Several studies have confirmed that HULIS are abundant organic species in the aqueous extract of rural, urban and biomass burn- ing aerosol. We have recently suggested that such compounds may be secondary (ternary?) aerosol constituents which are formed in the condensed phase from a vast array of low volatility organic precursors of primary or secondary origin. However, no experimental evidence has ever confirmed that such polymerisation reactions can indeed take place within the limited residence time of the accumulation mode aerosol. Normally, humification processes are generally assumed to take years and require spe- cial microbial environment which is barely available aloft. We studied polymerisation reactions of aromatic hydroxy-acids in the laboratory in solutions modelling the condi- tions prevalent in cloud water. In the solutions OH radicals were generated in Fenton- type reactions. The course of the reaction was monitored by UV-VIS spectrophotom- etry and liquid chromatography. The reaction products were characterised by fluo- rescence spectrometry, liquid chromatography-mass spectrometry and pyrolysis- gas chromatography-mass spectrometry. By monitoring the absorbance of the simulated cloud solution we demonstrated that chemical reactions took place in the solution pro- ducing measurable concentrations of chromophoric substances within the order of a few hours. The recorded UV-VIS spectra of the reaction products were very similar to those which had been observed in aqueous extracts of rural fine aerosol as well as in aqueous solutions of terrestrial humic and fulvic acids. Electrospray-mass spectra of the reaction products revealed that they consisted of an array of molecular species with a continuous molecular weight distribution peaking at a few hundred Dalton. Such spectra were also found to be typical of terrestrial humic and fulvic acids. Such similarities were also observed in the fluorescence and pyrolysis measurements. We hypothesized that free radical polymerisation proceeded via phenoxy radical interme- diates to yield dimeric and trimeric products, ill-defined humic-like substances. We therefore suggest that in hydrometeors similar reactions of polar aromatic compounds with hydroxyl radicals yield humic-like substances as secondary aerosol constituents.

Cosmogenic Cl-36 production rates in meteorites and the lunar surface

NASA Technical Reports Server (NTRS)

Nishiizumi, K.; Arnold, J. R.; Kubik, P. W.; Elmore, D.; Reedy, R. C.

1989-01-01

Activity vs. depth profiles of cosmic ray produced Cl-36 were measured in metal from two cores each in the St. Severin and Jilin chondrites and in lunar core 15008. Production of Cl-36 in these samples range from high-energy reactions with Fe and Ni to low-energy reactions with Ca and K and possibly neutron-capture reactions with Cl-36. The cross sections used in the Reedy-Arnold model for neutron-induced reactions were adjusted to get production rates that fit the measured Cl-36 activities in St. Severin metal and in the lunar soil of core 15008. The Cl-36 in metal from St. Severin has a fairly flat activity-vs-depth profile, unlike most other cosmogenic nuclides in bulk samples from St. Severin, which increase in concentration with depth. In metal from Jilin, a decrease in Cl-36 was observed near its center. The length of Jilin's most recent cosmic-ray exposure was approximately 0.5 My. Lunar core 15008 has an excess in Cl-36 of about 4 dpm/kg near its surface that was produced by solar-proton-induced reactions. The calculated production rates are consistent with these measured trends in 15008.

Fluorescence from the maillard reaction and its potential applications in food science.

PubMed

Matiacevich, Silvia B; Santagapita, Patricio R; Buera, M Pilar

2005-01-01

The chemistry of the Maillard reaction involves a complex set of steps, and its interpretation represents a challenge in basic and applied aspects of Food Science. Fluorescent compounds have been recognized as important early markers of the reaction in food products since 1942. However, the recent advances in the characterization of fluorophores' development were observed in biological and biomedical areas. The in vivo non-enzymatic glycosylation of proteins produces biological effects, promoting health deterioration. The characteristic fluorescence of advanced glycosylation end products (AGEs) is similar to that of Maillard food products and represents an indicator of the level of AGE-modified proteins, but the structure of the fluorescent groups is, typically, unknown. Application of fluorescence measurement is considered a potential tool for addressing key problems of food deterioration as an early marker or index of the damage of biomolecules. Fluorophores may be precursors of the brown pigments and/or end products. A general scheme of the Maillard reaction is proposed in this article, incorporating the pool concept. A correct interpretation of the effect of environmental and compositional conditions and their influences on the reaction kinetics may help to define the meaning of fluorescence development for each particular system.

Molecular Beam Chemistry: Reactions of Oxygen Atoms with Halogen Molecules.

DTIC Science & Technology

1982-10-15

nonlinear one has s = 3, r = 1, and n = 3/2. In the "loose" complex the bending modes go over to free rotation of the product diatomit molecule; thus s...contains no adjustable parameters. All observable properties *l of the reaction may be predicted including product velocity and angular dis- tributions...example, P. R. Bevington, Data Reduction and Error Analysis for the Physical Sciences (McGraw-Hill Book Co., New York, 1969). 65. Equation (3) is strictly

Surface chemistry of a pine-oil cleaner and other terpene mixtures with ozone on vinyl flooring tiles.

PubMed

Ham, Jason E; Wells, J Raymond

2011-04-01

Indoor environments are dynamic reactors where consumer products (such as cleaning agents, deodorants, and air fresheners) emit volatile organic compounds (VOCs) that can subsequently interact with indoor oxidants such as ozone (O(3)), hydroxyl radicals, and nitrate radicals. Typically, consumer products consist of mixtures of VOCs and semi-VOCs which can react in the gas-phase or on surfaces with these oxidants to generate a variety of oxygenated products. In this study, the reaction of a pine-oil cleaner (POC) with O(3) (100ppb) on a urethane-coated vinyl flooring tile was investigated at 5% and 50% relative humidity. These results were compared to previous α-terpineol+O(3) reactions on glass and vinyl surfaces. Additionally, other terpene and terpene alcohol mixtures were formulated to understand the emission profiles as seen in the POC data. Results showed that the α-terpineol+O(3) reaction products were the prominent species that were also observed in the POC/O(3) surface experiments. Furthermore, α-terpineol+O(3) reactions generate the largest fraction of oxygenated products even in equal mixtures of other terpene alcohols. This finding suggests that the judicial choice of terpene alcohols for inclusion in product formulations may be useful in reducing oxidation product emissions. Published by Elsevier Ltd.

Enlarging the substrate portfolio of the thermophilic esterase EST2 from Alicyclobacillus acidocaldarius.

PubMed

Pennacchio, Angela; Mandrich, Luigi; Manco, Giuseppe; Trincone, Antonio

2015-09-01

The enzymatic regioselective hydrolysis of (a) acetylated mono- to tetrasaccharides of different nature, (b) of acetylated aryl glycosides and (c) of different acetylated nucleosides was studied enlarging the portfolio of substrates that can be employed by the thermophilic esterase EST2 from Alicyclobacillus acidocaldarius. The reactions were optimised to the extent that the amount of enzyme needed was lowered of two orders of magnitude with respect to the previously reported reactions, namely from 4000 to 40 U of enzyme per reaction. New additional solvents were screened and dramatic changes in regioselectivity were observed depending on the amount and type of solvent used. For example, in the presence of 10 % DMF, only two α-D-glucose products 6-OH and 4,6-OH (in a 76:24 ratio) were detected, whereas with 25 % DMF, at least four products of similar amount were observed. This versatility adds specific value to the biocatalyst making possible the design of biocatalytic reactions with different hydrophobic ester substrates. As an additional remarkable example, EST2 catalysed with a good yield and high regioselectivity the hydrolysis of p-nitrophenyl β-D-xylopyranoside triacetate producing only the monoacetylated derivative with acetyl group in 3-O-position, in 2 min. The results with nucleosides as substrates are particularly interesting. The peracetates of 3',5'-di-O-acetylthymidine are converted almost quantitatively (95 %) to the monoacetylated derivative possessing free secondary OH; this regioselectivity is complementary to hydrolysis/alcoholysis reactions catalysed by CAL-B lipase or to other microbial hydrolytic biocatalysts, generally giving products with free primary OH groups. A docking analysis was undertaken with all analysed substrates suggesting a structural interpretation of the results. In most of cases, the best pose of the selected substrate was in line with the observed regioselectivity.

Acid-catalyzed hydrogenation during kerosene hydrodewaxing over H/ZSM-5

DOE Office of Scientific and Technical Information (OSTI.GOV)

Longstaff, D.C.; Hanson, F.V.

1996-11-01

Hydrogen addition to the products derived from cracking kerosene over H/ZSM-5 was observed at hydrogen pressures between 4.1-8.7 MPa and at 373-390{degrees}C. At low pressures, kerosene cracking over H/ZSM-5 yielded typical cracked products: aromatics, as well as low molecular weight saturates and olefins. Endothermic reactor temperature profiles were also observed, indicative of cracking reactions. At high hydrogen partial pressures product selectivity was altered in that kerosene cracking gave high yields of low molecular weight paraffins and low yields of olefins and aromatics. Reactor temperature profiles were exothermic, indicative of hydrocracking reactions. A mechanism for acid catalyzed hydrogenation is suggested. Althoughmore » hydrogenation was not observed at lower hydrogen pressures, hydrogen proved beneficial in maintaining catalyst activity at a stable level. Lost catalyst activity was restored by maintaining the catalyst under static hydrogen at 1.4 MPa and 370{degrees}C for 16h. 36 refs., 14 figs., 3 tabs.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pan, Huilin; Yang, Jiayue; Zhang, Dong

The effect of antisymmetric C–H stretching excitation of CH{sub 4} on the dynamics and reactivity of the O({sup 1}D) + CH{sub 4} → OH + CD{sub 3} reaction at the collision energy of 6.10 kcal/mol has been investigated using the crossed-beam and time-sliced velocity map imaging techniques. The antisymmetric C–H stretching mode excited CH{sub 4} molecule was prepared by direct infrared excitation. From the measured images of the CH{sub 3} products with the infrared laser on and off, the product translational energy and angular distributions were derived for both the ground and vibrationally excited reactions. Experimental results show that themore » vibrational energy of the antisymmetric stretching excited CH{sub 4} reagent is channeled exclusively into the vibrational energy of the OH co-products and, hence, the OH products from the excited-state reaction are about one vibrational quantum hotter than those from the ground-state reaction, and the product angular distributions are barely affected by the vibrational excitation of the CH{sub 4} reagent. The reactivity was found to be suppressed by the antisymmetric stretching excitation of CH{sub 4} for all observed CH{sub 3} vibrational states. The degree of suppression is different for different CH{sub 3} vibrational states: the suppression is about 40%–60% for the ground state and the umbrella mode excited CH{sub 3} products, while for the CH{sub 3} products with one quantum symmetric stretching mode excitation, the suppression is much less pronounced. In consequence, the vibrational state distribution of the CH{sub 3} product from the excited-state reaction is considerably different from that of the ground-state reaction.« less

Effects of iron-containing minerals on hydrothermal reactions of ketones

NASA Astrophysics Data System (ADS)

Yang, Ziming; Gould, Ian R.; Williams, Lynda B.; Hartnett, Hilairy E.; Shock, Everett L.

2018-02-01

Hydrothermal organic transformations occurring in geochemical processes are influenced by the surrounding environments including rocks and minerals. This work is focused on the effects of five common minerals on reactions of a model ketone substrate, dibenzylketone (DBK), in an experimental hydrothermal system. Ketones play a central role in many hydrothermal organic functional group transformations, such as those converting hydrocarbons to oxygenated compounds; however, how these minerals control the hydrothermal chemistry of ketones is poorly understood. Under the hydrothermal conditions of 300 °C and 70 MPa for up to 168 h, we observed that, while quartz (SiO2) and corundum (Al2O3) had no detectable effect on the hydrothermal reactions of DBK, iron-containing minerals, such as hematite (Fe2O3), magnetite (Fe3O4), and troilite (synthetic FeS), accelerated the reaction of DBK by up to an order of magnitude. We observed that fragmentation products, such as toluene and bibenzyl, dominated in the presence of hematite or magnetite, while use of troilite gave primarily the reduction products, e.g., 1, 3-diphenyl-propane and 1, 3-diphenyl-2-propanol. The roles of the three iron minerals in these transformations were further explored by (1) control experiments with various mineral surface areas, (2) measuring H2 in hydrothermal solutions, and (3) determining hydrogen balance among the organic products. These results suggest the reactions catalyzed by iron oxides (hematite and magnetite) are promoted mainly by the mineral surfaces, whereas the sulfide mineral (troilite) facilitated the reduction of ketone in the reaction solution. Therefore, this work not only provides a useful chemical approach to study and uncover complicated hydrothermal organic-mineral interactions, but also fosters a mechanistic understanding of ketone reactions in the deep carbon cycle.

Production of Excess CO2 relative to methane in peatlands: a new H2 sink

NASA Astrophysics Data System (ADS)

Wilson, R.; Woodcroft, B. J.; Varner, R. K.; Tyson, G. W.; Tfaily, M. M.; Sebestyen, S.; Saleska, S. R.; Rogers, K.; Rich, V. I.; McFarlane, K. J.; Kostka, J. E.; Kolka, R. K.; Keller, J.; Iversen, C. M.; Hodgkins, S. B.; Hanson, P. J.; Guilderson, T. P.; Griffiths, N.; de La Cruz, F.; Crill, P. M.; Chanton, J.; Bridgham, S. D.; Barlaz, M.

2015-12-01

Methane is generated as the end product of anaerobic organic matter degradation following a series of reaction pathways including fermentation and syntrophy. Along with acetate and CO2, syntrophic reactions generate H2 and are only thermodynamically feasible when coupled to an exothermic reaction that consumes H2. The usual model of organic matter degradation in peatlands has assumed that methanogenesis is that exothermic H2-consuming reaction. If correct, this paradigm should ultimately result in equimolar production of CO2 and methane from the degradation of the model organic compound cellulose: i.e. C6H12O6 à 3CO2 + 3CH4. However, dissolved gas measurement and modeling results from field and incubation experiments spanning peatlands across the northern hemisphere have failed to demonstrate equimolar production of CO2 and methane. Instead, in a flagrant violation of thermodynamics, these studies show a large bias favoring CO2 production over methane generation. In this talk, we will use an array of complementary analytical techniques including FT-IR, cellulose and lignin measurements, 13C-NMR, fluorescence spectroscopy, and ultra-high resolution mass spectrometry to describe organic matter degradation within a peat column and identify the important degradation mechanisms. Hydrogenation was the most common transformation observed in the ultra-high resolution mass spectrometry data. From these results we propose a new mechanism for consuming H2 generated during CO2 production, without concomitant methane formation, consistent with observed high CO2/CH4 ratios. While homoacetogenesis is a known sink for H2 in these systems, this process also consumes CO2 and therefore does not explain the excess CO2 measured in field and incubation samples. Not only does the newly proposed mechanism consume H2 without generating methane, but it also yields enough energy to balance the coupled syntrophic reactions, thereby restoring thermodynamic order. Schematic of organic matter degradation. Solid lines indicate traditional pathways from Conrad (1999), dashed lines indicates new proposed mechanism.

Glycation products in infant formulas: chemical, analytical and physiological aspects.

PubMed

Pischetsrieder, Monika; Henle, Thomas

2012-04-01

Infant formulas are milk-based products, which are adapted to the composition of human milk. To ensure microbiological safety and long shelf life, infant formulas usually undergo rigid heat treatment. As a consequence of the special composition and the heat regimen, infant formulas are more prone to thermally induced degradation reactions than regular milk products. Degradation reactions observed during milk processing comprise lactosylation yielding the Amadori product lactulosyllysine, the formation of advanced glycation end products (AGEs), and protein-free sugar degradation products, as well as protein or lipid oxidation. Several methods have been developed to estimate the heat impact applied during the manufacturing of infant formulas, including indirect methods such as fluorescence analysis as well as the analysis of defined reaction products. Most studies confirm a higher degree of damage in infant formulas compared to regular milk products. Differences between various types of infant formulas, such as liquid, powdered or hypoallergenic formulas depend on the analyzed markers and brands. A considerable portion of protein degradation products in infant formulas can be avoided when process parameters and the quality of the ingredients are carefully controlled. The nutritional consequences of thermal degradation products in infant formulas are largely unknown.

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

PubMed

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

2015-10-01

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

Better conditions for mammalian in vitro splicing provided by acetate and glutamate as potassium counterions

PubMed Central

Reichert, Vienna; Moore, Melissa J.

2000-01-01

We demonstrate here that replacing potassium chloride (KCl) with potassium acetate (KAc) or potassium glutamate (KGlu) routinely enhances the yield of RNA intermediates and products obtained from in vitro splicing reactions performed in HeLa cell nuclear extract. This effect was reproducibly observed with multiple splicing substrates. The enhanced yields are at least partially due to stabilization of splicing precursors and products in the KAc and KGlu reactions. This stabilization relative to KCl reactions was greatest with KGlu and was observed over an extended potassium concentration range. The RNA stability differences could not be attributed to heavy metal contamination of the KCl, since ultrapure preparations of this salt yielded similar results. After testing various methods for altering the salts, we found that substitution of KAc or KGlu for KCl and MgAc2 for MgCl2 in splicing reactions is the simplest and most effective. Since the conditions defined here more closely mimic in vivo ionic concentrations, they may permit the study of more weakly spliced substrates, as well as facilitate more detailed analyses of spliceosome structure and function. PMID:10606638

Structure reactivity and thermodynamic analysis on the oxidation of ampicillin drug by copper(III) complex in aqueous alkaline medium (stopped-flow technique)

NASA Astrophysics Data System (ADS)

Shetti, Nagaraj P.; Hegde, Rajesh N.; Nandibewoor, Sharanappa T.

2009-07-01

Oxidation of penicillin derivative, ampicillin (AMP) by diperiodatocuprate(III) (DPC) in alkaline medium at a constant ionic strength of 0.01-mol dm -3 was studied spectrophotometrically. The reaction between DPC and ampicillin in alkaline medium exhibits 1:4 stoichiometry (ampicillin:DPC). Intervention of free radicals was observed in the reaction. Based on the observed orders and experimental evidences, a mechanism involving the protonated form of DPC as the reactive oxidant species has been proposed. The oxidation reaction in alkaline medium has been shown to proceed via a DPC-AMP complex, which decomposes slowly in a rate determining step to yield phenyl glycine (PG) and free radical species of 6-aminopenicillanic acid (6-APA), followed by other fast steps to give the products. The two major products were characterized by IR, NMR, LC-MS and Spot test. The reaction constants involved in the different steps of the mechanism were calculated. The activation parameters with respect to slow step of the mechanism were computed and discussed and thermodynamic quantities were also determined.

Gas-phase products and secondary organic aerosol formation from the ozonolysis and photooxidation of myrcene

NASA Astrophysics Data System (ADS)

Böge, Olaf; Mutzel, Anke; Iinuma, Yoshiteru; Yli-Pirilä, Pasi; Kahnt, Ariane; Joutsensaari, Jorma; Herrmann, Hartmut

2013-11-01

In this study, the ozone and OH-radical reactions of myrcene were investigated in an aerosol chamber (at 292-295 K and 50% relative humidity) to examine the gas-phase oxidation products and secondary organic aerosol (SOA) formation. The ozone reaction studies were performed in the presence and absence of CO, which serves as an OH radical scavenger. In the photooxidation experiments OH radicals were generated by photolysis of methyl nitrite. The ozonolysis of myrcene in the presence of CO resulted in a substantial yield of 4-vinyl-4-pentenal (55.3%), measured as m/z 111 plus m/z 93 using proton transfer reaction-mass spectrometry (PTR-MS) and confirmed unambiguously as C7H10O by denuder measurements and HPLC/ESI-TOFMS analysis of its 2,4-dinitrophenylhydrazine (DNPH) derivative. Additionally, the formation of two different organic dicarbonyls with m/z 113 and a molecular formula of C6H8O2 were observed (2.1%). The yields of these dicarbonyls were higher in the ozonolysis experiments without an OH scavenger (5.4%) and even higher (13.8%) in the myrcene OH radical reaction. The formation of hydroxyacetone as a direct product of the myrcene reaction with ozone with a molar yield of 17.6% was also observed. The particle size distribution and volume concentrations were monitored and facilitated the calculation of SOA yields, which ranged from 0 to 0.01 (ozonolysis in the presence of CO) to 0.39 (myrcene OH radical reaction). Terpenylic acid was found in the SOA samples collected from the ozonolysis of myrcene in the absence of an OH scavenger and the OH radical-initiated reaction of myrcene but not in samples collected from the ozonolysis in the presence of CO as an OH radical scavenger, suggesting that terpenylic acid formation involves the reaction of myrcene with an OH radical. A reaction mechanism describing the formation of terpenylic acid is proposed.

Products of BVOC oxidation: ozone and organic aerosols

NASA Astrophysics Data System (ADS)

Wildt, Jürgen; Andres, Stefanie; Carriero, Giulia; Ehn, Mikael; Fares, Silvano; Hoffmann, Thorsten; Hacker, Lina; Kiendler-Scharr, Astrid; Kleist, Einhard; Paoletti, Elena; Pullinen, Iida; Rohrer, Franz; Rudich, Yinon; Springer, Monika; Tillmann, Ralf; Wahner, Andreas; Wu, Cheng; Mentel, Thomas

2015-04-01

Biogenic Volatile Organic Compounds (BVOC) are important precursors in photochemical O3 and secondary organic aerosol (SOA) formation. We conducted a series of laboratory experiments with OH-induced oxidation of monoterpenes to elucidate pathways and efficiencies of O3 and SOA formation. At high NOx conditions ([BVOC] / [NOx] < 7 ppbC / ppb) photochemical ozone formation was observed. For -pinene as individual BVOC as well as for the monoterpene mixes emitted from different plant species we observed increasing ozone formation with increasing [NOX]. Between 2 and 3 O3-molecules were formed from 1 monoterpene when ozone formation was BVOC limited. Under such high NOX conditions, new particle formation was suppressed. Increasing [BVOC] / [NOX] ratios caused increasing efficiency of new particle formation indicating that peroxy radicals are the key intermediates in both, photochemical ozone- and new particle formation. The classical chemistry of peroxy radicals is well established (e.g. Master Chemical Mechanism). Peroxy radicals are produced by addition of molecular oxygen to the alkyl radical formed after OH attack at the BVOC. They either react with NO which leads to ozone formation or they react with other peroxy radicals and form chemically stable products (hydroperoxides, alkoholes and ketones). Much less knowledge exists on such reactions for Highly Oxidized Peroxy Radicals, (HOPR). Such HOPR were observed during ozonolysis of several volatiles and, in case of monoterpenes as precursors, they can contain more than 12 Oxygen atoms (Mentel et al., 2015). Although the OH-initiated formation of HOPR is yet not fully understood, their basic gas phase reactions seem to follow classical photochemical rules. In reactions with NO they can act as precursor for O3 and in reactions with other HOPR or with classical less oxidized peroxy radicals they can form highly oxidized stable products and alkoxy radicals. In addition, HOPR-HOPR reactions lead to the formation of dimers that, in case of monoterpenes as reactants, consist of a skeleton with 20 carbon atoms. These dimers seem to play a major role in new particle formation and their existence may explain the observations of Wildt et al. (2014) who found power law dependence with an exponent approaching -2 between new particle formation and ozone formation. The monomer products of HOPR-HOPR reactions play a dominant role in SOA mass formation because their vapour pressures are low enough to allow condensation on pre-existing particulate matter (Ehn et al., 2014). Furthermore, the minor impacts of NOX on particle mass formation (Wildt et al., 2014) are explainable by similar yields of alkoxy radicals in HOPR-HOPR and HOPR-NO reactions, respectively.

A study of 3π production in γp → n -π +π +π - and γ-p → Δ + +π +π -π - with CLAS at Jefferson Lab ->n

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tsaris, Aristedis

2016-02-22

Apart from the mesons that the constituent quark model predicts, QCD allows for additional states beyond the qq system. Previous experiments have performed partial wave analysis on pion-production data and claim observation of an exotic J PC = 1 -+ state decaying via p-π. The g12 experiment took place at Jefferson Lab using the CLAS spectrometer, a liquid hydrogen target was used and a tagged photon beam. By studying the reactions γp → n -π +π +π - and γp → Δ + +π +π -π -, the photoproduction of mesons decaying to 3-pi was studied using two different butmore » complimentary channels. Events are selected with low four-momentum transfer to the baryon, in order to enhance one pion exchange production. For both 3-pi systems the data exhibit two intermediate decays, p-pi and f 2π. For the γp → n -π +π +π - reaction over 600k events were acquired resulting in the largest 3 photoproduction dataset to date. The exotic J PC = 1 -+ partial wave does not show resonant behavior and more so it is strongly consistent with a non-resonant non-interfering wave relative to a resonant π 2(1670). Furthermore, the partial wave analysis shows production of the a 2(1320) and π 2(1670) mesons. For the first time we report observation of a photoproduced a 1(1260) meson. For the γp → Δ + +π +π -π - reaction nearly 350k events were analyzed. A partial wave analysis was performed for the first time on this channel. The a1(1260), a2(1320), and the 2(1670) mesons were observed. Observation of the a1(1260) confirms the result first reported in γp → n -π +π +π - reaction.« less

Near-thermal reactions of Au(+)(1S,3D) with CH3X (X = F,Cl).

PubMed

Taylor, William S; Matthews, Cullen C; Hicks, Ashley J; Fancher, Kendall G; Chen, Li Chen

2012-01-26

Reactions of Au(+)((1)S) and Au(+)((3)D) with CH(3)F and CH(3)Cl have been carried out in a drift cell in He at a pressure of 3.5 Torr at both room temperature and reduced temperatures in order to explore the influence of the electronic state of the metal on reaction outcomes. State-specific product channels and overall two-body rate constants were identified using electronic state chromatography. These results indicate that Au(+)((1)S) reacts to yield an association product in addition to AuCH(2)(+) in parallel steps with both neutrals. Product distributions for association vs HX elimination were determined to be 79% association/21% HX elimination for X = F and 50% association/50% HX elimination when X = Cl. Reaction of Au(+)((3)D) with CH(3)F also results in HF elimination, which in this case is thought to produce (3)AuCH(2)(+). With CH(3)Cl, Au(+)((3)D) reacts to form AuCH(3)(+) and CH(3)Cl(+) in parallel steps. An additional product channel initiated by Au(+)((3)D) is also observed with both methyl halides, which yields CH(2)X(+) as a higher-order product. Kinetic measurements indicate that the reaction efficiency for both Au(+) states is significantly greater with CH(3)Cl than with CH(3)F. The observed two-body rate constant for depletion of Au(+)((1)S) by CH(3)F represents less than 5% of the limiting rate constant predicted by the average dipole orientation model (ADO) at room temperature and 226 K, whereas CH(3)Cl reacts with Au(+)((1)S) at the ADO limit at both room temperature and 218 K. Rate constants for depletion of Au(+)((3)D) by CH(3)F and CH(3)Cl were measured at 226 and 218 K respectively, and indicate that Au(+)((3)D) is consumed at approximately 2% of the ADO limit by CH(3)F and 69% of the ADO limit by CH(3)Cl. Product formation and overall efficiency for all four reactions are consistent with previous experimental results and available theoretical models.

Polar Diels-Alder reactions using electrophilic nitrobenzothiophenes. A combined experimental and DFT study

NASA Astrophysics Data System (ADS)

Della Rosa, Claudia D.; Mancini, Pedro M. E.; Kneeteman, Maria N.; Lopez Baena, Anna F.; Suligoy, Melisa A.; Domingo, Luis R.

2015-01-01

The reactions between 2- and 3-nitrobenzothiophenes with three dienes of different nucleophilicity, 1-methoxy-3-trimethylsilyloxy-1,3-butadiene, 1-trimethylsilyloxy-1,3-butadiene and isoprene developed in anhydrous benzene and alternative under microwave irradiation with molecular solvents or in free solvent conditions, respectively, for produce dibenzothiophenes permit to conclude that both nitroheterocycles act as electrophile with the cited dienes. In the cases of the dienes 1-methoxy-3-trimethylsilyloxy-1,3-butadiene and 1-trimethylsilyloxy-1,3-butadiene which posses major nucleophilicity the observed product is the normal cycloaddition one. However when the diene is isoprene the product with both electrophiles follow the hetero Diels-Alder way. These reactions are considered polar cycloaddition reactions and the yields are reasonables. Moreover the polar Diels-Alder reactions of nitrobenzothiophenes with electron rich dienes 1-trimethylsilyloxy-1,3-butadiene have been theoretically studied using DFT methods.

Improved Photoinduced Fluorogenic Alkene-Tetrazole Reaction for Protein Labeling.

PubMed

Shang, Xin; Lai, Rui; Song, Xi; Li, Hui; Niu, Wei; Guo, Jiantao

2017-11-15

The 1,3-dipolar cycloaddition reaction between an alkene and a tetrazole represents one elegant and rare example of fluorophore-forming bioorthogonal chemistry. This is an attractive reaction for imaging applications in live cells that requires less intensive washing steps and/or needs spatiotemporal resolutions. In the present work, as an effort to improve the fluorogenic property of the alkene-tetrazole reaction, an aromatic alkene (styrene) was investigated as the dipolarophile. Over 30-fold improvement in quantum yield of the reaction product was achieved in aqueous solution. According to our mechanistic studies, the observed improvement is likely due to an insufficient protonation of the styrene-tetrazole reaction product. This finding provides useful guidance to the future design of alkene-tetrazole reactions for biological studies. Fluorogenic protein labeling using the styrene-tetrazole reaction was demonstrated both in vitro and in vivo. This was realized by the genetic incorporation of an unnatural amino acid containing the styrene moiety. It is anticipated that the combination of styrene with different tetrazole derivatives can generally improve and broaden the application of alkene-tetrazole chemistry in real-time imaging in live cells.

Cationic Intermixing and Reactivity at the La2 Mo2 O9 /La0.8 Sr0.2 MnO3-δ Solid Oxide Fuel Cell Electrolyte-Cathode Interface.

PubMed

Ravella, Uday K; Liu, Jingjing; Corbel, Gwenaël; Skinner, Stephen J; Lacorre, Philippe

2016-08-23

Among standard high-temperature cathode materials for solid oxide fuel cells, La0.8 Sr0.2 MnO3-δ (LSM) displays the least reactivity with the oxide-ion conductor La2 Mo2 O9 (LMO), yet a reaction is observed at high processing temperatures, identified by using XRD and focused ion beam secondary-ion mass spectrometry (FIB-SIMS) after annealing at 1050 and 1150 °C. Additionally, Sr and Mn solutions were deposited and annealed on LMO pellets, as well as a Mo solution on a LSM pellet. From these studies several reaction products were identified by using XRD and located by using FIB-SIMS on the surface of pelletised samples. We used depth profiling to show that the reactivity extended up to ∼10 μm from the surface region. If Sr was present, a SrMoO4 -type scheelite phase was always observed as a reaction product, and if Mn was present, LaMnO3+δ single crystals were observed on the surface of the LMO pellets. Additional phases such as La2 MoO6 and La6 MoO12 were also detected depending on the configuration and annealing temperature. Reaction mechanisms and detailed reaction formulae are proposed to explain these observations. The strongest driving force for cationic diffusion appears to originate from Mo(6+) and Mn(3+) cations, rather than from Sr(2+) . © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Oxidation of alkylarenes to the corresponding acids using aqueous potassium permanganate by hydrodynamic cavitation.

PubMed

Ambulgekar, G V; Samant, S D; Pandit, A B

2004-05-01

Oxidation of toluene using aqueous potassium permanganate was studied under heterogeneous condition in the presence of hydrodynamic cavitation and compared with the results of the reaction under acoustic cavitation. Various parameters, such as quantity of potassium permanganate, toluene to aqueous phase ratio, reaction time and cavitation parameters such as orifice plate, and pump discharge pressure were optimized. The reaction was found to be considerably accelerated at ambient temperature in the presence of cavitation. On comparison, it was found that when 1 kJ of energy was passed to the reaction mixture in the case of acoustic cavitation, the product obtained was 4.63 x 10(-6) mol, whereas when 1 kJ of energy was passed to the reaction mixture in the case of hydrodynamic cavitation the product obtained was 2.70 x 10(-5) mol. Hence, about six times more product would be obtained in the case of hydrodynamic cavitation than in the case of acoustic cavitation at same energy dissipation. It has been observed that further optimization is possible.

Thermal Synthesis of Perchlorinated Oligosilanes: A Fresh Look at an Old Reaction.

PubMed

Neumeyer, Felix; Schweizer, Julia I; Meyer, Lioba; Sturm, Alexander G; Nadj, Andor; Holthausen, Max C; Auner, Norbert

2017-09-07

A combined experimental and theoretical study of the high-temperature reaction of SiCl 4 and elemental silicon is presented. The nature and reactivity of the product formed upon rapid cooling of the gaseous reaction mixture is investigated by comparison with the defined model compounds cyclo-Si 5 Cl 10 , n-Si 5 Cl 12 and n-Si 4 Cl 10 . A DFT assessment provides mechanistic insight into the oligosilane formation. Experimental 29 Si NMR investigations, supported by quantum-chemical 29 Si NMR calculations, consistently show that the reaction product is composed of discrete molecular perchlorinated oligosilanes. Low-temperature chlorination is an unexpectedly selective means for the transformation of cyclosilanes to acyclic species by endocyclic Si-Si bond cleavage, and we provide a mechanistic rationalization for this observation. In contrast to the raw material, the product obtained after low-temperature chlorination represents an efficient source of neo-Si 5 Cl 12 or the amine-stabilized disilene EtMe 2 N⋅SiCl 2 Si(SiCl 3 ) 2 through reaction with aliphatic amines. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guan, Jiwen; Song, Yang, E-mail: yang.song@uwo.ca; Department of Chemistry, University of Western Ontario, London, Ontario N6A 5B7

The polymerization process of condensed styrene to produce polystyrene as an industrially important polymeric material was investigated using a novel approach by combining external compression with ultraviolet radiation. The reaction evolution was monitored as a function of time and the reaction products were characterized by in situ Fourier transform infrared spectroscopy. By optimizing the loading pressures, we observed highly efficient and selective production of polystyrene of different tacticities. Specifically, at relatively low loading pressures, infrared spectra suggest that styrene monomers transform to amorphous atactic polystyrene (APS) with minor crystalline isotactic polystyrene. In contrast, APS was found to be the solemore » product when polymerization occurs at relatively higher loading pressures. The time-dependent reaction profiles allow the examination of the polymerization kinetics by analyzing the rate constant and activation volume as a function of pressure. As a result, an optimized pressure condition, which allows a barrierless reaction to proceed, was identified and attributed to the very desirable reaction yield and kinetics. Finally, the photoinitiated reaction mechanism and the growth geometry of the polymer chains were investigated from the energy diagram of styrene and by the topology analysis of the crystal styrene. This study shows strong promise to produce functional polymeric materials in a highly efficient and controlled manner.« less

Glyoxal-methylglyoxal cross-reactions in secondary organic aerosol formation.

PubMed

Schwier, Allison N; Sareen, Neha; Mitroo, Dhruv; Shapiro, Erica L; McNeill, V Faye

2010-08-15

Glyoxal (G) and methylglyoxal (MG) are potentially important secondary organic aerosol (SOA) precursors. Previous studies of SOA formation by G and MG have focused on either species separately; however, G and MG typically coexist in the atmosphere. We studied the formation of secondary organic material in aqueous aerosol mimic mixtures containing G and MG with ammonium sulfate. We characterized the formation of light-absorbing products using UV-vis spectrophotometry. We found that absorption at 280 nm can be described well using models for the formation of light-absorbing products by G and MG in parallel. Pendant drop tensiometry measurements showed that surface tension depression by G and MG in these solutions can be modeled as a linear combination of the effects of G and MG alone. Product species were identified using chemical ionization mass spectrometry with a volatilization flow tube inlet (Aerosol CIMS). Peaks consistent with G-MG cross-reaction products were observed, accounting for a significant fraction of detected product mass, but most peaks could be attributed to self-reaction. We conclude that cross-reactions contribute to SOA mass from uptake of G and MG, but they are not required to accurately model the effects of this process on aerosol surface tension or light absorption.

The Dynamics of the Photofragmentation of Ketene 3-Cyclopentenone, 3,5-Cycloheptadienone, and Tropone.

DTIC Science & Technology

1985-01-01

suggested that the concerted reaction should be allowed photochemically and the conrotatory mode should be favored. The data were in accord with this...crossing), or (4) reaction to form products, e.g., isomers or fragments, directly from the excited state. Further radiative, non-radiative, and photochemical ...processes can occur from intermediate excited states. Typical photochemical reactions observed in simple ketones in the gas phase are: (1) Norrish

Flash photolysis and pulse radiolysis studies on collagen Type I in acetic acid solution.

PubMed

Sionkowska, Alina

2006-07-03

An investigation of the photochemical properties of collagen Type I in acetic acid solution was carried out using nanosecond laser irradiation. The transient spectra of collagen solution excited at 266 nm show two bands. One of them with maximum at 295 nm and the second one with maximum at 400 nm. The peak at 400 nm is assigned to tyrosyl radicals. The first peak of the transient absorption spectra at 295 nm is probably due to photoionisation producing collagen radical cation. The transient for collagen solution in acetic acid at 640 nm was not observed. It is evidence that there is no hydrated electron in the irradiated collagen solution. The reactions of hydrated electrons and (*)OH radicals with collagen have been studied by pulse radiolysis. In the absorption spectra of products resulting from the reaction of collagen with e(aq)(-) no characteristic maximum absorption in UV and visible light region has been observed. In the absorption spectra of products resulting from the reaction of the hydroxyl radicals with collagen two bands have been observed. The first one at 320 nm and the second one at 405 nm. Reaction of (*)OH radicals with tyrosine residues in collagen chains gives rise to Tyr phenoxyl radicals (absorption at 400 nm).

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

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

Accurate Quantum Wave Packet Study of the Deep Well D+ + HD Reaction: Product Ro-vibrational State-Resolved Integral and Differential Cross Sections.

PubMed

He, Haixiang; Zhu, Weimin; Su, Wenli; Dong, Lihui; Li, Bin

2018-03-08

The H + + H 2 reaction and its isotopic variants as the simplest triatomic ion-molecule reactive system have been attracting much interests, however there are few studies on the titled reaction at state-to-state level until recent years. In this work, accurate state-to-state quantum dynamics studies of the titled reaction have been carried out by a reactant Jacobi coordinate-based time-dependent wave packet approach on diabatic potential energy surfaces constructed by Kamisaka et al. Product ro-vibrational state-resolved information has been calculated for collision energies up to 0.2 eV with maximal total angular momentum J = 40. The necessity of including all K-component for accounting the Coriolis coupling for the reaction has been illuminated. Competitions between the two product channels, (D + + HD' → D' + + HD and D + + HD' → H + + DD') were investigated. Total integral cross sections suggest that resonances enhance the reactivity of channel D + + HD'→ H + + DD', however, resonances depress the reactivity of the another channel D + + HD' → D' + + HD. The structures of the differential cross sections are complicated and depend strongly on collision energies of the two channels and also on the product rotational states. All of the product ro-vibrational state-resolved differential cross sections for this reaction do not exhibit rigorous backward-forward symmetry which may indicate that the lifetimes of the intermediate resonance complexes should not be that long. The dynamical observables of this deuterated isotopic reaction are quite different from the reaction of H + + H 2 → H 2 + H + reported previously.

Reaction pathway in vapour phase hydrogenation of maleic anhydride and its esters to {gamma}-butyrolactone

DOE Office of Scientific and Technical Information (OSTI.GOV)

Messori, M.; Vaccari, A.

1994-11-01

The catalytic reactivity of maleic anhydride (MA), succinic anhydride (SA) and their dimethyl esters (dimethyl maleate and dimethyl succinate) in the vapour phase hydrogenation to {gamma}-butyrolacetone (GBL) was investigated. In order to obtain general data, both a multicomponent catalyst (CAT 1: Cu/Zn/Mg/Cr = 40:5:5:50, atomic ratio %), obtained by reduction of a nonstoichiometric spinel-type precursor, and a commercial catalyst (CAT 2: Cu/Mn/Ba/Cr = 44:8:1:47, atomic ratio %) were used. The MA/GBL solution exhibited the highest GBL production, while the SA/GBL solution was converted only partially due to a competitive adsorption of GBL on the active sites, as evidenced by themore » similar reactivities observed with pure anhydrides. The best carbon balances were observed with the esters, probably the result of lowest light hydrocarbon synthesis and tar formation. With all the feedstocks, the activity of CAT 2 is higher than that of CAT 1, which, however, gives the best yield in GBL due its lower activity in the overhydrogenation and hydrogenolysis reaction. It was found that n-butanol (BuOH) and butyric acid (BuA) derived mainly from GBL. On this basis, the reactivities of the main products observed were investigated separately, confirming the stability of tetrahydrofuran (THF), which reacted only at high temperature with low conversions to ethanol. On the other hand, GBL gave rise to overhydrogenation and/or hydrogenolysis, with high conversion (mainly with CAT 2), confirming its key role in both reactions. Furthermore, the formation in the catalytic tests with BuA and BuOH of n-butanal, notwithstanding the high H{sub 2}/organic ratio, implies that it is the main intermediate in the hydrogenolysis reactions. A new reaction scheme is proposed, pointing out the key role of GBL as the {open_quotes}intersection{close_quotes} of two possible reaction pathways, giving rise to THF or overhydrogenation and hydrogenolysis products, respectively. 44 refs., 4 figs., 6 tabs.« less

Propensity approach to nonequilibrium thermodynamics of a chemical reaction network: Controlling single E-coli β-galactosidase enzyme catalysis through the elementary reaction stepsa)

NASA Astrophysics Data System (ADS)

Das, Biswajit; Banerjee, Kinshuk; Gangopadhyay, Gautam

2013-12-01

In this work, we develop an approach to nonequilibrium thermodynamics of an open chemical reaction network in terms of the elementary reaction propensities. The method is akin to the microscopic formulation of the dissipation function in terms of the Kullback-Leibler distance of phase space trajectories in Hamiltonian system. The formalism is applied to a single oligomeric enzyme kinetics at chemiostatic condition that leads the reaction system to a nonequilibrium steady state, characterized by a positive total entropy production rate. Analytical expressions are derived, relating the individual reaction contributions towards the total entropy production rate with experimentally measurable reaction velocity. Taking a real case of Escherichia coli β-galactosidase enzyme obeying Michaelis-Menten kinetics, we thoroughly analyze the temporal as well as the steady state behavior of various thermodynamic quantities for each elementary reaction. This gives a useful insight in the relative magnitudes of various energy terms and the dissipated heat to sustain a steady state of the reaction system operating far-from-equilibrium. It is also observed that, the reaction is entropy-driven at low substrate concentration and becomes energy-driven as the substrate concentration rises.

Observation of hydroxymethyl hydroperoxide in a reaction system containing CH{sub 2}OO and water vapor through pure rotational spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nakajima, Masakazu; Endo, Yasuki, E-mail: endo@bunshi.c.u-tokyo.ac.jp

Pure rotational transitions of hydroxymethyl hydroperoxide (HMHP) were observed in the discharged plasma of a CH{sub 2}I{sub 2}/O{sub 2}/water gas mixture, where the water complex with the simplest Criegee intermediate CH{sub 2}OO has been identified [M. Nakajima and Y. Endo, J. Chem. Phys. 140, 134302 (2014)]. Isotope experiments using heavy water support that the currently observed HMHP molecule was produced by the reaction of CH{sub 2}OO with water vapor. The observed species was identified as the most stable conformer with the help of quantum chemical calculations. We also clarified that productions of formic acid and dioxirane are promoted by themore » existence of water vapor in the discharged reaction system.« less

Reactions of Azine Anions with Nitrogen and Oxygen Atoms: Implications for Titan's Upper Atmosphere and Interstellar Chemistry.

PubMed

Wang, Zhe-Chen; Cole, Callie A; Demarais, Nicholas J; Snow, Theodore P; Bierbaum, Veronica M

2015-08-26

Azines are important in many extraterrestrial environments, from the atmosphere of Titan to the interstellar medium. They have been implicated as possible carriers of the diffuse interstellar bands in astronomy, indicating their persistence in interstellar space. Most importantly, they constitute the basic building blocks of DNA and RNA, so their chemical reactivity in these environments has significant astrobiological implications. In addition, N and O atoms are widely observed in the ISM and in the ionospheres of planets and moons. However, the chemical reactions of molecular anions with abundant interstellar and atmospheric atomic species are largely unexplored. In this paper, gas-phase reactions of deprotonated anions of benzene, pyridine, pyridazine, pyrimidine, pyrazine, and s-triazine with N and O atoms are studied both experimentally and computationally. In all cases, the major reaction channel is associative electron detachment; these reactions are particularly important since they control the balance between negative ions and free electron densities. The reactions of the azine anions with N atoms exhibit larger rate constants than reactions of corresponding chain anions. The reactions of azine anions with O atoms are even more rapid, with complex product patterns for different reactants. The mechanisms are studied theoretically by employing density functional theory; spin conversion is found to be important in determining some product distributions. The rich gas-phase chemistry observed in this work provides a better understanding of ion-atom reactions and their contributions to ionospheric chemistry as well as the chemical processing that occurs in the boundary layers between diffuse and dense interstellar clouds.

Investigation on the quasifission process by theoretical analysis of experimental data of fissionlike reaction products

NASA Astrophysics Data System (ADS)

Giardina, G.; Nasirov, A. K.; Mandaglio, G.; Curciarello, F.; De Leo, V.; Fazio, G.; Manganaro, M.; Romaniuk, M.; Saccá, C.

2011-02-01

The hindrance to complete fusion is a phenomenon presenting in the most part of the capture events in reactions with massive nuclei. This phenomenon is due to the onset of the quasifission process which competes with complete fusion during the evolution of the composed system formed at capture stage. The branching ratio between quasifission and complete fusion strongly depends from different characteristics of reacting nuclei in the entrance channel. The experimental and theoretical investigations of reaction dynamics connected with the formation of composed system is nowadays the main subject of the nuclear reactions. There is ambiguity in establishment of the reaction mechanism leading to the observed binary fissionlike fragments. The correct estimation of the fusion probability is important in planning experiments for the synthesis of superheavy elements. The experimental determination of evaporation residues only is not enough to restore the true reaction dynamics. The experimental observation of fissionlike fragments only cannot assure the correct distinguishing of products of the quasifission, fast fission, and fusion-fission processes which have overlapping in the mass (angular, kinetic energy) distributions of fragments. In this paper we consider a wide set of reactions (with different mass asymmetry and mass symmetry parameters) with the aim to explain the role played by many quantities on the reaction mechanisms. We also present the results of study of the 48Ca+249Bk reaction used to synthesize superheavy nuclei with Z = 117 by the determination of the evaporation residue cross sections and the effective fission barriers < Bf > of excited nuclei formed along the de-excitation cascade of the compound nucleus.

Pyrolysis-GCMS Analysis of Solid Organic Products from Catalytic Fischer-Tropsch Synthesis Experiments

NASA Technical Reports Server (NTRS)

Locke, Darren R.; Yazzie, Cyriah A.; Burton, Aaron S.; Niles, Paul B.; Johnson, Natasha M.

2015-01-01

Abiotic synthesis of complex organic compounds in the early solar nebula that formed our solar system is hypothesized to occur via a Fischer-Tropsch type (FTT) synthesis involving the reaction of hydrogen and carbon monoxide gases over metal and metal oxide catalysts. In general, at low temperatures (less than 200 C), FTT synthesis is expected to form abundant alkane compounds while at higher temperatures (greater than 200 C) it is expected to product lesser amounts of n-alkanes and greater amounts of alkene, alcohol, and polycyclic aromatic hydrocarbons (PAHs). Experiments utilizing a closed-gas circulation system to study the effects of FTT reaction temperature, catalysts, and number of experimental cycles on the resulting solid insoluble organic products are being performed in the laboratory at NASA Goddard Space Flight Center. These experiments aim to determine whether or not FTT reactions on grain surfaces in the protosolar nebula could be the source of the insoluble organic matter observed in meteorites. The resulting solid organic products are being analyzed at NASA Johnson Space Center by pyrolysis gas chromatography mass spectrometry (PY-GCMS). PY-GCMS yields the types and distribution of organic compounds released from the insoluble organic matter generated from the FTT reactions. Previously, exploratory work utilizing PY-GCMS to characterize the deposited organic materials from these reactions has been reported. Presented here are new organic analyses using magnetite catalyst to produce solid insoluble organic FTT products with varying reaction temperatures and number of experimental cycles.

Modeling Non-Steady Isotopologue and Isotopomer Speciation and Fractionation during Denitrification in Soils

NASA Astrophysics Data System (ADS)

Maggi, F.; Riley, W. J.

2009-12-01

The composition and location of 15N atoms on N2O isotopomers and isotopologues during isotope speciation has been used to characterize soil biological N cycling and N2O surface emissions. Although there exist few experimental observations, no attempt has been made to model N2O isotopomer speciation. The mathematical treatment of biological kinetic reactions in isotopic applications normally makes use of first-order and quasi steady-state complexation assumptions without taking into account changes in enzyme concentration, reaction stoichiometry, and isotopologue and isotopomer speciation. When multiatomic isotopically-labeled reactants are used in a multi-molecurar reaction, these assumptions may fail since they always lead to a constant fractionation factor and cannot describe speciation of isotopologues and isotopomers. We have developed a mathematical framework that is capable of describing isotopologue and isotopmer speciation and fractionation under the assumption of non-steady complexation during biological kinetic reactions that overcome the limitations mentioned above. This framework was applied to a case study of non-steady (variable and inverse) isotopic effects observed during N2O production and consumption in soils. Our mathematical treatment has led to generalized kinetic equations which replicate experimental observations with high accuracy and help interpret non-steady isotopic effects and isotopologue and isotopomer speciation. The kinetic equations introduced and applied here have general validity in describing isotopic effects in any biochemical reactions by considering: changing enzyme concentrations, mass and isotope conservation, and reaction stoichiometry. The equations also describe speciation of any isotopologue and isotopomer product from any isotopologue and isotopmer reactant.

Statistical Significance of the Maximum Hardness Principle Applied to Some Selected Chemical Reactions.

PubMed

Saha, Ranajit; Pan, Sudip; Chattaraj, Pratim K

2016-11-05

The validity of the maximum hardness principle (MHP) is tested in the cases of 50 chemical reactions, most of which are organic in nature and exhibit anomeric effect. To explore the effect of the level of theory on the validity of MHP in an exothermic reaction, B3LYP/6-311++G(2df,3pd) and LC-BLYP/6-311++G(2df,3pd) (def2-QZVP for iodine and mercury) levels are employed. Different approximations like the geometric mean of hardness and combined hardness are considered in case there are multiple reactants and/or products. It is observed that, based on the geometric mean of hardness, while 82% of the studied reactions obey the MHP at the B3LYP level, 84% of the reactions follow this rule at the LC-BLYP level. Most of the reactions possess the hardest species on the product side. A 50% null hypothesis is rejected at a 1% level of significance.

Experimental study of electrochemical fluorination of trichloroethylene

NASA Technical Reports Server (NTRS)

Polisena, C.; Liu, C. C.; Savinell, R. F.

1982-01-01

The electrochemical fluorination of trichloroethylene in anhydrous hydrogen fluoride at 0 C and at constant cell potential was investigated. A microprocessor-aided electrochemical fluorination reactor system that yields highly reproducible results was utilized. The following major two-carbon-chain products were observed: CHCl2-CCl2F, CHCl2-CClF2, CHClF-CCl2F, and CCl2F-CClF2. The first step in the reaction sequence was determined to be fluorine addition to the double bond, followed by replacement of first hydrogen and then chlorine by fluorine. Polymerization reactions yielded higher molecular weight or possible ring-type chlorofluorohydrocarbons. A comparison of the reaction products of electrochemical and chemical fluorinations of trichloroethylene is also discussed.

Involvement of Lipocalin-like CghA in Decalin-Forming Stereoselective Intramolecular [4+2] Cycloaddition

PubMed Central

Sato, Michio; Yagishita, Fumitoshi; Mino, Takashi; Uchiyama, Nahoko; Patel, Ashay; Chooi, Yit-Heng; Goda, Yukihiro; Xu, Wei; Noguchi, Hiroshi; Yamamoto, Tsuyoshi; Hotta, Kinya; Houk, Kendall N.; Tang, Yi

2016-01-01

Understanding enzymatic Diels—Alder (DA) reactions that can form complex natural product scaffold is of considerable interest. Sch 210972 1, a potential anti-HIV fungal natural product, contains a decalin core that is proposed to form via a DA reaction. We identified the gene cluster responsible for the biosynthesis of 1 and heterologously reconstituted the biosynthetic pathway in Aspergillus nidulans to characterize the enzymes involved. Most notably, deletion of cghA resulted in a loss of stereoselective decalin core formation, yielding both an endo 1 and a diastereomeric exo adducts of the proposed DA reaction. Complementation with cghA restored the sole formation of 1. Density functional theory computation of the proposed DA reaction provided a plausible explanation of the observed pattern of product formation. Based on our study, we propose that lipocalin-like CghA is responsible for the stereoselective intramolecular [4+2] cycloaddition that forms the decalin core of 1. PMID:26360642

Dehalogenation of arenes via SN2 reactions at bromine: competition with nucleophilic aromatic substitution.

PubMed

Gronert, Scott; Garver, John M; Nichols, Charles M; Worker, Benjamin B; Bierbaum, Veronica M

2014-11-21

The gas-phase reactions of carbon- and nitrogen-centered nucleophiles with polyfluorobromobenzenes were examined in a selected-ion flow tube (SIFT) and modeled computationally at the MP2/6-31+G(d,p)//MP2/6-31+G(d) level. In the gas-phase experiments, rate constants and branching ratios were determined. The carbon nucleophiles produce expected nucleophilic aromatic substitution (SNAr) and proton transfer products along with unexpected products that result from SN2 reactions at the bromine center (polyfluorophenide leaving group). With nitrogen nucleophiles, the SN2 at bromine channel is suppressed. In the SNAr channels, the "element effect" is observed, and fluoride loss competes with bromide loss. The computational modeling indicates that all the substitution barriers are well below the entrance channel and that entropy and dynamics effects control the product distributions.

REACTION PRODUCTS FROM THE CHLORINATION OF SEAWATER. CHAPTER 34

EPA Science Inventory

Much of the present information on the products formed when seawater is chlorinated is based on observations of laboratory experiments in which chlorine was added to seawater to stimulate conditions of electricity generating plants. Results are reported for a field study at the P...

Unravelling the Electronic State of NO2 Product in Ultrafast Photodissociation of Nitromethane.

PubMed

Adachi, Shunsuke; Kohguchi, Hiroshi; Suzuki, Toshinori

2018-01-18

The primary photochemical reaction of nitromethane (NM) after ππ* excitation is known to be C-N bond cleavage (CH 3 NO 2 + hν → CH 3 + NO 2 ). On the other hand, NO 2 can be formed in both the ground and excited states, and identification of the electronic state of the NO 2 product has been a central subject in the experimental and theoretical studies. Here we present time-resolved photoelectron spectroscopy using vacuum-ultraviolet probe pulses to observe all transient electronic states of NM and the reaction products. The result indicates that ultrafast internal conversion occurs down to S 1 and S 0 within 24 fs, and the dissociation proceeds on the S 1 surface (τ diss ≲ 50 fs), leading to comparable product yields of NO 2 (A) and NO 2 (X). The overall dissociation quantum yield within our observation time window (<2 ps) is estimated to be 0.29.

Zr-92(d,p)Zr-93 and Zr-92(d,t)Zr-91

NASA Technical Reports Server (NTRS)

Baron, N.; Fink, C. L.; Christensen, P. R.; Nickels, J.; Torsteinsen, T.

1972-01-01

The structures of Zr-93 and Zr-91 were studied by the stripping reaction Zr-92(d,p)Zr-93 and the pick-up reaction Zr-92(d,t)Zr-91 using 13 MeV incident deuterons. The reaction product particles were detected by counter telescope. Typical spectra from the reactions were analyzed by a nonlinear least squares peak fitting program which included a background search. Spin and parity assignments to observed excited levels were made by comparing experimental angular distributions with distorted wave Born approximation calculations.

Chemoselective SN2' Allylations of Detrifluoroacetylatively In Situ Generated 3-Fluoroindolin-2-one-Derived Tertiary Enolates with Morita-Baylis-Hillman Carbonates.

PubMed

Zhu, Yi; Mei, Haibo; Han, Jianlin; Soloshonok, Vadim A; Zhou, Jie; Pan, Yi

2017-12-15

The first example of the S N 2' reaction type of the detrifluoroacetylatively in situ generated tertiary fluoro-enolates in the uncatalyzed reactions with Morita-Baylis-Hillman derivatives has been described. The S N 2' substitution takes place in a highly chemoselective manner as no corresponding S N 2 products were observed in the reaction mixtures. Due to the excellent stereochemical outcome, the reactions seem to have an apparent synthetic value for the preparation of structurally new fluorinated oxindoles.

Characterization of microwave plasma CVD of diamond by mass analysis and optical emission spectroscopy

NASA Astrophysics Data System (ADS)

Weimer, Wayne A.; Johnson, Curtis E.

1990-12-01

A microwave plasma enhanced chemical vapor deposition system is characterized using optical emission spectroscopy and mass spectrometry. CH4 CH2 CH4 and CO were used as carbon source gases. The effects of 02 addition to the feed gas is examined. Emission from CH in the plasma is observed and CH4 is a stable reaction product for all carbon source gases used. 02 is fully consumed and converted to H20 and CO. Emission from C is observed for all hydrocarbon gases when 02 is added but is absent when CO is the carbon source gas. Addition of 02 also dramatically affects the relative amount of reaction products as the carbon in the system is converted to CO. 1.

Spectroscopic characteristics of carbon dots (C-dots) derived from carbon fibers and conversion to sulfur-bridged C-dots nanosheets.

PubMed

Vinci, John C; Ferrer, Ivonne M; Guterry, Nathan W; Colón, Verónica M; Destino, Joel F; Bright, Frank V; Colón, Luis A

2015-09-01

We synthesized sub-10 nm carbon nanoparticles (CNPs) consistent with photoluminescent carbon dots (C-dots) from carbon fiber starting material. The production of different C-dots fractions was monitored over seven days. During the course of the reaction, one fraction of C-dots species with relatively high photoluminescence was short-lived, emerging during the first hour of reaction but disappearing after one day of reaction. Isolation of this species during the first hour of the reaction was crucial to obtaining higher-luminescent C-dots species. When the reaction proceeded for one week, the appearance of larger nanostructures was observed over time, with lateral dimensions approaching 200 nm. The experimental evidence suggests that these larger species are formed from small C-dot nanoparticles bridged together by sulfur-based moieties between the C-dot edge groups, as if the C-dots polymerized by cross-linking the edge groups through sulfur bridges. Their size can be tailored by controlling the reaction time. Our results highlight the variety of CNP products, from sub-10 nm C-dots to ~200 nm sulfur-containing carbon nanostructures, that can be produced over time during the oxidation reaction of the graphenic starting material. Our work provides a clear understanding of when to stop the oxidation reaction during the top-down production of C-dots to obtain highly photoluminescent species or a target average particle size.

Removal of NO in NO/N2, NO/N2/O2, NO/CH4/N2, and NO/CH4/O2/N2 systems by flowing microwave discharges.

PubMed

Hueso, José L; Gonzalez-Elipe, Agustín R; Cotrino, José; Caballero, Alfonso

2007-02-15

In this paper, continuing previous work, we report on experiments carried out to investigate the removal of NO from simulated flue gas in nonthermal plasmas. The plasma-induced decomposition of small concentrations of NO in N2 used as the carrier gas and O2 and CH4 as minority components has been studied in a surface wave discharge induced with a surfatron launcher. The reaction products and efficiency have been monitored by mass spectrometry as a function of the composition of the mixture. NO is effectively decomposed into N2 and O2 even in the presence of O2, provided always that enough CH4 is also present in the mixture. Other majority products of the plasma reactions under these conditions are NH3, CO, and H2. In the absence of O2, decomposition of NO also occurs, although in that case HCN accompanies the other reaction products as a majority component. The plasma for the different reaction mixtures has been characterized by optical emission spectroscopy. Intermediate excited species of NO*, C*, CN*, NH*, and CH* have been monitored depending on the gas mixture. The type of species detected and their evolution with the gas composition are in agreement with the reaction products detected in each case. The observations by mass spectrometry and optical emission spectroscopy are in agreement with the kinetic reaction models available in literature for simple plasma reactions in simple reaction mixtures.

Abiotic dechlorination in rock matrices impacted by long-term exposure to TCE.

PubMed

Schaefer, Charles E; Towne, Rachael M; Lippincott, David R; Lacombe, Pierre J; Bishop, Michael E; Dong, Hailiang

2015-01-01

Field and laboratory tests were performed to evaluate the abiotic reaction of trichloroethene (TCE) in sedimentary rock matrices. Hydraulically conductive fractures, and the rock directly adjacent to the hydraulically conductive fractures, within a historically contaminated TCE bedrock aquifer were used as the basis for this study. These results were compared to previous work using rock that had not been exposed to TCE (Schaefer et al., 2013) to assess the impact of long-term TCE exposure on the abiotic dechlorination reaction, as the longevity of these reactions after long-term exposure to TCE was hitherto unknown. Results showed that potential abiotic TCE degradation products, including ethane, ethene, and acetylene, were present in the conductive fractures. Using minimally disturbed slices of rock core at and near the fracture faces, laboratory testing on the rocks confirmed that abiotic dechlorination reactions between the rock matrix and TCE were occurring. Abiotic daughter products measured in the laboratory under controlled conditions were consistent with those measured in the conductive fractures, except that propane also was observed as a daughter product. TCE degradation measured in the laboratory was well described by a first order rate constant through the 118-d study. Observed bulk first-order TCE degradation rate constants within the rock matrix were 1.3×10(-8) s(-1). These results clearly show that abiotic dechlorination of TCE is occurring within the rock matrix, despite decades of exposure to TCE. Furthermore, these observed rates of TCE dechlorination are expected to have a substantial impact on TCE migration and uptake/release from rock matrices. Copyright © 2014 Elsevier Ltd. All rights reserved.

Chemicl-looping combustion of coal with metal oxide oxygen carriers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Siriwardane, R.; Tian, H.; Richards, G.

2009-01-01

The combustion and reoxidation properties of direct coal chemical-looping combustion (CLC) over CuO, Fe2O3, Co3O4, NiO, and Mn2O3 were investigated using thermogravimetric analysis (TGA) and bench-scale fixed-bed flow reactor studies. When coal is heated in either nitrogen or carbon dioxide (CO2), 50% of weight loss was observed because of partial pyrolysis, consistent with the proximate analysis. Among various metal oxides evaluated, CuO showed the best reaction properties: CuO can initiate the reduction reaction as low as 500 °C and complete the full combustion at 700 °C. In addition, the reduced copper can be fully reoxidized by air at 700 °C.more » The combustion products formed during the CLC reaction of the coal/metal oxide mixture are CO2 and water, while no carbon monoxide was observed. Multicycle TGA tests and bench-scale fixed-bed flow reactor tests strongly supported the feasibility of CLC of coal by using CuO as an oxygen carrier. Scanning electron microscopy (SEM) images of solid reaction products indicated some changes in the surface morphology of a CuO-coal sample after reduction/oxidation reactions at 800 °C. However, significant surface sintering was not observed. The interactions of fly ash with metal oxides were investigated by X-ray diffraction and thermodynamic analysis. Overall, the results indicated that it is feasible to develop CLC with coal by metal oxides as oxygen carriers.« less

Effectiveness of using a magnetic spectrograph with the Trojan Horse method

NASA Astrophysics Data System (ADS)

Manwell, S.; Parikh, A.; Chen, A. A.; de Séréville, N.; Adsley, P.; Irvine, D.; Hammache, F.; Stefan, I.; Longland, R. F.; Tomlinson, J.; Morfuace, P.; Le Crom, B.

2018-01-01

The Trojan Horse method relies on performing reactions in a specific kinematic phase space that maximizes contributions of a quasi-free reaction mechanism. The hallmark of this method is that the incident particle can be accelerated to high enough energies to overcome the Coulomb barrier of the target, but once inside the target nucleus the relative motion of the clustered nuclei allows the reaction of interest to proceed at energies below this Coulomb Barrier. This method allows the experimentalist to probe reactions that have significance in astrophysics at low reaction energies that would otherwise be impossible due to the vanishing cross section. Traditionally the Trojan Horse method has been applied with the use of silicon detectors to observe the reaction products. In this study we apply the Trojan Horse method to a well studied reaction to examine the potential benefits of using a splitpole magnetic spectrograph to detect one of the reaction products. We have measure the three body 7Li(d,αn)α reaction to constrain the energy 7Li(d,α)α cross section. Measurements were first made using two silicon detectors, and then by replacing one detector with the magnetic spectrograph. The experimental design, limitations, and early results are discussed.

Catalytic photodegradation of pharmaceuticals - homogeneous and heterogeneous photocatalysis.

PubMed

Klementova, S; Kahoun, D; Doubkova, L; Frejlachova, K; Dusakova, M; Zlamal, M

2017-01-18

Photocatalytic degradation of pharmaceuticals (hydrocortisone, estradiol, and verapamil) and personal care product additives (parabens-methyl, ethyl, and propyl derivatives) was investigated in the homogeneous phase (with ferric ions as the catalyst) and on TiO 2 . Ferric ions in concentrations corresponding to concentrations in natural water bodies were shown to be a significant accelerator of the degradation in homogeneous reaction mixtures. In heterogeneous photocatalytic reactions on TiO 2 , lower reaction rates, but mineralisation to higher extents, were observed.

Remarkable nanoconfinement effects on chemical equilibrium manifested in nucleotide dimerization and H-D exchange reactions.

PubMed

Polak, Micha; Rubinovich, Leonid

2011-10-06

Nanoconfinement entropic effects on chemical equilibrium involving a small number of molecules, which we term NCECE, are revealed by two widely diverse types of reactions. Employing statistical-mechanical principles, we show how the NCECE effect stabilizes nucleotide dimerization observed within self-assembled molecular cages. Furthermore, the effect provides the basis for dimerization even under an aqueous environment inside the nanocage. Likewise, the NCECE effect is pertinent to a longstanding issue in astrochemistry, namely the extra deuteration commonly observed for molecules reacting on interstellar dust grain surfaces. The origin of the NCECE effect is elucidated by means of the probability distributions of the reaction extent and related variations in the reactant-product mixing entropy. Theoretical modelling beyond our previous preliminary work highlights the role of the nanospace size in addition to that of the nanosystem size, namely the limited amount of molecules in the reaction mixture. Furthermore, the NCECE effect can depend also on the reaction mechanism, and on deviations from stoichiometry. The NCECE effect, leading to enhanced, greatly variable equilibrium "constants", constitutes a unique physical-chemical phenomenon, distinguished from the usual thermodynamical properties of macroscopically large systems. Being significant particularly for weakly exothermic reactions, the effects should stabilize products in other closed nanoscale structures, and thus can have notable implications for the growing nanotechnological utilization of chemical syntheses conducted within confined nanoreactors.

Oxidation Dynamics of Methionine with Singlet Oxygen: Effects of Methionine Ionization and Microsolvation.

PubMed

Liu, Fangwei; Liu, Jianbo

2015-06-25

We report an in-depth study on the gas-phase reactions of singlet O2[a(1)Δg] with methionine (Met) at different ionization and hydration states (including deprotonated [Met - H](-), hydrated deprotonated [Met - H](-)(H2O)1,2, and hydrated protonated MetH(+)(H2O)1,2), using guided-ion-beam scattering mass spectrometry. The measurements include the effects of collision energy (Ecol) on reaction cross sections over a center-of-mass Ecol range from 0.05 to 1.0 eV. The aim of this study is to probe the influences of Met ionization and hydration on its oxidation mechanism and dynamics. Density functional theory calculations, Rice-Ramsperger-Kassel-Marcus modeling, and quasi-classical, direct dynamics trajectory simulations were performed to examine the properties of various complexes and transition states that might be important along reaction coordinates, probe reaction potential energy surfaces, and to establish the atomic-level mechanism for the Met oxidation process. No oxidation products were observed for the reaction of [Met - H](-) with (1)O2 due to the high-energy barriers located in the product channels for this system. However, this nonreactive property was altered by the microsolvation of [Met - H](-); as a result, hydroperoxides were captured as the oxidation products for [Met - H](-)(H2O)1,2 + (1)O2. For the reaction of MetH(+)(H2O)1,2 + (1)O2, besides formation of hydroperoxides, an H2O2 elimination channel was observed. The latter channel is similar to what was found in the reaction of dehydrated MetH(+) with (1)O2 (J. Phys. Chem. B 2011, 115, 2671). The reactions of hydrated protonated and deprotonated Met are all inhibited by Ecol, becoming negligible at Ecol ≥ 0.5 eV. The kinetic and dynamical consequences of microsolvation on Met oxidation and their biological implications are discussed.

The dynamics of surface-catalyzed reactions studied by infrared chemiluminescence of the CO and CO{sub 2} products

DOE Office of Scientific and Technical Information (OSTI.GOV)

Watanabe, K.; Uetsuka, H.; Ohnuma, H.

The infrared chemiluminescence technique has been applied to the selective formation of syngas (CO + H{sub 2}) from the oxidation of small alkanes on Pt, the decomposition and oxidation of CH{sub 3}OH and HCOOH on Pt and Ni, and CO oxidation on Pd(111) and Pd(110). The different internal (vibrational and rotational) energy states of the CO and CO{sub 2} products have been observed, which reflect the difference in the dynamics of these reactions.

Dynamic kinetic asymmetric cross-benzoin additions of β-stereogenic α-keto esters.

PubMed

Goodman, C Guy; Johnson, Jeffrey S

2014-10-22

The dynamic kinetic resolution of β-halo α-keto esters via an asymmetric cross-benzoin reaction is described. A chiral N-heterocyclic carbene catalyzes the umpolung addition of aldehydes to racemic α-keto esters. The resulting fully substituted β-halo glycolic ester products are obtained with high levels of enantio- and diastereocontrol. The high chemoselectivity observed is a result of greater electrophilicity of the α-keto ester toward the Breslow intermediate. The reaction products are shown to undergo highly diastereoselective substrate-controlled reduction to give highly functionalized stereotriads.

Dynamic Kinetic Asymmetric Cross-Benzoin Additions of β-Stereogenic α-Keto Esters

PubMed Central

2015-01-01

The dynamic kinetic resolution of β-halo α-keto esters via an asymmetric cross-benzoin reaction is described. A chiral N-heterocyclic carbene catalyzes the umpolung addition of aldehydes to racemic α-keto esters. The resulting fully substituted β-halo glycolic ester products are obtained with high levels of enantio- and diastereocontrol. The high chemoselectivity observed is a result of greater electrophilicity of the α-keto ester toward the Breslow intermediate. The reaction products are shown to undergo highly diastereoselective substrate-controlled reduction to give highly functionalized stereotriads. PMID:25299730

Study of the impact of organic nitrate production on ozone production in a southeastern mixed forest environment using a 0-D photochemical model

NASA Astrophysics Data System (ADS)

Mcavey, K. M.; Groff, C. J.; Xiong, F.; Seeley, J. V.; Starn, T.; Feiner, P. A.; Zhang, L.; Brune, W. H.; Baumann, K.; Misztal, P. K.; Koss, A.; De Gouw, J. A.; Olson, K. F.; Goldstein, A. H.; Bertman, S. B.; Shepson, P. B.

2014-12-01

Organic nitrates (RONO2 + ROONO2) act as an important sink for both organic alkoxy and peroxy and NOx (NO+NO2) radicals, and thus their production can have a significant limiting impact on ozone production. However, there remains significant uncertainty on the formation yields and fates of organic nitrates in the atmosphere. This certainly applies to the biogenic volatile organic compounds (BVOCs), which can often be the dominant reaction partner for OH and thus precursors to the peroxy radicals that produce ozone. Observations of BVOCs and total isoprene and monoterpene nitrates were measured as part of the Southern Oxidant and Aerosol Study in the summer of 2013, at the SEARCH Centreville site in rural, central Alabama. A 0-D box model was constructed to observe the effect of individual and total organic nitrates on ozone production potential, to determine the relative importance of each species in organic nitrate formation. Here we examine the impact of yield uncertainty, and secondary oxidation reactions that might release NOx from the primary organic nitrates.

Observation of isoprene hydroxynitrates in the southeastern United States and implications for the fate of NOx

NASA Astrophysics Data System (ADS)

Xiong, F.; McAvey, K. M.; Pratt, K. A.; Groff, C. J.; Hostetler, M. A.; Lipton, M. A.; Starn, T. K.; Seeley, J. V.; Bertman, S. B.; Teng, A. P.; Crounse, J. D.; Nguyen, T. B.; Wennberg, P. O.; Misztal, P. K.; Goldstein, A. H.; Guenther, A. B.; Koss, A. R.; Olson, K. F.; de Gouw, J. A.; Baumann, K.; Edgerton, E. S.; Feiner, P. A.; Zhang, L.; Miller, D. O.; Brune, W. H.; Shepson, P. B.

2015-10-01

Isoprene hydroxynitrates (IN) are tracers of the photochemical oxidation of isoprene in high NOx environments. Production and loss of IN have a significant influence on the NOx cycle and tropospheric O3 chemistry. To better understand IN chemistry, a series of photochemical reaction chamber experiments was conducted to determine the IN yield from isoprene photooxidation at high NO concentrations (> 100 ppt). By combining experimental data and calculated isomer distributions, a total IN yield of 9(+4/-3) % was derived. The result was applied in a zero-dimensional model to simulate production and loss of ambient IN observed in a temperate forest atmosphere, during the Southern Oxidant and Aerosol Study (SOAS) field campaign, from 27 May to 11 July 2013. The 9 % yield was consistent with the observed IN/(MVK+MACR) ratios observed during SOAS. By comparing field observations with model simulations, we identified NO as the limiting factor for ambient IN production during SOAS, but vertical mixing at dawn might also contribute (~ 27 %) to IN dynamics. A close examination of isoprene's oxidation products indicates that its oxidation transitioned from a high-NO dominant chemical regime in the morning into a low-NO dominant regime in the afternoon. A significant amount of IN produced in the morning high NO regime could be oxidized in the low NO regime, and a possible reaction scheme was proposed.

Ultracold Chemical Reactions of a Single Rydberg Atom in a Dense Gas

DOE PAGES

Schlagmüller, Michael; Liebisch, Tara Cubel; Engel, Felix; ...

2016-08-10

Within a dense environment (ρ ≈ 10 14 atoms/cm 3) at ultracold temperatures (T < 1 μK), a single atom excited to a Rydberg state acts as a reaction center for surrounding neutral atoms. At these temperatures, almost all neutral atoms within the Rydberg orbit are bound to the Rydberg core and interact with the Rydberg atom. We have studied the reaction rate and products for nS 87Rb Rydberg states, and we mainly observe a state change of the Rydberg electron to a high orbital angular momentum l, with the released energy being converted into kinetic energy of the Rydberg atom. Unexpectedly, the measurements show a threshold behavior at n ≈ 100 for the inelastic collision time leading to increased lifetimes of the Rydberg state independent of the densities investigated. Even at very high densities (ρ ≈ 4.8 x 10 14 cm -3), the lifetime of a Rydberg atom exceeds 10 μs at n > 140 compared to 1 μs at n = 90. In addition, a second observed reaction mechanism, namely, Rbmore » $$+\\atop{2}$$ molecule formation, was studied. Both reaction products are equally probable for n = 40, but the fraction of Rb + 2 created drops to below 10% for n ≥ 90.« less

Ce(x)O(y)⁻ (x = 2-3) + D₂O reactions: stoichiometric cluster formation from deuteroxide decomposition and anti-Arrhenius behavior.

PubMed

Felton, Jeremy A; Ray, Manisha; Waller, Sarah E; Kafader, Jared O; Jarrold, Caroline Chick

2014-10-30

Reactions between small cerium oxide cluster anions and deuterated water were monitored as a function of both water concentration and temperature in order to determine the temperature dependence of the rate constants. Sequential oxidation reactions of the Ce(x)O(y)⁻ (x = 2, 3) suboxide cluster anions were found to exhibit anti-Arrhenius behavior, with activation energies ranging from 0 to -18 kJ mol⁻¹. Direct oxidation of species up to y = x was observed, after which, -OD abstraction and D₂O addition reactions were observed. However, the stoichiometric Ce₂O₄⁻ and Ce₃O₆⁻ cluster anions also emerge in reactions between D₂O and the respective precursors, Ce₂O₃D⁻ and Ce₃O₅D₂⁻. Ce₂O₄⁻ and Ce₃O₆⁻ product intensities diminish relative to deuteroxide complex intensities with increasing temperature. The kinetics of these reactions are compared to the kinetics of the previously studied Mo(x)O(y)⁻ and W(x)O(y)⁻ reactions with water, and the possible implications for the reaction mechanisms are discussed.

Calculational and Experimental Investigations of the Pressure Effects on Radical - Radical Cross Combinations Reactions: C2H5 + C2H3

NASA Technical Reports Server (NTRS)

Fahr, Askar; Halpern, Joshua B.; Tardy, Dwight C.

2007-01-01

Pressure-dependent product yields have been experimentally determined for the cross-radical reaction C2H5 + C2H3. These results have been extended by calculations. It is shown that the chemically activated combination adduct, 1-C4H8*, is either stabilized by bimolecular collisions or subject to a variety of unimolecular reactions including cyclizations and decompositions. Therefore the "apparent" combination/disproportionation ratio exhibits a complex pressure dependence. The experimental studies were performed at 298 K and at selected pressures between about 4 Torr (0.5 kPa) and 760 Torr (101 kPa). Ethyl and vinyl radicals were simultaneously produced by 193 nm excimer laser photolysis of C2H5COC2H3 or photolysis of C2H3Br and C2H5COC2H5. Gas chromatograph/mass spectrometry/flame ionization detection (GC/MS/FID) were used to identify and quantify the final reaction products. The major combination reactions at pressures between 500 (66.5 kPa) and 760 Torr are (1c) C2H5 + C2H3 yields 1-butene, (2c) C2H5 + C2H5 yields n-butane, and (3c) C2H3 + C2H3 yields 1,3-butadiene. The major products of the disproportionation reactions are ethane, ethylene, and acetylene. At moderate and lower pressures, secondary products, including propene, propane, isobutene, 2-butene (cis and trans), 1-pentene, 1,4-pentadiene, and 1,5-hexadiene are also observed. Two isomers of C4H6, cyclobutene and/or 1,2-butadiene, were also among the likely products. The pressure-dependent yield of the cross-combination product, 1-butene, was compared to the yield of n-butane, the combination product of reaction (2c), which was found to be independent of pressure over the range of this study. The [ 1-C4H8]/[C4H10] ratio was reduced from approx.1.2 at 760 Torr (101 kPa) to approx.0.5 at 100 Torr (13.3 kPa) and approx.0.1 at pressures lower than about 5 Torr (approx.0.7 kPa). Electronic structure and RRKM calculations were used to simulate both unimolecular and bimolecular processes. The relative importance of C-C and C-H bond ruptures, cyclization, decyclization, and complex decompositions are discussed in terms of energetics and structural properties. The pressure dependence of the product yields were computed and dominant reaction paths in this chemically activated system were determined. Both modeling and experiment suggest that the observed pressure dependence of [1-C4H8]/[C4H10] is due to decomposition of the chemically activated combination adduct 1-C4H8* in which the weaker allylic C-C bond is broken: H2C=CHCH2CH3 yields C3H5 + CH3. This reaction occurs even at moderate pressures of approx.200 Torr (26 kPa) and becomes more significant at lower pressures. The additional products detected at lower pressures are formed from secondary radical-radical reactions involving allyl, methyl, ethyl, and vinyl radicals. The modeling studies have extended the predictions of product distributions to different temperatures (200-700 K) and a wider range of pressures (10(exp -3) - 10(exp 5) Torr). These calculations indicate that the high-pressure [1-C4H8]/[C4H10] yield ratio is 1.3 +/- 0.1.

Modeling the Transition From Predominantly Gas- to Predominantly Aerosol-Phase Products From OH Reactions With the Homologous Series of C10 to C15 n- Alkanes

NASA Astrophysics Data System (ADS)

Jordan, C. E.; Ziemann, P. J.; Griffin, R. J.; Lim, Y. B.; Atkinson, R.; Arey, J.

2006-12-01

Recent laboratory studies have shown significant formation of secondary organic aerosol (SOA) from OH reactions with a homologous series of n-alkanes. SOA mass yields of 56% were observed for pentadecane (C15), while only 0.5% yield was observed from octane (C8, the smallest alkane in the series). A rapid transition in SOA yield is observed from C10 to C13, with SOA yields increasing from 4% to 49%. In standard gas-aerosol partitioning theory, the vapor pressure controls the amount of material that can condense into the particle phase. However, the rapid transition observed here suggests there may also be a shift in the predominant reaction pathways for longer chain alkanes, leading to greater production of lower vapor pressure products. Here we present an investigation of the role of vapor pressure versus the role of shifting branching ratios to test the influence of each of these on SOA mass yields. We have added each of the alkanes in this series to the Caltech Atmospheric Chemistry Mechanism (CACM). This mechanism was developed in part to predict explicitly concentrations of secondary and tertiary semivolatile oxidation products that potentially form SOA. Although it is has been developed to lump similar compounds together for computational efficiency, it is nonetheless easily adapted and ideally suited for a detailed zero-dimensional modeling study of this kind. This gas-phase mechanism is linked to the aerosol partitioning module MPMPO (Model to Predict the Multi- phase Partitioning of Organics). MPMPO is a fully coupled module that allows the simultaneous partitioning of semi-volatile species to both an aqueous and an organic aerosol phase.

Some chemical and physical properties of nisin, a small-protein antibiotic produced by Lactococcus lactis.

PubMed Central

Liu, W; Hansen, J N

1990-01-01

Nisin is a small gene-encoded antimicrobial protein produced by Lactococcus lactis that contains unusual dehydroalanine and dehydrobutyrine residues. The reactivity of these residues toward nucleophiles was explored by reacting nisin with a variety of mercaptans. The kinetics of reaction with 2-mercaptoethane-sulfonate and thioglycolate indicated that the reaction pathway includes a binding step. Reaction of nisin at high pH resulted in the formation of multimeric products, apparently as a result of intramolecular and intermolecular reactions between nucleophilic groups and the dehydro residues. One of the nucleophiles had a pKa of about 9.8. The unique vinyl protons of the dehydro residues that give readily identifiable proton nuclear magnetic resonances were used to observe the addition of nucleophiles to the dehydro moiety. After reaction with nucleophiles, nisin lost its antibiotic activity and no longer showed the dehydro resonances, indicating that the dehydro groups had been modified. The effect of pH on the solubility of nisin was determined; the solubility was quite high at low pH (57 mg/ml at pH 2) and was much lower at high pH (0.25 mg/ml at pH 8 to 12), as measured before significant pH-induced chemical modification had occurred. High-performance liquid chromatography on a C18 column was an effective technique for separating unmodified nisin from its reaction products. The cyanogen bromide cleavage products of nisin were about 90% less active toward inhibition of bacterial spore outgrowth than was native nisin. These results are consistent with earlier observations, which suggested that the dehydro residues of nisin have a role in the mechanism of antibiotic action, in which they act as electrophilic Michael acceptors toward nucleophiles in the cellular target. Images PMID:2119570

Double and Triple Si-H-M Bridge Bonds: Matrix Infrared Spectra and Theoretical Calculations for Reaction Products of Silane with Ti, Zr, and Hf Atoms.

PubMed

Xu, Bing; Shi, Peipei; Huang, Tengfei; Wang, Xuefeng; Andrews, Lester

2017-05-25

Infrared spectra of matrix isolated dibridged Si(μ-H) 2 MH 2 and tribridged Si(μ-H) 3 MH molecules (M = Zr and Hf) were observed following the laser-ablated metal atom reactions with SiH 4 during condensation in excess argon and neon, but only the latter species was observed with titanium. Assignments of the major vibrational modes, which included terminal MH, MH 2 and hydrogen bridge Si-H-M stretching modes, were confirmed by the appropriate SiD 4 isotopic shifts and density functional vibrational frequency calculations (B3LYP and BPW91). The Si-H-M hydrogen bridge bond is calculated as weak covalent interaction and compared with the C-H···M agostic interaction in terms of electron localization function (ELF) analysis and noncovalent interaction index (NCI) calculations. Furthermore, the different products of Ti, Zr, and Hf reactions with SiH 4 are discussed in detail.

Dissolution and ionization of sodium superoxide in sodium–oxygen batteries

PubMed Central

Kim, Jinsoo; Park, Hyeokjun; Lee, Byungju; Seong, Won Mo; Lim, Hee-Dae; Bae, Youngjoon; Kim, Haegyeom; Kim, Won Keun; Ryu, Kyoung Han; Kang, Kisuk

2016-01-01

With the demand for high-energy-storage devices, the rechargeable metal–oxygen battery has attracted attention recently. Sodium–oxygen batteries have been regarded as the most promising candidates because of their lower-charge overpotential compared with that of lithium–oxygen system. However, conflicting observations with different discharge products have inhibited the understanding of precise reactions in the battery. Here we demonstrate that the competition between the electrochemical and chemical reactions in sodium–oxygen batteries leads to the dissolution and ionization of sodium superoxide, liberating superoxide anion and triggering the formation of sodium peroxide dihydrate (Na2O2·2H2O). On the formation of Na2O2·2H2O, the charge overpotential of sodium–oxygen cells significantly increases. This verification addresses the origin of conflicting discharge products and overpotentials observed in sodium–oxygen systems. Our proposed model provides guidelines to help direct the reactions in sodium–oxygen batteries to achieve high efficiency and rechargeability. PMID:26892931

Dissolution and ionization of sodium superoxide in sodium-oxygen batteries.

PubMed

Kim, Jinsoo; Park, Hyeokjun; Lee, Byungju; Seong, Won Mo; Lim, Hee-Dae; Bae, Youngjoon; Kim, Haegyeom; Kim, Won Keun; Ryu, Kyoung Han; Kang, Kisuk

2016-02-19

With the demand for high-energy-storage devices, the rechargeable metal-oxygen battery has attracted attention recently. Sodium-oxygen batteries have been regarded as the most promising candidates because of their lower-charge overpotential compared with that of lithium-oxygen system. However, conflicting observations with different discharge products have inhibited the understanding of precise reactions in the battery. Here we demonstrate that the competition between the electrochemical and chemical reactions in sodium-oxygen batteries leads to the dissolution and ionization of sodium superoxide, liberating superoxide anion and triggering the formation of sodium peroxide dihydrate (Na2O2·2H2O). On the formation of Na2O2·2H2O, the charge overpotential of sodium-oxygen cells significantly increases. This verification addresses the origin of conflicting discharge products and overpotentials observed in sodium-oxygen systems. Our proposed model provides guidelines to help direct the reactions in sodium-oxygen batteries to achieve high efficiency and rechargeability.

The oleic acid-ozone heterogeneous reaction system: products, kinetics, secondary chemistry, and atmospheric implications of a model system a review

NASA Astrophysics Data System (ADS)

Zahardis, J.; Petrucci, G. A.

2006-11-01

The heterogeneous processing of organic aerosols by trace oxidants has many implications to atmospheric chemistry and climate regulation. This review covers a model heterogeneous reaction system (HRS): the oleic acid-ozone HRS and other reaction systems featuring fatty acids, and their derivatives. The analysis of the primary products of ozonolysis (azelaic acid, nonanoic acid, 9-oxononanoic acid, nonanal) is described. Anomalies in the relative product yields are noted and explained by the observation of secondary chemical reactions. The secondary reaction products arising from reactive Criegee intermediates are mainly peroxidic, notably secondary ozonides and α-acyloxyalkyl hydroperoxide polymers. These highly oxygenated products are of low volatility and hydrophilic which may enhance the ability of particles to act as cloud condensation nuclei. The kinetic description of this HRS is critically reviewed. Most kinetic studies suggest this oxidative processing is either a near surface reaction that is limited by the diffusion of ozone or a surface based reaction. Internally mixed particles and coatings represent the next stage in the progression towards more realistic proxies of tropospheric organic aerosols and a description of the products and the kinetics resulting from the ozonolysis of these proxies, which are based on fatty acids or their derivatives, is presented. Finally, a series of atmospheric implications of oxidative processing of particulate containing fatty acids is presented. These implications include the extended lifetime of unsaturated species in the troposphere facilitated by the presence of solids, semisolids or viscous phases, and an enhanced rate of ozone uptake by particulate unsaturates compared to corresponding gas phase organics. Ozonolysis of oleic acid enhances its CCN activity, which implies that oxidatively processed particulate may contribute to indirect forcing of radiation. Other effects, including the potential role of aldehydic products of ozonolysis in increasing the oxidative capacity of the troposphere, are also discussed.

Gas-phase reactions of uranate ions, UO(2)(-), UO(3)(-), UO(4)(-), and UO(4)H(-), with methanol: a convergence of experiment and theory.

PubMed

Michelini, Maria Del Carmen; Marçalo, Joaquim; Russo, Nino; Gibson, John K

2010-04-19

Bimolecular reactions of uranium oxide molecular anions with methanol have been studied experimentally, by Fourier transform ion cyclotron resonance mass spectrometry, and computationally, by density functional theory (DFT). The primary goals were to provide fundamental insights into mechanistic and structural details of model reactions of uranium oxides with organics, and to examine the validity of theoretical modeling of these types of reactions. The ions UO(3)(-), UO(4)(-), and UO(4)H(-) each reacted with methanol to give a singular product; the primary products each exhibited sequential reactions with two additional methanol molecules to again give singular products. The observed reactions were elimination of water, formaldehyde, or hydrogen, and in one case addition of a methanol molecule. The potential energy profiles were computed for each reaction, and isotopic labeling experiments were performed to probe the validity of the computed mechanisms and structures-in each case where the experiments could be compared with the theory there was concurrence, clearly establishing the efficacy of the employed DFT methodologies for these and related reaction systems. The DFT results were furthermore in accord with the surprisingly inert nature of UO(2)(-). The results provide a basis to understand mechanisms of key reactions of uranium oxides with organics, and a foundation to extend DFT methodologies to more complex actinide systems which are not amenable to such direct experimental studies.

Theoretical investigation of the reaction of Mn+ with ethylene oxide.

PubMed

Li, Yuanyuan; Guo, Wenyue; Zhao, Lianming; Liu, Zhaochun; Lu, Xiaoqing; Shan, Honghong

2012-01-12

The potential energy surfaces of Mn(+) reaction with ethylene oxide in both the septet and quintet states are investigated at the B3LYP/DZVP level of theory. The reaction paths leading to the products of MnO(+), MnO, MnCH(2)(+), MnCH(3), and MnH(+) are described in detail. Two types of encounter complexes of Mn(+) with ethylene oxide are formed because of attachments of the metal at different sites of ethylene oxide, i.e., the O atom and the CC bond. Mn(+) would insert into a C-O bond or the C-C bond of ethylene oxide to form two different intermediates prior to forming various products. MnO(+)/MnO and MnH(+) are formed in the C-O activation mechanism, while both C-O and C-C activations account for the MnCH(2)(+)/MnCH(3) formation. Products MnO(+), MnCH(2)(+), and MnH(+) could be formed adiabatically on the quintet surface, while formation of MnO and MnCH(3) is endothermic on the PESs with both spins. In agreement with the experimental observations, the excited state a(5)D is calculated to be more reactive than the ground state a(7)S. This theoretical work sheds new light on the experimental observations and provides fundamental understanding of the reaction mechanism of ethylene oxide with transition metal cations.

Experimental and theoretical study of the reactions between neutral vanadium oxide clusters and ethane, ethylene, and acetylene.

PubMed

Dong, Feng; Heinbuch, Scott; Xie, Yan; Rocca, Jorge J; Bernstein, Elliot R; Wang, Zhe-Chen; Deng, Ke; He, Sheng-Gui

2008-02-13

Reactions of neutral vanadium oxide clusters with small hydrocarbons, namely C2H6, C2H4, and C2H2, are investigated by experiment and density functional theory (DFT) calculations. Single photon ionization through extreme ultraviolet (EUV, 46.9 nm, 26.5 eV) and vacuum ultraviolet (VUV, 118 nm, 10.5 eV) lasers is used to detect neutral cluster distributions and reaction products. The most stable vanadium oxide clusters VO2, V2O5, V3O7, V4O10, etc. tend to associate with C2H4 generating products V(m)O(n)C2H4. Oxygen-rich clusters VO3(V2O5)(n=0,1,2...), (e.g., VO3, V3O8, and V5O13) react with C2H4 molecules to cause a cleavage of the C=C bond of C2H4 to produce (V2O5)(n)VO2CH2 clusters. For the reactions of vanadium oxide clusters (V(m)O(n)) with C2H2 molecules, V(m)O(n)C2H2 are assigned as the major products of the association reactions. Additionally, a dehydration reaction for VO3 + C2H2 to produce VO2C2 is also identified. C2H6 molecules are quite stable toward reaction with neutral vanadium oxide clusters. Density functional theory calculations are employed to investigate association reactions for V2O5 + C2H(x). The observed relative reactivity of C2 hydrocarbons toward neutral vanadium oxide clusters is well interpreted by using the DFT calculated binding energies. DFT calculations of the pathways for VO3+C2H4 and VO3+C2H2 reaction systems indicate that the reactions VO3+C2H4 --> VO2CH2 + H2CO and VO3+C2H2 --> VO2C2 + H2O are thermodynamically favorable and overall barrierless at room temperature, in good agreement with the experimental observations.

Low NO Concentration Dependence of Reductive Nitrosylation Reaction of Hemoglobin*

PubMed Central

Tejero, Jesús; Basu, Swati; Helms, Christine; Hogg, Neil; King, S. Bruce; Kim-Shapiro, Daniel B.; Gladwin, Mark T.

2012-01-01

The reductive nitrosylation of ferric (met)hemoglobin is of considerable interest and remains incompletely explained. We have previously observed that at low NO concentrations the reaction with tetrameric hemoglobin occurs with an observed rate constant that is at least 5 times faster than that observed at higher concentrations. This was ascribed to a faster reaction of NO with a methemoglobin-nitrite complex. We now report detailed studies of this reaction of low NO with methemoglobin. Nitric oxide paradoxically reacts with ferric hemoglobin with faster observed rate constants at the lower NO concentration in a manner that is not affected by changes in nitrite concentration, suggesting that it is not a competition between NO and nitrite, as we previously hypothesized. By evaluation of the fast reaction in the presence of allosteric effectors and isolated β- and α-chains of hemoglobin, it appears that NO reacts with a subpopulation of β-subunit ferric hemes whose population is influenced by quaternary state, redox potential, and hemoglobin dimerization. To further characterize the role of nitrite, we developed a system that oxidizes nitrite to nitrate to eliminate nitrite contamination. Removal of nitrite does not alter reaction kinetics, but modulates reaction products, with a decrease in the formation of S-nitrosothiols. These results are consistent with the formation of NO2/N2O3 in the presence of nitrite. The observed fast reductive nitrosylation observed at low NO concentrations may function to preserve NO bioactivity via primary oxidation of NO to form nitrite or in the presence of nitrite to form N2O3 and S-nitrosothiols. PMID:22493289

Synthesis of Formamide and Related Organic Species in the Interstellar Medium via Chemical Dynamics Simulations

NASA Astrophysics Data System (ADS)

Spezia, Riccardo; Jeanvoine, Yannick; Hase, William L.; Song, Kihyung; Largo, Antonio

2016-08-01

We show, by means of direct dynamics simulations, how it is possible to define possible reactants and mechanisms leading to the formation of formamide in the interstellar medium. In particular, different ion-molecule reactions in the gas phase were considered: NH3OH+, NH2OH{}2+, H2COH+, and NH4 + for the ions and NH2OH, H2CO, and NH3 for the partner neutrals. These calculations were combined with high level ab initio calculations to investigate possible further evolution of the products observed. In particular, for formamide, we propose that the NH2OH{}2+ + H2CO reaction can produce an isomer, NH2OCH{}2+, that, after dissociative recombination, can produce neutral formamide, which was observed in space. The direct dynamics do not pre-impose any reaction pathways and in other reactions, we did not observe the formation of formamide or any possible precursor. On the other hand, we obtained other interesting reactions, like the formation of NH2CH{}2+. Finally, some radiative association processes are proposed. All of the results obtained are discussed in light of the species observed in radioastronomy.

Associative charge transfer reactions. Temperature effects and mechanism of the gas-phase polymerization of propene initiated by a benzene radical cation.

PubMed

Ibrahim, Yehia; Meot-Ner Mautner, Michael; El-Shall, M Samy

2006-07-13

In associative charge transfer (ACT) reactions, a core ion activates ligand molecules by partial charge transfer. The activated ligand polymerizes, and the product oligomer takes up the full charge from the core ion. In the present system, benzene(+*) (Bz(+*)) reacts with two propene (Pr) molecules to form a covalently bonded ion, C(6)H(6)(+*) + 2 C(3)H(6) --> C(6)H(12)(+*) + C(6)H(6). The ACT reaction is activated by a partial charge transfer from Bz(+*) to Pr in the complex, and driven to completion by the formation of a covalent bond in the polymerized product. An alternative channel forms a stable association product (Bz.Pr)(+*), with an ACT/association product ratio of 60:40% that is independent of pressure and temperature. In contrast to the Bz(+*)/propene system, ACT polymerization is not observed in the Bz(+*)/ethylene (Et) system since charge transfer in the Bz(+*)(Et) complex is inefficient to activate the reaction. The roles of charge transfer in these complexes are verified by ab initio calculations. The overall reaction of Bz(+*) with Pr follows second-order kinetics with a rate constant of k (304 K) = 2.1 x 10(-12) cm(3) s(-1) and a negative temperature coefficient of k = aT(-5.9) (or an activation energy of -3 kcal/mol). The kinetic behavior is similar to sterically hindered reactions and suggests a [Bz(+*) (Pr)]* activated complex that proceeds to products through a low-entropy transition state. The temperature dependence shows that ACT reactions can reach a unit collision efficiency below 100 K, suggesting that ACT can initiate polymerization in cold astrochemical environments.

Anti-inflammatory effect of sugar-amino acid Maillard reaction products on intestinal inflammation model in vitro and in vivo.

PubMed

Oh, Jun-Gu; Chun, Su-Hyun; Kim, Da Hyun; Kim, Jin Hye; Shin, Hye Soo; Cho, Yong Soo; Kim, Yong Ki; Choi, Hee-Don; Lee, Kwang-Won

2017-09-08

The Maillard reaction is a nonenzymatic reaction between an amino acid and a reducing sugar that usually occurs upon heating. This reaction occurs routinely in cooking, generates numerous products, which are collectively referred to as Maillard reaction products (MRPs) contributing to aroma and color features. Advanced glycation end-products (AGEs) transformed from MRPs are participated in many types of inflammation reaction. In this study, various sugar-amino acid MRPs were prepared from three different amino acids (lysine, arginine, and glycine) and sugars (glucose, fructose, and galactose) for 1 h with heating at 121 °C. Treatment of lipopolysaccharide-stimulated RAW264.7 macrophages with the MRPs decreased nitric oxide (NO) expression compared to control without MRPs treatment. MRPs derived from lysine and galactose (Lys-Gal MRPs) significantly inhibited NO expression. The retentate fraction of Lys-Gal MRPs with cut-off of molecular weight of 3-10 kDa (LGCM) suppressed NO expression more effectively than did Lys-Gal MRPs. The anti-inflammatory effect of LGCM was evaluated using a co-culture system consisting of Caco-2 (apical side) and RAW264.7 or THP-1 (basolateral side) cells to investigate the gut inflammation reaction by stimulated macrophage cells. In this system, LGCM prevented a decreased transepithelial electrical resistance, and decreased both tumor necrosis factor-α production in macrophages and interleukin (IL)-8 and IL-1β mRNA expression in Caco-2 cells. In co-culture and in vivo dextran sulfate sodium (DSS)-induced colitis model study, we also observed the anti-inflammatory activity of LGCM. Copyright © 2017 Elsevier Ltd. All rights reserved.

An overview on incomplete fusion reaction dynamics at energy range ∼ 3-8 MeV/A

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ali, Rahbar, E-mail: rahbarali1@rediffmail.com; Singh, D.; Ansari, M. Afzal

2014-08-14

The information of ICF reaction has been obtained from the measurement of excitation function (EF) of ERs populated in the interaction of {sup 20}Ne and {sup 16}O on {sup 55}Mn, {sup 159}Tb and {sup 156}Gd targets. Sizable enhancement in the measured cross-sections has been observed in α-emitting channels over theoretical predictions, which has been attributed to ICF of the projectile. In order to confirm the findings of the measurements and analysis of EFs, the forward recoil range distributions of ERs populated in {sup 20}Ne+{sup 159}Tb (E ∼165MeV) and {sup 16}O+{sup 156}Gd (E ∼ 72, 82 and 93MeV) systems, have beenmore » measured. It has been observed that peaks appearing at different cumulative thicknesses in the stopping medium are related with different degree of linear momentum transfer from projectile to target nucleus by adopting the break-up fusion model consideration. In order to deduce the angular momentum involved in various CF and / or ICF reaction products, spin distribution and side-feeding intensity profiles of radio-nuclides populated via CF and ICF channels in {sup 16}O+{sup 160}Gd system at energy, E ∼ 5.6 MeV/A, have been studied. Spin distribution of ICF products are found to be distinctly different than that observed from CF products.« less

Incomplete reactions in nanothermite composites

NASA Astrophysics Data System (ADS)

Jacob, Rohit J.; Ortiz-Montalvo, Diana L.; Overdeep, Kyle R.; Weihs, Timothy P.; Zachariah, Michael R.

2017-02-01

Exothermic reactions between oxophilic metals and transition/post transition metal-oxides have been well documented owing to their fast reaction time scales (≈10 μs). This article examines the extent of the reaction in nano-aluminum based thermite systems through a forensic inspection of the products formed during reaction. Three nanothermite systems (Al/CuO, Al/Bi2O3, and Al/WO3) were selected owing to their diverse combustion characteristics, thereby providing sufficient generality and breadth to the analysis. Microgram quantities of the sample were coated onto a fine platinum wire, which was resistively heated at high heating rates (≈105 K/s) to ignite the sample. The subsequent products were captured/quenched very rapidly (≈500 μs) in order to preserve the chemistry/morphology during initiation and subsequent reaction and were quantitatively analyzed using electron microscopy and focused ion beam cross-sectioning followed by energy dispersive X-ray spectroscopy. Elemental examination of the cross-section of the quenched particles shows that oxygen is predominantly localized in the regions containing aluminum, implying the occurrence of the redox reaction. The Al/CuO system, which has simultaneous gaseous oxygen release and ignition (TIgnition ≈ TOxygen Release), shows a substantially lower oxygen content within the product particles as opposed to Al/Bi2O3 and Al/WO3 thermites, which are postulated to undergo a condensed phase reaction (TIgnition ≪ TOxygen Release). An effective Al:O composition for the interior section was obtained for all the mixtures, with the smaller particles generally showing a higher oxygen content than the larger ones. The observed results were further corroborated with the reaction temperature, obtained using a high-speed spectro-pyrometer, and bomb calorimetry conducted on larger samples (≈15 mg). The results suggest that thermites that produce sufficient amounts of gaseous products generate smaller product particles and achieve higher extents of completion.

A characterization of the two-step reaction mechanism of phenol decomposition by a Fenton reaction

NASA Astrophysics Data System (ADS)

Valdés, Cristian; Alzate-Morales, Jans; Osorio, Edison; Villaseñor, Jorge; Navarro-Retamal, Carlos

2015-11-01

Phenol is one of the worst contaminants at date, and its degradation has been a crucial task over years. Here, the decomposition process of phenol, in a Fenton reaction, is described. Using scavengers, it was observed that decomposition of phenol was mainly influenced by production of hydroxyl radicals. Experimental and theoretical activation energies (Ea) for phenol oxidation intermediates were calculated. According to these Ea, phenol decomposition is a two-step reaction mechanism mediated predominantly by hydroxyl radicals, producing a decomposition yield order given as hydroquinone > catechol > resorcinol. Furthermore, traces of reaction derived acids were detected by HPLC and GS-MS.

Radical production from the interaction of ozone and PUFA as demonstrated by electron spin resonance spin-trapping techniques

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pryor, W.A.; Prier, D.G.; Church, D.F.

1981-02-01

There is considerable evidence that indicates that a fraction of the damage caused by ozone to cellular systems involves radical-mediated reactions. The most direct method for probing the mechanism by which ozone reacts with target molecules such as polyunsaturated fatty acids involves the use of electron spin resonance. In 1968, Goldstein et al. reported that ESR signals were observed when 40 ppM ozone in air is bubbled through linoleic acid. We have repeated this experiment and have performed several experiments modified from this design; in none of these do we observe ESR signals. We have studied the reaction of ozonemore » with PUFA at -78/sup 0/C using spin traps. Spin traps themselves react with ozone, but the following protocol avoids that reaction. (1) Ozone in air or oxygen-free ozone is allowed to bubble through the sample in Freon-11 in an ESR tube at -78/sup 0/C; no ESR absorption is observed. (2) Unreacted ozone is flushed out with argon or nitrogen. (3) The spin trap in Freon-11 is added to give a 0.1 M solution, still at -78/sup 0/C; no ESR signal is observed. (4) The tube is allowed to warm slowly. At about -45/sup 0/C, the ESR spectra of spin adducts appear. Using this method with methyl linoleate we observe spin adducts of alkoxy radicals and also a signal that is consistent with a carbon radical with one ..cap alpha..-H. We hypothesize that an intermediate is formed from the reaction of ozone with PUFA that is stable at -78/sup 0/Cbut decomposes to form radicals at about -45/sup 0/C. We tentatively identify the intermediate as a trioxide on the basis of analogies and its temperature profile for decomposition to radicals. It appears reasonable to suggest that the reaction(s) responsible for the production of radicals under these low-temperature conditions also occurs at room temperature. Although the low-temperature intermediate cannot be observed at ambient temperatures, radicals from it could be responsible for the effects on autoxidation that are induced by ozone.« less

Predictive Finite Rate Model for Oxygen-Carbon Interactions at High Temperature

NASA Astrophysics Data System (ADS)

Poovathingal, Savio

An oxidation model for carbon surfaces is developed to predict ablation rates for carbon heat shields used in hypersonic vehicles. Unlike existing empirical models, the approach used here was to probe gas-surface interactions individually and then based on an understanding of the relevant fundamental processes, build a predictive model that would be accurate over a wide range of pressures and temperatures, and even microstructures. Initially, molecular dynamics was used to understand the oxidation processes on the surface. The molecular dynamics simulations were compared to molecular beam experiments and good qualitative agreement was observed. The simulations reproduced cylindrical pitting observed in the experiments where oxidation was rapid and primarily occurred around a defect. However, the studies were limited to small systems at low temperatures and could simulate time scales only of the order of nanoseconds. Molecular beam experiments at high surface temperature indicated that a majority of surface reaction products were produced through thermal mechanisms. Since the reactions were thermal, they occurred over long time scales which were computationally prohibitive for molecular dynamics to simulate. The experiments provided detailed dynamical data on the scattering of O, O2, CO, and CO2 and it was found that the data from molecular beam experiments could be used directly to build a model. The data was initially used to deduce surface reaction probabilities at 800 K. The reaction probabilities were then incorporated into the direct simulation Monte Carlo (DSMC) method. Simulations were performed where the microstructure was resolved and dissociated oxygen convected and diffused towards it. For a gas-surface temperature of 800 K, it was found that despite CO being the dominant surface reaction product, a gas-phase reaction forms significant CO2 within the microstructure region. It was also found that surface area did not play any role in concentration of reaction products because the reaction probabilities were in the diffusion dominant regime. The molecular beam data at different surface temperatures was then used to build a finite rate model. Each reaction mechanism and all rate parameters of the new model were determined individually based on the molecular beam data. Despite the experiments being performed at near vacuum conditions, the finite rate model developed using the data could be used at pressures and temperatures relevant to hypersonic conditions. The new model was implemented in a computational fluid dynamics (CFD) solver and flow over a hypersonic vehicle was simulated. The new model predicted similar overall mass loss rates compared to existing models, however, the individual species production rates were completely different. The most notable difference was that the new model (based on molecular beam data) predicts CO as the oxidation reaction product with virtually no CO2 production, whereas existing models predict the exact opposite trend. CO being the dominant oxidation product is consistent with recent high enthalpy wind tunnel experiments. The discovery that measurements taken in molecular beam facilities are able to determine individual reaction mechanisms, including dependence on surface coverage, opens up an entirely new way of constructing ablation models.

The formation of molecules in interstellar clouds from singly and multiply ionized atoms

NASA Technical Reports Server (NTRS)

Langer, W. D.

1978-01-01

The suggestion is considered that multiply ionized atoms produced by K- and L-shell X-ray ionization and cosmic-ray ionization can undergo ion-molecule reactions and also initiate molecule production. The role of X-rays in molecule production in general is discussed, and the contribution to molecule production of the C(+) radiative association with hydrogen is examined. Such gas-phase reactions of singly and multiply ionized atoms are used to calculate molecular abundances of carbon-, nitrogen-, and oxygen-bearing species. The column densities of the molecules are evaluated on the basis of a modified version of previously developed isobaric cloud models. It is found that reactions of multiply ionized carbon with H2 can contribute a significant fraction of the observed CH in diffuse interstellar clouds in the presence of diffuse X-ray structures or discrete X-ray sources and that substantial amounts of CH(+) can be produced under certain conditions.

S-Nitroglutathione, a product of the reaction between peroxynitrite and glutathione that generates nitric oxide.

PubMed

Balazy, M; Kaminski, P M; Mao, K; Tan, J; Wolin, M S

1998-11-27

Peroxynitrite (ONOO-) has been shown in studies on vascular relaxation and guanylate cyclase activation to react with glutathione (GSH), generating an intermediate product that promotes a time-dependent production of nitric oxide (NO). In this study, reactions of ONOO- with GSH produced a new substance, which was characterized by liquid chromatography, ultraviolet spectroscopy, and electrospray tandem mass spectrometry. The mass spectrometric data provided evidence that the product of this reaction was S-nitroglutathione (GSNO2) and that S-nitrosoglutathione (GSNO) was not a detectable product of this reaction. Further evidence was obtained by comparison of the spectral and chromatographic properties with synthetic standards prepared by reaction of GSH with nitrosonium or nitronium borofluorates. Both the synthetic and ONOO-/GSH-derived GSNO2 generated a protonated ion, GSNO2H+, at m/z 353, which was unusually resistant to decomposition under collision activation, and no fragmentation was observed at collision energy of 25 eV. In contrast, an ion at m/z 337 (GSNOH+), generated from the synthetic GSNO, readily fragmented with the abundant loss of NO at 9 eV. Reactions of ONOO- with GSH resulted in the generation of NO, which was detected by the head space/NO-chemiluminescence analyzer method. The generation of NO was inhibited by the presence of glucose and/or CO2 in the buffers employed. Synthetic GSNO2 spontaneously generated NO in a manner that was not significantly altered by glucose or CO2. Thus, ONOO- reacts with GSH to form GSNO2, and GSNO2 decomposes in a manner that generates NO.

Mechanisms of polymer degradation using an oxygen plasma generator

NASA Technical Reports Server (NTRS)

Colony, Joe A.; Sanford, Edward L.

1987-01-01

An RF oxygen plasma generator was used to produce polymer degradation which appears to be similar to that which has been observed in low Earth orbit. Mechanisms of this type of degradation were studied by collecting the reaction products in a cryogenic trap and identifying the molecular species using infrared, mass spectral, and X-ray diffraction techniques. No structurally dependent species were found from Kapton, Teflon, or Saran polymers. However, very reactive free radical entities are produced during the polymer degradation, as well as carbon dioxide and water. Reactions of the free radicals with the glass reaction vessel, with copper metal in the cold trap, and with a triphenyl phosphate scavenger in the cold trap, demonstrated the reactivity of the primary products.

Use of Isobestic and Isoemission Points in Absorption and Luminescence Spectra for Study of the Transformation of Radiation Defects in Lithium Fluoride

NASA Astrophysics Data System (ADS)

Voitovich, A. P.; Kalinov, V. S.; Stupak, A. P.; Runets, L. P.

2015-03-01

Isobestic and isoemission points are recorded in the combined absorption and luminescence spectra of two types of radiation defects involved in complex processes consisting of several simultaneous parallel and sequential reactions. These points are observed if a constant sum of two terms, each formed by the product of the concentration of the corresponding defect and a characteristic integral coefficient associated with it, is conserved. The complicated processes involved in the transformation of radiation defects in lithium fluoride are studied using these points. It is found that the ratio of the changes in the concentrations of one of the components and the reaction product remains constant in the course of several simultaneous reactions.

Heterogeneous reaction of particulate chlorpyrifos with NO3 radicals: Products, pathways, and kinetics

NASA Astrophysics Data System (ADS)

Li, Nana; Zhang, Peng; Yang, Bo; Shu, Jinian; Wang, Youfeng; Sun, Wanqi

2014-08-01

Chlorpyrifos is a typical chlorinated organophosphorus pesticide. The heterogeneous reaction of chlorpyrifos particles with NO3 radicals was investigated using a vacuum ultraviolet photoionization aerosol time-of-flight mass spectrometer (VUV-ATOFMS) and a real-time atmospheric gas analysis mass spectrometer. Chlorpyrifos oxon, 3,5,6-trichloro-2-pyridinol, O,O-diethyl O-hydrogen phosphorothioate, O,O-diethyl ester thiophosphoric acid, diethyl hydrogen phosphate and a phosphinyl disulfide compound were identified as the main degradation products. The heterogeneous reaction pathways were proposed and their kinetic processes were investigated via a mixed-phase relative rate method. The observed effective rate constant is 3.4 ± 0.2 × 10-12 cm3 molecule-1 s-1.

Highly efficient and selective pressure-assisted photon-induced polymerization of styrene

NASA Astrophysics Data System (ADS)

Guan, Jiwen; Song, Yang

2016-06-01

The polymerization process of condensed styrene to produce polystyrene as an industrially important polymeric material was investigated using a novel approach by combining external compression with ultraviolet radiation. The reaction evolution was monitored as a function of time and the reaction products were characterized by in situ Fourier transform infrared spectroscopy. By optimizing the loading pressures, we observed highly efficient and selective production of polystyrene of different tacticities. Specifically, at relatively low loading pressures, infrared spectra suggest that styrene monomers transform to amorphous atactic polystyrene (APS) with minor crystalline isotactic polystyrene. In contrast, APS was found to be the sole product when polymerization occurs at relatively higher loading pressures. The time-dependent reaction profiles allow the examination of the polymerization kinetics by analyzing the rate constant and activation volume as a function of pressure. As a result, an optimized pressure condition, which allows a barrierless reaction to proceed, was identified and attributed to the very desirable reaction yield and kinetics. Finally, the photoinitiated reaction mechanism and the growth geometry of the polymer chains were investigated from the energy diagram of styrene and by the topology analysis of the crystal styrene. This study shows strong promise to produce functional polymeric materials in a highly efficient and controlled manner.

Physical, Chemical and Mineralogical Characteristics of Important Mississippi Soils

Treesearch

R. R. Bruce; W. A. Raney; W. M. Broadfoot; H. B. Vanderford

1958-01-01

To realize the crop production potential of soils it is necessary to first have a knowledge of their chemical, physical and biological properties and reactions and then to so alter these properties and reactions to effect a medium optimum for plant growth. In the past, soils have been classified primarily on the basis of physical characteristics observable in the field...

Real time monitoring of accelerated chemical reactions by ultrasonication-assisted spray ionization mass spectrometry.

PubMed

Lin, Shu-Hsuan; Lo, Ta-Ju; Kuo, Fang-Yin; Chen, Yu-Chie

2014-01-01

Ultrasonication has been used to accelerate chemical reactions. It would be ideal if ultrasonication-assisted chemical reactions could be monitored by suitable detection tools such as mass spectrometry in real time. It would be helpful to clarify reaction intermediates/products and to have a better understanding of reaction mechanism. In this work, we developed a system for ultrasonication-assisted spray ionization mass spectrometry (UASI-MS) with an ~1.7 MHz ultrasonic transducer to monitor chemical reactions in real time. We demonstrated that simply depositing a sample solution on the MHz-based ultrasonic transducer, which was placed in front of the orifice of a mass spectrometer, the analyte signals can be readily detected by the mass spectrometer. Singly and multiply charged ions from small and large molecules, respectively, can be observed in the UASI mass spectra. Furthermore, the ultrasonic transducer used in the UASI setup accelerates the chemical reactions while being monitored via UASI-MS. The feasibility of using this approach for real-time acceleration/monitoring of chemical reactions was demonstrated. The reactions of Girard T reagent and hydroxylamine with steroids were used as the model reactions. Upon the deposition of reactant solutions on the ultrasonic transducer, the intermediate/product ions are readily generated and instantaneously monitored using MS within 1 s. Additionally, we also showed the possibility of using this reactive UASI-MS approach to assist the confirmation of trace steroids from complex urine samples by monitoring the generation of the product ions. Copyright © 2014 John Wiley & Sons, Ltd.

Monitoring dediazoniation product formation by high-performance liquid chromatography after derivatization.

PubMed

Bravo-Díaz, Carlos; González-Romero, Elisa

2003-03-14

A derivatization protocol that exploits the rapid reaction between arenediazonium ions and a suitable coupling agent followed by high-performance liquid chromatography analyses of the reaction mixture was employed to determine the product distribution, the rate constants for product formation and the association constant of 4-nitrobenzenediazonium, PNBD, ion with beta-cyclodextrin, beta-CD. The derivatization of PNBD with the coupling agent leads to the formation of a stable azo dye that prevents by-side reactions of PNBD with the solvents of the mobile phase, including water, or the metallic parts of the chromatographic system that would eventually lead to erroneous identification and quantification of dediazoniation products. The results show that in the presence of beta-CD, nitrobenzene is formed at the expense of 4-nitrophenol, which is the major product in its absence. The observed rate constants for the interaction between PNBD and beta-CD increase upon increasing [beta-CD] showing a saturation profile indicative of the formation of an inclusion complex between PNBD and beta-CD. By fitting the experimental data to a simplified Lineaweaver-Burk equation, the corresponding association constant and the maximum acceleration rate of beta-CD towards PNBD were estimated. The protocol is applicable under a variety of experimental conditions provided that the rate of the coupling reaction is much faster than that of dediazoniation.

Photoproduction of I2, Br2, and Cl2 on n-semiconducting powder

NASA Technical Reports Server (NTRS)

Reichman, B.; Byvik, C. E.

1981-01-01

The photosynthetic production of Br2 and Cl2 and the photocatalytic production of I2 from aqueous solutions of the respective halide ions in the presence of platinized semiconducting n-TiO2 powder are reported. Reactions were produced in 2-3 M oxygen-saturated aqueous solutions of KI, KBr or NaCl containing Pt-TiO2 powder which were irradiated by a high-pressure mercury lamp at a power of 400 mW/sq cm. Halogens are found to be produced in greater quantities when platinized TiO2 powders are used rather than pure TiO2, and rates of halogen production are observed to increase from Cl2 to Br2 to I2. The presence of the synthetic reactions producing Br2 and Cl2 with a net influx of energy indicates that an effective separation of the photoproduced electron-hole pair occurs in the semiconductor. Quantum efficiencies of the reaction, which increase with decreasing solution pH, are found to be as high as 30%, implying a solar-to-chemical energy conversion efficiency between 0.03% and 3% for the case of chlorine production. It is concluded that the photoproduction of halogens may be of practical value if product halogens are efficiently removed from the reaction cell.

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

PubMed Central

Lietzan, Adam D.; St. Maurice, Martin

2014-01-01

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

In situ observation of self-propagating high temperature syntheses of Ta5Si3, Ti5Si3 and TiB2 by proton and X-ray radiography

NASA Astrophysics Data System (ADS)

Bernert, T.; Winkler, B.; Haussühl, E.; Trouw, F.; Vogel, S. C.; Hurd, A. J.; Smilowitz, L.; Henson, B. F.; Merrill, F. E.; Morris, C. L.; Mariam, F. G.; Saunders, A.; Juarez-Arellano, E. A.

2013-08-01

Self-propagating high temperature reactions of tantalum and titanium with silicon and titanium with boron were studied using proton and X-ray radiography, small-angle neutron scattering, neutron time-of-flight, X-ray and neutron diffraction, dilatometry and video recording. We show that radiography allows the observation of the propagation of the flame front in all investigated systems and the determination of the widths of the burning zones. X-ray and neutron diffraction showed that the reaction products consisted of ≈90 wt% of the main phase and one or two secondary phases. For the reaction 5Ti + 3Si → Ti5Si3 flame front velocities of 7.1(3)-34.2(4) mm/s were determined depending on the concentration of a retardant added to the starting material, the geometry and the green density of the samples. The flame front width was determined to be 1.17(4)-1.82(8) mm and depends exponentially on the flame front velocity. Similarly, for the reaction Ti + 2B → TiB2 flame front velocities of 15(2)-26.6(4) mm/s were determined, while for a 5Ta + 3Si → Ta5Si3 reaction the flame front velocity was 7.05(4) mm/s. The micro structure of the product phase Ta5Si3 shows no texture. From SANS measurements the dependence of the specific surface of the product phase on the particle sizes of the starting materials was studied.

Mechanistic investigations of CO-photoextrusion and oxidative addition reactions of early transition-metal carbonyls: (η(5)-C5H5)M(CO)4 (M = V, Nb, Ta).

PubMed

Su, Shih-Hao; Su, Ming-Der

2016-06-28

The mechanisms for the photochemical Si-H bond activation reaction are studied theoretically using a model system of the group 5 organometallic compounds, η(5)-CpM(CO)4 (M = V, Nb, and Ta), with the M06-2X method and the Def2-SVPD basis set. Three types of reaction pathways that lead to final insertion products are identified. The structures of the intersystem crossings, which play a central role in these photo-activation reactions, are determined. The intermediates and transitional structures in either the singlet or triplet states are also calculated to provide a mechanistic explanation of the reaction pathways. All of the potential energy surfaces for the group 5 η(5)-CpM(CO)4 complexes are quite similar. In particular, the theoretical evidence suggests that after irradiation using light, η(5)-CpM(CO)4 quickly loses one CO ligand to yield two tricarbonyls, in either the singlet or the triplet states. The triplet tricarbonyl 16-electron intermediates, ([η(5)-CpM(CO)3](3)), play a key role in the formation of the final oxidative addition product, η(5)-CpM(CO)3(H)(SiMe3). However, the singlet counterparts, ([η(5)-CpM(CO)3](1)), play no role in the formation of the final product molecule, but their singlet metal centers interact weakly with solvent molecules ((Me3)SiH) to produce alkyl-solvated organometallic complexes, which are observable experimentally. This theoretical evidence is in accordance with the available experimental observations.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schlagmüller, Michael; Liebisch, Tara Cubel; Engel, Felix

Within a dense environment (ρ ≈ 10 14 atoms/cm 3) at ultracold temperatures (T < 1 μK), a single atom excited to a Rydberg state acts as a reaction center for surrounding neutral atoms. At these temperatures, almost all neutral atoms within the Rydberg orbit are bound to the Rydberg core and interact with the Rydberg atom. We have studied the reaction rate and products for nS 87Rb Rydberg states, and we mainly observe a state change of the Rydberg electron to a high orbital angular momentum l, with the released energy being converted into kinetic energy of the Rydberg atom. Unexpectedly, the measurements show a threshold behavior at n ≈ 100 for the inelastic collision time leading to increased lifetimes of the Rydberg state independent of the densities investigated. Even at very high densities (ρ ≈ 4.8 x 10 14 cm -3), the lifetime of a Rydberg atom exceeds 10 μs at n > 140 compared to 1 μs at n = 90. In addition, a second observed reaction mechanism, namely, Rbmore » $$+\\atop{2}$$ molecule formation, was studied. Both reaction products are equally probable for n = 40, but the fraction of Rb + 2 created drops to below 10% for n ≥ 90.« less

Reaction of tetracycline with biologically relevant chloramines

NASA Astrophysics Data System (ADS)

Benavides, J.; Barrias, P.; Piro, N.; Arenas, A.; Orrego, A.; Pino, E.; Villegas, L.; Dorta, E.; Aspée, A.; López-Alarcón, C.

2017-05-01

Helicobacter pylori (H. pylori) infection triggers inflammatory processes with the consequent production of hypochlorous acid (HOCl), monochloramine (NH2Cl), and protein-derived chloramines. As the therapy for eradicating H. pylori is partially based on the use of tetracycline, we studied the kinetic of its consumption elicited by HOCl, NH2Cl, N-chloro-n-butylamine (NHCl-But, used as a lysine-derived chloramine model), and lysozyme-derived chloramines. In the micromolar concentration range, tetracycline reacted rapidly with HOCl, generating in the first few seconds intermediates of short half-life. In contrast, a slow tetracycline consumption was observed in the presence of high NH2Cl and NHCl-But concentrations (millimolar range). Similar chlorinated products of tetracycline were identified by mass spectrometry, in the presence of HOCl and NH2Cl. These results evidenced that tautomers of tetracycline are pivotal intermediates in all reactions. In spite of the low reactivity of chloramines towards tetracycline, it is evident that, in the concentration range where they are produced in a H. pylori infection (millimolar range), the reactions lead to oxidation and/or chlorination of tetracycline. This kind of reactions, which were also observed triggered by lysozyme-derived chloramines, could limit the efficiency of the tetracycline-based therapy.

Adenosine triphosphatase activity of cutaneous nerve fibers.

PubMed

Idé, C; Saito, T

1980-02-01

The histochemical study of Mg++-activated adenosine triphosphatase (Mg++-ATPase) activity was carried out on the peripheral nerves of mouse digital skin by light and electron microscopy. Under the light microscope, the ATPase activity was clearly demonstrated on the nerve fibers as a fine network in the subepidermal regions. Under the electron microscope, the reaction product of enzyme activity was located in the interspace between axolemma and the surrounding Schwann cells of the unmyelinated nerve fibers. No reaction product was observed in the space between the axolemma and the Schwann cells associated with myelinated nerve fibers. Demonstrable activity was absent at the nodes of Ranvier as well as on the para- and internodal regions of these myelinated axons. The part of the axolemma lacking a Schwann cell sheath failed to show a reaction product. The perineural epithelial cells surrounding the nerve fibers displayed reaction product in the caveolae. These results suggest a functional difference in the axon-Schwann interface of myelinated as compared to unmyelinated nerve fibers. The function of the perineural epithelial cell would be expected to be a regulatory one in transferring materials across the epithelium to keep the proper humoral environment around nerve fibers.

Infrared matrix isolation and theoretical studies of reactions of ozone with bicyclic alkenes: α-pinene, norbornene, and norbornadiene.

PubMed

Kugel, Roger W; Ault, Bruce S

2015-01-15

The reactions of ozone with three bicyclic alkenes, α-pinene, norbornene, and norbornadiene, were studied by low-temperature (14 K), argon matrix isolation infrared spectroscopy including (18)O isotope-labeling studies. Theoretical calculations of some of the proposed reaction intermediates and products were carried out using the Gaussian 09 suite of programs, applying density functional theory (DFT), the B3LYP functional, and the 6-311G++(d,2p) basis set. In the α-pinene/ozone system, the thermal reaction between α-pinene and ozone was too slow to observe under the twin-jet or merged-jet deposition conditions of these experiments. However, red light (λ ≥ 600 nm) irradiation of the argon matrixes containing α-pinene and ozone caused new infrared peaks to appear that could be readily assigned to reaction products of α-pinene with O((3)P) resulting from ozone photolysis: α-pinene oxide (with an epoxide ring) and two isomeric ketones. Norbornene and norbornadiene were both found to react with ozone in the gas phase during twin-jet or merged-jet deposition of these mixtures with argon. New peaks observed in the infrared spectra were assigned to the primary ozonides, Criegee intermediates, and secondary ozonides of norbornene and norbornadiene, indicating that the bulk of these reactions proceeded via the "classic" Criegee mechanism for ozonolysis of alkenes. Calculated infrared frequencies and molecular energies support these conclusions. Ultraviolet irradiation of these mixtures resulted in complete decomposition of the early intermediates and the formation of acids, aldehydes, alcohols, carbon dioxide, and carbon monoxide. In any case, no evidence for "unusual" chemistry, prompted by the bicyclic nature of the reactants, was observed.

Characterization of the Kinetics of NF3-Fluorination of NpO2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Casella, Andrew M.; Scheele, Randall D.; McNamara, Bruce K.

2015-12-23

The exploitation of selected actinide and fission product fluoride volatilities has long been considered as a potentially attractive compact method for recycling used nuclear fuels to avoid generating the large volumes of radioactive waste arising from aqueous reprocessing [1-7]. The most developed process uses the aggressive and hazardous fluorinating agents hydrogen fluoride (HF) and/or molecular fluorine (F2) at high temperatures to volatilize the greatest fraction of the used nuclear fuel into a single gas stream. The volatilized fluorides are subsequently separated using a series of fractionation and condensation columns to recover the valuable fuel constituents and fission products. In pursuitmore » of a safer and less complicated approach, we investigated an alternative fluoride volatility-based process using the less hazardous fluorinating agent nitrogen trifluoride (NF3) and leveraging its less aggressive nature to selectively evolve fission product and actinide fluorides from the solid phase based on their reaction temperatures into a single recycle stream [8-15]. In this approach, successive isothermal treatments using NF3 will first evolve the more thermally susceptible used nuclear fuel constituents leaving the other constituents in the residual solids until subsequent isothermal temperature treatments cause these others to volatilize. During investigation of this process, individual neat used fuel components were treated with isothermal NF3 in an attempt to characterize the kinetics of each fluorination reaction to provide input into the design of a new volatile fluoride separations approach. In these directed investigations, complex behavior was observed between NF3 and certain solid reactants such as the actinide oxides of uranium, plutonium, and neptunium. Given the similar thermal reaction susceptibilities of neptunium oxide (NpO2) and uranium dioxide (UO2) and the importance of Np and U, we initially focused our efforts on determining the reaction kinetic parameters for NpO2. Characterizing the NF3 fluorination of NpO2 using established models for gas-solid reactions [16] proved unsuccessful so we developed a series of successive fundamental reaction mechanisms to characterize the observed successive fluorination reactions leading to production of the volatile neptunium hexafluoride (NpF6).« less

Photofragmentation of Gas-Phase Lanthanide Cyclopentadienyl Complexes: Experimental and Time-Dependent Excited-State Molecular Dynamics

PubMed Central

2015-01-01

Unimolecular gas-phase laser-photodissociation reaction mechanisms of open-shell lanthanide cyclopentadienyl complexes, Ln(Cp)3 and Ln(TMCp)3, are analyzed from experimental and computational perspectives. The most probable pathways for the photoreactions are inferred from photoionization time-of-flight mass spectrometry (PI-TOF-MS), which provides the sequence of reaction intermediates and the distribution of final products. Time-dependent excited-state molecular dynamics (TDESMD) calculations provide insight into the electronic mechanisms for the individual steps of the laser-driven photoreactions for Ln(Cp)3. Computational analysis correctly predicts several key reaction products as well as the observed branching between two reaction pathways: (1) ligand ejection and (2) ligand cracking. Simulations support our previous assertion that both reaction pathways are initiated via a ligand-to-metal charge-transfer (LMCT) process. For the more complex chemistry of the tetramethylcyclopentadienyl complexes Ln(TMCp)3, TMESMD is less tractable, but computational geometry optimization reveals the structures of intermediates deduced from PI-TOF-MS, including several classic “tuck-in” structures and products of Cp ring expansion. The results have important implications for metal–organic catalysis and laser-assisted metal–organic chemical vapor deposition (LCVD) of insulators with high dielectric constants. PMID:24910492

Cinnamic aldehyde: a survey of consumer patch-test sensitization.

PubMed

Danneman, P J; Booman, K A; Dorsky, J; Kohrman, K A; Rothenstein, A S; Sedlak, R I; Steltenkamp, R J; Thompson, G R

1983-12-01

The potential for cinnamic aldehyde, an important fragrance and flavour ingredient, to induce or to elicit delayed contact hypersensitivity reactions in man was evaluated by analysing patch-test data. Results of studies involving a total of 4117 patch tests on various consumer products and fragrance blends containing cinnamic aldehyde and on the material itself were collected from fragrance and formulator companies. The data indicate that cinnamic aldehyde contained in consumer products and fragrance blends at concentrations up to 6 X 10(-1)%, and patch-tested at concentrations up to 8 X 10(-3)%, has no detectable potential to induce hypersensitivity. Cinnamic aldehyde when tested alone induced a dose-related hypersensitivity response. According to published reports, cinnamic aldehyde elicited positive delayed hypersensitivity responses in dermatitic patients. However, results of the current survey show that when cinnamic aldehyde was tested alone or as part of a mixture in subjects in the general population, no pre-existing hypersensitivity reactions to the fragrance material were observed in any of the 4117 patch tests which constituted the survey. Cinnamic aldehyde at the concentrations contained in consumer products and fragrances, has a very low potential to induce hypersensitivity ('induced' reactions) or to elicit sensitization reactions ('elicited' reactions) in the general population.

In situ FTIR studies on the oxidation of isopropyl alcohol over SnO2 as a function of temperature up to 600 °C and a comparison to the analogous plasma-driven process.

PubMed

Christensen, P A; Mashhadani, Z T A W; Md Ali, Abd Halim Bin

2018-04-04

This paper reports the application of in situ reflectance Fourier Transform InfraRed spectroscopy to the study of the thermal and plasma driven reaction of IsoPropyl Alcohol (IPA) at SnO2-coated Macor, the latter a ceramic material comprised of the oxides of Al, Mg and Si. The data so obtained were compared to those obtained using uncoated Macor. When uncoated Macor was employed, no reaction of the IPA was observed up to 600 °C in the thermal experiments, whereas a number of products were observed in the plasma-driven experiments. The results obtained using coated Macor were somewhat different, with no reaction taking place in the plasma-driven experiments, whilst significant reaction took place in the thermally-driven process. In the latter experiments, the chemistry was observed to show four distinct temperature regions, with electron injection into the conduction band of the SnO2 playing a significant role, culminating in the production of CO2. The data were interpreted in terms of a model in which physisorbed IPA was converted to two forms of isopropoxide: this was converted to acetone and acetaldehyde via adsorbed enolate. The data clearly support the catalytic activity of Macor in the plasma-driven conversion of IPA.

Energy partitioning in polyatomic chemical reactions: Quantum state resolved studies of highly exothermic atom abstraction reactions from molecules in the gas phase and at the gas-liquid interface

NASA Astrophysics Data System (ADS)

Zolot, Alexander M.

This thesis recounts a series of experiments that interrogate the dynamics of elementary chemical reactions using quantum state resolved measurements of gas-phase products. The gas-phase reactions F + HCl → HF + Cl and F + H2O → HF + OH are studied using crossed supersonic jets under single collision conditions. Infrared (IR) laser absorption probes HF product with near shot-noise limited sensitivity and high resolution, capable of resolving rovibrational states and Doppler lineshapes. Both reactions yield inverted vibrational populations. For the HCl reaction, strongly bimodal rotational distributions are observed, suggesting microscopic branching of the reaction mechanism. Alternatively, such structure may result from a quantum-resonance mediated reaction similar to those found in the well-characterized F + HD system. For the H2O reaction, a small, but significant, branching into v = 2 is particularly remarkable because this manifold is accessible only via the additional center of mass collision energy in the crossed jets. Rotationally hyperthermal HF is also observed. Ab initio calculations of the transition state geometry suggest mechanisms for both rotational and vibrational excitation. Exothermic chemical reaction dynamics at the gas-liquid interface have been investigated by colliding a supersonic jet of F atoms with liquid squalane (C30H62), a low vapor pressure hydrocarbon compatible with the high vacuum environment. IR spectroscopy provides absolute HF( v,J) product densities and Doppler resolved velocity component distributions perpendicular to the surface normal. Compared to analogous gas-phase F + hydrocarbon reactions, the liquid surface is a more effective "heat sink," yet vibrationally excited populations reveal incomplete thermal accommodation with the surface. Non-Boltzmann J-state populations and hot Doppler lineshapes that broaden with HF excitation indicate two competing scattering mechanisms: (i) a direct reactive scattering channel, whereby newly formed molecules leave the surface without equilibrating, and (ii) a partially accommodated fraction that shares vibrational, rotational, and translational energy with the liquid surface before returning to the gas phase. Finally, a velocity map ion imaging apparatus has been implemented to investigate reaction dynamics in crossed molecular beams. Resonantly enhanced multiphoton ionization (REMPI) results in rotational, vibrational, and electronic state selectivity. Velocity map imaging measurements provide differential cross sections and information about the internal energy distribution of the undetected collision partner.

Ultraviolet-gas phase and -photocatalytic synthesis from CO and NH3. [photolysis products

NASA Technical Reports Server (NTRS)

Hubbard, J. S.; Voecks, G. E.; Hobby, G. L.; Ferris, J. P.; Williams, E. A.; Nicodem, D. E.

1975-01-01

Ammonium cyanate is identified as the major product of the photolysis of gaseous NH3-CO mixtures at 206.2 or 184.9 nm. Lesser amounts of urea, biurea, biuret semicarbazide, formamide and cyanide are observed. A series of 18 reactions underlying the formation of photolysis products is presented and discussed. Photocatalytic syntheses of C-14-urea, -formamide, and -formaldehyde are carried out through irradiation of (C-14)O and NH3 in the presence of Vycor, silica gel, or volcanic ash shale surfaces. The possible contributions of the relevant reactions to the abiotic synthesis of organic nitrogen compounds on Mars, the primitive earth, and in interstellar space are examined.

OZONE PRODUCTION FROM IRRADIATION OF ACETYLENE/CHLORINE MIXTURES IN AIR

EPA Science Inventory

The reaction of chlorine radicals with acetylene in air in the absence of oxides of nitrogen result In the formation of ozone. o ozone is observed when chlorine radicals react with methylacetylene or ethylacetylene under similar conditions. ormyl chloride is observed in all syste...

Fingerprint detection

DOEpatents

Saunders, George C.

1992-01-01

A method for detection and visualization of latent fingerprints is provided and includes contacting a substrate containing a latent print thereon with a colloidal metal composition for time sufficient to allow reaction of said colloidal metal composition with said latent print, and preserving or recording the observable print. Further, the method for detection and visualization of latent fingerprints can include contacting the metal composition-latent print reaction product with a secondary metal-containing solution for time sufficient to allow precipitation of said secondary metal thereby enhancing the visibility of the latent print, and preserving or recording the observable print.

Properties of Cerium Hydroxides from Matrix Infrared Spectra and Electronic Structure Calculations.

PubMed

Fang, Zongtang; Thanthiriwatte, K Sahan; Dixon, David A; Andrews, Lester; Wang, Xuefeng

2016-02-15

Reactions of laser ablated cerium atoms with hydrogen peroxide or hydrogen and oxygen mixtures diluted in argon and condensed at 4 K produced the Ce(OH)3 and Ce(OH)2 molecules and Ce(OH)2(+) cation as major products. Additional minor products were identified as the Ce(OH)4, HCeO, and OCeOH molecules. These new species were identified from their matrix infrared spectra with D2O2, D2, and (18)O2 isotopic substitution and correlating observed frequencies with values calculated by density functional theory. We find that the amounts of Ce(OH)3 and of the Ce(OH)2(+) cation increase on UV (λ > 220 nm) photolysis, while Ce(OH)2, Ce(OH)4, and HCeO are photosensitive. The observed major species for Ce are in the +III or +II oxidation state, and the minor product, Ce(OH)4, is in the +IV oxidation state. The calculations for the vibrational frequencies with the B3LYP functional agree well with the experiment. The NBO analysis shows significant backbonding to the metal 4f and 5d orbitals for the closed shell species. Most open shell species have the excess spin in the 4f with paired spin in the 5d due to backbonding. The heats of formation of the observed species were derived from the available data from experiment and the calculated reaction energies. The major products in this study are different from similar reactions for Th where the tetrahydroxide was the major species.

Establishment and performance assessment of preparation technology of internal quality control products for blood transfusion compatibility testing.

PubMed

Yu, Yang; Ma, Chunya; Feng, Qian; Chen, Xin; Guan, Xiaozhen; Zhang, Xiaojuan; Chen, Linfeng; Lin, Zilin; Pan, Jichun; Zhang, Ting; Luo, Qun; Wang, Deqing

2013-05-01

The aim of this study was to establish and to optimize the preparation technology of whole blood internal quality control (IQC) products for blood transfusion compatibility testing. Several B-type RhD-negative blood samples collected from healthy donors were mixed. Two groups of whole blood IQC products, namely, the preservative solution group (PS group) and the saline group, were prepared. The agglutination intensity of IQC sample red cells and anti-B antibody, IgM anti-A antibody and reverse-typing A cell, IgG anti-D and O-type RhD-positive red cells, as well as free hemoglobin concentration in the supernatant of the two groups were detected. The erythrocytes in both groups were damaged to a certain extent during storage, but no evident (above moderate) hemolysis was observed in the stored sample within 42 days. The red cells remained structurally complete and the reaction activity of IgG anti-D reagent remained generally unchanged (P>0.05). Although the reaction activity oscillation of IgM anti-A reagent was observed, the agglutination intensity varied within an acceptable range of 1+. No difference was observed between the preparation methods of the samples, i.e., between the erythrocyte washed with saline and the one washed with red cell preservative solution (P>0.05). The long shelf life, low variance between tubes and stable antigen-antibody reaction activity of the whole blood IQC products prepared using the proposed method can meet the requirements of blood transfusion compatibility testing.

Product screening of fast reactions in IR-laser-heated liquid water filaments in a vacuum by mass spectrometry.

PubMed

Charvat, A; Stasicki, B; Abel, B

2006-03-09

In the present article a novel approach for rapid product screening of fast reactions in IR-laser-heated liquid microbeams in a vacuum is highlighted. From absorbed energies, a shock wave analysis, high-speed laser stroboscopy, and thermodynamic data of high-temperature water the enthalpy, temperature, density, pressure, and the reaction time window for the hot water filament could be characterized. The experimental conditions (30 kbar, 1750 K, density approximately 1 g/cm3) present during the lifetime of the filament (20-30 ns) were extreme and provided a unique environment for high-temperature water chemistry. For the probe of the reaction products liquid beam desorption mass spectrometry was employed. A decisive feature of the technique is that ionic species, as well as neutral products and intermediates may be detected (neutrals as protonated aggregates) via time-of-flight mass spectrometry without any additional ionization laser. After the explosive disintegration of the superheated beam, high-temperature water reactions are efficiently quenched via expansion and evaporative cooling. For first exploratory experiments for chemistry in ultrahigh-temperature, -pressure and -density water, we have chosen resorcinol as a benchmark system, simple enough and well studied in high-temperature water environments much below 1000 K. Contrary to oxidation reactions usually present under less extreme and dense supercritical conditions, we have observed hydration and little H-atom abstraction during the narrow time window of the experiment. Small amounts of radicals but no ionic intermediates other than simple proton adducts were detected. The experimental findings are discussed in terms of the energetic and dense environment and the small time window for reaction, and they provide firm evidence for additional thermal reaction channels in extreme molecular environments.

Formation of nitrogen-containing oligomers by methylglyoxal and amines in simulated evaporating cloud droplets.

PubMed

De Haan, David O; Hawkins, Lelia N; Kononenko, Julia A; Turley, Jacob J; Corrigan, Ashley L; Tolbert, Margaret A; Jimenez, Jose L

2011-02-01

Reactions of methylglyoxal with amino acids, methylamine, and ammonium sulfate can take place in aqueous aerosol and evaporating cloud droplets. These processes are simulated by drying droplets and bulk solutions of these compounds (at low millimolar and 1 M concentrations, respectively) and analyzing the residuals by scanning mobility particle sizing, nuclear magnetic resonance, aerosol mass spectrometry (AMS), and electrospray ionization MS. The results are consistent with imine (but not diimine) formation on a time scale of seconds, followed by the formation of nitrogen-containing oligomers, methylimidazole, and dimethylimidazole products on a time scale of minutes to hours. Measured elemental ratios are consistent with imidazoles and oligomers being major reaction products, while effective aerosol densities suggest extensive reactions take place within minutes. These reactions may be a source of the light-absorbing, nitrogen-containing oligomers observed in urban and biomass-burning aerosol particles.

Probing the kinetic energy-release dynamics of H-atom products from the gas-phase reaction of O(3P) with vinyl radical C2H3.

PubMed

Jang, Su-Chan; Choi, Jong-Ho

2014-11-21

The gas-phase radical-radical reaction dynamics of ground-state atomic oxygen O((3)P) with vinyl radicals C2H3 has been studied by combining the results of vacuum-ultraviolet laser-induced fluorescence spectroscopy in a crossed beam configuration with ab initio calculations. The two radical reactants O((3)P) and C2H3 were produced by photolysis of NO2 and supersonic flash pyrolysis of C2H3I, respectively. Doppler profile analysis of the kinetic energy release of the nascent H-atom products from the title reaction O((3)P) + C2H3→ H((2)S) + CH2CO (ketene) revealed that the average translational energy of the products and the average fraction of the total available energy were 7.03 ± 0.30 kcal mol(-1) and 7.2%. The empirical data combined with CBS-QB3 level ab initio theory and statistical calculations demonstrated that the title oxygen-hydrogen exchange reaction is a major reaction channel, through an addition-elimination mechanism involving the formation of a short-lived, dynamical complex on the doublet potential energy surface. On the basis of systematic comparison with several exchange reactions of hydrocarbon radicals, the observed kinetic energy release can be explained in terms of the weak impulse at the moment of decomposition in the loose transition state with a product-like geometry and a small reverse barrier along the exit channel.

Impact of phloretin and phloridzin on the formation of Maillard reaction products in aqueous models composed of glucose and L-lysine or its derivatives.

PubMed

Ma, Jinyu; Peng, Xiaofang; Ng, Kwan-Ming; Che, Chi-Ming; Wang, Mingfu

2012-02-01

In the present study, the effects of phloretin and phloridzin on the formation of Maillard reaction products in a lysine-glucose model with different reactant ratios were systematically investigated. In terms of the formation of Maillard-type volatiles, phloretin and phloridzin treatmen could significantly reduce their generation, where the effects depend on the ratio of lysine to glucose used in the model systems. Phloretin and phloridzin could also affect the colour development of Maillard reactions; especially phloretin, which could significantly promote the formation of brown products in the system with the lowest ratio of lysine to glucose. Based on the carbon module labelling (CAMOLA) technique and HPLC-DAD-ESI/MS analysis, it was found that phloretin and phloridzin could actively participate in the Maillard reaction and directly react with different reactive carbonyl species. The effect of phloretin and phloridzin treatment in both N(α)-acetyllysine-glucose (AC-glu), and N-acetyl-gly-lys methyl ester acetate salt-glucose (AG-glu) model systems, which are close to the Maillard reactions occurring in real food, where the free amino groups of lysine residues were considered as the reactive site, were further investigated. Similar impacts on the formation of Maillard-type volatiles and brown products as in the lysine-glucose models were observed which can also be explained by the capability of phloretin and phloridzin to quench sugar fragments formed in these model reactions.

Metal Carbonation of Forsterite in Supercritical CO2 and H2O Using Solid State 29Si, 13C NMR Spectroscop

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kwak, Ja Hun; Hu, Jian Z.; Hoyt, David W.

2010-03-11

Ex situ solid state NMR was used for the first time to study fundamental mineral carbonation processes and reaction extent relevant to geologic carbon sequestration (GCS) using a model silicate mineral forsterite (Mg2SiO4)+supercriticalCO2 with and without H2O. Run conditions were 80 C and 96 atm. 29Si NMR clearly shows that in the absence of CO2, the role of H2O is to hydrolyze surface Mg-O-Si bonds to produce dissolved Mg2+, and mono- and oligomeric hydroxylated silica species. Surface hydrolysis products contain only Q0 (Si(OH)4) and Q1(Si(OH)3OSi) species. An equilibrium between Q0, Q1 and Mg2+ with a saturated concentration equivalent to lessmore » than 3.2% of the Mg2SiO4 conversion is obtained at a reaction time of up to 7 days. Using scCO2 without H2O, no reaction is observed within 7 days. Using both scCO2 and H2O, the surface reaction products for silica are mainly Q3 (SiOH(OSi)3) species accompanied by a lesser amount of Q2 (Si(OH)2(OSi)2) and Q4 (Si(OSi)4). However, no Q0 and Q1 were detected, indicating the carbonic acid formation/deprotonation and magnesite (MgCO3) precipitation reactions are faster than the forsterite hydrolysis process. Thus it can be concluded that the Mg2SiO4 hydrolysis process is the rate limiting step of the overall mineral carbonation process. 29Si NMR combined with XRD, TEM, SAED and EDX further reveal that the reaction is a surface reaction with the Mg2SiO4 crystallite in the core and with condensed Q2-Q4 species forming amorphous surface layers. 13C MAS NMR identified a possible reaction intermediate as (MgCO3)4-Mg(OH)2-5H2O. However, at long reaction times only crystallite magnesite MgCO3 products are observed.« less

Secondary organic aerosol formation from isoprene photooxidation

NASA Astrophysics Data System (ADS)

Kroll, J. H.; Ng, N. L.; Murphy, S. M.; Flagan, R. C.; Seinfeld, J. H.

2005-12-01

We report chamber studies of the formation of secondary organic aerosol (SOA) from the oxidation of isoprene (2-methyl-1,3-butadiene). Isoprene is the most abundant non-methane hydrocarbon emitted into the troposphere (source strength of ~500 Tg/year), so even small SOA yields may have a large impact on global SOA production. Reactions are carried out in Caltech's dual 28 m3 Teflon chambers, and aerosol growth is monitored by a differential mobility analyzer (DMA) and an Aerodyne time-of-flight aerosol mass spectrometer (AMS). Isoprene oxidation is initiated by the UV irradiation of isoprene in the presence of hydrogen peroxide, with NO added for high-NOx experiments. These conditions ensure that isoprene oxidation is initiated by reaction with the OH radical, with negligible interference from other oxidants (ozone, nitrate radicals, and O atoms). Aerosol growth is observed under both high-NOx and low-NOx conditions, at isoprene concentrations lower than measured in previous studies (down to 8 ppb). SOA yields are found to be in the range of 1-2%. Yields exhibit a complex dependence on NOx concentration, likely a result of changes in the chemistry of organic peroxy radicals. It is shown that condensable compounds are formed from further reactions of first-generation isoprene oxidation products; the rates and products of such gas-phase reactions are at present poorly understood. Additionally, measurements of SOA composition indicate that these products undergo reactions in the aerosol phase, leading to the formation of low-volatility oligomeric products.

Near-infrared kinetic spectroscopy of the HO2 and C2H5O2 self-reactions and cross reactions.

PubMed

Noell, A C; Alconcel, L S; Robichaud, D J; Okumura, M; Sander, S P

2010-07-08

The self-reactions and cross reactions of the peroxy radicals C2H5O2 and HO2 were monitored using simultaneous independent spectroscopic probes to observe each radical species. Wavelength modulation (WM) near-infrared (NIR) spectroscopy was used to detect HO2, and UV absorption monitored C2H5O2. The temperature dependences of these reactions were investigated over a range of interest to tropospheric chemistry, 221-296 K. The Arrhenius expression determined for the cross reaction, k2(T) = (6.01(-1.47)(+1.95)) x 10(-13) exp((638 +/- 73)/T) cm3 molecules(-1) s(-1) is in agreement with other work from the literature. The measurements of the HO2 self-reaction agreed with previous work from this lab and were not further refined. The C2H5O2 self-reaction is complicated by secondary production of HO2. This experiment performed the first direct measurement of the self-reaction rate constant, as well as the branching fraction to the radical channel, in part by measurement of the secondary HO2. The Arrhenius expression for the self-reaction rate constant is k3(T) = (1.29(-0.27)(+0.34)) x 10(-13)exp((-23 +/- 61)/T) cm3 molecules(-1) s(-1), and the branching fraction value is alpha = 0.28 +/- 0.06, independent of temperature. These values are in disagreement with previous measurements based on end product studies of the branching fraction. The results suggest that better characterization of the products from RO2 self-reactions are required.

Distance-dependent radiation chemistry: Oxidation versus hydrogenation of CO in electron-irradiated H2O/CO/H2O ices

DOE Office of Scientific and Technical Information (OSTI.GOV)

Petrik, Nikolay G.; Monckton, Rhiannon J.; Koehler, Sven

Electron-stimulated oxidation of CO in layered H2O/CO/H2O ices was investigated with infrared reflection-absorption spectroscopy (IRAS) as function of the distance of the CO layer from the water/vacuum interface. The results show that while both oxidation and reduction reactions occur within the irradiated water films, there are distinct regions where either oxidation or reduction reactions are dominant. At depths less than ~ 15 ML, CO oxidation dominates over the sequential hydrogenation of CO to methanol (CH3OH), and CO2 is the major product of CO oxidation, consistent with previous observations. At its highest yield, CO2 accounts for ~45% of all the reactedmore » CO. Another oxidation product is identified as the formate anion (HCO2-). In contrast, for CO buried more than ~ 35 ML below the water/vacuum interface, the CO-to-methanol conversion efficiency is close to 100%. Production of CO2 and formate are not observed for the more deeply buried CO layers, where hydrogenation dominates. Experiments with CO dosed on pre-irradiated ASW samples suggest that OH radicals are primarily responsible for the oxidation reactions. Possible mechanisms of CO oxidation, involving primary and secondary processes of water radiolysis at low temperature, are discussed. The observed distance-dependent radiation chemistry results from the higher mobility of hydrogen atoms that are created by the interaction of the 100 eV electrons with the water films. These hydrogen atoms, which are primarily created at or near the water/vacuum interface, can desorb from or diffuse into the water films, while the less-mobile OH radicals remain in the near-surface zone resulting in preferential oxidation reactions there. The diffusing hydrogen atoms are responsible for the hydrogenation reactions that are dominant for the more deeply buried CO layers.« less

COAL/POLYMER COPROCESSING WITH EFFICIENT USE OF HYDROGEN

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dr. Linda J. Broadbelt; Matthew J. DeWitt; Hsi-Wu Wong

2000-09-30

The final project period was devoted to investigating the binary mixture pyrolysis of polypropylene and polystyrene. Their interactions were assessed in order to provide a baseline for experiments with multicomponent mixtures of polymers with coal. Pyrolysis of polypropylene, polystyrene and their binary mixture was investigated at temperatures of 350 C and 420 C with reaction times from 1 to 180 minutes. Two different loadings, 10 mg and 20 mg, were studied for neat polypropylene and polystyrene to assess the effect of total pressure on product yields and selectivities. For neat pyrolysis of polypropylene, total conversion was much higher at 420more » C, and no significant effect of loading on the total conversion was observed. Four classes of products, alkanes, alkenes, dienes, and aromatic compounds, were observed, and their distribution was explained by a typical free radical mechanism. For neat polystyrene pyrolysis, conversion reached approximately 75% at 350 C, while at 420 C the conversion reached a maximum around 90% at 10 minutes and decreased at longer times because of condensation reactions. The selectivities to major products were slightly different for the two different loadings due to the effect of total reaction pressure on secondary reactions. For binary mixture pyrolysis, the overall conversion was higher than the average of the two neat cases. The conversion of polystyrene remained the same, but a significant enhancement in the polypropylene conversion was observed. This suggests that the less reactive polypropylene was initiated by polystyrene-derived radicals. These results are summarized in detail in an attached manuscript that is currently in preparation. The other results obtained during the lifetime of this grant are documented in the set of attached manuscripts.« less

Indium-mediated asymmetric Barbier-type propargylations: additions to aldehydes and ketones and mechanistic investigation of the organoindium reagents.

PubMed

Haddad, Terra D; Hirayama, Lacie C; Buckley, Jannise J; Singaram, Bakthan

2012-01-20

We report a simple, efficient, and general method for the indium-mediated enantioselective propargylation of aromatic and aliphatic aldehydes under Barbier-type conditions in a one-pot synthesis affording the corresponding chiral alcohol products in very good yield (up to 90%) and enantiomeric excess (up to 95%). The extension of this methodology to ketones demonstrated the need for electrophilic ketones more reactive than acetophenone as the reaction would not proceed with just acetophenone. Using the Lewis acid indium triflate [In(OTf)(3)] induced regioselective formation of the corresponding homoallenic alcohol product from acetophenone. However, this methodology demonstrated excellent chemoselectivity in formation of only the corresponding secondary homopropargylic alcohol product in the presence of a ketone functionality. Investigation of the organoindium intermediates under our reaction conditions shows the formation of allenylindium species, and we suggest that these species contain an indium(III) center. In addition, we have observed the presence of a shiny, indium(0) nugget throughout the reaction, irrespective of the stoichiometry, indicating disproportionation of indium halide byproduct formed during the reaction.

Possible Increase in Nitric Oxide Production by Lightning Discharges Due to Catalytic Effects of Ice Particles

NASA Technical Reports Server (NTRS)

Peterson, Harold; Beasley, William

2011-01-01

We address the question of whether ice crystals with habits typically encountered by lightning discharges may serve as catalysts for the production of NOx by lightning. If so, and if the effect is sufficiently large, it would need to be taken into account in estimates of global NOx production by lightning. In this study, we make a series of plausible assumptions about the temperatures and concentrations of reactant species in the environment of discharges and we postulate a mechanism by which ice crystals could adsorb nitrogen atoms. We then compare production rates between uncatalyzed and catalyzed reactions at 2000 K, 3000 K, and 4000 K, temperatures observed in lightning channels during the cool-down period after a return stroke. Catalyzed NO production rates are greater at 2000 K, whereas uncatalyzed production occurs most rapidly at 4000 K. The channel temperature stays around 2000 K for a longer period of time than at 4000 K. The longer residence time at 2000 K is sufficient to allow fresh reactants to participate in the mix in. Therefore, our results suggest that nearly three times as much NO per flash is produced by ice-catalyzed reactions as compared with uncatalyzed reactions.

Bromine, Dioxide, OBrO: Spectroscopic Properties, Molecular Structure, and Harmonic Force Field

NASA Technical Reports Server (NTRS)

Mueller, G.; Miller, C.; Cohen, E.

1996-01-01

The unstable OBrO radical, which might play a role in atmospheric chemistry, has been observed in the gas phase over a solid product of the O + Br subscript 2 reaction. Under certain conditions BrO, OBrO, and Br subscript 2 O could be observed simultaneously.

Experimental study of the replacement of calcite by calcium sulphates

NASA Astrophysics Data System (ADS)

Ruiz-Agudo, E.; Putnis, C. V.; Hövelmann, J.; Álvarez-Lloret, P.; Ibáñez-Velasco, A.; Putnis, A.

2015-05-01

Among the most relevant mineral replacement reactions are those involving sulphates and carbonates, which have important geological and technological implications. Here it is shown experimentally that during the interaction of calcite (CaCO3) cleavage surfaces with sulphate-bearing acidic solutions, calcite is ultimately replaced by gypsum (CaSO4 2H2O) and anhydrite (CaSO4), depending on the reaction temperature. Observations suggest that this occurs most likely via an interface-coupled dissolution-precipitation reaction, in which the substrate is replaced pseudomorphically by the product. At 120 and 200 °C gypsum and/or bassanite (CaSO4·0.5H2O) form as precursor phases for the thermodynamically stable anhydrite. Salinity promotes the formation of less hydrated precursor phases during the replacement of calcite by anhydrite. The reaction stops before equilibrium with respect to calcite is reached and during the course of the reaction most of the bulk solutions are undersaturated with respect to the precipitating phase(s). A mechanism consisting of the dissolution of small amounts of solid in a thin layer of fluid at the mineral-fluid interface and the subsequent precipitation of the product phase from this layer is in agreement with these observations. PHREEQC simulations performed in the framework of this mechanism highlight the relevance of transport and surface reaction kinetics on the volume change associated with the CaCO3-CaSO4 replacement. Under our experimental conditions, this reaction occurs with a positive volume change, which ultimately results in passivation of the unreacted substrate before calcite attains equilibrium with respect to the bulk solution.

Ion chemistry of NOO+

NASA Astrophysics Data System (ADS)

Midey, A. J.; Fernandez, A. I.; Viggiano, A. A.; Zhang, P.; Morokuma, K.

2006-03-01

The kinetics for the reactions of NOO+ ions with neutral molecules having ionization potentials (IPs) from 9.27to15.58eV was measured in a selected ion flow tube at 298K. The NOO+ ions are produced from the reaction of N3++O2 and have been reacted with the following: NO, C6F6, CS2, CF3I, C3F6, OCS, C2H6, Xe, SO2, O3, N2O, CO2, Kr, CO, D2, and N2. Numerous types of reactions were observed with the various neutral reagents, including production of NO+ (which may involve loss of an O from the ion or addition of O to the neutral reactant, although the two channels could not be distinguished here), charge transfer, isomerization of NOO+ to ONO+, and hydride abstraction. High level theoretical calculations of the structures and energetics of the various isomers, electronic states, and transition states of NOO and NOO+ were performed to better understand the observed reactivity. All neutral species with an IP ⩽11.18eV were observed to react with NOO+ in part by charge transfer. Detailed calculations showed that the recommended adiabatic and vertical IPs of NOO are 10.4 and 11.7eV, respectively, at the MRCISD(Q)/AVQZ level of theory. The observed experimental limit for charge transfer of 11.18eV agreed well with the energetics of the final products obtained from theory if dissociation of the neutral metastable product occurred, i.e., the products were X++[O(P3)+NO(Π2)], where [O(P3)+NO(Π2)] formed via dissociation of metastable NOO. Charge exchange with neutral reagent X would, therefore, be exothermic if IP(X )<[IPad(NOO)-ΔE(O+NO)-NOO]=˜11.1eV, where IPad(NOO) is the adiabatic IP. The potential energy surface for the reaction of NOO+ with C2H6 was also calculated, indicating that two pathways for formation of HNO2+C2H5+ exist.

The influence of minerals on decomposition of the n-alkyl-α-amino acid norvaline under hydrothermal conditions

NASA Astrophysics Data System (ADS)

McCollom, Thomas M.

2013-03-01

Laboratory experiments were conducted to observe the effect of iron oxide and sulfide minerals on decomposition reactions of norvaline, a representative of a group of alkyl-α-amino acids observed in meteorites and prebiotic synthesis experiments. The primary products observed during heating of aqueous solutions of norvaline at temperatures of 156-186 °C in the presence of minerals included CO2, NH3, butyric acid, and valeric acid. The products indicated that norvaline predominantly decomposed by a combination of pathways that included both decarboxylation followed rapidly by oxidative deamination (norvaline → butanamide + CO2 → butyric acid + NH3) and deamination directly to valeric acid (norvaline → valeric acid + NH3). An experiment performed with alanine under similar conditions showed it decomposed by analogous reactions that produced acetic and propionic acids along with CO2 and NH3. For both amino acids, the presence of minerals accelerated decomposition rates as well as altered the final products of reaction, when compared with decomposition in the absence of mineral substrates. In addition, decomposition of norvaline was found to proceed much faster in the presence of the mineral assemblage hematite-magnetite-pyrite (HMP) than with the assemblage pyrite-pyrrhotite-magnetite (PPM), a trend that has been observed for several other organic compounds. The influence of minerals on decomposition reactions of these amino acids appears to be attributable to a combination of surface catalysis and production of dissolved sulfur compounds. Overall, the results indicate that minerals may exert a substantial influence on amino acid stability in many geologic environments, and emphasize the need to consider the impact of minerals when evaluating the lifetimes and decomposition rates of amino acids in terrestrial and planetary systems. Estimated half-lives for alkyl-α-amino acids based on the experimental results indicate that moderately hot hydrothermal environments (<˜100 °C) would have been the most favorable for accumulation of these amino acids in the early solar system, and that the predominance of alkyl-α-amino acids in some meteorites may only be compatible with temperature remaining below about 60 °C following their formation.

Multiplexed photoionization mass spectrometry investigation of the O( 3P) + propyne reaction

DOE PAGES

Savee, John D.; Borkar, Sampada; Welz, Oliver; ...

2015-05-18

Here, the reaction of O( 3P) + propyne (C 3H 4) was investigated at 298 K and 4 Torr using time-resolved multiplexed photoionization mass spectrometry and a synchrotron-generated tunable vacuum ultraviolet light source. The time-resolved mass spectra of the observed products suggest five major channels under our conditions: C 2H 3 + HCO, CH 3 + HCCO, H + CH 3CCO, C 2H 4 + CO, and C 2H 2 + H 2 + CO. The relative branching ratios for these channels were found to be 1.00, (0.35 ± 0.11), (0.18 ± 0.10), (0.73 ± 0.27), and (1.31 ± 0.62).more » In addition, we observed signals consistent with minor production of C 3H 3 + OH and H 2 + CH 2CCO, although we cannot conclusively assign them as direct product channels from O( 3P) + propyne. The direct abstraction mechanism plays only a minor role (≤1%), and we estimate that O( 3P) addition to the central carbon of propyne accounts for 10% of products, with addition to the terminal carbon accounting for the remaining 89%. The isotopologues observed in experiments using d1-propyne (CH 3CCD) and analysis of product branching in light of previously computed stationary points on the singlet and triplet potential energy surfaces (PESs) relevant to O( 3P) + propyne suggest that, under our conditions, (84 ± 14)% of the observed product channels from O( 3P) + propyne result from intersystem crossing from the initial triplet PES to the lower-lying singlet PES.« less

Reactions of Atomic Carbon with Butene Isomers: Implications for Molecular Growth in Carbon-Rich Environments

DOE PAGES

Bourgalais, J.; Spencer, Michael; Osborn, David L.; ...

2016-10-31

We carried out the product detection studies of C( 3P) atom reactions with butene (C 4H 8) isomers (but-1-ene, cis-but-2-ene, trans-but-2-ene) in a flow tube reactor at 353 K and 4 Torr under multiple collision conditions. Ground state carbon atoms are generated by 248 nm laser photolysis of tetrabromomethane, CBr 4, in a buffer of helium. Thermalized reaction products are detected using synchrotron tunable VUV photoionization and time-of-flight mass spectrometry. The temporal profiles of the detected ions are used to discriminate products from side or secondary reactions. Furthermore, for the C( 3P) + trans-but-2-ene and C( 3P) + cis-but-2-ene reactions,more » various isomers of C 4H 5 and C 5H 7 are identified as reaction products formed via CH 3 and H elimination. Assuming equal ionization cross sections for all C 4H 5 and C 5H 7 isomers, C 4H 5:C 5H 7 branching ratios of 0.63:1 and 0.60:1 are derived for the C( 3P) + trans-but-2-ene and the C( 3P) + cis-but-2-ene reactions, respectively. For the C( 3P) + but-1-ene reaction, two reaction channels are observed: the H-elimination channel, leading to the formation of the ethylpropargyl isomer, and the C 3H 3 + C 2H 5 channel. Assuming equal ionization cross sections for ethylpropargyl and C 3H 3 radicals, a branching ratio of 1:0.95 for the C 3H 3 + C 2H 5 and H + ethylpropargyl channels is derived. Finally, the experimental results are compared to previous H atom branching ratios and used to propose the most likely mechanisms for the reaction of ground state carbon atoms with butene isomers.« less

The Production of Biodiesel from Cottonseed Oil Using Rhizopus oryzae Whole Cell Biocatalysts

NASA Astrophysics Data System (ADS)

Athalye, Sneha Kishor

Biodiesel is an environmentally friendly alternative to fossil fuels which have become increasingly expensive in recent times. An alternate approach to alkaline biodiesel production is needed as catalyst miscibility with the glycerol by-product, generation of large amounts of waste water, and saponification of the feedstock are major disadvantages associated with the process. Lipases are water soluble enzymes which act as catalysts in many lipid based reactions. Reuse of lipases can significantly reduce cost of enzymatic biodiesel production; however retention of lipolytic activity still remains a challenge. Use of microbial cells immobilized on various surfaces like sponge, foam and plastics as biocatalysts instead of extracted enzyme could help overcome this problem. A novel, rigid biomass support with high surface area made from recyclable polyethylene (Bioblok(TM)) was used in this study. Several fungal and bacterial species have been reported to possess appreciable levels of lipase activity. The biomass production and immobilization as well as lipase activity of three different species; Candida rugosa (ATCC #38772), Aspergillus oryzae (ATCC #58299), and Rhizopus oryzae (ATTC #34612) were tested. C. rugosa did not attach well to the support particles while A.oryzae had lower biomass accumulation of 6.1 g (dry cell wt)/L compared to 11.8 g (dry cell wt)/L for R.oryzae. Hence Rhizopus oryzae, fungal specie with cell surface bound lipase was selected for the current study. The study investigated the influence of media composition and growth time of the R.oryzae whole cell biocatalysts, immobilized on the BSPs, for FAME production from cottonseed oil. R.oryzae BSPs grown in basal media supplemented with 1% (w/v) of glucose or oil or both for 48 h, 72 h or 90 h were used in a 36 h transesterification reaction with cottonseed oil and methanol. BSPs grown in both glucose and oil supplemented medium for 72 h had the highest conversion of 22.4% (wt/wt) and a biomass accumulation of 15.6 g (dry cell wt)/L. A reduction in dynamic viscosity of the reaction mixture from 47.3 centipoise to 30.6 centipoise was observed. The impact of moisture addition to the reaction mixture and use of ethanol as acylating agent on R.oryzae BSP fatty acid alkyl ester production was also tested. The presence of 10 wt % moisture in the reaction system had a significant effect (p ≤ 0.05) on the transesterification reaction with ethanol unlike methanol. Fatty acid ethyl ester concentration tripled from 39.3 to 129.1 g/L when moisture was added during transesterification .When oil to acyl acceptor ratio was increased from 1:3 and 1:6 to determine effect of excess alcohol on conversion, an ester conversion of 128.1 g/L for methanol and 129.1 g/L for ethanol were observed. Use of excess amount of acylating agent had a significant adverse effect (p ≤ 0.05) on the overall FAAE production due to deactivation of lipases on contact with large amounts of insoluble alcohol in the oil phase of the reaction. The effect of short chain alcohols on the enzymatic transesterification of cottonseed oil using freeze dried Rhizopus oryzae biomass was examined with and without water addition using methanol, ethanol, 1-Propanol and 1-Butanol at various molar ratios. 1- Butanol in the absence of water resulted in a significantly higher (p . 0.1) conversion of cottonseed oil to 12.5 % fatty acid butyl esters (FABEs). Addition of 10 % water to the reaction mixture significantly reduced (p ≤ 0.1) conversion. No significant difference (p > 0.1) between the conversions was observed for time points after 24 h for a 72 h reaction. 1- Butanol in ratios higher than 3:1 to cottonseed oil had a significant impact (p ≤ 0.1) on conversion. Increasing the amount of biomass used during the reaction lead to significantly higher conversion (p ≤ 0.1). The highest conversion of 27.9 % was observed for the transesterification reaction between cottonseed oil and 1-Butanol, in a 1:6 molar ratio, in the absence of water, when 100 mg of freeze dried R.oryzae biomass was used. The present study concluded that R.oryzae biomass attached better to the Bioblok. material and had highest lipase activity when grown in presence of oil and glucose for 72h. Addition of water to the reaction system gave higher fatty acid alkyl ester conversion when whole immobilized R.oryzae BSPs were used but absence of water promoted conversion with freeze dried biomass.

Observation of isoprene hydroxynitrates in the southeastern United States and implications for the fate of NO x

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xiong, F.; McAvey, Kevin; Pratt, Kerri A.

2015-10-09

Isoprene hydroxynitrates (IN) are tracers of the photochemical oxidation of isoprene in high NO x environ-ments. Production and loss of IN have a significant influ-ence on the NO x cycle and tropospheric O 3 chemistry. To better understand IN chemistry, a series of photochemical re-action chamber experiments was conducted to determine the IN yield from isoprene photooxidation at high NO concentra-tions (> 100 ppt). By combining experimental data and cal-culated isomer distributions, a total IN yield of 9(+4/-3) %was derived. The result was applied in a zero-dimensional model to simulate production and loss of ambient IN ob-served in a temperatemore » forest atmosphere, during the Southern Oxidant and Aerosol Study (SOAS) field campaign, from 27 May to 11 July 2013. The 9 % yield was consistent with the observed IN/(MVK+MACR) ratios observed during SOAS. By comparing field observations with model simulations, we identified NO as the limiting factor for ambient IN produc-tion during SOAS, but vertical mixing at dawn might also contribute (~ 27 %) to IN dynamics. A close examination of isoprene’s oxidation products indicates that its oxidation transitioned from a high-NO dominant chemical regime in the morning into a low-NO dominant regime in the after-noon. A significant amount of IN produced in the morning high NO regime could be oxidized in the low NO regime, and a possible reaction scheme was proposed.« less

Kinetic modeling of ethane pyrolysis at high conversion.

PubMed

Xu, Chen; Al Shoaibi, Ahmed Sultan; Wang, Chenguang; Carstensen, Hans-Heinrich; Dean, Anthony M

2011-09-29

The primary objective of this study is to develop an improved first-principle-based mechanism that describes the molecular weight growth kinetics observed during ethane pyrolysis. A proper characterization of the kinetics of ethane pyrolysis is a prerequisite for any analysis of hydrocarbon pyrolysis and oxidation. Flow reactor experiments were performed with ~50/50 ethane/nitrogen mixtures with temperatures ranging from 550 to 850 °C at an absolute pressure of ~0.8 atm and a residence time of ~5 s. These conditions result in ethane conversions ranging from virtually no reaction to ~90%. Comparisons of predictions using our original mechanism to these data yielded very satisfactory results in terms of the temperature dependence of ethane conversion and prediction of the major products ethylene and hydrogen. However, there were discrepancies in some of the minor species concentrations that are involved in the molecular weight growth kinetics. We performed a series of CBS-QB3 analyses for the C(3)H(7), C(4)H(7), and C(4)H(9) potential energy surfaces to better characterize the radical addition reactions that lead to molecular weight growth. We also extended a published C(6)H(9) PES to include addition of vinyl to butadiene. The results were then used to calculate pressure-dependent rate constants for the multiple reaction pathways of these addition reactions. Inclusion of the unadjusted rate constants resulting from these analyses in the mechanism significantly improved the description of several of the species involved in molecular weight growth kinetics. We compare the predictions of this improved model to those obtained with a consensus model recently published as well as to ethane steam cracking data. We find that a particularly important reaction is that of vinyl addition to butadiene. Another important observation is that several radical addition reactions are partially equilibrated. Not only does this mean that reliable thermodynamic parameters are essential for an accurate model, but also that the reaction set describing molecular weight growth chemistry must include a final product that is sufficiently stable to shift the equilibrium toward this product despite the decrease in entropy that accompanies molecular weight growth. Another reaction, H addition to olefins, was found to inhibit molecular weight growth by leading to the production of a lower olefin plus methyl radicals.

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

NASA Astrophysics Data System (ADS)

Hopkins, Frances; Bell, Thomas; Yang, Mingxi

2017-04-01

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

40 CFR 721.9672 - Amides, tall-oil fatty, N-[2-[2-hydroxyethyl)amino]ethyl], reaction products with sulfur dioxide...

Code of Federal Regulations, 2011 CFR

2011-07-01

...-hydroxyethyl)amino]ethyl], reaction products with sulfur dioxide; fatty acids, tall-oil, reaction products with 1-piperazineethanamine and sulfur dioxide; fatty acids, tall-oil reaction products with sulfur...)amino]ethyl], reaction products with sulfur dioxide; fatty acids, tall-oil, reaction products with 1...

40 CFR 721.9672 - Amides, tall-oil fatty, N-[2-[2-hydroxyethyl)amino]ethyl], reaction products with sulfur dioxide...

Code of Federal Regulations, 2010 CFR

2010-07-01

...-hydroxyethyl)amino]ethyl], reaction products with sulfur dioxide; fatty acids, tall-oil, reaction products with 1-piperazineethanamine and sulfur dioxide; fatty acids, tall-oil reaction products with sulfur...)amino]ethyl], reaction products with sulfur dioxide; fatty acids, tall-oil, reaction products with 1...

40 CFR 721.9672 - Amides, tall-oil fatty, N-[2-[2-hydroxyethyl)amino]ethyl], reaction products with sulfur dioxide...

Code of Federal Regulations, 2013 CFR

2013-07-01

...-hydroxyethyl)amino]ethyl], reaction products with sulfur dioxide; fatty acids, tall-oil, reaction products with 1-piperazineethanamine and sulfur dioxide; fatty acids, tall-oil reaction products with sulfur...)amino]ethyl], reaction products with sulfur dioxide; fatty acids, tall-oil, reaction products with 1...

The degradation mechanism of phenol induced by ozone in wastes system.

PubMed

Youmin, Sun; Xiaohua, Ren; Zhaojie, Cui; Guiqin, Zhang

2012-08-01

A distinct understanding for the degradation mechanism of phenol induced by ozone is very essential because the ozonation process, one of the advanced oxidation processes (AOPs), is attractive and popular in wastewater treatment. In the present work, the detailed reactions of ozone and phenol are investigated employing the density functional theory B3LYP method with the 6-311++G (d, p) basis set. The profiles of the potential energy surface are constructed and the possible reaction pathways are indicated. These detailed calculation results suggest two degradation reaction mechanisms. One is phenolic H atom abstraction mechanism, and the other is cyclo-addition and ring-opening mechanism. Considering the effect of solvent water, the calculated energy barriers and reaction enthalpies for the reaction of O3 and phenol in water phase are both lower than those in gas phase, though the degradation mechanisms are not changed. This reveals that these degradation reactions are more favorable in the water solvent. The main reaction products are C(6)H(5)OO· radical, a crucial precursor for forming PCDD/Fs and one ring-opening product, which are in good agreement with the experimental observations.

The stoichiometry of the cytochrome P-450-catalyzed metabolism of methoxyflurane and benzphetamine in the presence and absence of cytochrome b5.

PubMed

Gruenke, L D; Konopka, K; Cadieu, M; Waskell, L

1995-10-20

The complete stoichiometry of the metabolism of the cytochrome b5 (cyt b5)-requiring substrate, methoxyflurane, by purified cytochrome P-450 2B4 was compared to that of another substrate, benzphetamine, which does not require cyt b5 for its metabolism. Cyt b5 invariably improved the efficiency of product formation. That is, in the presence of cyt b5 a greater percentage of the reducing equivalents from NADPH were utilized to generate substrate metabolites, primarily at the expense of the side product, superoxide. With methoxyflurane, cyt b5 addition always resulted in an increased rate of product formation, while with benzphetamine the rate of product formation remained unchanged, increased or decreased. The apparently contradictory observations of increased reaction efficiency but decrease in total product formation for benzphetamine can be explained by a second effect of cyt b5. Under some experimental conditions cyt b5 inhibits total NADPH consumption. Whether stimulation, inhibition, or no change in product formation is observed in the presence of cyt b5 depends on the net effect of the stimulatory and inhibitory effects of cyt b5. When total NADPH consumption is inhibited by cyt b5, the rapidly metabolized, highly coupled (approximately equal to 50%) substrate, benzphetamine, undergoes a net decrease in metabolism not counterbalanced by the increase in the efficiency (2-20%) of the reaction. In contrast, in the presence of the slowly metabolized, poorly coupled (approximately equal to 0.5-3%) substrate, methoxyflurane, inhibition of total NADPH consumption by cyt b5 was never sufficient to overcome the stimulation of product formation due to an increase in efficiency of the reaction.

Ozonation of trimethoprim in aqueous solution: identification of reaction products and their toxicity.

PubMed

Kuang, Jiangmeng; Huang, Jun; Wang, Bin; Cao, Qiming; Deng, Shubo; Yu, Gang

2013-05-15

This work aimed to better understand the ozonation process of a typical antibiotic pharmaceutical, trimethoprim in aqueous solution. The parent compound was almost completely degraded with ozone dose up to 3.5 mg/L with no mineralization. Twenty one degradation products were identified using an electrospray quadrupole time-of-flight mass spectrometer. Several ozonation pathways were proposed including hydroxylation, demethylation, carbonylation, deamination and methylene group cleavage. Two species of luminescent bacteria Photobacterium phosphoreum and Vibrio qinghaiensis were selected to assess the toxicity of ozonation products. For P. phosphoreum, higher level of toxicity was observed compared to the parent compound, but a negligible toxicity change was observed for V. qinghaiensis, indicating different modes of action for the same water sample. This was further confirmed by quantitative structure-active relationship analysis. This work proves the dominant role of ozone rather than hydroxyl radicals in the reaction and the potential risk after ozonation. Copyright © 2013 Elsevier Ltd. All rights reserved.

Infrared identification of the σ-complex of Cl-C6H6 in the reaction of chlorine atom and benzene in solid para-hydrogen.

PubMed

Bahou, Mohammed; Witek, Henryk; Lee, Yuan-Pern

2013-02-21

The reaction of a chlorine atom with benzene (C6H6) is important in organic chemistry, especially in site-selective chlorination reactions, but its product has been a subject of debate for five decades. Previous experimental and theoretical studies provide no concrete conclusion on whether the product is a π- or σ-form of the Cl-C6H6 complex. We took advantage of the diminished cage effect of para-hydrogen (p-H2) to produce Cl in situ to react with C6H6 (or C6D6) upon photolysis of a Cl2/C6H6 (or C6D6)/p-H2 matrix at 3.2 K. The infrared spectrum, showing intense lines at 1430.5, 833.6, 719.8, 617.0, and 577.4 cm(−1), and several weaker ones for Cl-C6H6, and the deuterium shifts of observed new lines unambiguously indicate that the product is a 6-chlorocyclohexadienyl radical, i.e., the σ-complex of Cl-C6H6. Observation of the σ-complex rather than the π-complex indicates that the σ-complex is more stable in solid p-H2 at 3.2 K. The spectral information is crucial for further investigations of the Cl + C6H6 reaction either in the gaseous or solution phase.

Deamidation of Protonated Asparagine-Valine Investigated by a Combined Spectroscopic, Guided Ion Beam, and Theoretical Study.

PubMed

Kempkes, L J M; Boles, G C; Martens, J; Berden, G; Armentrout, P B; Oomens, J

2018-03-08

Peptide deamidation of asparaginyl residues is a spontaneous post-translational modification that is believed to play a role in aging and several diseases. It is also a well-known small-molecule loss channel in the MS/MS spectra of protonated peptides. Here we investigate the deamidation reaction, as well as other decomposition pathways, of the protonated dipeptide asparagine-valine ([AsnVal + H] + ) upon low-energy activation in a mass spectrometer. Using a combination of infrared ion spectroscopy, guided ion beam tandem mass spectrometry, and theoretical calculations, we have been able to identify product ion structures and determine the energetics and mechanisms for decomposition. Deamidation proceeds via ammonia loss from the asparagine side chain, initiated by a nucleophilic attack of the peptide bond oxygen on the γ-carbon of the Asn side chain. This leads to the formation of a furanone ring containing product ion characterized by a threshold energy of 129 ± 5 kJ/mol (15 kJ/mol higher in energy than dehydration of [AsnVal + H] + , the lowest energy dissociation channel available to the system). Competing formation of a succinimide ring containing product, as has been observed for protonated asparagine-glycine ([AsnGly + H] + ) and asparagine-alanine ([AsnAla + H] + ), was not observed here. Quantum-chemical modeling of the reaction pathways confirms these subtle differences in dissociation behavior. Measured reaction thresholds are in agreement with predicted theoretical reaction energies computed at several levels of theory.

Photoelectron velocity-map imaging spectroscopic and theoretical study on the reactivity of the gold atom toward CH3SH, CH3OH, and H2O.

PubMed

Qin, Zhengbo; Cong, Ran; Wu, Xia; Liu, Zhiling; Xie, Hua; Tang, Zichao; Jiang, Ling; Fan, Hongjun

2013-07-21

Photoelectron velocity-map imaging spectroscopy has been used to study the reaction of the anionic gold atom with the HR (R = SCH3, OCH3, OH) molecules. The solvated [Au···HR](-) and inserted [HAuR](-) products have been experimentally observed for R = SCH3, whereas only solvated [Au⋯HR](-) products were found for R = OCH3 and OH. This significant difference in the photoelectron spectra suggests the different reactivity of the Au(-) toward the CH3SH, CH3OH, and H2O molecules. Second order Møller-Plesset perturbation theory and coupled-cluster single double triple excitation calculations have been performed to aid the structural assignment of the spectra and to explore the reaction mechanism. Activation energies for the isomerizations of the solvated structures to the inserted ones in the Au(-)∕Au + HR reactions (R = OCH3 and OH) are predicted to be much higher than those for the Au(-)∕Au + CH3SH reactions, supporting the experimental observation. Theoretical calculations provide the evidence that the intriguing [HAuSCH3](-) product may be formed by the attachment of the electron onto the neutral HAuSCH3 species or the isomerization from the anionic [Au···HSCH3](-) one. These findings should be helpful for understanding the feature that the thiols are able to form the staple motifs, whereas CH3OH and H2O are not.

Methane Activation by 5 d Transition Metals: Energetics, Mechanisms, and Periodic Trends.

PubMed

Armentrout, Peter B

2017-01-01

Although it has been known for almost three decades that several 5d transition-metal cations will activate methane at room temperature, a more detailed examination of these reactions across the periodic table has only recently been completed. In this Minireview, we compare and contrast studies of the kinetic energy dependence of these reactions as studied using guided-ion-beam tandem mass spectrometry. Thermochemistry for the various products observed (MH + , MH 2 + , MC + , MCH + , MCH 2 + , and MCH 3 + ) are collected and periodic trends evaluated and discussed. The mechanisms for the reactions as elucidated by synergistic quantum chemical calculations are also reviewed. Recent spectroscopic evidence for the structures of the MCH 2 + dehydrogenation products are discussed as well. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Gold-nanoparticle-based catalysts for the oxidative esterification of 1,4-butanediol into dimethyl succinate.

PubMed

Brett, Gemma L; Miedziak, Peter J; He, Qian; Knight, David W; Edwards, Jennifer K; Taylor, Stuart H; Kiely, Christopher J; Hutchings, Graham J

2013-10-01

The oxidation of 1,4-butanediol and butyrolactone have been investigated by using supported gold, palladium and gold-palladium nanoparticles. The products of such reactions are valuable chemical intermediates and, for example, can present a viable pathway for the sustainable production of polymers. If both gold and palladium were present, a significant synergistic effect on the selective formation of dimethyl succinate was observed. The support played a significant role in the reaction, with magnesium hydroxide leading to the highest yield of dimethyl succinate. Based on structural characterisation of the fresh and used catalysts, it was determined that small gold-palladium nanoalloys supported on a basic Mg(OH)2 support provided the best catalysts for this reaction. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Laser-induced plasma chemistry of the explosive RDX with various metallic nanoparticles.

PubMed

Gottfried, Jennifer L

2012-03-01

The feasibility of exploiting plasma chemistry to study the chemical reactions between metallic nanoparticles and molecular explosives such as cyclotrimethylenetrinitramine (RDX) has been demonstrated. This method, based on laser-induced breakdown spectroscopy, involves the production of nanoparticles in a laser-induced plasma and the simultaneous observation of time-resolved atomic and molecular emission characteristic of the species involved in the intermediate chemical reactions of the nanoenergetic material in the plasma. Using this method, it has been confirmed that the presence of aluminum promotes the ejection process of carbon from the intermediate products of RDX. The time evolution of species formation, the effects of laser pulse energy, and the effects of trace metal content on the chemical reactions were also studied. © 2012 Optical Society of America

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

NASA Astrophysics Data System (ADS)

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

2017-04-01

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

Requirement for transient metal ions revealed through computational analysis for DNA polymerase going in reverse

PubMed Central

Perera, Lalith; Freudenthal, Bret D.; Beard, William A.; Shock, David D.; Pedersen, Lee G.; Wilson, Samuel H.

2015-01-01

DNA polymerases facilitate faithful insertion of nucleotides, a central reaction occurring during DNA replication and repair. DNA synthesis (forward reaction) is “balanced,” as dictated by the chemical equilibrium by the reverse reaction of pyrophosphorolysis. Two closely spaced divalent metal ions (catalytic and nucleotide-binding metals) provide the scaffold for these reactions. The catalytic metal lowers the pKa of O3′ of the growing primer terminus, and the nucleotide-binding metal facilitates substrate binding. Recent time-lapse crystallographic studies of DNA polymerases have identified an additional metal ion (product metal) associated with pyrophosphate formation, leading to the suggestion of its possible involvement in the reverse reaction. Here, we establish a rationale for a role of the product metal using quantum mechanical/molecular mechanical calculations of the reverse reaction in the confines of the DNA polymerase β active site. Additionally, site-directed mutagenesis identifies essential residues and metal-binding sites necessary for pyrophosphorolysis. The results indicate that the catalytic metal site must be occupied by a magnesium ion for pyrophosphorolysis to occur. Critically, the product metal site is occupied by a magnesium ion early in the pyrophosphorolysis reaction path but must be removed later. The proposed dynamic nature of the active site metal ions is consistent with crystallographic structures. The transition barrier for pyrophosphorolysis was estimated to be significantly higher than that for the forward reaction, consistent with kinetic activity measurements of the respective reactions. These observations provide a framework to understand how ions and active site changes could modulate the internal chemical equilibrium of a reaction that is central to genome stability. PMID:26351676

Observation of isoprene hydroxynitrates in the Southeastern United States and implications for the fate of NOx

NASA Astrophysics Data System (ADS)

Xiong, F.; McAvey, K. M.; Pratt, K. A.; Groff, C. J.; Hostetler, M. A.; Lipton, M. A.; Starn, T. K.; Seeley, J. V.; Bertman, S. B.; Teng, A. P.; Crounse, J. D.; Nguyen, T. B.; Wennberg, P. O.; Misztal, P. K.; Goldstein, A. H.; Guenther, A. B.; Koss, A. R.; Olson, K. F.; de Gouw, J. A.; Baumann, K.; Edgerton, E. S.; Feiner, P. A.; Zhang, L.; Miller, D. O.; Brune, W. H.; Shepson, P. B.

2015-07-01

Isoprene hydroxynitrates (IN) are tracers of the photochemical oxidation of isoprene in high NOx environments. Production and loss of IN have a significant influence on the NOx cycle and tropospheric O3 chemistry. To better understand IN chemistry, a series of photochemical reaction chamber experiments were conducted to determine the IN yield from isoprene photooxidation at high NO concentrations (> 100 ppt). By combining experimental data and calculated isomer distributions, a total IN yield of 9(+4/-3) % was derived. The result was applied in a zero-dimensional model to simulate production and loss of ambient IN observed in a temperate forest atmosphere, during the Southern Oxidant and Aerosol Study (SOAS) field campaign, from 27 May to 11 July 2013. By comparing field observations with model simulations, we identified NO as the limiting factor for ambient IN production during SOAS, but vertical mixing at dawn might also contribute (~ 27 %) to IN dynamics. A close examination of isoprene's oxidation products indicates that its oxidation transitioned from a high-NO dominant chemical regime in the morning into a low-NO dominant regime in the afternoon. A significant amount of IN produced in the morning high NO regime could be oxidized in the low NO regime, and a possible reaction scheme was proposed.

Clusters, Assemble: Growth of Intermetallic Compounds from Metal Flux Reactions.

PubMed

Latturner, Susan E

2018-01-16

Metal flux synthesis involves the reaction of metals and metalloids in a large excess of a low-melting metal that acts as a solvent. This technique makes use of an unusual temperature regime (above the temperatures used for solvothermal methods and below the temperatures used in traditional solid state synthesis) and facilitates the growth of products as large crystals. It has proven to be a fruitful method to discover new intermetallic compounds. However, little is known about the chemistry occurring within a molten metal solvent; without an understanding of the nature of precursor formation and assembly, it is difficult to predict product structures and target properties. Organic chemists have a vast toolbox of well-known reagents and reaction mechanisms to use in directing their synthesis toward a desired molecular structure. This is not yet the case for the synthesis of inorganic extended structures. We have carried out extensive explorations of the growth of new magnetic intermetallic compounds from a variety of metal fluxes. This Account presents a review of some of our results and recent reports by other groups; this work indicates that products with common building blocks and homologous series with identical structural motifs are repeatedly seen in metal flux chemistry. For instance, fluorite-type layers comprised of transition metals coordinated by eight main group metal atoms are found in the Th 2 (Au x Si 1-x )[AuAl 2 ] n Si 2 and R[AuAl 2 ] n Al 2 (Au x Si 1-x ) 2 series grown from aluminum flux, the Ce n PdIn 3n+2 series grown from indium flux, and CePdGa 6 and Ce 2 PdGa 10 grown from gallium flux. Similarly, our investigations of reactions of heavy main group metals, M, in rare earth/transition metal eutectic fluxes reveal that the R/T/M/M' products usually feature M-centered rare earth clusters M@R 8-12 , which share faces to form layers and networks that surround transition metal building blocks. These structural trends, temperature dependence of products formed in the flux, and interconversions observed by differential scanning calorimetry support the idea that these clusters likely form in the melt, existing as precursors and assembling into different crystalline products depending on time, temperature, and reaction ratio. Proof of this mechanism will require future investigations using techniques such as pair distribution function analysis of flux melts to observe cluster formation and in situ diffraction during cooling to detect various phases as they crystallize and interconvert. These data will aid in understanding the parameters that control cluster formation and assembly in metal melts, allow for prediction of products of flux reactions, and will potentially enable the tailoring of reaction conditions to promote the formation of structures with desirable properties.

Detection of different oxidation states of individual manganese porphyrins during their reaction with oxygen at a solid/liquid interface.

PubMed

den Boer, Duncan; Li, Min; Habets, Thomas; Iavicoli, Patrizia; Rowan, Alan E; Nolte, Roeland J M; Speller, Sylvia; Amabilino, David B; De Feyter, Steven; Elemans, Johannes A A W

2013-07-01

Manganese porphyrins have been extensively investigated as model systems for the natural enzyme cytochrome P450 and as synthetic oxidation catalysts. Here, we report single-molecule studies of the multistep reaction of manganese porphyrins with molecular oxygen at a solid/liquid interface, using a scanning tunnelling microscope (STM) under environmental control. The high lateral resolution of the STM, in combination with its sensitivity to subtle differences in the electronic properties of molecules, allowed the detection of at least four distinct reaction species. Real-space and real-time imaging of reaction dynamics enabled the observation of active sites, immobile on the experimental timescale. Conversions between the different species could be tuned by the composition of the atmosphere (argon, air or oxygen) and the surface bias voltage. By means of extensive comparison of the results to those obtained by analogous solution-based chemistry, we assigned the observed species to the starting compound, reaction intermediates and products.

Mineralization of Basalts in the CO 2-H 2O-H 2S System

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schaef, Herbert T.; McGrail, B. Peter; Owen, Antionette T.

2013-05-10

Basalt samples representing five different formations were immersed in water equilibrated with supercritical carbon dioxide containing 1% hydrogen sulfide (H2S) at reservoir conditions (100 bar, 90°C) for up to 3.5 years. Surface coatings in the form of pyrite and metal cation substituted carbonates were identified as reaction products associated with all five basalts. In some cases, high pressure tests contained excess H2S, which produced the most corroded basalts and largest amount of secondary products. In comparison, tests containing limited amounts of H2S appeared least reacted with significantly less concentrations of reaction products. In all cases, pyrite appeared to precede carbonation,more » and in some instances, was observed in the absence of carbonation such as in cracks, fractures, and within the porous glassy mesostasis. Armoring reactions from pyrite surface coatings observed in earlier shorter duration tests were found to be temporary with carbonate mineralization observed with all the basalts tested in these long duration experiments. Geochemical simulations conducted with the geochemical code EQ3/6 accurately predicted early pyrite precipitation followed by formation of carbonates. Reactivity with H2S was correlated with measured Fe(II)/Fe(III) ratios in the basalts with more facile pyrite formation occurring with basalts containing more Fe(III) phases. These experimental and modeling results confirm potential for long term sequestration of acid gas mixtures in continental flood basalt formations.« less

Enantiomer-Selective Photo-Induced Reaction of Protonated Tryptophan with Disaccharides in the Gas Phase

NASA Astrophysics Data System (ADS)

Doan, Thuc N.; Fujihara, Akimasa

2018-03-01

In order to investigate chemical evolution in interstellar molecular clouds, enantiomer-selective photo-induced chemical reactions between an amino acid and disaccharides in the gas phase were examined using a tandem mass spectrometer containing an electrospray ionization source and a cold ion trap. Ultraviolet photodissociation mass spectra of cold gas-phase noncovalent complexes of protonated tryptophan (Trp) enantiomers with disaccharides consisting of two d-glucose units, such as d-maltose or d-cellobiose, were obtained by photoexcitation of the indole ring of Trp. NH2CHCOOH loss via cleavage of the Cα-Cβ bond in Trp induced by hydrogen atom transfer from the NH3 + group of a protonated Trp was observed in a noncovalent heterochiral H+( l-Trp)( d-maltose) complex. In contrast, a photo-induced chemical reaction forming the product ion with m/z 282 occurs in homochiral H+( d-Trp)( d-maltose). For d-cellobiose, both NH2CHCOOH elimination and the m/z 282 product ion were observed, and no enantiomer-selective phenomena occurred. The m/z 282 product ion indicates that the photo-induced C-glycosylation, which links d-glucose residues to the indole moiety of Trp via a C-C bond, can occur in cold gas-phase noncovalent complexes, and its enantiomer-selectivity depends on the structure of the disaccharide.

Measles-Mumps-Rubella vaccine for children with egg allergy: Is admission for inpatient vaccination necessary?

PubMed

Tan, M S; Teoh, E J; Hor, C P; Yeoh, A A C

2016-08-01

Children who develop any hypersensitivity reaction to eggs are routinely referred to hospital for Measles-Mumps-Rubella (MMR) vaccination as inpatients to prevent anaphylaxis. We aimed to study the association between hypersensitivity reactions after egg exposure and similar reactions after MMR immunisation; and examine the necessity of hospital admission for vaccination. A prospective observational study was conducted in Paediatric Department in Bukit Mertajam Hospital, Penang, between March and December 2014. Children referred from local polyclinics for inpatient MMR vaccination because of a history of egg allergy were recruited. The children were observed in the ward for post vaccination allergic reactions. Concurrently, a group of children without egg allergy was recruited from those admitted for other illnesses but had recent MMR vaccination at polyclinics. Parents of these children were interviewed and asked if they had observed any reactions post vaccination. In both groups, sociodemographics, medical history and family history of atopy were collected. Eighty-seven subjects were recruited in this study. Fifty-four infants with egg allergy had previous mild allergic reactions after exposure to eggs or egg-related products. They were associated with a family history of egg hypersensitivity, personal history of acute gastroenteritis and upper respiratory tract infections. Two of them developed cutaneous rashes post vaccination during observation, but none developed anaphylactic or anaphylactoid reactions. Two infants among those without egg allergy had post vaccination fever. There was no association between egg allergy and hypersensitivity reactions to MMR vaccine (p=0.632). MMR vaccine can be safely administered to children with mild egg allergy, hence admission for vaccination in the hospital is not warranted. Risk stratification is required to ensure only infants with severe reactions will be admitted for vaccination.

Effect of calcinations temperature of CuO nanoparticle on the kinetics of decontamination and decontamination products of sulphur mustard.

PubMed

Mahato, T H; Singh, Beer; Srivastava, A K; Prasad, G K; Srivastava, A R; Ganesan, K; Vijayaraghavan, R

2011-09-15

Present study investigates the potential of CuO nanoparticles calcined at different temperature for the decontamination of persistent chemical warfare agent sulphur mustard (HD) at room temperature (30 ± 2 °C). Nanoparticles were synthesized by precipitation method and characterized by using SEM, EDAX, XRD, and Raman Spectroscopy. Synthesized nanoparticles were tested as destructive adsorbents for the degradation of HD. Reactions were monitored by GC-FID technique and the reaction products characterized by GC-MS. It was observed that the rate of degradation of HD decreases with the increase in calcination temperature and there is a change in the percentage of product of HD degradation. GC-MS data indicated that the elimination product increases with increase in calcination temperature whereas the hydrolysis product decreases. Copyright © 2011 Elsevier B.V. All rights reserved.

Bio-aviation fuel production from hydroprocessing castor oil promoted by the nickel-based bifunctional catalysts.

PubMed

Liu, Siyang; Zhu, Qingqing; Guan, Qingxin; He, Liangnian; Li, Wei

2015-05-01

Bio-aviation fuel was firstly synthesized by hydroprocessing castor oil in a continuous-flow fixed-bed microreactor with the main objective to obtain the high yield of aviation fuel and determine the elemental compositions of the product phases as well as the reaction mechanism. Highest aviation range alkane yields (91.6 wt%) were achieved with high isomer/n-alkane ratio (i/n) 4.4-7.2 over Ni supported on acidic zeolites. In addition, different fuel range alkanes can be obtained by adjusting the degree of hydrodeoxygenation (HDO) and hydrocracking. And the observations are rationalized by a set of reaction pathways for the various product phases. Copyright © 2015 Elsevier Ltd. All rights reserved.

Synthesis of terpene and steroid dimers and trimers having cyclobutadienyl-Co and aromatic tethers.

PubMed

Sierra, Miguel A; Torres, M Rosario; Torre, María C de la; Alvaro, Elsa

2007-05-25

The reaction of natural product derived propargylic alcohols with CpCo(CO)2 produces three new types of natural product hybrids having two or three terpene or steroid fragments. The tether joining the natural product subunits is built during the reaction. Type 1 hybrids have two terpene or steroid moieties joined by a CpCo-cyclobutadiene tether, with the two units disposed in a 1,2-arrangement (9, 14, 22). Type 2 hybrids have a Co-cyclopentadienone tether (10). Type 3 has three units of terpene or steroid joined to a benzene ring (11, 12, 15). An unusual Co-mediated beta-carbon elimination pathway of propargylic alcohols leading to ketones (an unknown process in this chemistry) has been observed.

Highly Viscous States Affect the Browning of Atmospheric Organic Particulate Matter

PubMed Central

2018-01-01

Initially transparent organic particulate matter (PM) can become shades of light-absorbing brown via atmospheric particle-phase chemical reactions. The production of nitrogen-containing compounds is one important pathway for browning. Semisolid or solid physical states of organic PM might, however, have sufficiently slow diffusion of reactant molecules to inhibit browning reactions. Herein, organic PM of secondary organic material (SOM) derived from toluene, a common SOM precursor in anthropogenically affected environments, was exposed to ammonia at different values of relative humidity (RH). The production of light-absorbing organonitrogen imines from ammonia exposure, detected by mass spectrometry and ultraviolet–visible spectrophotometry, was kinetically inhibited for RH < 20% for exposure times of 6 min to 24 h. By comparison, from 20% to 60% RH organonitrogen production took place, implying ammonia uptake and reaction. Correspondingly, the absorption index k across 280 to 320 nm increased from 0.012 to 0.02, indicative of PM browning. The k value across 380 to 420 nm increased from 0.001 to 0.004. The observed RH-dependent behavior of ammonia uptake and browning was well captured by a model that considered the diffusivities of both the large organic molecules that made up the PM and the small reactant molecules taken up from the gas phase into the PM. Within the model, large-molecule diffusivity was calculated based on observed SOM viscosity and evaporation. Small-molecule diffusivity was represented by the water diffusivity measured by a quartz-crystal microbalance. The model showed that the browning reaction rates at RH < 60% could be controlled by the low diffusivity of the large organic molecules from the interior region of the particle to the reactive surface region. The results of this study have implications for accurate modeling of atmospheric brown carbon production and associated influences on energy balance. PMID:29532020

Physical and biochemical energy balance during an isometric tetanus and steady state recovery in frog sartorius at 0 degree C

PubMed Central

1983-01-01

Frog sartorius muscle stimulated isometrically for 3 s every 256 s to attain a steady state in which initial heat (QI), recovery heat (QR), rate of O2 consumption (JO2), and isometric force (PO) generated are constant for each cycle. For a 3-s tetanus given every 256 s, JO2 was 0.106 mumol/(min . g blotted weight), approximately 71% of the maximum rate observed, whereas lactate production was negligible under these conditions. QI, QT(= QI + QR), and QT/QI were 88.2, 181.5, 2.06 mJ/g blotted weight, respectively. The high-energy phosphate breakdown (delta approximately P) breakdown during the first 3-s tetanus was not different from that during a contraction in the steady state and averaged 1.1 mumol/g blotted weight. Less than half of the initial heat could be accounted for in terms of the extent of the known chemical reactions occurring during contraction. From the stoichiometry of the theoretical biochemical pathways, the amount of ATP synthesized in the steady state exceeds delta approximately P during contraction by more than twofold, corresponding to an apparent ADP:O ratio of 1.5. If it is assumed that carbohydrate oxidation is the only net chemical reaction in the steady state, the total heat production can be explained on the basis of the measured JO2. Under this assumption, heat production during recovery was less than that expected on the basis of the oxygen consumption and delta approximately P during contraction. These observations support the hypothesis that the unexplained enthalpy production and low apparent ADP:O ratio are causally related, i.e., that the reaction(s) producing the unexplained heat during contraction is reversed during the recovery period. PMID:6601686

Highly Viscous States Affect the Browning of Atmospheric Organic Particulate Matter.

PubMed

Liu, Pengfei; Li, Yong Jie; Wang, Yan; Bateman, Adam P; Zhang, Yue; Gong, Zhaoheng; Bertram, Allan K; Martin, Scot T

2018-02-28

Initially transparent organic particulate matter (PM) can become shades of light-absorbing brown via atmospheric particle-phase chemical reactions. The production of nitrogen-containing compounds is one important pathway for browning. Semisolid or solid physical states of organic PM might, however, have sufficiently slow diffusion of reactant molecules to inhibit browning reactions. Herein, organic PM of secondary organic material (SOM) derived from toluene, a common SOM precursor in anthropogenically affected environments, was exposed to ammonia at different values of relative humidity (RH). The production of light-absorbing organonitrogen imines from ammonia exposure, detected by mass spectrometry and ultraviolet-visible spectrophotometry, was kinetically inhibited for RH < 20% for exposure times of 6 min to 24 h. By comparison, from 20% to 60% RH organonitrogen production took place, implying ammonia uptake and reaction. Correspondingly, the absorption index k across 280 to 320 nm increased from 0.012 to 0.02, indicative of PM browning. The k value across 380 to 420 nm increased from 0.001 to 0.004. The observed RH-dependent behavior of ammonia uptake and browning was well captured by a model that considered the diffusivities of both the large organic molecules that made up the PM and the small reactant molecules taken up from the gas phase into the PM. Within the model, large-molecule diffusivity was calculated based on observed SOM viscosity and evaporation. Small-molecule diffusivity was represented by the water diffusivity measured by a quartz-crystal microbalance. The model showed that the browning reaction rates at RH < 60% could be controlled by the low diffusivity of the large organic molecules from the interior region of the particle to the reactive surface region. The results of this study have implications for accurate modeling of atmospheric brown carbon production and associated influences on energy balance.

Computed Potential Energy Surfaces and Minimum Energy Pathway for Chemical Reactions

NASA Technical Reports Server (NTRS)

Walch, Stephen P.; Langhoff, S. R. (Technical Monitor)

1994-01-01

Computed potential energy surfaces are often required for computation of such observables as rate constants as a function of temperature, product branching ratios, and other detailed properties. We have found that computation of the stationary points/reaction pathways using CASSCF/derivative methods, followed by use of the internally contracted CI method with the Dunning correlation consistent basis sets to obtain accurate energetics, gives useful results for a number of chemically important systems. Applications to complex reactions leading to NO and soot formation in hydrocarbon combustion are discussed.

Kaon photoproduction at SAPHIR for photon energies up to 2.6 GeV

NASA Astrophysics Data System (ADS)

Glander, K.-H.; Saphir Collaboration

2005-05-01

The measurement of photoproduction reactions with open strangeness is one of the central issues of the physics program at SAPHIR. We report here on the analysis of the reactions γp→KΣ and γp→KΣ in the photon energy range between threshold and 2.6 GeV using data taken in the years 1997-1998. The measured cross sections suggest contributions from resonance production for both reactions. Coupled channel analysis of the two mentioned isospin channels together with the reaction γp→KΛ also measured by SAPHIR, should help to extract resonance informations in these reactions. Upcoming data from different experiments on the photoproduction of kaon-hyperon pairs on the neutron and electroproduction of strangeness, including cross sections and polarization observables, will even improve this situation. However, for an initial discussion of what one could learn from strangeness production in the future final data for the reaction γp→KΣ the preliminary SAPHIR results for the reaction γp→KΣ are compared here with an isobar model designed for the previous SAPHIR data. The latter had less energy and a smaller kaon production angle resolution than new SAPHIR data and delivered data for γp→KΛ and γp→KΣ only up to 2.0 GeV and for γp→KΣ up to 1.55 GeV. The new data show clearly that such a model must be refined to describe the new SAPHIR data, because these data are more sensitive to background and resonance contributions.

Shellfish allergy.

PubMed

Lopata, A L; O'Hehir, R E; Lehrer, S B

2010-06-01

Seafood plays an important role in human nutrition and health. The growing international trade in seafood species and products has added to the popularity and frequency of consumption of a variety of seafood products across many countries. This increased production and consumption of seafood has been accompanied by more frequent reports of adverse health problems among consumers as well as processors of seafood. Adverse reactions to seafood are often generated by contaminants but can also be mediated by the immune system and cause allergies. These reactions can result from exposure to the seafood itself or various non-seafood components in the product. Non-immunological reactions to seafood can be triggered by contaminants such as parasites, bacteria, viruses, marine toxins and biogenic amines. Ingredients added during processing and canning of seafood can also cause adverse reactions. Importantly all these substances are able to trigger symptoms which are similar to true allergic reactions, which are mediated by antibodies produced by the immune system against specific allergens. Allergic reactions to 'shellfish', which comprises the groups of crustaceans and molluscs, can generate clinical symptoms ranging from mild urticaria and oral allergy syndrome to life-threatening anaphylactic reactions. The prevalence of crustacean allergy seems to vary largely between geographical locations, most probably as a result of the availability of seafood. The major shellfish allergen is tropomyosin, although other allergens may play an important part in allergenicity such as arginine kinase and myosin light chain. Current observations regard tropomyosin to be the major allergen responsible for molecular and clinical cross-reactivity between crustaceans and molluscs, but also to other inhaled invertebrates such as house dust mites and insects. Future research on the molecular structure of tropomyosins with a focus on the immunological and particularly clinical cross-reactivity will improve diagnosis and management of this potentially life-threatening allergy and is essential for future immunotherapy.

Reactions of the selected ion flow tube mass spectrometry reagent ions H3O(+) and NO(+) with a series of volatile aldehydes of biogenic significance.

PubMed

Smith, David; Chippendale, Thomas W E; Španěl, Patrik

2014-09-15

It has been shown that aldehydes are often present in biogenic media. For their analysis by selected ion flow tube mass spectrometry (SIFT-MS), the rate coefficients and the product ion distributions for the reactions of the analyte ions H3O(+) and NO(+) with volatile aldehydes in the presence of water vapour are required. The reactions of H3O(+) and NO(+) ions have been studied with a series of n-aldehydes ranging from acetaldehyde (designated as C2), through undecanal (C11) under the conditions used for SIFT-MS analyses (1 Torr He, 0.1 Torr air sample, 300 K) and over a range of sample gas absolute humidity from 1% to 7%. For comparison, the C5 pentanal isomer 3-methyl butanal, the unsaturated trans-2-pentenal and trans-2-octenal and the aromatic benzaldehyde were also included in the study. The H3O(+) reactions led to the formation of protonated molecules MH(+) and their hydrates MH(+)(H2O)0,1,2,3 , and (MH(+)-H2O). The NO(+) reactions resulted in the production of NO(+)M adduct ions and of [M-H](+) fragment ions. The percentages of the different product ions for each aldehyde are seen to be dependent on the air sample humidity. Kinetic modelling was used to quantitatively explain these observations and to obtain rate coefficients for the association reactions producing NO(+) M adduct ions. This detailed study has provided the kinetics data, in particular the product ion distributions, for the reactions of a number of volatile aldehydes, which allows their analyses by SIFT-MS in humid air, including exhaled breath, food emanations and other biogenic media. Copyright © 2014 John Wiley & Sons, Ltd.

The effect of freezing on reactions with environmental impact.

PubMed

O'Concubhair, Ruairí; Sodeau, John R

2013-11-19

The knowledge that the freezing process can accelerate certain chemical reactions has been available since the 1960s, particularly in relation to the food industry. However, investigations into such effects on environmentally relevant reactions have only been carried out since the late 1980s. Some 20 years later, the field has matured and scientists have conducted research into various important processes such as the oxidation of nitrite ions to nitrates, sulfites to sulfates, and elemental mercury to inorganic mercury. Field observations mainly carried out in the polar regions have driven this work. For example, researchers have found that both ozone and mercury are removed from the troposphere completely (and almost instantaneously) at the time of Arctic polar sunrise. The monitoring activities suggested that both the phenomena were caused by involvement of bromine (and possibly iodine) chemistry. Scientists investigating the production of interhalide products (bromine and iodine producing interhalides) in frozen aqueous solutions have found that these reactions result in both rate accelerations and unexpected products. Furthermore, these scientists did this research with environmentally relevant concentrations of reagents, thereby suggesting that these reactions could occur in the polar regions. The conversion of elemental mercury to more oxidized forms has also shown that the acceleration of reactions can occur when environmentally relevant concentrations of Hg(0) and oxidants are frozen together in aqueous solutions. These observations, coupled with previous investigations into the effect of freezing on environmental reactions, lead us to conclude that this type of chemistry could potentially play a significant role in the chemical processing of a wide variety of inorganic components in polar regions. More recently, researchers have recognized the implications of these complementary field and laboratory findings toward human health and climate change. In this Account, we focus on the chemical and physical mechanisms that may promote novel chemistry and rate accelerations when water-ice is present. Future prospects will likely concentrate, once again, on the low-temperature chemistry of organic compounds, such as the humic acids, which are known cryospheric contaminants. Furthermore, data on the kinetics and thermodynamics of all types of reaction promoted by the freezing process would provide much assistance in determining their implications to environmental computer models.

Strangeness suppression of qq creation observed in exclusive reactions.

PubMed

Mestayer, M D; Park, K; Adhikari, K P; Aghasyan, M; Pereira, S Anefalos; Ball, J; Battaglieri, M; Batourine, V; Bedlinskiy, I; Biselli, A S; Boiarinov, S; Briscoe, W J; Brooks, W K; Burkert, V D; Carman, D S; Celentano, A; Chandavar, S; Charles, G; Colaneri, L; Cole, P L; Contalbrigo, M; Cortes, O; Crede, V; D'Angelo, A; Dashyan, N; De Vita, R; Deur, A; Djalali, C; Doughty, D; Dupre, R; El Alaoui, A; El Fassi, L; Elouadrhiri, L; Eugenio, P; Fedotov, G; Fleming, J A; Forest, T A; Garillon, B; Garçon, M; Ghandilyan, Y; Gilfoyle, G P; Giovanetti, K L; Girod, F X; Goetz, J T; Golovatch, E; Gothe, R W; Griffioen, K A; Guegan, B; Guidal, M; Hakobyan, H; Hanretty, C; Hattawy, M; Holtrop, M; Hughes, S M; Hyde, C E; Ilieva, Y; Ireland, D G; Jiang, H; Jo, H S; Joo, K; Keller, D; Khandaker, M; Kim, A; Kim, W; Koirala, S; Kubarovsky, V; Kuleshov, S V; Lenisa, P; Levine, W I; Livingston, K; Lu, H Y; MacGregor, I J D; Mayer, M; McKinnon, B; Meyer, C A; Mirazita, M; Mokeev, V; Montgomery, R A; Moody, C I; Moutarde, H; Movsisyan, A; Camacho, C Munoz; Nadel-Turonski, P; Niccolai, S; Niculescu, G; Niculescu, I; Osipenko, M; Ostrovidov, A I; Pappalardo, L L; Paremuzyan, R; Peng, P; Phelps, W; Pisano, S; Pogorelko, O; Pozdniakov, S; Price, J W; Protopopescu, D; Puckett, A J R; Raue, B A; Rimal, D; Ripani, M; Rizzo, A; Rosner, G; Roy, P; Sabatié, F; Saini, M S; Schott, D; Schumacher, R A; Simonyan, A; Sokhan, D; Strauch, S; Sytnik, V; Tang, W; Tian, Ye; Ungaro, M; Vernarsky, B; Vlassov, A V; Voskanyan, H; Voutier, E; Walford, N K; Watts, D P; Wei, X; Weinstein, L B; Wood, M H; Zachariou, N; Zhang, J; Zhao, Z W; Zonta, I

2014-10-10

We measured the ratios of electroproduction cross sections from a proton target for three exclusive meson-baryon final states: ΛK(+), pπ(0), and nπ(+), with the CLAS detector at Jefferson Lab. Using a simple model of quark hadronization, we extract qq creation probabilities for the first time in exclusive two-body production, in which only a single qq pair is created. We observe a sizable suppression of strange quark-antiquark pairs compared to nonstrange pairs, similar to that seen in high-energy production.

Mass spectrometric study of the negative and positive secondary ions emitted from ethanol microdroplets by MeV-energy heavy ion impact

NASA Astrophysics Data System (ADS)

Kitajima, Kensei; Majima, Takuya; Nishio, Tatsuya; Oonishi, Yoshiki; Mizutani, Shiori; Kohno, Jun-ya; Saito, Manabu; Tsuchida, Hidetsugu

2018-06-01

We have investigated the negative and positive secondary ions emitted from ethanol droplets by 4.0-MeV C3+ impact to reveal the characteristic features of the reaction processes induced by fast heavy ions at the liquid ethanol surface. Analysis of the secondary ions was performed by time-of-flight mass spectrometry for microdroplet targets in a high vacuum environment. Fragment ions, deprotonated cluster ions, and trace amounts of the reaction product ions are observed in the negative secondary ions. The main fragment anions are C2HmO- (m = 1, 3, and 5) and C2H- generated by loss of hydrogen and oxygen atoms. The reaction product anions include deprotonated glycols, larger alcohols, and their dehydrated and dehydrogenated forms generated by secondary reactions between fragments and radicals. Furthermore, C3Hm- (m = 0-2) and C4Hm- (m = 0 and 1) are observed, which could be produced through a plasma state generated in the heavy ion track. Deprotonated ethanol cluster ions, [(EtOH)n - H]-, are observed up to about n = 25. [(EtOH)n - H]- have smaller kinetic energies than the protonated cluster ions (EtOH)nH+. This probably represents the effect of the positive Coulomb potential transiently formed in the ion track. We also discuss the size distributions and structures of the water- and CH2OH-radical-attached ethanol cluster ions.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nachtmann, O., E-mail: O.Nachtmann@thphys.uni-heidelberg.de

We review ideas on the structure of the QCD vacuum which had served as motivation for the discussion of various non-standard QCD effects in high-energy reactions in articles from 1984 to 1995. These effects include, in particular, transverse-momentum and spin correlations in the Drell–Yan process and soft photon production in hadron–hadron collisions. We discuss the relation of the approach introduced in the above-mentioned articles to the approach, developed later, using transverse-momentum-dependent parton distributions (TDMs). The latter approach is a special case of our more general one which allows for parton entanglement in high-energy reactions. We discuss signatures of parton entanglementmore » in the Drell–Yan reaction. Also for Higgs-boson production in pp collisions via gluon–gluon annihilation effects of entanglement of the two gluons are discussed and are found to be potentially important. These effects can be looked for in the current LHC experiments. In our opinion studying parton-entanglement effects in high-energy reactions is, on the one hand, very worthwhile by itself and, on the other hand, it allows to perform quantitative tests of standard factorisation assumptions. Clearly, the experimental observation of parton-entanglement effects in the Drell–Yan reaction and/or in Higgs-boson production would have a great impact on our understanding how QCD works in high-energy collisions.« less

Temperature-programmed desorption study of NO reactions on rutile TiO 2(110)-1×1

DOE PAGES

Kim, Boseong; Dohnalek, Zdenek; Szanyi, Janos; ...

2016-02-24

In this study, systematic temperature-programmed desorption (TPD) studies of NO adsorption and reactions on rutile TiO 2(110)-1 × 1 surface reveal several distinct reaction channels in a temperature range of 50–500 K. NO readily reacts on TiO 2(110) to form N 2O, which desorbs between 50 and 200 K (LT N 2O channels), which leaves the TiO 2 surface populated with adsorbed oxygen atoms (O a) as a by-product of N 2O formation. In addition, we observe simultaneous desorption peaks of NO and N 2O at 270 K (HT1 N 2O) and 400 K (HT2 N 2O), respectively, both ofmore » which are attributed to reaction-limited processes. No N-derived reaction product desorbs from TiO 2(110) surface above 500 K or higher, while the surface may be populated with Oa's and oxidized products such as NO 2 and NO 3. The adsorbate-free TiO 2 surface with oxygen vacancies can be regenerated by prolonged annealing at 850 K or higher. Detailed analysis of the three N 2O desorption yields reveals that the surface species for the HT channels are likely to be various forms of NO dimers.« less

Chemical reactivity of SiC fibre-reinforced SiC with beryllium and lithium ceramic breeder materials

NASA Astrophysics Data System (ADS)

Kleykamp, H.

2000-12-01

SiC fibre-reinforced SiC fabrics (f-SiC/SiC) are considered for structural materials of advanced fusion blanket concepts. Priority tasks are compatibility studies of SiC with Li breeder ceramics and the Be neutron multiplier. Isothermal and anisothermal powder reactions by DTA up to 1220°C were examined between Li 4SiO 4, Li 2ZrO 3 and Li 2TiO 3, respectively, and SiC and SiC/SiO 2 mixtures, respectively. The SiC/SiO 2 mixture simulated the chemical state of Nicalon fibres. Solid state reactions between SiC and Be pellets were studied by capsule experiments. The reaction products Be 2C and Si were observed between the initial phases after annealing at 800°C and 900°C. A parabolic time law with a chemical diffusion coefficient D˜=2.6×10 -15 m 2/s of Be in the products was deduced at 900°C. Additional oxygen released from SiO 2 as a component of the simulated fibres oxidised the reaction products via the gas phase by formation of a Be 2SiO 4 layer. All reactions are kinetically hindered below 700°C.

Modifications of hemoglobin and myoglobin by Maillard reaction products (MRPs).

PubMed

Ioannou, Aristos; Varotsis, Constantinos

2017-01-01

High performance liquid chromatography (HPLC) coupled with a Fraction Collector was employed to isolate Maillard reaction products (MRPs) formed in model systems comprising of asparagine and monosaccharides in the 60-180°C range. The primary MRP which is detected at 60°C is important for Acrylamide content and color/aroma development in foods and also in the field of food biotechnology for controlling the extent of the Maillard reaction with temperature. The discrete fractions of the reaction products were reacted with Hemoglobin (Hb) and Myoglobin (Mb) at physiological conditions and the reaction adducts were monitored by UV-vis and Attenuated Total Reflection-Fourier transform infrared (FTIR) spectrophotometry. The UV-vis kinetic profiles revealed the formation of a Soret transition characteristic of a low-spin six-coordinated species and the ATR-FTIR spectrum of the Hb-MRP and Mb-MRP fractions showed modifications in the protein Amide I and II vibrations. The UV-vis and the FTIR spectra of the Hb-MRPs indicate that the six-coordinated species is a hemichrome in which the distal E7 Histidine is coordinated to the heme Fe and blocks irreversibly the ligand binding site. Although the Mb-MRPs complex is a six-coordinated species, the 1608 cm-1 FTIR band characteristic of a hemichrome was not observed.

Recoil-α-fission and recoil-α-α-fission events observed in the reaction 48Ca + 243Am

NASA Astrophysics Data System (ADS)

Forsberg, U.; Rudolph, D.; Andersson, L.-L.; Di Nitto, A.; Düllmann, Ch. E.; Fahlander, C.; Gates, J. M.; Golubev, P.; Gregorich, K. E.; Gross, C. J.; Herzberg, R.-D.; Heßberger, F. P.; Khuyagbaatar, J.; Kratz, J. V.; Rykaczewski, K.; Sarmiento, L. G.; Schädel, M.; Yakushev, A.; Åberg, S.; Ackermann, D.; Block, M.; Brand, H.; Carlsson, B. G.; Cox, D.; Derkx, X.; Dobaczewski, J.; Eberhardt, K.; Even, J.; Gerl, J.; Jäger, E.; Kindler, B.; Krier, J.; Kojouharov, I.; Kurz, N.; Lommel, B.; Mistry, A.; Mokry, C.; Nazarewicz, W.; Nitsche, H.; Omtvedt, J. P.; Papadakis, P.; Ragnarsson, I.; Runke, J.; Schaffner, H.; Schausten, B.; Shi, Yue; Thörle-Pospiech, P.; Torres, T.; Traut, T.; Trautmann, N.; Türler, A.; Ward, A.; Ward, D. E.; Wiehl, N.

2016-09-01

Products of the fusion-evaporation reaction 48Ca + 243Am were studied with the TASISpec set-up at the gas-filled separator TASCA at the GSI Helmholtzzentrum für Schwerionenforschung, Darmstadt, Germany. Amongst the detected thirty correlated α-decay chains associated with the production of element Z = 115, two recoil-α-fission and five recoil- α- α-fission events were observed. The latter five chains are similar to four such events reported from experiments performed at the Dubna gas-filled separator, and three such events reported from an experiment at the Berkeley gas-filled separator. The four chains observed at the Dubna gas-filled separator were assigned to start from the 2n-evaporation channel 289115 due to the fact that these recoil- α- α-fission events were observed only at low excitation energies. Contrary to this interpretation, we suggest that some of these recoil- α- α-fission decay chains, as well as some of the recoil- α- α-fission and recoil-α-fission decay chains reported from Berkeley and in this article, start from the 3n-evaporation channel 288115.

Patch testing with fragrances: results of a multicenter study of the European Environmental and Contact Dermatitis Research Group with 48 frequently used constituents of perfumes.

PubMed

Frosch, P J; Pilz, B; Andersen, K E; Burrows, D; Camarasa, J G; Dooms-Goossens, A; Ducombs, G; Fuchs, T; Hannuksela, M; Lachapelle, J M

1995-11-01

The objective of this study was to determine the frequency of reactivity to a series of commonly used fragrances in dermatological patients. A total of 48 fragrances (FF) were chosen, based on the publication of Fenn in 1989 in which the top 25 constituents of 3 types (1. perfumes, 2. household products, 3. soaps) of 400 commercial products on the US market had been determined. In a pilot study on a total of 1069 patients in 11 centres, the appropriate test concentration and vehicle were examined. For most fragrances, 1% and 5% were chosen, and petrolatum proved to be the best vehicle in comparison to isopropyl myristate and diethyl phthalate. In the main study, a set of 5 to 10 fragrances at 2 concentrations was patch tested in each centre on a minimum of 100 consecutive patients seen in the patch test clinic. These patients were also patch tested to a standard series with the 8% fragrance mix (FM) and its 8 constituents. In patients with a positive reaction to any of the 48 FF, a careful history with regard to past or present reactions to perfumed products was taken. A total of 1323 patients were tested in 11 centres. The 8% FM was positive in 89 patients (8.3% of 1072 patients). Allergic reactions to the constituents were most frequent to oak moss (24), isoeugenol (20), eugenol (13), cinnamic aldehyde (10) and geraniol (8). Reactions read as allergic on day 3/4 were observed only 10X to 7 materials of the new series (Iso E Super (2), Lyral (3), Cyclacet (1), DMBCA (1), Vertofix (1), citronellol (1) and amyl salicylate (1)). The remaining 41 fragrances were negative. 28 irritant or doubtful reactions on day 3/4 were observed to a total of 19 FF materials (more than 1 reaction: 5% citronellol (2), 1% amyl salicylate (2), 1% isononyl acetate (3), 0.1% musk xylol (2), 1% citral (2), and 1% ionone beta (2)). Clinical relevance of positive reactions to any of the FF series was not proved in a single case. This included the 4 reactions in patients who were negative to the 8% FM. In conclusion, the top 25 fragrances commonly found in various products caused few reactions in dermatological patients and these few appeared to be clinically irrelevant, with the possible exception of Lyral. However, this data should be interpreted in the light of the relatively small number of patients tested (only 100 in most centres).

Cross section measurement of residues produced in proton- and deuteron-induced spallation reactions on 93Zr at 105 MeV/u using the inverse kinematics method

NASA Astrophysics Data System (ADS)

Kawase, Shoichiro; Watanabe, Yukinobu; Wang, He; Otsu, Hideaki; Sakurai, Hiroyoshi; Takeuchi, Satoshi; Togano, Yasuhiro; Nakamura, Takashi; Maeda, Yukie; Ahn, Deuk Soon; Aikawa, Masayuki; Araki, Shouhei; Chen, Sidong; Chiga, Nobuyuki; Doornenbal, Pieter; Fukuda, Naoki; Ichihara, Takashi; Isobe, Tadaaki; Kawakami, Shunsuke; Kin, Tadahiro; Kondo, Yosuke; Koyama, Shunpei; Kubo, Toshiyuki; Kubono, Shigeru; Kurokawa, Meiko; Makinaga, Ayano; Matsushita, Masafumi; Matsuzaki, Teiichiro; Michimasa, Shin'ichiro; Momiyama, Satoru; Nagamine, Shunsuke; Nakano, Keita; Niikura, Megumi; Ozaki, Tomoyuki; Saito, Atsumi; Saito, Takeshi; Shiga, Yoshiaki; Shikata, Mizuki; Shimizu, Yohei; Shimoura, Susumu; Sumikama, Toshiyuki; Söderström, Pär-Anders; Suzuki, Hiroshi; Takeda, Hiroyuki; Taniuchi, Ryo; Tsubota, Jun'ichi; Watanabe, Yasushi; Wimmer, Kathrin; Yamamoto, Tatsuya; Yoshida, Koichi

2017-09-01

Isotopic production cross sections in the proton- and deuteron-induced spallation reactions on 93Zr at an energy of 105 MeV/u were measured in inverse kinematics conditions for the development of realistic nuclear transmutation processes for long-lived fission products (LLFPs) with neutron and light-ion beams. The experimental results were compared to the PHITS calculations describing the intra-nuclear cascade and evaporation processes. Although an overall agreement was obtained, a large overestimation of the production cross sections for the removal of a few nucleons was seen. A clear shell effect associated with the neutron magic number N = 50 was observed in the measured isotopic production yields of Zr and Y isotopes, which can be reproduced reasonably by the PHITS calculation.

Hydrogen production from carbonaceous material

DOEpatents

Lackner, Klaus S.; Ziock, Hans J.; Harrison, Douglas P.

2004-09-14

Hydrogen is produced from solid or liquid carbon-containing fuels in a two-step process. The fuel is gasified with hydrogen in a hydrogenation reaction to produce a methane-rich gaseous reaction product, which is then reacted with water and calcium oxide in a hydrogen production and carbonation reaction to produce hydrogen and calcium carbonate. The calcium carbonate may be continuously removed from the hydrogen production and carbonation reaction zone and calcined to regenerate calcium oxide, which may be reintroduced into the hydrogen production and carbonation reaction zone. Hydrogen produced in the hydrogen production and carbonation reaction is more than sufficient both to provide the energy necessary for the calcination reaction and also to sustain the hydrogenation of the coal in the gasification reaction. The excess hydrogen is available for energy production or other purposes. Substantially all of the carbon introduced as fuel ultimately emerges from the invention process in a stream of substantially pure carbon dioxide. The water necessary for the hydrogen production and carbonation reaction may be introduced into both the gasification and hydrogen production and carbonation reactions, and allocated so as transfer the exothermic heat of reaction of the gasification reaction to the endothermic hydrogen production and carbonation reaction.

Reductive transformation of dioxins: An assessment of the contribution of dissolved organic matter to dechlorination reactions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fu, Q.S.; Barkovskii, A.L.; Adriaens, P.

1999-11-01

The susceptibility of dioxins to dissolved organic carbon (DOC)-mediated dechlorination reactions was investigated using 1,2,3,4,6,7,9-heptachlorodibenzo-p-dioxin (HpCDD), Aldrich humic acid (AHA), and polymaleic acid (PMA) as model compounds. The dechlorination yields were on the order of 4--20% which, when normalized to phenolic acidity, was comparable to yields observed in the presence of the humic constituents catechol and resorcinol. Based on the ratio of dechlorination yields as a function of phenolic acidity and electron transfer capacity, differences in electron transfer efficiency to dioxins are likely combined effects of specific interactions with the functional groups and nonspecific hydrophobic interactions. Hexa- and pentaCDD homologuesmore » were dominant in all incubations, and diCDD constituted the final product of dechlorination. The rates of appearance of lesser chlorinated products were similar to those observed in sediment systems and followed thermodynamic considerations as they decreased with a decrease in level of chlorination. Generally, both absolute and phenolic acidity-normalized rate constants for AHA-mediated reactions were up to 2-fold higher than those effected by PMA. These results indicate that the electron shuttling capacity of sediment DOC may significantly affect the fate of dioxins, in part through dechlorination reactions.« less

Study of the laser-induced decomposition of energetic materials at static high-pressure by time-resolved absorption spectroscopy

NASA Astrophysics Data System (ADS)

Hebert, Philippe; Saint-Amans, Charles

2013-06-01

A detailed description of the reaction rates and mechanisms occurring in shock-induced decomposition of condensed explosives is very important to improve the predictive capabilities of shock-to-detonation transition models. However, direct measurements of such experimental data are difficult to perform during detonation experiments. By coupling pulsed laser ignition of an explosive in a diamond anvil cell (DAC) with time-resolved streak camera recording of transmitted light, it is possible to make direct observations of deflagration phenomena at detonation pressure. We have developed an experimental set-up that allows combustion front propagation rates and time-resolved absorption spectroscopy measurements. The decomposition reactions are initiated using a nanosecond YAG laser and their kinetics is followed by time-resolved absorption spectroscopy. The results obtained for two explosives, nitromethane (NM) and HMX are presented in this paper. For NM, a change in reactivity is clearly seen around 25 GPa. Below this pressure, the reaction products are essentially carbon residues whereas at higher pressure, a transient absorption feature is first observed and is followed by the formation of a white amorphous product. For HMX, the evolution of the absorption as a function of time indicates a multi-step reaction mechanism which is found to depend on both the initial pressure and the laser fluence.

Prion Infected Meat-and-Bone Meal Is Still Infectious after Biodiesel Production

PubMed Central

Bruederle, Cathrin E.; Hnasko, Robert M.; Kraemer, Thomas; Garcia, Rafael A.; Haas, Michael J.; Marmer, William N.; Carter, John Mark

2008-01-01

The epidemic of bovine spongiform encephalopathy (BSE) has led to a world-wide drop in the market for beef by-products, such as Meat-and-Bone Meal (MBM), a fat-containing but mainly proteinaceaous product traditionally used as an animal feed supplement. While normal rendering is insufficient, the production of biodiesel from MBM has been suggested to destroy infectivity from transmissible spongiform encephalopathies (TSEs). In addition to producing fuel, this method simultaneously generates a nutritious solid residue. In our study we produced biodiesel from MBM under defined conditions using a modified form of alkaline methanolysis. We evaluated the presence of prion in the three resulting phases of the biodiesel reaction (Biodiesel, Glycerol and Solid Residue) in vitro and in vivo. Analysis of the reaction products from 263K scrapie infected MBM led to no detectable immunoreactivity by Western Blot. Importantly, and in contrast to the biochemical results the solid MBM residue from the reaction retained infectivity when tested in an animal bioassay. Histochemical analysis of hamster brains inoculated with the solid residue showed typical spongiform degeneration and vacuolation. Re-inoculation of these brains into a new cohort of hamsters led to onset of clinical scrapie symptoms within 75 days, suggesting that the specific infectivity of the prion protein was not changed during the biodiesel process. The biodiesel reaction cannot be considered a viable prion decontamination method for MBM, although we observed increased survival time of hamsters and reduced infectivity greater than 6 log orders in the solid MBM residue. Furthermore, results from our study compare for the first time prion detection by Western Blot versus an infectivity bioassay for analysis of biodiesel reaction products. We could show that biochemical analysis alone is insufficient for detection of prion infectivity after a biodiesel process. PMID:18698417

Comparative efficacy of microwave, visible light and ultrasound irradiation for green synthesis of dihydropyrimidinones in fruit juice medium

NASA Astrophysics Data System (ADS)

Pramanik, Tanay; Padan, Simarjit Kaur; Gupta, Richa; Bedi, Pooja; Singh, Gurinderpal

2017-07-01

Dihydropyrimidinones (DHPM) were synthesized via multi component condensation reaction employing urea, ethyl acetoacetate and aromatic aldehydes as reactants. Apple, pomegranate, grape juice were used individually as biodegradable, eco friendly, and green reaction medium whereas microwave, visible light and ultrasound irradiation were applied individually as green source of energy for carrying out the aforesaid reactions. It was observed that the reactions under microwave irradiation were taking minimum time to go for completion whereas the reactions under ultrasound and visible light irradiation were taking approximately same time duration to form products. This is the first of its kind study where the three different reaction methodologies based on three different sources of green energies were compared with each other for their effectiveness and efficiency towards multi component condensation reactions.

Reactivity of seventeen- and nineteen-valence electron complexes in organometallic chemistry

NASA Technical Reports Server (NTRS)

Stiegman, Albert E.; Tyler, David R.

1986-01-01

A guideline to the reactivity of 17- and 19-valence electron species in organometallic chemistry is proposed which the authors believe will supersede all others. The thesis holds that the reactions of 17-electron metal radicals are associatively activated with reactions proceeding through a 19-valence electron species. The disparate reaction chemistry of the 17-electron metal radicals are unified in terms of this associative reaction pathway, and the intermediacy of 19-valence electron complexes in producing the observed products is discussed. It is suggested that related associatively activated pathways need to be considered in some reactions that are thought to occur by more conventional routes involving 16- and 18-electron intermediates. The basic reaction chemistry and electronic structures of these species are briefly discussed.

Degradation of hydraulic fracturing additive 2-butoxyethanol using heat activated persulfate in the presence of shale rock.

PubMed

Manz, Katherine E; Carter, Kimberly E

2018-09-01

Changes in fluid composition during hydraulic fracturing (HF) for natural gas production can impact well productivity and the water quality of the fluids returning to the surface during productivity. Shale formation conditions can influence the extent of fluid transformation. Oxidizers, such as sodium persulfate, likely play a strong role in fluid transformation. This study investigates the oxidation of 2-butoxyethanol (2-BE), a surfactant used in HF, by sodium persulfate in the presence of heat, pH changes, Fe(II), and shale rock. Increasing temperature and Fe(II) concentrations sped up 2-BE oxidation, while pH played little to no role in 2-BE degradation. The presence of shale rock impeded 2-BE oxidation with increasing shale concentrations causing decreasing pseudo-first-order reaction rate constant to be observed. Over the course of reactions containing shales, dissolved solids were tracked to better understand how reactions with minerals in the shale impact water quality. Copyright © 2018 Elsevier Ltd. All rights reserved.

State-to-State Mode Specificity: Energy Sequestration and Flow Gated by Transition State.

PubMed

Zhao, Bin; Sun, Zhigang; Guo, Hua

2015-12-23

Energy flow and sequestration at the state-to-state level are investigated for a prototypical four-atom reaction, H2 + OH → H + H2O, using a transition-state wave packet (TSWP) method. The product state distribution is found to depend strongly on the reactant vibrational excitation, indicating mode specificity at the state-to-state level. From a local-mode perspective, it is shown that the vibrational excitation of the H2O product derives from two different sources, one attributable to the energy flow along the reaction coordinate into the newly formed OH bond and the other due to the sequestration of the vibrational energy in the OH spectator moiety during the reaction. The analysis provided a unified interpretation of some seemingly contradicting experimental observations. It is further shown that the transfer of vibrational energy from the OH reactant to H2O product is gated by the transition state, accomplished coherently by multiple TSWPs with the corresponding OH vibrational excitation.

Preference for internucleotide linkages as a function of the number of constituents in a mixture

NASA Technical Reports Server (NTRS)

Kanavarioti, A.

1998-01-01

Phosphoimidazolide-activated ribomononucleotides (*pN; see Scheme I) are useful substrates for the nonenzymatic synthesis of oligonucleotides. In the presence of metal ions dilute neutral aqueous solutions of *pN (0.01 M) typically yield only small amounts of dimers and traces of oligomers; most of *pN hydrolyzes to yield nucleoside 5'-monophosphate (5'NMP). An earlier investigation of *pN reactions in highly concentrated aqueous solutions (up to 1.4 M) showed, as expected, that the percentage yield of the condensation products increases and the yield of the hydrolysis product correspondingly decreases with *pN concentration (Kanavarioti 1997). Here we report product distributions in reactions with one, two, or three reactive components at the same total nucleotide concentration. *pN used as substrates were the nucleoside 5'-phosphate 2-methylimidazolides, 2-MeImpN, with N = cytidine (C), uridine (U), or guanosine (G). Reactions were conducted as self-condensations, i. e., one nucleotide only, with two components in the three binary U,C, U,G, and C,G mixtures, and with three components in the ternary U,C, G mixture. The products are 5'NMP, 5',5'-pyrophosphate-, 2',5'-, 3', 5'-linked dimers, cyclic dimers, and a small percentage of longer oligomers. The surprising finding was that, under identical conditions, including the same total monomer concentration, the product distribution differs substantially from one reaction to another, most likely due to changing intermolecular interactions depending on the constituents. Even more unexpected was the observed trend according to which reactions of the U,C,G mixture produce the highest yield of internucleotide-linked dimers, whereas the self-condensations produce the least and the reactions with the binary mixtures produce yields that fall in between. What is remarkable is that the approximately two-fold increase in the percentage yield of internucleotide-linked dimers is not due to a concentration effect or a catalyst, but to the increased complexity of the system from a single to two and three components. These observations, perhaps, provide an example of how increased complexity in relatively simple chemical systems leads to organization of the material and consequently to chemical evolution. A possible link between prebiotic chemistry and the postulated RNA world is discussed.

Fusion-fission and quasifission in the reactions with heavy ions leading to the formation of Hs

NASA Astrophysics Data System (ADS)

Itkis, I. M.; Itkis, M. G.; Knyazheva, G. N.; Kozulin, E. M.

2012-10-01

Mass and energy distributions of binary reaction products obtained in the reactions 22Ne+249Cf,26Mg+248Cm,36S+238U and 58Fe+208Pb leading to Hs isotopes have been measured. At energies below the Coulomb barrier the bimodal fission of Hs*, formed in the reaction 26Mg+248Cm, is observed. In the reaction 36S+238U the considerable part of the symmetric fragments arises from the quasifission process. At energies above the Coulomb barrier the symmetric fragments originate mainly from fusion-fission process for both reactions with Mg and S ions. In the case of the 58Fe+208Pb reaction the quasifission process dominates at all measured energies. The pre- and post-scission neutron multiplicities as a function of the fragment mass have been obtained for the reactions studied.

Reaction front dynamics under shear flow for arbitrary Damköhler numbers

NASA Astrophysics Data System (ADS)

Bandopadhyay, Aditya; Méheust, Yves; Le Borgne, Tanguy

2016-04-01

Reaction fronts where two reactive fluids displace one another play an important role in a range of applications, including contaminant plume transport and reaction, soil and aquifer remediation, CO2 sequestration, geothermal dipoles and the development of hotspots of reaction in mixing zones. The background flow induces enhanced mixing, and therefore reaction, through interfacial shear. Hence the coupling of fluid flow with chemical reactions is pivotal in understanding and quantifying effective reaction kinetics in reaction fronts. While this problem has been addressed in the limit of fast reactions (e.g. de Simoni 2005, Le Borgne 2014), in natural systems reactions can span a large range of Damköhler numbers since their characteristic reaction times vary over a large range of typical values. Here the coupling of shear flow and reversible chemical reactions is studied for a reaction front with initially separated reactants at arbitrary Damköhler numbers. Approximate analytical expressions for the global production rate are derived based on a reactive lamella approach. We observe three distinct regimes, each of them characterized by different scalings of the global production rate and width of the reactive zone. We describe the dependency of these scalings and the associated characteristic transition times as a function of Damköhler and Péclet numbers. These results are validated against 2D numerical simulations. The study is expected to shed light on the inherently complex cases of reactive mixing with varying reaction rates under the influence of an imposed flow. de Simoni et al. (2005) Water Resour. Res., 41, W11410 Le Borgne et al. (2014) GRL, 41(22), 7898

Drug-enhanced carbon monoxide production from heme by cytochrome P450 reductase.

PubMed

Vukomanovic, Dragic; Rahman, Mona N; Jia, Zongchao; Nakatsu, Kanji

2017-01-01

Carbon monoxide (CO) formed endogenously is considered to be cytoprotective, and the vast majority of CO formation is attributed to the degradation of heme by heme oxygenases-1 and -2 (HO-1, HO-2). Previously, we observed that brain microsomes containing HO-2 produced many-fold more CO in the presence of menadione and its congeners; herein we explored these observations further. We determined the effects of various drugs on CO production of rat brain microsomes and recombinant human cytochrome P450 reductase (CPR); CO was measured by gas chromatography with reductive detection. Brain microsomes of Sprague-Dawley rats or recombinant human cytochrome P450 reductase (CPR) were incubated with NADPH and various drugs in closed vials in phosphate buffer at pH 7.4 and 37°C. After 15 minutes, the reaction was stopped by cooling in dry ice, and the headspace gas was analyzed for CO production using gas chromatography with reductive (mercuric oxide) detection. We observed drug-enhanced CO production in the presence of both microsomes and recombinant CPR alone; the presence of HO was not required. A range of structurally diverse drugs were capable of amplifying this CO formation; these molecules had structures consistent with redox cycling capability. The addition of catalase to a reaction mixture, that contained activating drugs, inhibited the production of CO. Drug-enhanced CO formation can be catalyzed by CPR. The mechanism of CPR activation was not through classical drug-receptor mediation. Redox cycling may be involved in the drug-induced amplification of CO production by CPR through the production of reactive oxygen species.

Conformational dependence of a protein kinase phosphate transfer reaction.

PubMed

Henkelman, Graeme; LaBute, Montiago X; Tung, Chang-Shung; Fenimore, P W; McMahon, Benjamin H

2005-10-25

Atomic motions and energetics for a phosphate transfer reaction catalyzed by the cAMP-dependent protein kinase are calculated by plane-wave density functional theory, starting from structures of proteins crystallized in both the reactant conformation (RC) and the transition-state conformation (TC). In TC, we calculate that the reactants and products are nearly isoenergetic with a 20-kJ/mol barrier, whereas phosphate transfer is unfavorable by 120 kJ/mol in the RC, with an even higher barrier. With the protein in TC, the motions involved in reaction are small, with only P(gamma) and the catalytic proton moving >0.5 A. Examination of the structures reveals that in the RC the active site cleft is not completely closed and there is insufficient space for the phosphorylated serine residue in the product state. Together, these observations imply that the phosphate transfer reaction occurs rapidly and reversibly in a particular conformation of the protein, and that the reaction can be gated by changes of a few tenths of an angstrom in the catalytic site.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ota, S.; Burke, J. T.; Casperson, R. J.

Here, the effect of the production mechanism on the decay of a compound nucleus is investigated. The nucleus 90Zr was produced by three different reactions, namely 90Zr (p,p') 90Zr, 91Zr (p,d) 90Zr, and 92Zr (p,t) 90Zr , which served as surrogate reactions for 89Zr (n,γ). The spin-parity (J π) distributions of the states populated by these reactions were studied to investigate the surrogate reaction approach, which aims at indirectly determining cross sections for compound-nuclear reactions involving unstable targets such as 89Zr. Discrete γ rays, associated with transitions in 90Zr and 89Zr, were measured in coincidence with light ions for scatteringmore » angles of 25°–60° and 90Zr excitation energies extending above the neutron separation energy. The measured transition systematics were used to gain insights into the J π distributions of 90Zr. The 90Zr (p,p') reaction was found to produce fewer γ rays associated with transitions involving high spin states (J = 6–8 ℏ) than the other two reactions, suggesting that inelastic scattering preferentially populates states in 90Zr that have lower spins than those populated in the transfer reactions investigated. The γ-ray production was also observed to vary by factors of 2–3 with the angle at which the outgoing particle was detected. These findings are relevant to the application of the surrogate reaction approach.« less

Electronic quenching of O({sup 1}D) by Xe: Oscillations in the product angular distribution and their dependence on collision energy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Garofalo, Lauren A.; Smith, Mica C.; Dagdigian, Paul J., E-mail: pjdagdigian@jhu.edu

2015-08-07

The dynamics of the O({sup 1}D) + Xe electronic quenching reaction was investigated in a crossed beam experiment at four collision energies. Marked large-scale oscillations in the differential cross sections were observed for the inelastic scattering products, O({sup 3}P) and Xe. The shape and relative phases of the oscillatory structure depend strongly on collision energy. Comparison of the experimental results with time-independent scattering calculations shows qualitatively that this behavior is caused by Stueckelberg interferences, for which the quantum phases of the multiple reaction pathways accessible during electronic quenching constructively and destructively interfere.

HSO2+ Formation from Ion-Molecule Reactions of SO2⋅+ with Water and Methane: Two Fast Reactions with Reverse Temperature-Dependent Kinetic Trend.

PubMed

Cartoni, Antonella; Catone, Daniele; Bolognesi, Paola; Satta, Mauro; Markus, Pal; Avaldi, Lorenzo

2017-05-17

In this work an experimental and theoretical study on the formation of HSO 2 + ion from the SO 2 ⋅+ +CH 4 and SO 2 ⋅+ +H 2 O ion-molecule reactions at different temperatures is reported. Tunable synchrotron radiation was used to produce the SO 2 ⋅+ ion in excited ro-vibrational levels of the ionic ground state X 2 A 1 and mass spectrometry was employed to identify the product ions. Calculations in the frame of the density functional theory and variational transition state theory were combined to explore the dynamics of the reactions. The experimental results show that HSO 2 + is the only product in both reactions. Its yield decreases monotonically with photon energy in the SO 2 ⋅+ +H 2 O reaction, while it decreases at first and then increases in the SO 2 ⋅+ +CH 4 reaction. Theory confirms this trend by calculating the rate constants at different temperatures and explains the results by means of the polar, spin and charge effects as well as structural reorganization occurring in the reaction coordinate. The dynamic behavior observed in these two reactions is of general and fundamental interest. It can also provide some insights on the role of these reactions in astrochemistry as well as in their use as models for bond-activation reactions. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Atmospheric reaction of Cl + methacrolein: a theoretical study on the mechanism, and pressure- and temperature-dependent rate constants.

PubMed

Sun, Cuihong; Xu, Baoen; Zhang, Shaowen

2014-05-22

Methacrolein is a major degradation product of isoprene, the reaction of methacrolein with Cl atoms may play some roles in the degradation of isoprene where these species are relatively abundant. However, the energetics and kinetics of this reaction, which govern the reaction branching, are still not well understood so far. In the present study, two-dimensional potential energy surfaces were constructed to analyze the minimum energy path of the barrierless addition process between Cl and the C═C double bond of methacrolein, which reveals that the terminal addition intermediate is directly formed from the addition reaction. The terminal addition intermediate can further yield different products among which the reaction paths abstracting the aldehyde hydrogen atom and the methyl hydrogen atom are dominant reaction exits. The minimum reaction path for the direct aldehydic hydrogen atom abstraction is also obtained. The reaction kinetics was calculated by the variational transition state theory in conjunction with the master equation method. From the theoretical model we predicted that the overall rate constant of the Cl + methacrolein reaction at 297 K and atmospheric pressure is koverall = 2.3× 10(-10) cm(3) molecule(-1) s(-1), and the branching ratio of the aldehydic hydrogen abstraction is about 12%. The reaction is pressure dependent at P < 10 Torr with the high pressure limit at about 100 Torr. The calculated results could well account for the experimental observations.

A combined plant and reaction chamber setup to investigate the effect of pollution and UV-B radiation on biogenic emissions

NASA Astrophysics Data System (ADS)

Timkovsky, J.; Gankema, P.; Pierik, R.; Holzinger, R.

2012-12-01

Biogenic emissions account for almost 90% of total non-methane organic carbon emissions in the atmosphere. The goal of this project is to study the effect of pollution (ozone, NOx) and UV radiation on the emission of real plants. We have designed and built a setup where we combine plant chambers with a reaction chamber (75L volume) allowing the addition of pollutants at different locations. The main analytical tool is a PTR-TOF-MS instrument that can be optionally coupled with a GC system for improved compound identification. The setup is operational since March 2012 and first measurements indicate interesting results, three types of experiments will be presented: 1. Ozonolysis of b-pinene. In this experiment the reaction chamber was flushed with air containing b-pinene at approximate levels of 50 nmol/mol. After ~40 min b-pinene levels reached equilibrium in the reaction chamber and a constant supply of ozone was provided. Within 30 minutes this resulted in a 10 nmol/mol decrease of b-pinene levels in accordance with a reaction rate constant of 1.5*10-17 cm3molec-1s-1 and a residence time of 10 minutes in the reaction chamber. In addition we observed known oxidation products such as formaldehyde, acetone, and nopinone the molar yields of which were also in accordance with reported values. 2. Ozonolysis of biogenic emissions from tomato plants. The air containing the emissions from tomato plants was supplied to the reaction chamber. After adding ozone we observed the decrease of monoterpene concentrations inside the reaction chamber. The observed decrease is consistent for online PTR-MS and GC/PTR-MS measurements. Several ozonolysis products have been observed in the chamber. 3. The effect of UV-B radiation on biogenic emissions of tomato plants. Tomato plants were exposed to UV-B radiation and their emissions measured during and after the treatment. We observed significant changes in the emissions of volatile organic compounds, with specific compounds increasing at different times during the first 24h of the experiment. In situ BVOC emission changes as response to UV-B radiation provide interesting clues to the biological functions of the emitted compounds. These first results show the potential of this system to be a powerful tool to study the effect of pollution and UV radiation on real emissions from plants.

Impact of the propylene glycol-water-borax coolant on material recovery operations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Duerksen, W.K.; Taylor, P.A.

1983-05-01

The reaction of the propylene glycol-water-borax coolant with nitric acid has now been studied in some detail. This document is intended to provide a summary of the results. Findings are summarized under nine headings. Tests have also been conducted to determine if the new coolant would have any adverse effects on the uranium recycle systems. Experiments were scientifically designed after observation of the production operations so that accurate response to the immediate production concerns could be provided. Conclusions from these studies are: formation of glycol nitrates is very improbable; the reaction of concentrated (70%) nitric acid with pure propylene glycolmore » is very violent and hazardous; dilution of the nitric acid-glycol mixture causes a drastic decrease in the rate and intensity of the reaction; the mechanism of the nitric acid propylene glycol reaction is autocatalytic in nitrous acid; no reaction is observed between coolant and 30% nitric acid unless the solution is heated; the coolant reacts fairly vigorously with 55% nitric acid after a concentration-dependent induction time; experiments showed that the dissolution of uranium chips that had been soaked in coolant proceeded at about the same rate as if the chips had not previously contacted glycol; thermodynamic calculations show that the enthalpy change (heat liberated) by the reaction of nitric acid (30%) with propylene glycol is smaller than if the same amount of nitric acid reacted with uranium. Each of these conclusions is briefly discussed. The effect of new coolant on uranium recycle operations is then briefly discussed.« less

The Calvin Cycle Inevitably Produces Sugar-Derived Reactive Carbonyl Methylglyoxal During Photosynthesis: A Potential Cause of Plant Diabetes

PubMed Central

Takagi, Daisuke; Inoue, Hironori; Odawara, Mizue; Shimakawa, Ginga; Miyake, Chikahiro

2014-01-01

Sugar-derived reactive carbonyls (RCs), including methylglyoxal (MG), are aggressive by-products of oxidative stress known to impair the functions of multiple proteins. These advanced glycation end-products accumulate in patients with diabetes mellitus and cause major complications, including arteriosclerosis and cardiac insufficiency. In the glycolytic pathway, the equilibration reactions between dihydroxyacetone phosphate and glyceraldehyde 3-phosphate (GAP) have recently been shown to generate MG as a by-product. Because plants produce vast amounts of sugars and support the same reaction in the Calvin cycle, we hypothesized that MG also accumulates in chloroplasts. Incubating isolated chloroplasts with excess 3-phosphoglycerate (3-PGA) as the GAP precursor drove the equilibration reaction toward MG production. The rate of oxygen (O2) evolution was used as an index of 3-PGA-mediated photosynthesis. The 3-PGA- and time-dependent accumulation of MG in chloroplasts was confirmed by HPLC. In addition, MG production increased with an increase in light intensity. We also observed a positive linear relationship between the rates of MG production and O2 evolution (R = 0.88; P < 0.0001). These data provide evidence that MG is produced by the Calvin cycle and that sugar-derived RC production is inevitable during photosynthesis. Furthermore, we found that MG production is enhanced under high-CO2 conditions in illuminated wheat leaves. PMID:24406631

Synthesis of nano-sized crystalline oxide ion conducting fluorite-type Y 2O 3-doped CeO 2 using perovskite-like BaCe 0.9Y 0.1O 2.95 (BCY) and study of CO 2 capture properties of BCY

NASA Astrophysics Data System (ADS)

Sneha, B. R.; Thangadurai, V.

2007-10-01

Formation of nano-sized Y 2O 3-doped CeO 2 (YCO) was observed in the chemical reaction between proton conducting Y 2O 3-doped BaCeO 3 (BCY) and CO 2 in the temperature range 700-1000 °C, which is generally prepared by wet-chemical methods that include sol-gel, hydrothermal, polymerization, combustion, and precipitation reactions. BCY can capture CO 2 of 0.13 g per ceramic gram at 700 °C, which is comparable to that of the well-known Li 2ZrO 3 (0.15 g per ceramic gram at 600 °C). Powder X-ray diffraction (PXRD), energy dispersive X-ray analysis (EDX), laser particle size analysis (LPSA), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and ac impedance spectroscopy were employed to characterize the reaction product obtained from reaction between BCY and CO 2 and subsequent acid washing. PXRD study reveals presence of fluorite-like CeO 2 ( a=5.410 (1) Å) structure and BaCO 3 in reaction products. TEM investigation of the acid washed product showed the formation of nano-sized material with particle sizes of about 50 nm. The electrical conductivity of acid washed product (YCO) in air was found to be about an order higher than the undoped CeO 2 reported in the literature.

Carbon Isotope Measurements of Experimentally-Derived Hydrothermal Mineral-Catalyzed Organic Products by Pyrolysis-Isotope Ratio Mass Spectrometry

NASA Technical Reports Server (NTRS)

Socki, Richard A.; Fu, Qi; Niles, Paul B.

2011-01-01

We report results of experiments to measure the C isotope composition of mineral catalyzed organic compounds derived from high temperature and high pressure synthesis. These experiments make use of an innovative pyrolysis technique designed to extract and measure C isotopes. To date, our experiments have focused on the pyrolysis and C isotope ratio measurements of low-molecular weight intermediary hydrocarbons (organic acids and alcohols) and serve as a proof of concept for making C and H isotope measurements on more complicated mixtures of solid-phase hydrocarbons and intermediary products produced during high temperature and high pressure synthesis on mineral-catalyzed surfaces. The impetus for this work stems from recently reported observations of methane detected within the Martian atmosphere [1-4], coupled with evidence showing extensive water-rock interaction during Martian history [5-7]. Methane production on Mars could be the result of synthesis by mineral surface-catalyzed reduction of CO2 and/or CO by Fischer-Tropsch Type (FTT) reactions during serpentization reactions [8,9]. Others have conducted experimental studies to show that FTT reactions are plausible mechanisms for low-molecular weight hydrocarbon formation in hydrothermal systems at mid-ocean ridges [10-12]. Further, recent experiments by Fu et al. [13] focus on examining detailed C isotope measurements of hydrocarbons produced by surface-catalyzed mineral reactions. Work described in this paper details the experimental techniques used to measure intermediary organic reaction products (alcohols and organic acids).

Harnessing the Efficiency of 0(1D) Insertion Reactions for Prebiotic Astrochemistry

NASA Astrophysics Data System (ADS)

Widicus Weaver, Susanna

We propose a THz spectroscopic study of the small prebiotic molecules aminomethanol, methanediol, and methoxymethanol. These target molecules are predicted as the dominant products of photo-driven grain surface chemistry in interstellar environments, and are precursors to important prebiotic molecules like sugars and amino acids. These molecules are also expected to be major contributors to the spectral line density in the submillimeter spectral surveys from the Herschel and SOFIA observatories. We will use our custom mixing source to produce these molecules through O(1D) insertion reactions with the precursor molecules methyl amine, methanol, and dimethyl ether, respectively. We will then record their rotational spectra across the THz frequency range using our existing submillimeter spectrometer. This research will increase the science return from NASA missions because the target molecules serve as tracers of the simplest organic chemistry that can occur in starforming regions. This chemistry begins with methanol, which is the predominant organic molecule observed in interstellar ices. Methanol photodissociation leads to small organic radicals such as CH3O, CH2OH, and CH3. These radicals can undergo combination reactions on interstellar ices to form many of the complex organic molecules that are routinely observed in star-forming regions. Our target molecules aminomethanol, methanediol, and methoxymethanol are some of the simplest molecules that can form from this type of chemistry, and serve as tracers of ice mantle liberation in star-forming regions. These molecules also participate in gas-phase reactions that lead to amino acids and sugars, and as such are fundamentally important prebiotic molecules in interstellar environments. These types of small organic molecules also have high spectral line density, and are major contributors to line confusion in observational spectral surveys such as those conducted by Herschel and SOFIA. Therefore, the proposed research will aid in full data interpretation from Herschel and SOFIA observations. Currently there is no spectral information available for these molecules to guide observational studies, despite their importance in astrochemistry. This is because these molecules are difficult to study in laboratory settings due to their instability and reactivity. We are using highly exothermic O(1D) insertion reactions to produce these molecules in a supersonic expansion, and investigating the products using THz spectroscopy. This work builds on the work involved in our previous APRA award (Grant NNX11AI07G) "New THz Tools to Support Herschel Observations: Integrative Studies in Laboratory Spectroscopy, Observational Astronomy, and Chemical Modeling". In this previous award, we laid the groundwork for these experiments by constructing and benchmarking the spectrometer, designing and testing the molecular source used for the O(1D) reactions, and studying the proposed formation reactions for the laboratory work through computational studies. We have confirmed production of methanol from O(1D) insertion into methane, and then applied this chemistry to produce vinyl alcohol from ethylene. We have now also obtained preliminary spectra of aminomethanol. Here we propose to extend this work by finishing the aminomethanol characterization as well as examining methanediol and methoxymethanol during the next proposal period.

Progress of Chiral Schiff Bases with C1 Symmetry in Metal-Catalyzed Asymmetric Reactions.

PubMed

Hayashi, Masahiko

2016-12-01

In this Personal Account, various chiral Schiff base-metal-catalyzed enantioselective organic reactions are reported; the Schiff bases used were O,N,O- as well as N,N,P-tridentate ligands and N,N-bidentate ligands having C 1 symmetry. In particular, the enantioselective addition of trimethylsilyl cyanide, dialkylzinc, and organozinc halides to aldehydes, enantioselective 1,4-addition of dialkylzinc to cyclic and acyclic enones, and asymmetric allylic oxidation are reported. Typically, ketimine-type Schiff base-metal complexes exhibited higher reactivity and enantioselectivity compared with the corresponding aldimine-type Schiff base-metal complexes. Notably, remarkable ligand acceleration was observed for all reactions. The obtained products can be used as key intermediates for optically active natural products and pharmaceuticals. © 2016 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Magnetic nanoparticles conjugated to chiral imidazolidinone as recoverable catalyst

NASA Astrophysics Data System (ADS)

Mondini, Sara; Puglisi, Alessandra; Benaglia, Maurizio; Ramella, Daniela; Drago, Carmelo; Ferretti, Anna M.; Ponti, Alessandro

2013-11-01

The immobilization of an ad hoc designed chiral imidazolidin-4-one onto iron oxide magnetic nanoparticles (MNPs) is described, to afford MNP-supported MacMillan's catalyst. Morphological and structural analysis of the materials, during preparation, use, and recycle, has been carried out by transmission electron microscopy. The supported catalyst was tested in the Diels-Alder reaction of cyclopentadiene with cinnamic aldehyde, affording the products in good yields and enantiomeric excesses up to 93 %, comparable to those observed with the non-supported catalyst. Recovery of the chiral catalyst has been successfully performed by simply applying an external magnet to achieve a perfect separation of the MNPs from the reaction product. The recycle of the catalytic system has been also investigated. Noteworthy, this immobilized MacMillan's catalyst proved to be able to efficiently promote the reaction in pure water.

Z-Selective iridium-catalyzed cross-coupling of allylic carbonates and α-diazo esters.

PubMed

Thomas, Bryce N; Moon, Patrick J; Yin, Shengkang; Brown, Alex; Lundgren, Rylan J

2018-01-07

A well-defined Ir-allyl complex catalyzes the Z -selective cross-coupling of allyl carbonates with α-aryl diazo esters. The process overrides the large thermodynamic preference for E -products typically observed in metal-mediated coupling reactions to enable the synthesis of Z , E -dieneoates in good yield with selectivities consistently approaching or greater than 90 : 10. This transformation represents the first productive merger of Ir-carbene and Ir-allyl species, which are commonly encountered intermediates in allylation and cyclopropanation/E-H insertion catalysis. Potentially reactive functional groups (aryl halides, ketones, nitriles, olefins, amines) are tolerated owing to the mildness of reaction conditions. Kinetic analysis of the reaction suggests oxidative addition of the allyl carbonate to an Ir-species is rate-determining. Mechanistic studies uncovered a pathway for catalyst activation mediated by NEt 3 .

Missing-mass spectroscopy of the 12C(p ,d ) reaction near the η'-meson production threshold

NASA Astrophysics Data System (ADS)

Tanaka, Y. K.; Itahashi, K.; Fujioka, H.; Ayyad, Y.; Benlliure, J.; Brinkmann, K.-T.; Friedrich, S.; Geissel, H.; Gellanki, J.; Guo, C.; Gutz, E.; Haettner, E.; Harakeh, M. N.; Hayano, R. S.; Higashi, Y.; Hirenzaki, S.; Hornung, C.; Igarashi, Y.; Ikeno, N.; Iwasaki, M.; Jido, D.; Kalantar-Nayestanaki, N.; Kanungo, R.; Knöbel, R.; Kurz, N.; Metag, V.; Mukha, I.; Nagae, T.; Nagahiro, H.; Nanova, M.; Nishi, T.; Ong, H. J.; Pietri, S.; Prochazka, A.; Rappold, C.; Reiter, M. P.; Rodríguez-Sánchez, J. L.; Scheidenberger, C.; Simon, H.; Sitar, B.; Strmen, P.; Sun, B.; Suzuki, K.; Szarka, I.; Takechi, M.; Tanihata, I.; Terashima, S.; Watanabe, Y. N.; Weick, H.; Widmann, E.; Winfield, J. S.; Xu, X.; Yamakami, H.; Zhao, J.; η-PRiME/Super-FRS Collaboration

2018-01-01

Excitation-energy spectra of 11C nuclei near the η'-meson production threshold have been measured by missing-mass spectroscopy using the 12C(p ,d ) reaction. A carbon target has been irradiated with a 2.5 GeV proton beam supplied by the synchrotron SIS-18 at GSI to produce η'-meson bound states in 11C nuclei. Deuterons emitted at 0∘ in the reaction have been momentum analyzed by the fragment separator (FRS), used as a high-resolution spectrometer. No distinct structure due to the formation of η'-mesic states is observed although a high statistical sensitivity is achieved in the experimental spectra. Upper limits on the formation cross sections of η'-mesic states are determined, and thereby a constraint imposed on the η'-nucleus interaction is discussed.

Characterization of thermochemical properties of Al nanoparticle and NiO nanowire composites

PubMed Central

2013-01-01

Thermochemical properties and microstructures of the composite of Al nanoparticles and NiO nanowires were characterized. The nanowires were synthesized using a hydrothermal method and were mixed with these nanoparticles by sonication. Electron microscopic images of these composites showed dispersed NiO nanowires decorated with Al nanoparticles. Thermal analysis suggests the influence of NiO mass ratio was insignificant with regard to the onset temperature of the observed thermite reaction, although energy release values changed dramatically with varying NiO ratios. Reaction products from the fuel-rich composites were found to include elemental Al and Ni, Al2O3, and AlNi. The production of the AlNi phase, confirmed by an ab initio molecular dynamics simulation, was associated with the formation of some metallic liquid spheres from the thermite reaction. PMID:23601907

Characterization of thermochemical properties of Al nanoparticle and NiO nanowire composites

NASA Astrophysics Data System (ADS)

Wen, John Z.; Ringuette, Sophie; Bohlouli-Zanjani, Golnaz; Hu, Anming; Nguyen, Ngoc Ha; Persic, John; Petre, Catalin F.; Zhou, Y. Norman

2013-04-01

Thermochemical properties and microstructures of the composite of Al nanoparticles and NiO nanowires were characterized. The nanowires were synthesized using a hydrothermal method and were mixed with these nanoparticles by sonication. Electron microscopic images of these composites showed dispersed NiO nanowires decorated with Al nanoparticles. Thermal analysis suggests the influence of NiO mass ratio was insignificant with regard to the onset temperature of the observed thermite reaction, although energy release values changed dramatically with varying NiO ratios. Reaction products from the fuel-rich composites were found to include elemental Al and Ni, Al2O3, and AlNi. The production of the AlNi phase, confirmed by an ab initio molecular dynamics simulation, was associated with the formation of some metallic liquid spheres from the thermite reaction.

Characterization of thermochemical properties of Al nanoparticle and NiO nanowire composites.

PubMed

Wen, John Z; Ringuette, Sophie; Bohlouli-Zanjani, Golnaz; Hu, Anming; Nguyen, Ngoc Ha; Persic, John; Petre, Catalin F; Zhou, Y Norman

2013-04-20

Thermochemical properties and microstructures of the composite of Al nanoparticles and NiO nanowires were characterized. The nanowires were synthesized using a hydrothermal method and were mixed with these nanoparticles by sonication. Electron microscopic images of these composites showed dispersed NiO nanowires decorated with Al nanoparticles. Thermal analysis suggests the influence of NiO mass ratio was insignificant with regard to the onset temperature of the observed thermite reaction, although energy release values changed dramatically with varying NiO ratios. Reaction products from the fuel-rich composites were found to include elemental Al and Ni, Al2O3, and AlNi. The production of the AlNi phase, confirmed by an ab initio molecular dynamics simulation, was associated with the formation of some metallic liquid spheres from the thermite reaction.

Comparison of salicylate and D-phenylalanine for detection of hydroxyl radicals in chemical and biological reactions.

PubMed

Bailey, S M; Fauconnet, A L; Reinke, L A

1997-02-01

Hydroxylation of salicylate and D-phenylalanine was measured to test the usefulness of these compounds for hydroxyl radical (HO(•)) detection in chemical and biological systems. When HO(•) were produced by the photolytic decomposition of hydrogen peroxide, nearly equal amounts of 2,5- and 2,3-dihydroxybenzoic acid (DHBA) were produced from salicylate, with catechol as a minor product. In the photolytic reaction, nearly equal concentrations of p-,m-, and o-tyrosine were formed from D-phenylalanine. When salicylate or D-phenylalanine was present with Fenton reagents or in iron(II) autoxidation systems, the relative proportions of hydroxylated products were similar to those observed after photolysis, although less total products were usually detected. In contrast, when similar experiments were conducted with isolated hepatic microsomes and perfused livers, 2,5-DHBA was the primary product from salicylate, and p-tyrosine was the major product from D-phenylalanine. Cytochrome P-450 enzymes can hydroxylate salicylate to produce 2,5-DHBA, and it is likely that phenylalanine hydroxylase produces most of the p-tyrosine detected in hepatic tissues. Thus, although both salicylate and D-phenylalanine are useful probes for hydroxyl radical formation in chemical systems, hydroxylated products formed from enzymatic reactions complicate interpretation of data from both compounds in vivo.

Experimental and theoretical study of the influence of water on hydrolyzed product formation during the feruloylation of vegetable oil.

PubMed

Compton, David L; Evans, Kervin O; Appell, Michael

2017-07-01

Feruloylated vegetable oil is a valuable green bioproduct that has several cosmeceutical applications associated with its inherent anti-oxidant and ultraviolet-absorption properties. Hydrolyzed vegetable oil by-products can influence product quality and consistency. The formation of by-products by residual water in the enzymatic synthesis of feruloylated vegetable oil was investigated using chemical theory and experimental studies by monitoring the reaction over a 22-day period. The hydrolysis of vegetable oil is thermodynamically favored over the hydrolysis of the ethyl ferulate starting material. These results suggest that hydrolyzed vegetable oil products will be experimentally observed in greater concentrations compared to hydrolyzed ethyl ferulate products. Quantum chemical studies identified several reaction mechanisms that explain the formation of side products by water, suggesting that residual water influences product quality. Efforts to reduce residual water can improve product consistency and reduce purification costs. Published 2016. This article is a U.S. Government work and is in the public domain in the USA. Published 2016. This article is a U.S. Government work and is in the public domain in the USA.

Indistinguishability and identifiability of kinetic models for the MurC reaction in peptidoglycan biosynthesis.

PubMed

Hattersley, J G; Pérez-Velázquez, J; Chappell, M J; Bearup, D; Roper, D; Dowson, C; Bugg, T; Evans, N D

2011-11-01

An important question in Systems Biology is the design of experiments that enable discrimination between two (or more) competing chemical pathway models or biological mechanisms. In this paper analysis is performed between two different models describing the kinetic mechanism of a three-substrate three-product reaction, namely the MurC reaction in the cytoplasmic phase of peptidoglycan biosynthesis. One model involves ordered substrate binding and ordered release of the three products; the competing model also assumes ordered substrate binding, but with fast release of the three products. The two versions are shown to be distinguishable; however, if standard quasi-steady-state assumptions are made distinguishability cannot be determined. Once model structure uniqueness is ensured the experimenter must determine if it is possible to successfully recover rate constant values given the experiment observations, a process known as structural identifiability. Structural identifiability analysis is carried out for both models to determine which of the unknown reaction parameters can be determined uniquely, or otherwise, from the ideal system outputs. This structural analysis forms an integrated step towards the modelling of the full pathway of the cytoplasmic phase of peptidoglycan biosynthesis. Copyright © 2010 Elsevier Ireland Ltd. All rights reserved.

Reactions of substituted benzene anions with N and O atoms: Chemistry in Titan's upper atmosphere and the interstellar medium

NASA Astrophysics Data System (ADS)

Wang, Zhe-Chen; Bierbaum, Veronica M.

2016-06-01

The likely existence of aromatic anions in many important extraterrestrial environments, from the atmosphere of Titan to the interstellar medium (ISM), is attracting increasing attention. Nitrogen and oxygen atoms are also widely observed in the ISM and in the ionospheres of planets and moons. In the current work, we extend previous studies to explore the reactivity of prototypical aromatic anions (deprotonated toluene, aniline, and phenol) with N and O atoms both experimentally and computationally. The benzyl and anilinide anions both exhibit slow associative electron detachment (AED) processes with N atom, and moderate reactivity with O atom in which AED dominates but ionic products are also formed. The reactivity of phenoxide is dramatically different; there is no measurable reaction with N atom, and the moderate reactivity with O atom produces almost exclusively ionic products. The reaction mechanisms are studied theoretically by employing density functional theory calculations, and spin conversion is found to be critical for understanding some product distributions. This work provides insight into the rich gas-phase chemistry of aromatic ion-atom reactions and their relevance to ionospheric and interstellar chemistry.

Gas and particulate phase products from the ozonolysis of acenaphthylene

NASA Astrophysics Data System (ADS)

Riva, Matthieu; Healy, Robert M.; Tomaz, Sophie; Flaud, Pierre-Marie; Perraudin, Emilie; Wenger, John C.; Villenave, Eric

2016-10-01

Polycyclic aromatic hydrocarbons (PAHs) are recognized as important secondary organic aerosol (SOA) precursors in the urban atmosphere. In this work, the gas-phase ozonolysis of acenaphthylene was investigated in an atmospheric simulation chamber using a proton transfer reaction time-of-flight-mass spectrometer (PTR-TOF-MS) and an aerosol time-of-flight-mass spectrometer (ATOFMS) for on-line characterization of the oxidation products in the gas and particle phases, respectively. SOA samples were also collected on filters and analyzed by ultra performance liquid chromatography/electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (UPLC/ESI-HR-QTOFMS) and gas chromatography/electron impact ionization-mass spectrometry (GC/EI-MS). The major gas-phase products included a range of oxygenated naphthalene derivatives such as 1,8-naphthalic anhydride, naphthalene 1,8-dicarbaldehyde and naphthaldehyde, as well as a secondary ozonide. Possible reaction mechanisms are proposed for the formation of these products and favoured pathways have been suggested. Many of these products were also found in the particle phase along with a range of oligomeric compounds. The same range of gas and particle phase products was observed in the presence and absence of excess cyclohexane, an OH scavenger, indicating that OH radical production from the ozonolysis of acenaphthylene is negligible. SOA yields in the range 23-37% were determined and indicate that acenaphthylene ozonolysis may contribute to part of the SOA observed in urban areas.

Chemical reaction and dust formation studies in laboratory hydrocarbon plasmas.

NASA Astrophysics Data System (ADS)

Hippler, Rainer; Majumdar, Abhijit; Thejaswini, H. C.

Plasma chemical reaction studies with relevance to, e.g., Titan's atmosphere have been per-formed in various laboratory plasmas [1,2]. Chemical reactions in a dielectric barrier discharge at medium pressure of 250-300 mbar have been studied in CH4 /N2 and CH4 /Ar gas mixtures by means of mass spectrometry. The main reaction scheme is production of H2 by fragmenta-tion of CH4 , but also production of larger hydrocarbons like Cn Hm with n up to 10 including formation of different functional CN groups is observed. [1] A. Majumdar and R. Hippler, Development of dielectric barrier discharge plasma processing apparatus for mass spectrometry and thin film deposition, Rev. Sci. Instrum. 78, 075103 (2007) [2] H.T. Do, G. Thieme, M. Frühlich, H. Kersten, and R. Hippler, Ion Molecule and Dust Particle Formation in Ar/CH4 , Ar/C2 H2 and Ar/C3 H6 Radio-frequency Plasmas, Contrib. Plasma Phys. 45, No. 5-6, 378-384 (2005)

Shock induced reaction of Ni/Al nanopowder mixture.

PubMed

Meng, C M; Wei, J J; Chen, Q Y

2012-11-01

Nanopowder Ni/Al mixture (mixed in Al:Ni = 2:1 stoichiometry) was shock compressed by employing single and two-stage light gas gun. The particle size of Al and Ni are 100-200 nm and 50-70 nm respectively, morphologies of Al and Ni are sphere like either. Recovered product was characterized by scanning electron microscope (SEM) and X-ray diffraction (XRD) analysis. According to the XRD spectrum, the mixed powder undergo complete reaction under shock compression, reaction product consist of Ni2Al3, NiAl and corundum structure Al2O3 compound. Grain size of Ni-Al compound is less than 100 nm. With the shock pressure increasing, the ratio of Ni2Al3 decreased obviously. The corundum crystal size is 400-500 nm according to the SEM observation. The results of shock recovery experiments and analysis show that the threshold pressure for reaction of nano size powder Ni/Al mixture is much less than that of micro size powder.

Formation of N-nitrosodimethylamine (NDMA) from dimethylamine during chlorination.

PubMed

Mitch, William A; Sedlak, David L

2002-02-15

Chlorine disinfection of secondary wastewater effluent and drinking water can result in the production of the potent carcinogen N-nitrosodimethylamine (NDMA) at concentrations of approximately 100 and 10 parts per trillion (ng/L), respectively. Laboratory experiments with potential NDMA precursors indicate that NDMA formation can form during the chlorination of dimethylamine and other secondary amines. The formation of NDMA during chlorination may involve the slow formation of 1,1-dimethylhydrazine by the reaction of monochloramine and dimethylamine followed by its rapid oxidation to NDMA and other products including dimethylcyanamide and dimethylformamide. Other pathways also lead to NDMA formation during chlorination such as the reaction of sodium hypochlorite with dimethylamine. However, the rate of NDMA formation is approximately an order of magnitude slower than that observed when monochloramine reacts with dimethylamine. The reaction exhibits a strong pH dependence due to competing reactions. It may be possible to reduce NDMA formation during chlorination by removing ammonia prior to chlorination, by breakpoint chlorination, or by avoidance of the use of monochloramine for drinking water disinfection.

Effects of macromolecular crowding on biochemical reaction equilibria: a molecular thermodynamic perspective.

PubMed

Hu, Zhongqiao; Jiang, Jianwen; Rajagopalan, Raj

2007-09-01

A molecular thermodynamic model is developed to investigate the effects of macromolecular crowding on biochemical reactions. Three types of reactions, representing protein folding/conformational isomerization, coagulation/coalescence, and polymerization/association, are considered. The reactants, products, and crowders are modeled as coarse-grained spherical particles or as polymer chains, interacting through hard-sphere interactions with or without nonbonded square-well interactions, and the effects of crowder size and chain length as well as product size are examined. The results predicted by this model are consistent with experimentally observed crowding effects based on preferential binding or preferential exclusion of the crowders. Although simple hard-core excluded-volume arguments do in general predict the qualitative aspects of the crowding effects, the results show that other intermolecular interactions can substantially alter the extent of enhancement or reduction of the equilibrium and can even change the direction of the shift. An advantage of the approach presented here is that competing reactions can be incorporated within the model.

Development of a polymerase chain reaction-based assay for the detection of Alternaria fungal contamination in food products.

PubMed

Zur, G; Hallerman, E M; Sharf, R; Kashi, Y

1999-10-01

Alternaria sp. are important fungal contaminants of vegetable, fruit, and grain products, including Alternaria alternata, a contaminant of tomato products. To date, the Howard method, based on microscopic observation of fungal filaments, has been the standard examination for inspection of tomato products. We report development of a polymerase chain reaction (PCR)-based method for detection of Alternaria DNA. PCR primers were designed to anneal to the internal transcribed regions ITS1 and ITS2 of the 5.8S rRNA gene of Alternaria but not to other microbial or tomato DNA. We demonstrate use of the PCR assay to detect Alternaria DNA in experimentally infested and commercially obtained tomato sauce and tomato powder. Use of the PCR method offers a rapid and sensitive assay for the presence of Alternaria DNA in tomato products. The apparent breakdown of DNA in tomato sauce may limit the utility of the assay to freshly prepared products. The assay for tomato powder is not affected by storage time.

Mechanism of Mg2+-Accompanied Product Release in Sugar Nucleotidyltransferases.

PubMed

Vithani, Neha; Ankush Jagtap, Pravin Kumar; Verma, Sunil Kumar; Tripathi, Ravi; Awasthi, Shalini; Nair, Nisanth N; Prakash, Balaji

2018-03-06

The nucleotidyl transfer reaction, catalyzed by sugar nucleotidyltransferases (SNTs), is assisted by two active site Mg 2+ ions. While studying this reaction using X-ray crystallography, we captured snapshots of the pyrophosphate (product) as it exits along a pocket. Surprisingly, one of the active site Mg 2+ ions remains coordinated to the exiting pyrophosphate. This hints at the participation of Mg 2+ in the process of product release, besides its role in catalyzing nucleotidyl transfer. These observations are further supported by enhanced sampling molecular dynamics simulations. Free energy computations suggest that the product release is likely to be rate limiting in SNTs, and the origin of the high free energy barrier for product release could be traced back to the "slow" conformational change of an Arg residue at the exit end of the pocket. These results establish a dual role for Mg 2+ , and propose a general mechanism of product release during the nucleotidyl transfer by SNTs. Copyright © 2018 Elsevier Ltd. All rights reserved.

Millimeter and Submillimeter Studies of O(^1D) Insertion Reactions to Form Molecules of Astrophysical Interest

NASA Astrophysics Data System (ADS)

Hays, Brian; Wehres, Nadine; Deprince, Bridget Alligood; Roy, Althea A. M.; Laas, Jacob; Widicus Weaver, Susanna L.

2015-06-01

While both the number of detected interstellar molecules and their chemical complexity continue to increase, understanding of the processes leading to their formation is lacking. Our research group combines laboratory spectroscopy, observational astronomy, and astrochemical modeling for an interdisciplinary examination of the chemistry of star and planet formation. This talk will focus on our laboratory studies of O(^1D) insertion reactions with organic molecules to produce molecules of astrophysical interest. By employing these reactions in a supersonic expansion, we are able to produce interstellar organic reaction intermediates that are unstable under terrestrial conditions; we then probe the products using millimeter and submillimeter spectroscopy. We benchmarked this setup using the well-studied O(^1D) + methane reaction to form methanol. After optimizing methanol production, we moved on to study the O(^1D) + ethylene reaction to form vinyl alcohol (CH_2CHOH), and the O(^1D) + methyl amine reaction to form aminomethanol (NH_2CH_2OH). Vinyl alcohol measurements have now been extended up to 450 GHz, and the associated spectral analysis is complete. A possible detection of aminomethanol has also been made, and continued spectral studies and analysis are underway. We will present the results from these experiments and discuss future applications of these molecular and spectroscopic techniques.

Indoor Secondary Pollutants from Household Product Emissions inthe Presence of Ozone: A Bench-Scale Chamber Study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Destaillats, Hugo; Lunden, Melissa M.; Singer, Brett C.

2005-10-01

Ozone-driven chemistry is a major source of indoor secondary pollutants of health concern. This study investigates secondary air pollutants formed from reactions between constituents of household products and ozone. Gas-phase product emissions were introduced along with ozone at constant rates into a 198-L Teflon-lined reaction chamber. Gas-phase concentrations of reactive terpenoids and oxidation products were measured. Formaldehyde was a predominant oxidation byproduct for the three studied products, with yields under most conditions of 20-30% with respect to ozone consumed. Acetaldehyde, acetone, glycolaldehyde, formic acid and acetic acid were each also detected for two or three of the products. Immediately uponmore » mixing of reactants, a scanning mobility particle sizer detected particle nucleation events that were followed by a significant degree of ultrafine particle growth. The production of secondary gaseous pollutants and particles depended primarily on the ozone level and was influenced by other parameters such as the air-exchange rate. Hydroxyl radical concentrations in the range 0.04-200 x 10{sup 5} molecules cm{sup -3} were measured. OH concentrations were observed to vary strongly with residual ozone level in the chamber, which was in the range 1-25 ppb, as is consistent with expectations from a simplified kinetic model. In a separate test, we exposed the dry residue of two products to ozone in the chamber and observed the formation of gas-phase and particle-phase secondary oxidation products.« less

Indoor secondary pollutants from household product emissions in the presence of ozone: A bench-scale chamber study.

PubMed

Destaillats, Hugo; Lunden, Melissa M; Singer, Brett C; Coleman, Beverly K; Hodgson, Alfred T; Weschler, Charles J; Nazaroff, William W

2006-07-15

Ozone-driven chemistry is a source of indoor secondary pollutants of potential health concern. This study investigates secondary air pollutants formed from reactions between constituents of household products and ozone. Gas-phase product emissions were introduced along with ozone at constant rates into a 198-L Teflon-lined reaction chamber. Gas-phase concentrations of reactive terpenoids and oxidation products were measured. Formaldehyde was a predominant oxidation byproduct for the three studied products, with yields for most conditions of 20-30% with respect to ozone consumed. Acetaldehyde, acetone, glycolaldehyde, formic acid, and acetic acid were each also detected for two or three of the products. Immediately upon mixing of reactants, a scanning mobility particle sizer detected particle nucleation events that were followed by a significant degree of secondary particle growth. The production of secondary gaseous pollutants and particles depended primarily on the ozone level and was influenced by other parameters such as the air-exchange rate. Hydroxyl radical concentrations in the range 0.04-200 x 10(5) molecules cm(-3) were determined by an indirect method. OH concentrations were observed to vary strongly with residual ozone level in the chamber, which was in the range 1-25 ppb, as is consistent with expectations from a simplified kinetic model. In a separate chamber study, we exposed the dry residue of two products to ozone and observed the formation of gas-phase and particle-phase secondary oxidation products.

Kinetics of the Reactions of F((sup 2)P) and Cl((sup 2)P) with HNO3

NASA Technical Reports Server (NTRS)

Wine, P. H.; Wells, J. R.; Nicovich, J. M.

1997-01-01

The kinetics of the reactions of HNO3 with fluorine (k(sub 1)) and Chlorine (k(sub 2)) atoms have been studied by using a time-resolved long-path laser absorption technique to monitor the appearance of product NO3 radicals following 351-nm pulsed laser photolysis of X2/HNO3/He mixtures (X = F,Cl). Absolute rate coefficients for the F((sup 2)P) + HNO reaction have been determined over the temperature range 260-373 K. Between 260 and 320 K, the data are adequately represented by the Arrhenius expression k(sub 1)(T) = (6.0 +/- 2.6) x 10(exp -12) exp[(40 +/- 120)/T]cu cm/(molecule.s). Between 335 and 373 K, the rate coefficient is found to be (2.0 +/- 0.3) x 10(exp -11)cu cm/(molecule.s) independent of temperature. The observed temperature dependence suggests that reaction proceeds via competing direct abstraction and complex pathways. No NO3 production was observed in the experiments with X equals Cl, thus establishing that k(sub 2)(298 K) is less than 2 x 10(exp -16) cu cm/(molecule.s). The Cl((sup 2)P) + HNO reaction was also investigated by using a pulsed laser photolysis-resonance fluorescence technique to monitor the decay of Cl((sup 2)P). Upper limit values for k(sub 2) obtained from these experiments, in units of 10(exp -16)cu cm/(molecule.s), are 13 at 298 K and 10 at 400 K.

Scope and limitations of the Heck-Matsuda-coupling of phenol diazonium salts and styrenes: a protecting-group economic synthesis of phenolic stilbenes.

PubMed

Schmidt, Bernd; Elizarov, Nelli; Berger, René; Hölter, Frank

2013-06-14

4-Phenol diazonium salts undergo Pd-catalyzed Heck reactions with various styrenes to 4'-hydroxy stilbenes. In almost all cases higher yields and fewer side products were observed, compared to the analogous 4-methoxy benzene diazonium salts. In contrast, the reaction fails completely with 2- and 3-phenol diazonium salts. For these substitution patterns the methoxy-substituted derivatives are superior.

Reactivity of OH and CH3OH Between 22 and 64 K: Modelling the Gas Phase Production of CH3O in Barnard 1B

PubMed Central

Antiñolo, M.; Agúndez, M.; Jiménez, E.; Ballesteros, B.; Canosa, A.; Dib, G. El; Albaladejo, J.; Cernicharo, J.

2016-01-01

In the last years, ultra-low temperature chemical kinetic experiments have demonstrated that some gas-phase reactions are much faster than previously thought. One example is the reaction between OH and CH3OH, which has been recently found to be accelerated at low temperatures yielding CH3O as main product. This finding opened the question of whether the CH3O observed in the dense core Barnard 1b could be formed by the gas-phase reaction of CH3OH and OH. Several chemical models including this reaction and grain-surface processes have been developed to explain the observed abundance of CH3O with little success. Here we report for the first time rate coefficients for the gas-phase reaction of OH and CH3OH down to a temperature of 22 K, very close to those in cold interstellar clouds. Two independent experimental set-ups based on the supersonic gas expansion technique coupled to the pulsed laser photolysis-laser induced fluorescence technique were used to determine rate coefficients in the temperature range 22-64 K. The temperature dependence obtained in this work can be expressed as k(22-64 K) = (3.6 ± 0.1) × 10−12(T/300 K)−(1.0±0.2) cm3 molecule−1 s−1. Implementing this expression in a chemical model of a cold dense cloud results in CH3O/CH3OH abundance ratios similar or slightly lower than the value of ∼ 3 × 10−3 observed in Barnard 1b. This finding confirms that the gas-phase reaction between OH and CH3OH is an important contributor to the formation of interstellar CH3O. The role of grain-surface processes in the formation of CH3O, although it cannot be fully neglected, remains controversial. PMID:27279655

Reactivity of OH and CH3OH Between 22 and 64 K: Modelling the Gas Phase Production of CH3O in Barnard 1B.

PubMed

Antiñolo, M; Agúndez, M; Jiménez, E; Ballesteros, B; Canosa, A; Dib, G El; Albaladejo, J; Cernicharo, J

2016-05-20

In the last years, ultra-low temperature chemical kinetic experiments have demonstrated that some gas-phase reactions are much faster than previously thought. One example is the reaction between OH and CH 3 OH, which has been recently found to be accelerated at low temperatures yielding CH 3 O as main product. This finding opened the question of whether the CH 3 O observed in the dense core Barnard 1b could be formed by the gas-phase reaction of CH 3 OH and OH. Several chemical models including this reaction and grain-surface processes have been developed to explain the observed abundance of CH 3 O with little success. Here we report for the first time rate coefficients for the gas-phase reaction of OH and CH 3 OH down to a temperature of 22 K, very close to those in cold interstellar clouds. Two independent experimental set-ups based on the supersonic gas expansion technique coupled to the pulsed laser photolysis-laser induced fluorescence technique were used to determine rate coefficients in the temperature range 22-64 K. The temperature dependence obtained in this work can be expressed as k (22-64 K) = (3.6 ± 0.1) × 10 -12 ( T/ 300 K) -(1.0±0.2) cm 3 molecule -1 s -1 . Implementing this expression in a chemical model of a cold dense cloud results in CH 3 O/CH 3 OH abundance ratios similar or slightly lower than the value of ∼ 3 × 10 -3 observed in Barnard 1b. This finding confirms that the gas-phase reaction between OH and CH 3 OH is an important contributor to the formation of interstellar CH 3 O. The role of grain-surface processes in the formation of CH 3 O, although it cannot be fully neglected, remains controversial.

Divergent reaction pathways for one-pot, three-component synthesis of novel 4H-pyrano[3,2-h]quinolines under ultrasound irradiation.

PubMed

Al-Bogami, Abdullah S; Saleh, Tamer S; Zayed, Ehab M

2013-09-01

The present paper deal with the multi-component condensation of 8-hydroxy quinoline, aromatic aldehydes, and sulfone derivatives catalyzed by p-toluenesulfonic acid for the synthesis of a series of 4H-pyrano[3,2-h]quinoline derivatives in ethanol under ultrasonic irradiations. We provide a series of quinoline derivatives containing sulfone moiety interesting for biological screening tests. The reactions were carried out under both conventional and ultrasonic irradiation conditions. In general, improvement in rates and yields were observed when reactions were carried out under sonication compared with classical silent conditions. Also, also, sonochemical reaction give different reaction pathway other than silent reaction. These remarkable effects appeared in sonicated reactions can be reasonably interpreted in terms of acoustic cavitation phenomenon. Structures of the products were established on analytical and spectral data. Copyright © 2013 Elsevier B.V. All rights reserved.

G-Quadruplex Folds of the Human Telomere Sequence Alter the Site Reactivity and Reaction Pathway of Guanine Oxidation Compared to Duplex DNA

PubMed Central

Fleming, Aaron M.; Burrows, Cynthia J.

2013-01-01

Telomere shortening occurs during oxidative and inflammatory stress with guanine (G) as the major site of damage. In this work, a comprehensive profile of the sites of oxidation and structures of products observed from G-quadruplex and duplex structures of the human telomere sequence was studied in the G-quadruplex folds (hybrid (K+), basket (Na+), and propeller (K+ + 50% CH3CN)) resulting from the sequence 5’-(TAGGGT)4T-3’ and in an appropriate duplex containing one telomere repeat. Oxidations with four oxidant systems consisting of riboflavin photosensitization, carbonate radical generation, singlet oxygen, and the copper Fenton-like reaction were analyzed under conditions of low product conversion to determine relative reactivity. The one-electron oxidants damaged the 5’-G in G-quadruplexes leading to spiroiminodihydantoin (Sp) and 2,2,4-triamino-2H-oxazol-5-one (Z) as major products as well as 8-oxo-7,8-dihydroguanine (OG) and 5-guanidinohydantoin (Gh) in low relative yields, while oxidation in the duplex context produced damage at the 5’- and middle-Gs of GGG sequences and resulted in Gh being the major product. Addition of the reductant N-acetylcysteine (NAC) to the reaction did not alter the riboflavin-mediated damage sites, but decreased Z by 2-fold and increased OG by 5-fold, while not altering the hydantoin ratio. However, NAC completely quenched the CO3•− reactions. Singlet oxygen oxidations of the G-quadruplex showed reactivity at all Gs on the exterior faces of G-quartets and furnished the product Sp, while no oxidation was observed in the duplex context under these conditions, and addition of NAC had no effect. Because a long telomere sequence would have higher-order structures of G-quadruplexes, studies were also conducted with 5’-(TAGGGT)8-T-3’, and it provided similar oxidation profiles to the single G-quadruplex. Lastly, CuII/H2O2-mediated oxidations were found to be indiscriminate in the damage patterns, and 5-carboxamido-5-formamido-2-iminohydantoin (2Ih) was found to be a major duplex product, while nearly equal yields of 2Ih and Sp were observed in G-quadruplex contexts. These findings indicate that the nature of the secondary structure of folded DNA greatly alters both the reactivity of G toward oxidative stress as well as the product outcome and suggest that recognition of damage in telomeric sequences by repair enzymes may be profoundly different from that of B-form duplex DNA. PMID:23438298

Oxidation of sulfamethoxazole by UVA radiation and modified Fenton reagent: toxicity and biodegradability of by-products.

PubMed

Marciocha, D; Kalka, J; Turek-Szytow, J; Wiszniowski, J; Surmacz-Górska, J

2009-01-01

Improvement of sulfamethoxazole (4-amino-N-(5-methylisoxazol-3-yl)-benzenesulfonamide-SMX) biodegradability using a modified Fenton's reaction has been studied. The modification consists of replacing hydrogen peroxide with atmospheric air and adding copper sulphate as a reaction promoter. Two series of experiments were carried out. The first (Series 1) was conducted using only the catalysts with aeration. In the second series (Series 2), cycles of UVA radiation and aeration were used. During UVA radiation, the removal of sulfamethoxazole proceeds less rapidly than in only aerated solution. After 1.5 h of these two processes, the SMX degradation was 23% in Series 2 and 59% in Series 1. The opposite trend was observed for mineralization and the removal of DOC was about 5% higher in Series 2 than in Series 1. The FTIR spectra of the extracts of reaction products yielded by four organic solvents of varying polarity revealed a wide diversity of functional groups in the post-reaction mixture in comparison to the extracts from sulfamethoxazole solution. Based on FTIR analysis, several oxidation products of sulfamethoxazole are proposed. Apparently, hydroxyl radicals initially attack sulphonamide bonds, resulting in the formation of sulfanilic acid and 3-amino-5-methylisoxazole. Irrespective of the reference organism used in toxicity tests, the post-reaction mixture in the Series 2 was more toxic than the post-reaction mixture in Series 1. In contrast, the biodegradability calculated as BOD(5)/DOC ratio, was higher for post-reaction mixture 2 and amounted to 0.43.

Thermal Decomposition of the Solid Phase of Nitromethane: Ab Initio Molecular Dynamics Simulations

NASA Astrophysics Data System (ADS)

Chang, Jing; Lian, Peng; Wei, Dong-Qing; Chen, Xiang-Rong; Zhang, Qing-Ming; Gong, Zi-Zheng

2010-10-01

The Car-Parrinello molecular dynamics simulations were employed to investigate thermal decomposition of the solid nitromethane. It is found that it undergoes chemical decomposition at about 2200 K under ambient pressure. The initiation of reactions involves both proton transfer and commonly known C-N bond cleavage. About 75 species and 100 elementary reactions were observed with the final products being H2O, CO2, N2, and CNCNC. It represents the first complete simulation of solid-phase explosive reactions reported to date, which is of far-reaching implication for design and development of new energetic materials.

Theoretical Study on the Dynamics of the Reaction of HNO((1)A') with HO2((2)A″).

PubMed

Mousavipour, S Hosein; Asemani, S Somayeh

2015-06-04

We used stochastic one-dimensional chemical master equation (CME) simulation to gain insight into the dynamics of the reaction of HNO((1)A') with HO2((2)A″). The reaction takes place over a multiwell, multichannel potential energy surface that is based on the computations at the CBS-QB3 level of theory. The calculated multipath potential energy surface consists of three potential wells and three van der Waals complexes. In solving the master equation, the Lennard-Jones potential is used to model the collision between the collider gases. The fractional population of different intermediates and products in the early stages of the reaction is examined to determine the role of the energized intermediates and van der Waals complexes on the kinetics of the title reaction. The major products of the title reaction at lower temperatures are OH, HNO2, HNOH, and O2(X(3)Σg(-)). The temperature- and pressure-dependence of the reaction over a wide range of temperature (300-3000 K) and pressure (0.1-2000 Torr) are studied. No sign of pressure dependence was being observed for the title reaction over the stated range of pressure. The calculated rate constants from the CME simulation are compared with those obtained from the RRKM-SSA method that is based on strong collision assumption. Our results indicate that the strong collision assumption increases the calculated rate constant for the formation of the main products (HNO2 + OH) by a factor of 2 at 300 K and 1 atm pressure, compared to the results of CME simulation, although the results are in good agreement at higher temperatures.

Analysis of large oxygenated and nitrated polycyclic aromatic hydrocarbons formed under simulated diesel engine exhaust conditions (by compound fingerprints with SPE/LC-API-MS)

PubMed Central

Adelhelm, Christoph; Niessner, Reinhard; Pöschl, Ulrich

2008-01-01

The analysis of organic compounds in combustion exhaust particles and the chemical transformation of soot by nitrogen oxides are key aspects of assessment and mitigation of the climate and health effects of aerosol emissions from fossil fuel combustion and biomass burning. In this study we present experimental and analytical techniques for efficient investigation of oxygenated and nitrated derivatives of large polycyclic aromatic hydrocarbons (PAHs), which can be regarded as well-defined soot model substances. For coronene and hexabenzocoronene exposed to nitrogen dioxide under simulated diesel exhaust conditions, several reaction products with high molecular mass could be characterized by liquid chromatography-atmospheric pressure chemical (and photo) ionization-mass spectrometry (LC-APCI-MS and LC-APPI-MS). The main products of coronene contained odd numbers of nitrogen atoms (m/z 282, 256, 338), whereas one of the main products of hexabenzocoronene exhibited an even number of nitrogen atoms (m/z 391). Various reaction products containing carbonyl and nitro groups could be tentatively identified by combining chromatographic and mass spectrometric information, and changes of their relative abundance were observed to depend on the reaction conditions. This analytical strategy should highlight a relatively young technique for the characterization of various soot-contained, semi-volatile, and semi-polar reaction products of large PAHs. Figure LC-APCI-MS analysis of nitrated coronene (and HBC): Total-Ion-Chromatogram (TIC), Extracted Ion Chromatograms (EICs) and corresponding mass spectrum (top). PMID:18560812

Integration of whole-cell reaction and product isolation: Highly hydrophobic solvents promote in situ substrate supply and simplify extractive product isolation.

PubMed

Leis, Dorothea; Lauß, Bernhard; Macher-Ambrosch, Robert; Pfennig, Andreas; Nidetzky, Bernd; Kratzer, Regina

2017-09-10

Product isolation from aqueous-organic reaction mixtures that contain high concentrations of whole cells constitutes a challenging task in bioprocessing. Stirring of the biphasic reaction media leads to the formation of solvent droplets coated by cells and other surface active components and an emulsion forms. We used an early focus on phase separation to simplify a whole-cell bioreduction. Octanol, heptanol, hexanol, hexane and dipropylether were tested as co-solvents in the E. coli catalyzed reduction of o-chloroacetophenone. All solvents showed very similar performance in bioreductions and highest yields were obtained with low organic-to-aqueous phase ratios. Reaction mixtures were directly investigated for organic-phase recovery. Phase separation was optimized in small-scale settling experiments and confirmed by the isolation of 20.4g (S)-1-(2-chlorophenyl)ethanol from a 0.5L batch reduction containing 40g CDW /L whole-cell catalyst. Solvent consumption during product isolation could be halved by the simple addition of sodium hydroxide prior to product extraction. Basification to pH 13.5 and three extraction steps with a total of 1.2v/v hexane led to an isolated yield of 87% (97% reduction yield). A general emulsion destabilizing effect under harsh conditions, as extreme pH values and presence of toxic reactants, was observed. Copyright © 2016 The Authors. Published by Elsevier B.V. All rights reserved.

Limonene and its ozone-initiated reaction products attenuate allergic lung inflammation in mice.

PubMed

Hansen, Jitka S; Nørgaard, Asger W; Koponen, Ismo K; Sørli, Jorid B; Paidi, Maya D; Hansen, Søren W K; Clausen, Per Axel; Nielsen, Gunnar D; Wolkoff, Peder; Larsen, Søren Thor

2016-11-01

Inhalation of indoor air pollutants may cause airway irritation and inflammation and is suspected to worsen allergic reactions. Inflammation may be due to mucosal damage, upper (sensory) and lower (pulmonary) airway irritation due to activation of the trigeminal and vagal nerves, respectively, and to neurogenic inflammation. The terpene, d-limonene, is used as a fragrance in numerous consumer products. When limonene reacts with the pulmonary irritant ozone, a complex mixture of gas and particle phase products is formed, which causes sensory irritation. This study investigated whether limonene, ozone or the reaction mixture can exacerbate allergic lung inflammation and whether airway irritation is enhanced in allergic BALB/cJ mice. Naïve and allergic (ovalbumin sensitized) mice were exposed via inhalation for three consecutive days to clean air, ozone, limonene or an ozone-limonene reaction mixture. Sensory and pulmonary irritation was investigated in addition to ovalbumin-specific antibodies, inflammatory cells, total protein and surfactant protein D in bronchoalveolar lavage fluid and hemeoxygenase-1 and cytokines in lung tissue. Overall, airway allergy was not exacerbated by any of the exposures. In contrast, it was found that limonene and the ozone-limonene reaction mixture reduced allergic inflammation possibly due to antioxidant properties. Ozone induced sensory irritation in both naïve and allergic mice. However, allergic but not naïve mice were protected from pulmonary irritation induced by ozone. This study showed that irritation responses might be modulated by airway allergy. However, aggravation of allergic symptoms was observed by neither exposure to ozone nor exposure to ozone-initiated limonene reaction products. In contrast, anti-inflammatory properties of the tested limonene-containing pollutants might attenuate airway allergy.

Nuclear waste viewed in a new light; a synchrotron study of uranium encapsulated in grout.

PubMed

Stitt, C A; Hart, M; Harker, N J; Hallam, K R; MacFarlane, J; Banos, A; Paraskevoulakos, C; Butcher, E; Padovani, C; Scott, T B

2015-03-21

How do you characterise the contents of a sealed nuclear waste package without breaking it open? This question is important when the contained corrosion products are potentially reactive with air and radioactive. Synchrotron X-rays have been used to perform micro-scale in-situ observation and characterisation of uranium encapsulated in grout; a simulation for a typical intermediate level waste storage packet. X-ray tomography and X-ray powder diffraction generated both qualitative and quantitative data from a grout-encapsulated uranium sample before, and after, deliberately constrained H2 corrosion. Tomographic reconstructions provided a means of assessing the extent, rates and character of the corrosion reactions by comparing the relative densities between the materials and the volume of reaction products. The oxidation of uranium in grout was found to follow the anoxic U+H2O oxidation regime, and the pore network within the grout was observed to influence the growth of uranium hydride sites across the metal surface. Powder diffraction analysis identified the corrosion products as UO2 and UH3, and permitted measurement of corrosion-induced strain. Together, X-ray tomography and diffraction provide means of accurately determining the types and extent of uranium corrosion occurring, thereby offering a future tool for isolating and studying the reactions occurring in real full-scale waste package systems. Copyright © 2014 Elsevier B.V. All rights reserved.

Strangeness suppression of q q ¯ creation observed in exclusive reactions

DOE PAGES

Mestayer, M. D.; Park, K.; Adhikari, K. P.; ...

2014-10-10

In this study, we measured the ratios of electroproduction cross sections from a proton target for three exclusive meson-baryon final states: ΛK +, pπ 0, and nπ +, with the CLAS detector at Jefferson Lab. Using a simple model of quark hadronization, we extract qq¯ creation probabilities for the first time in exclusive two-body production, in which only a single qq¯ pair is created. We observe a sizable suppression of strange quark-antiquark pairs compared to nonstrange pairs, similar to that seen in high-energy production.

Strangeness Suppression of qq ¯ Creation Observed in Exclusive Reactions

NASA Astrophysics Data System (ADS)

Mestayer, M. D.; Park, K.; Adhikari, K. P.; Aghasyan, M.; Pereira, S. Anefalos; Ball, J.; Battaglieri, M.; Batourine, V.; Bedlinskiy, I.; Biselli, A. S.; Boiarinov, S.; Briscoe, W. J.; Brooks, W. K.; Burkert, V. D.; Carman, D. S.; Celentano, A.; Chandavar, S.; Charles, G.; Colaneri, L.; Cole, P. L.; Contalbrigo, M.; Cortes, O.; Crede, V.; D'Angelo, A.; Dashyan, N.; De Vita, R.; Deur, A.; Djalali, C.; Doughty, D.; Dupre, R.; Alaoui, A. El; Fassi, L. El; Elouadrhiri, L.; Eugenio, P.; Fedotov, G.; Fleming, J. A.; Forest, T. A.; Garillon, B.; Garçon, M.; Ghandilyan, Y.; Gilfoyle, G. P.; Giovanetti, K. L.; Girod, F. X.; Goetz, J. T.; Golovatch, E.; Gothe, R. W.; Griffioen, K. A.; Guegan, B.; Guidal, M.; Hakobyan, H.; Hanretty, C.; Hattawy, M.; Holtrop, M.; Hughes, S. M.; Hyde, C. E.; Ilieva, Y.; Ireland, D. G.; Jiang, H.; Jo, H. S.; Joo, K.; Keller, D.; Khandaker, M.; Kim, A.; Kim, W.; Koirala, S.; Kubarovsky, V.; Kuleshov, S. V.; Lenisa, P.; Levine, W. I.; Livingston, K.; Lu, H. Y.; MacGregor, I. J. D.; Mayer, M.; McKinnon, B.; Meyer, C. A.; Mirazita, M.; Mokeev, V.; Montgomery, R. A.; Moody, C. I.; Moutarde, H.; Movsisyan, A.; Camacho, C. Munoz; Nadel-Turonski, P.; Niccolai, S.; Niculescu, G.; Niculescu, I.; Osipenko, M.; Ostrovidov, A. I.; Pappalardo, L. L.; Paremuzyan, R.; Peng, P.; Phelps, W.; Pisano, S.; Pogorelko, O.; Pozdniakov, S.; Price, J. W.; Protopopescu, D.; Puckett, A. J. R.; Raue, B. A.; Rimal, D.; Ripani, M.; Rizzo, A.; Rosner, G.; Roy, P.; Sabatié, F.; Saini, M. S.; Schott, D.; Schumacher, R. A.; Simonyan, A.; Sokhan, D.; Strauch, S.; Sytnik, V.; Tang, W.; Tian, Ye; Ungaro, M.; Vernarsky, B.; Vlassov, A. V.; Voskanyan, H.; Voutier, E.; Walford, N. K.; Watts, D. P.; Wei, X.; Weinstein, L. B.; Wood, M. H.; Zachariou, N.; Zhang, J.; Zhao, Z. W.; Zonta, I.; CLAS Collaboration

2014-10-01

We measured the ratios of electroproduction cross sections from a proton target for three exclusive meson-baryon final states: ΛK+, pπ0, and nπ+, with the CLAS detector at Jefferson Lab. Using a simple model of quark hadronization, we extract qq ¯ creation probabilities for the first time in exclusive two-body production, in which only a single qq ¯ pair is created. We observe a sizable suppression of strange quark-antiquark pairs compared to nonstrange pairs, similar to that seen in high-energy production.

Strangeness suppression of q q ¯ creation observed in exclusive reactions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mestayer, M. D.; Park, K.; Adhikari, K. P.

In this study, we measured the ratios of electroproduction cross sections from a proton target for three exclusive meson-baryon final states: ΛK +, pπ 0, and nπ +, with the CLAS detector at Jefferson Lab. Using a simple model of quark hadronization, we extract qq¯ creation probabilities for the first time in exclusive two-body production, in which only a single qq¯ pair is created. We observe a sizable suppression of strange quark-antiquark pairs compared to nonstrange pairs, similar to that seen in high-energy production.

The Path of Carbon in Photosynthesis XI. The Role of Glycolic Acid

DOE R&D Accomplishments Database

Schou, L.; Benson, A. A.; Bassham, J. A.; Calvin, M.

1950-09-11

The metabolism of C{sup 14} labeled glycolic acid by Scenedesmus has been studied using radiochromatographic techniques for the separation and identification of products. When the pH of the medium was 2.8, appreciable assimilation occurred. The products were identical to those observed in C{sup 14}O{sub 2} photosynthesis. A major reaction anaerobically in the dark resulted in incorporation of C{sup 14} in almost equal amounts in the glycine and serine reservoirs. When the algae were illuminated, a diminution in the amount of glycine was observed.

Reactions of CH3SH and CH3SSCH3 with gas-phase hydrated radical anions (H2O)n(•-), CO2(•-)(H2O)n, and O2(•-)(H2O)n.

PubMed

Höckendorf, Robert F; Hao, Qiang; Sun, Zheng; Fox-Beyer, Brigitte S; Cao, Yali; Balaj, O Petru; Bondybey, Vladimir E; Siu, Chi-Kit; Beyer, Martin K

2012-04-19

The chemistry of (H(2)O)(n)(•-), CO(2)(•-)(H(2)O)(n), and O(2)(•-)(H(2)O)(n) with small sulfur-containing molecules was studied in the gas phase by Fourier transform ion cyclotron resonance mass spectrometry. With hydrated electrons and hydrated carbon dioxide radical anions, two reactions with relevance for biological radiation damage were observed, cleavage of the disulfide bond of CH(3)SSCH(3) and activation of the thiol group of CH(3)SH. No reactions were observed with CH(3)SCH(3). The hydrated superoxide radical anion, usually viewed as major source of oxidative stress, did not react with any of the compounds. Nanocalorimetry and quantum chemical calculations give a consistent picture of the reaction mechanism. The results indicate that the conversion of e(-) and CO(2)(•-) to O(2)(•-) deactivates highly reactive species and may actually reduce oxidative stress. For reactions of (H(2)O)(n)(•-) with CH(3)SH as well as CO(2)(•-)(H(2)O)(n) with CH(3)SSCH(3), the reaction products in the gas phase are different from those reported in the literature from pulse radiolysis studies. This observation is rationalized with the reduced cage effect in reactions of gas-phase clusters. © 2012 American Chemical Society

Constraining the Symmetry Energy:. a Journey in the Isospin Physics from Coulomb Barrier to Deconfinement

NASA Astrophysics Data System (ADS)

di Toro, M.; Colonna, M.; Greco, V.; Ferini, G.; Rizzo, C.; Rizzo, J.; Baran, V.; Gaitanos, T.; Prassa, V.; Wolter, H. H.; Zielinska-Pfabe, M.

Heavy Ion Collisions (HIC) represent a unique tool to probe the in-medium nuclear interaction in regions away from saturation. In this work we present a selection of reaction observables in dissipative collisions particularly sensitive to the isovector part of the interaction, i.e.to the symmetry term of the nuclear Equation of State (EoS). At low energies the behavior of the symmetry energy around saturation influences dissipation and fragment production mechanisms. We will first discuss the recently observed Dynamical Dipole Radiation, due to a collective neutron-proton oscillation during the charge equilibration in fusion and deep-inelastic collisions. Important Iso - EOS are stressed. Reactions induced by unstable 132Sn beams appear to be very promising tools to test the sub-saturation Isovector EoS. New Isospin sensitive observables are also presented for deep-inelastic, fragmentation collisions and Isospin equilibration measurements (Imbalance Ratios). The high density symmetry term can be derived from isospin effects on heavy ion reactions at relativistic energies (few AGeV range), that can even allow a "direct" study of the covariant structure of the isovector interaction in the hadron medium. Rather sensitive observables are proposed from collective flows and from pion/kaon production. The possibility of the transition to a mixed hadron-quark phase, at high baryon and isospin density, is finally suggested. Some signatures could come from an expected "neutron trapping" effect. The importance of studying violent collisions with radioactive beams from low to relativistic energies is finally stressed.

Reprint of "How do components of real cloud water affect aqueous pyruvate oxidation?"

NASA Astrophysics Data System (ADS)

Boris, Alexandra J.; Desyaterik, Yury; Collett, Jeffrey L.

2015-01-01

Chemical oxidation of dissolved volatile or semi-volatile organic compounds within fog and cloud droplets in the atmosphere could be a major pathway for secondary organic aerosol (SOA) formation. This proposed pathway consists of: (1) dissolution of organic chemicals from the gas phase into a droplet; (2) reaction with an aqueous phase oxidant to yield low volatility products; and (3) formation of particle phase organic matter as the droplet evaporates. The common approach to simulating aqueous SOA (aqSOA) reactions is photo-oxidation of laboratory standards in pure water. Reactions leading to aqSOA formation should be studied within real cloud and fog water to determine whether additional competing processes might alter apparent rates of reaction as indicated by rates of reactant loss or product formation. To evaluate and identify the origin of any cloud water matrix effects on one example of observed aqSOA production, pyruvate oxidation experiments simulating aqSOA formation were monitored within pure water, real cloud water samples, and an aqueous solution of inorganic salts. Two analysis methods were used: online electrospray ionization high-resolution time-of-flight mass spectrometry (ESI-HR-ToF-MS), and offline anion exchange chromatography (IC) with quantitative conductivity and qualitative ESI-HR-ToF-MS detection. The apparent rate of oxidation of pyruvate was slowed in cloud water matrices: overall measured degradation rates of pyruvate were lower than in pure water. This can be at least partially accounted for by the observed formation of pyruvate from reactions of other cloud water components. Organic constituents of cloud water also compete for oxidants and/or UV light, contributing to the observed slowed degradation rates of pyruvate. The oxidation of pyruvate was not significantly affected by the presence of inorganic anions (nitrate and sulfate) at cloud-relevant concentrations. Future bulk studies of aqSOA formation reactions using simplified simulated cloud solutions and model estimates of generated aqSOA mass should take into account possible generation of, or competition for, oxidant molecules by organic components found in the complex matrices typically associated with real atmospheric water droplets. Additionally, it is likely that some components of real atmospheric waters have not yet been identified as aqSOA precursors, but could be distinguished through further simplified bulk oxidations of known atmospheric water components.

Three different product types from reactions of lithiated cyclic aminals with trivalent organometal chlorides.

PubMed

Hellmann, Benjamin J; Kamps, Ina; Mix, Andreas; Neumann, Beate; Stammler, Hans-Georg; Mitzel, Norbert W

2010-09-21

The reaction of 2-lithio-1,3,5-trimethyl-1,3,5-triazacyclohexane with YCp(2)Cl leads to the formation of a donor-functionalised mono-anionic amide ligand, 1,3,5-trimethyl-2-(methylamidomethyl)-1,3,5-triazacyclohexane, bonded to the YCp(2) unit. The reaction involves a cleavage of the 1,3,5-triazacyclohexane ring and such a cleavage is also observed in the analogous reaction with (Me(3)C)(2)GaCl, where a MeN[double bond, length as m-dash]CH(-) fragment is formed. No such cleavage occurs in the reaction of the related dilithiated bicyclic bis(3-methyl-1,3-diazacyclohex-1-yl)methane with YCpCl(2).3thf, which affords a mixed lithium-yttrium organyl.

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

PubMed

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

2010-01-01

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

Fischer-Tropsch synthesis in near-critical n-hexane: Pressure-tuning effects

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bochniak, D.J.; Subramaniam, B.

For Fe-catalyzed Fischer-Tropsch (FT) synthesis with near-critical n-hexane (P{sub c} = 29.7 bar; T{sub c} = 233.7 C) as the reaction medium, isothermal pressure tuning from 1.2--2.4 P{sub c} (for n-hexane) at the reaction temperature (240 C) significantly changes syngas conversion and product selectivity. For fixed feed rates of syngas (H{sub 2}/CO = 0.5; 50 std. cm{sup 3}/g catalyst) and n-hexane (1 mL/min), syngas conversion attains a steady state at all pressures, increasing roughly threefold in this pressure range. Effective rate constants, estimated assuming a first-order dependence of syngas conversion on hydrogen, reveal that the catalyst effectiveness increases with pressuremore » implying the alleviation of pore-diffusion limitations. Pore accessibilities increase at higher pressures because the extraction of heavier hydrocarbons from the catalyst pores is enhanced by the liquid-like densities, yet better-than-liquid transport properties, of n-hexane. This explanation is consistent with the single {alpha} (= 0.78) Anderson-Schulz-Flory product distribution, the constant chain termination probability, and the higher primary product (1-olefin) selectivities ({approximately}80%) observed at the higher pressures. Results indicate that the pressure tunability of the density and transport properties of near-critical reaction media offers a powerful tool to optimize catalyst activity and product selectivity during FT reactions on supported catalysts.« less

Reaction of Titanium and Zirconium Particles in Cylindrical Explosive Charges

NASA Astrophysics Data System (ADS)

Frost, David; Cairns, Malcolm; Goroshin, Samuel; Zhang, Fan

2007-06-01

The critical conditions for the reaction of high melting-point metallic particles (Ti, Zr) dispersed during the detonation of long cylindrical explosive charges have been investigated experimentally. The charges consisted of packed beds of either spherical titanium particles (with diameters of 35, 90, or 215 μm; AP&C, Inc.) or nonspherical zirconium particles (250 -- 500 μm or 500 -- 600 μm, Atlantic Equipment Eng., NJ) saturated with sensitized liquid nitromethane. For the titanium particles, a threshold particle diameter exists, above which self-sustained particle reaction is not observed, although some particle reaction occurs immediately behind the detonation front then rapidly quenches. For the smallest particles, the proportion of the conical particle cloud that reacts increases with charge diameter, suggesting that the reaction initiation is a competition between particle heating and expansion cooling of the products. For zirconium particles, no critical conditions exist; particle ignition was observed for all particle and charge diameters tested. In this case, interaction of the high pressure detonation wave with the particles is sufficient to initiate reaction at the particle surface after a delay time (˜ 10's μs), which is much less than the time required for thermal equilibration of the particles.

Reaction of Titanium and Zirconium Particles in Cylindrical Explosive Charges

NASA Astrophysics Data System (ADS)

Frost, David L.; Cairns, Malcolm; Goroshin, Samuel; Zhang, Fan

2007-12-01

The critical conditions for the reaction of particles of the transition metals titanium (Ti) and zirconium (Zr) dispersed during the detonation of long cylindrical explosive charges have been investigated experimentally. The charges consisted of packed beds of either spherical Ti particles or irregularly shaped Zr particles saturated with sensitized liquid nitromethane. For the Ti particles, a threshold particle diameter exists of 65±25 μm, above which self-sustained particle reaction is not observed for charge diameters up to 49 mm, although some particle reaction occurs immediately behind the detonation front then rapidly quenches. For the smallest particles (40 μm), the proportion of the conical particle cloud that reacts increases with charge diameter, suggesting that the reaction is a competition between particle heating and expansion cooling of the products. For 375 and 550 μm Zr particles, particle ignition was observed for 19 and 41 mm dia charges. In this case, interaction of the detonation wave with the particles is sufficient to initiate reaction at the particle surface after a delay time (˜5 μs), which is much less than the time required for thermal equilibration of the particles.

Use of ESI-MS to determine reaction pathway for hydrogen sulphide scavenging with 1,3,5-tri-(2-hydroxyethyl)-hexahydro-s-triazine.

PubMed

Madsen, Henrik T; Søgaard, Erik G

2012-01-01

To study the reaction between hydrogen sulphide and 1,3,5-tri-(2-hydroxyethyl)-hexahydro-s-triazine, which is an often used hydrogen sulphide scavenger, electro spray ionisation mass spectrometry (ESI-MS) was used. The investigation was carried out in positive mode, and tandem mass spectrometry was used to investigate the nature of unknown peaks in the mass spectra. The reaction was found to proceed as expected from theory with the triazine reacting with hydrogen sulphide to form the corresponding thiadiazine. This species subsequently reacted with a second hydrogen sulphide molecule to form the dithiazine species, hereby confirming previously obtained results and showing the ability of the ESI-MS method for studying the scavenging reaction. The final theoretical product s-trithiane was not detected. Furthermore, fragmentation products of thiadiazine and dithiazine were detected in the solution, and possible pathways and structures were suggested to describe the observed fragments. In these, thiadiazine fragmented to 2-(methylidene amino)-ethanol and 2-(1,3-thiazetidin-3-yl)-ethanol and N-(2-hydroxyethyl)-N-(sulfanylmethyl)-ethaniminium, which underwent a further fragmentation to N-methyl-N-(2-oxoethyl)-methaniminium. Dithiazine fragmented to N-methyl-N-(2-oxoethyl)-methaniminium as well. The by-product from this reaction is methanedithiol, which was not detected due to its low polarity.

Selective C-O Hydrogenolysis and Decarboxylation of Biomass-Derived Heterocyclic Compounds over Heterogeneous Catalysts

NASA Astrophysics Data System (ADS)

Chia, Mei

The catalytic deoxygenation of biomass-derived compounds through selective C-O hydrogenolysis, catalytic transfer hydrogenation and lactonization, and decarboxylation to value-added chemicals over heterogeneous catalysts was examined under liquid phase reaction conditions. The reactions studied involve the conversion or production of heterocyclic compounds, specifically, cyclic ethers, lactones, and 2-pyrones. A bimetallic RhRe/C catalyst was found to be selective for the hydrogenolysis of secondary C-O bonds for a broad range cyclic ethers and polyols. Results from experimentally-observed reactivity trends, NH3 temperature-programmed desorption, fructose dehydration reaction studies, and first-principles density functional theory (DFT) calculations are consistent with the hypothesis of a bifunctional catalyst which facilitates acid-catalyzed ring-opening and dehydration coupled with metal-catalyzed hydrogenation. C-O hydrogenolysis and fructose dehydration activities were observed to decrease with an increase in reduction temperature and a decrease in the number of surface metallic Re atoms measured by in situ X-ray absorption spectroscopy. No C-O hydrogenolysis activity was detected over RhRe/C under water-free conditions. The activation of water molecules by Re atoms on the surface of metallic Rh is suggested to result in the formation of Bronsted acidity over RhRe/C. The catalytic transfer hydrogenation and lactonization of levulinic acid and its esters to gamma-valerolactone was accomplished through the Meerwein-Ponndorf-Verley reaction over metal oxide catalysts using secondary alcohols as the hydrogen donor. ZrO2 was a highly active material for CTH under batch and continuous flow reaction conditions; the initial activity of the catalyst was repeatedly regenerable by calcination in air, with no observable loss in catalytic activity. Lastly, the 2-pyrone, triacetic acid lactone, is shown to be a promising biorenewable platform chemical from which a wide range of chemical intermediates and end products can be obtained using heterogeneous catalysts or by thermal decomposition. Mechanistic insights from experimentally-observed reactivity trends and results from DFT calculations indicate that 2-pyrones undergo reactions unique to their structure such as keto-enol tautomerization, retro Diels-Alder, and nucleophilic attack by water. Ring-opening and decarboxylation reactions were found to be governed by key structural features such as the degree of saturation in the ring (e.g., C4=C5 bond), nature of the solvent, and presence of an acid catalyst.

Mechanism of alkoxy groups substitution by Grignard reagents on aromatic rings and experimental verification of theoretical predictions of anomalous reactions.

PubMed

Jiménez-Osés, Gonzalo; Brockway, Anthony J; Shaw, Jared T; Houk, K N

2013-05-01

The mechanism of direct displacement of alkoxy groups in vinylogous and aromatic esters by Grignard reagents, a reaction that is not observed with expectedly better tosyloxy leaving groups, is elucidated computationally. The mechanism of this reaction has been determined to proceed through the inner-sphere attack of nucleophilic alkyl groups from magnesium to the reacting carbons via a metalaoxetane transition state. The formation of a strong magnesium chelate with the reacting alkoxy and carbonyl groups dictates the observed reactivity and selectivity. The influence of ester, ketone, and aldehyde substituents was investigated. In some cases, the calculations predicted the formation of products different than those previously reported; these predictions were then verified experimentally. The importance of studying the actual system, and not simplified models as computational systems, is demonstrated.

Mechanism of Alkoxy Groups Substitution by Grignard Reagents on Aromatic Rings and Experimental Verification of Theoretical Predictions of Anomalous Reactions

PubMed Central

Jiménez-Osés, Gonzalo; Brockway, Anthony J.; Shaw, Jared T.; Houk, K. N.

2013-01-01

The mechanism of direct displacement of alkoxy groups in vinylogous and aromatic esters by Grignard reagents, a reaction that is not observed with expectedly better tosyloxy leaving groups, is elucidated computationally. The mechanism of this reaction has been determined to proceed through the inner-sphere attack of nucleophilic alkyl groups from magnesium to the reacting carbons via a metalaoxetane transition state. The formation of a strong magnesium chelate with the reacting alkoxy and carbonyl groups dictates the observed reactivity and selectivity. The influence of ester, ketone and aldehyde substituents was investigated. In some cases, the calculations predicted the formation of products different than those previously reported; these predictions were then verified experimentally. The importance of studying the actual system, and not simplified models as computational systems, is demonstrated. PMID:23601086

Cellulase retention and sugar removal by membrane ultrafiltration during lignocellulosic biomass hydrolysis.

PubMed

Knutsen, Jeffrey S; Davis, Robert H

2004-01-01

Technologies suitable for the separation and reuse of cellulase enzymes during the enzymatic saccharification of pretreated corn stover are investigated to examine the economic and technical viability of processes that promote cellulase reuse while removing inhibitory reaction products such as glucose and cellobiose. The simplest and most suitable separation is a filter with relatively large pores on the order of 20-25 mm that retains residual corn stover solids while passing reaction products such as glucose and cellobiose to form a sugar stream for a variety of end uses. Such a simple separation is effective because cellulase remains bound to the residual solids. Ultrafiltration using 50-kDa polyethersulfone membranes to recover cellulase enzymes in solution was shown not to enhance further the saccharification rate or overall conversion. Instead, it appears that the necessary cellulase enzymes, including beta-glucosidase, are tightly bound to the substrate; when fresh corn stover is contacted with highly washed residual solids, without the addition of fresh enzymes, glucose is generated at a high rate. When filtration was applied multiple times, the concentration of inhibitory reaction products such as glucose and cellobiose was reduced from 70 to 10 g/L. However, an enhanced saccharification performance was not observed, most likely because the concentration of the inhibitory products remained too high. Further reduction in the product concentration was not investigated, because it would make the reaction unnecessarily complex and result in a product stream that is much too dilute to be useful. Finally, an economic analysis shows that reuse of cellulase can reduce glucose production costs, especially when the enzyme price is high. The most economic performance is shown to occur when the cellulase enzyme is reused and a small amount of fresh enzyme is added after each separation step to replace lost or deactivated enzyme.

OH-LIF measurement of H2/O2/N2 flames in a micro flow reactor with a controlled temperature profile

NASA Astrophysics Data System (ADS)

Shimizu, T.; Nakamura, H.; Tezuka, T.; Hasegawa, S.; Maruta, K.

2014-11-01

This paper presents combustion and ignition characteristic of H2/O2/N2 flames in a micro flow reactor with a controlled temperature profile. OH-LIF measurement was conducted to capture flame images. Flame responses were investigated for variable inlet flow velocity, U, and equivalence ratio, phi. Three kinds of flame responses were experimentally observed for the inlet flow velocities: stable flat flames (normal flames) in the high inlet flow velocity regime; unstable flames called Flames with Repetitive Extinction and Ignition (FREI) in the intermediate flow velocity regime; and stable weak flames in the low flow velocity regime, at phi = 0.6, 1.0 and 1.2. On the other hand, weak flame was not observed at phi = 3.0 by OH-LIF measurement. Computational OH mole fractions showed lower level at the rich conditions than those at stoichiometric and lean conditions. To examine this response of OH signal to equivalence ratio, rate of production analysis was conducted and four kinds of major contributed reaction for OH production: R3(O + H2 <=> H + OH); R38(H + O2 <=> O + OH); R46(H + HO2 <=> 2OH); and R86(2OH <=> O + H2O), were found. Three reactions among them, R3, R38 and R46, did not showed significant difference in rate of OH production for different equivalence ratios. On the other hand, rate of OH production from R86 at phi = 3.0 was extremely lower than those at phi = 0.6 and 1.0. Therefore, R86 was considered to be a key reaction for the reduction of the OH production at phi = 3.0.

A dual substrate kinetic model for cytochrome P450BM3-F87G catalysis: simultaneous binding of long chain aldehydes and 4-fluorophenol.

PubMed

Ledford, Chelsea; McMahon, Monica; Whitesell, Ashley; Khan, Ghalib; Kandagatla, Suneel K; Hurst, Dow P; Reggio, Patricia H; Raner, Gregory M

2017-02-01

To develop a model for binding and catalysis associated with the stimulation of 4-fluorophenol (4-FP) oxidation in the presence of long chain aldehydes by the enzymatic catalyst, cytochrome P450 BM3 -F87G. A variation of the Michaeli-Menten kinetic model was employed to describe interactions at the active site of the enzyme, along with computer aided modeling approaches. In addition to the hydroquinone product arising from de-fluorination of 4-FP, a second product (p-fluorocatechol) was also observed and, like the hydroquinone, its rate of formation increased in the presence of the aldehyde. When only aldehyde was present with the enzyme, BM3-F87G catalyzed its oxidation to the corresponding carboxylic acid; however, this activity was inhibited when 4-FP was added to the reaction. A 3D computer model of the active site containing both aldehyde and 4-FP was generated, guided by these kinetic observations. Finally, partitioning between the two phenolic products was examined with an emphasis on the conditions directing the initial epoxidation at either the 2,3- or 3,4-positions on the substrate. Temperature, reaction time, substrate concentration, and the structure of the aldehyde had no substantial effect on the overall product ratios, however the NADPH coupling efficiency decreased when unsaturated aldehydes were included, or when the temperature of the reaction was reduced. The unsaturated aldehyde, trans-2-decenal, stimulates BM3-F87G catalyzed oxidation of 4-fluorophenol through a cooperative active site binding mode that doesn't influence product distributions or coupling efficiencies, while 4-fluorophenol acts as a competitive inhibitor of aldehyde oxidation.

Hydrogen addition reactions of aliphatic hydrocarbons in comets

NASA Astrophysics Data System (ADS)

Kobayashi, Hitomi; Watanabe, N.; Watanabe, Y.; Fukushima, T.; Kawakita, H.

2013-10-01

Comets are thought as remnants of early solar nebula. Their chemical compositions are precious clue to chemical and physical evolution of the proto-planetary disk. Some hydrocarbons such as C2H6, C2H2 and CH4 in comets have been observed by using near-infrared spectroscopy. Although the compositions of C2H6 were about 1% relative to the water in normal comets, there are few reports on the detection of C2H6 in ISM. Some formation mechanisms of C2H6 in ISM have been proposed, and there are two leading hypotheses; one is the dimerizations of CH3 and another is the hydrogen addition reactions of C2H2 on cold icy grains. To evaluate these formation mechanisms for cometary C2H6 quantitatively, it is important to search the C2H4 in comets, which is the intermediate product of the hydrogen addition reactions toward C2H6. However, it is very difficult to detect the C2H4 in comets in NIR (3 microns) regions because of observing circumstances. The hydrogen addition reactions of C2H2 at low temperature conditions are not well characterized both theoretically and experimentally. For example, there are no reports on the reaction rate coefficients of those reaction system. To determine the production rates of those hydrogen addition reactions, we performed the laboratory experiments of the hydrogenation of C2H2 and C2H4. We used four types of the initial composition of the ices: pure C2H4, pure C2H2, C2H2 on amorphous solid water (ASW) and C2H4 on ASW at three different temperatures of 10, 20, and 30K. We found 1) reactions are more efficient when there are ASW in the initial compositions of the ice; 2) hydrogenation of C2H4 occur more rapid than that of C2H2.

Influence of temperature on linear stability in buoyancy-driven fingering of reaction-diffusion fronts.

PubMed

Levitán, D; D'Onofrio, A

2012-09-01

A vertical Hele-Shaw cell was used to study the influence of temperature on Rayleigh-Taylor instabilities on reaction-diffusion fronts. The propagation of the chemical front can thus be observed, and experimental results can be obtained via image treatment. A chemical front produced by the coupling between molecular diffusion and the auto-catalysis of the chlorite-tetrathionate reaction, descends through the cell, consuming the reactants below while the product is formed above. Buoyancy-driven instabilities are formed due to the density difference between reactants and products, and the front takes a fingering pattern, whose growth rate has temperature dependence. In this study, the effect of temperature on the linear regime of the instability (that is, when the effects of such instability start to appear) was analyzed. To measure the instability, Fourier transform analysis is performed, in order to obtain the different wave numbers and their power as a function of time. Thus, the growth rate for each wave number and the most unstable wave number is obtained for each of the temperatures under study. Based on repeated experiments, a decrease in the growth rate for the most unstable wave number can be observed with the increase of temperature.

Impact of Polymer Electrolyte Membrane Degradation Products on Oxygen Reduction Reaction Activity for Platinum Electrocatalysts

DOE PAGES

Christ, J. M.; Neyerlin, K. C.; Wang, H.; ...

2014-10-30

The impact of model membrane degradation compounds on the relevant electrochemical parameters for the oxygen reduction reaction (i.e. electrochemical surface area and catalytic activity), was studied for both polycrystalline Pt and carbon supported Pt electrocatalysts. Model compounds, representing previously published, experimentally determined polymer electrolyte membrane degradation products, were in the form of perfluorinated organic acids that contained combinations of carboxylic and/or sulfonic acid functionality. Perfluorinated carboxylic acids of carbon chain length C1 – C6 were found to have an impact on electrochemical surface area (ECA). The longest chain length acid also hindered the observed oxygen reduction reaction (ORR) performance, resultingmore » in a 17% loss in kinetic current (determined at 0.9 V). Model compounds containing sulfonic acid functional groups alone did not show an effect on Pt ECA or ORR activity. Lastly, greater than a 44% loss in ORR activity at 0.9V was observed for diacid model compounds DA-Naf (perfluoro(2-methyl-3-oxa-5-sulfonic pentanoic) acid) and DA-3M (perfluoro(4-sulfonic butanoic) acid), which contained both sulfonic and carboxylic acid functionalities.« less

Cascade production in the reactions γp→K+K+(X) and γp→K+K+π-(X)

NASA Astrophysics Data System (ADS)

Guo, L.; Weygand, D. P.; Battaglieri, M.; Vita, R. De; Kubarovsky, V.; Stoler, P.; Amaryan, M. J.; Ambrozewicz, P.; Anghinolfi, M.; Asryan, G.; Avakian, H.; Bagdasaryan, H.; Baillie, N.; Ball, J. P.; Baltzell, N. A.; Batourine, V.; Battaglieri, M.; Bedlinskiy, I.; Bellis, M.; Benmouna, N.; Berman, B. L.; Biselli, A. S.; Blaszczyk, L.; Bouchigny, S.; Boiarinov, S.; Bradford, R.; Branford, D.; Briscoe, W. J.; Brooks, W. K.; Bültmann, S.; Burkert, V. D.; Butuceanu, C.; Calarco, J. R.; Careccia, S. L.; Carman, D. S.; Chen, S.; Cole, P. L.; Collins, P.; Coltharp, P.; Crabb, D.; Crannell, H.; Crede, V.; Cummings, J. P.; Dashyan, N.; Masi, R. De; Vita, R. De; Sanctis, E. De; Degtyarenko, P. V.; Deur, A.; Dharmawardane, K. V.; Dickson, R.; Djalali, C.; Dodge, G. E.; Donnelly, J.; Doughty, D.; Dugger, M.; Dzyubak, O. P.; Egiyan, H.; Egiyan, K. S.; Fassi, L. El; Elouadrhiri, L.; Eugenio, P.; Fedotov, G.; Feldman, G.; Funsten, H.; Garçon, M.; Gavalian, G.; Gilfoyle, G. P.; Giovanetti, K. L.; Girod, F. X.; Goetz, J. T.; Gonenc, A.; Gordon, C. I. O.; Gothe, R. W.; Griffioen, K. A.; Guidal, M.; Guler, N.; Gyurjyan, V.; Hadjidakis, C.; Hafidi, K.; Hakobyan, H.; Hakobyan, R. S.; Hanretty, C.; Hardie, J.; Hersman, F. W.; Hicks, K.; Hleiqawi, I.; Holtrop, M.; Hyde-Wright, C. E.; Ilieva, Y.; Ireland, D. G.; Ishkhanov, B. S.; Isupov, E. L.; Ito, M. M.; Jenkins, D.; Johnstone, R.; Jo, H. S.; Joo, K.; Juengst, H. G.; Kalantarians, N.; Kellie, J. D.; Khandaker, M.; Kim, W.; Klein, A.; Klein, F. J.; Klimenko, A. V.; Kossov, M.; Krahn, Z.; Kramer, L. H.; Kuhn, J.; Kuhn, S. E.; Kuleshov, S. V.; Lachniet, J.; Laget, J. M.; Langheinrich, J.; Lawrence, D.; Lee, T.; Li, Ji; Livingston, K.; Lu, H. Y.; MacCormick, M.; Markov, N.; Mattione, P.; McKinnon, B.; Mecking, B. A.; Melone, J. J.; Mestayer, M. D.; Meyer, C. A.; Mibe, T.; Mikhailov, K.; Minehart, R.; Mirazita, M.; Miskimen, R.; Mokeev, V.; Moriya, K.; Morrow, S. A.; Moteabbed, M.; Munevar, E.; Mutchler, G. S.; Nadel-Turonski, P.; Nasseripour, R.; Niccolai, S.; Niculescu, G.; Niculescu, I.; Niczyporuk, B. B.; Niroula, M. R.; Niyazov, R. A.; Nozar, M.; Osipenko, M.; Ostrovidov, A. I.; Park, K.; Pasyuk, E.; Paterson, C.; Pereira, S. Anefalos; Pierce, J.; Pivnyuk, N.; Pocanic, D.; Pogorelko, O.; Pozdniakov, S.; Price, J. W.; Prok, Y.; Protopopescu, D.; Raue, B. A.; Riccardi, G.; Ricco, G.; Ripani, M.; Ritchie, B. G.; Ronchetti, F.; Rosner, G.; Rossi, P.; Sabatié, F.; Salamanca, J.; Salgado, C.; Santoro, J. P.; Sapunenko, V.; Schumacher, R. A.; Serov, V. S.; Sharabian, Y. G.; Sharov, D.; Shvedunov, N. V.; Smith, E. S.; Smith, L. C.; Sober, D. I.; Sokhan, D.; Stavinsky, A.; Stepanyan, S. S.; Stepanyan, S.; Stokes, B. E.; Strakovsky, I. I.; Strauch, S.; Taiuti, M.; Tedeschi, D. J.; Thoma, U.; Tkabladze, A.; Tkachenko, S.; Todor, L.; Tur, C.; Ungaro, M.; Vineyard, M. F.; Vlassov, A. V.; Watts, D. P.; Weinstein, L. B.; Williams, M.; Wolin, E.; Wood, M. H.; Yegneswaran, A.; Zana, L.; Zhang, J.; Zhao, B.; Zhao, Z. W.

2007-08-01

Photoproduction of the cascade resonances has been investigated in the reactions γp→K+K+(X) and γp→K+K+π-(X). The mass splitting of the ground state (Ξ-,Ξ0) doublet is measured to be 5.4±1.8 MeV/c2, consistent with existing measurements. The differential (total) cross sections for the Ξ- have been determined for photon beam energies from 2.75 to 3.85 (4.75) GeV and are consistent with a production mechanism of Y*→K+Ξ- through a t-channel process. The reaction γp→K+K+π-[Ξ0] has also been investigated to search of excited cascade resonances. No significant signal of excited cascade states other than the Ξ-(1530) is observed. The cross-section results of the Ξ-(1530) have also been obtained for photon beam energies from 3.35 to 4.75 GeV.

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

PubMed

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

2008-10-09

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

Thermogravimetric analysis of the gasification of microalgae Chlorella vulgaris.

PubMed

Figueira, Camila Emilia; Moreira, Paulo Firmino; Giudici, Reinaldo

2015-12-01

The gasification of microalgae Chlorella vulgaris under an atmosphere of argon and water vapor was investigated by thermogravimetric analysis. The data were interpreted by using conventional isoconversional methods and also by the independent parallel reaction (IPR) model, in which the degradation is considered to happen individually to each pseudo-component of biomass (lipid, carbohydrate and protein). The IPR model allows obtaining the kinetic parameters of the degradation reaction of each component. Three main stages were observed during the gasification process and the differential thermogravimetric curve was satisfactorily fitted by the IPR model considering three pseudocomponents. The comparison of the activation energy values obtained by the methods and those found in the literature for other microalgae was satisfactory. Quantification of reaction products was performed using online gas chromatography. The major products detected were H2, CO and CH4, indicating the potential for producing fuel gas and syngas from microalgae. Copyright © 2015 Elsevier Ltd. All rights reserved.

Accuracy and Calibration of High Explosive Thermodynamic Equations of State

NASA Astrophysics Data System (ADS)

Baker, Ernest L.; Capellos, Christos; Stiel, Leonard I.; Pincay, Jack

2010-10-01

The Jones-Wilkins-Lee-Baker (JWLB) equation of state (EOS) was developed to more accurately describe overdriven detonation while maintaining an accurate description of high explosive products expansion work output. The increased mathematical complexity of the JWLB high explosive equations of state provides increased accuracy for practical problems of interest. Increased numbers of parameters are often justified based on improved physics descriptions but can also mean increased calibration complexity. A generalized extent of aluminum reaction Jones-Wilkins-Lee (JWL)-based EOS was developed in order to more accurately describe the observed behavior of aluminized explosives detonation products expansion. A calibration method was developed to describe the unreacted, partially reacted, and completely reacted explosive using nonlinear optimization. A reasonable calibration of a generalized extent of aluminum reaction JWLB EOS as a function of aluminum reaction fraction has not yet been achieved due to the increased mathematical complexity of the JWLB form.

Vibrational Mode-Specific Reaction of Methane with a Nickel Surface

NASA Astrophysics Data System (ADS)

Beck, Rainer

2004-03-01

The dissociation of methane on a nickel catalyst is a key step in steam reforming of natural gas for hydrogen production. Despite substantial effort in both experiment and theory, there is still no atomic scale description of this important gas-surface reaction. To elucidate its dynamics, we have performed quantum state resolved studies of vibrationally excited methane reacting on the Ni(100) surface using pulsed laser and molecular beam techniques. We observed up to a factor of 5 greater reaction probability for methane-d2 with two quanta of excitation in one C-H bond versus a nearly isoenergetic state with one quanta in each of two C-H bonds. The observed reactivities point to a transition state structure which has one of the C-H bonds significantly elongated. Our results also clearly exclude the possibility of statistical models correctly describing the mechanism of this process and emphasize the importance of full-dimensional calculations of the reaction dynamics.

Levels in 227Ac populated in the 230Th( p, α) reaction

NASA Astrophysics Data System (ADS)

Burke, D. G.; Garrett, P. E.; Qu, Tao

2003-09-01

The 230,232Th(p, α) 227,229Ac reactions were studied using 20 MeV protons and a magnetic spectrograph to analyze the reaction products. Relative populations of levels in 229Ac correlated well with previously published (t, α) results for the same final levels, showing that the similarity of the two reactions observed empirically in the deformed rare earth region extends to actinides. The most strongly populated level in 227Ac is at 639 keV, and is assigned as the 1/2 +[4 0 0] bandhead. The 435 keV level, previously adopted as the 1/2 +[6 6 0] bandhead, also has a significant intensity that is attributed to Δ N=2 mixing between these two K=1/2 proton orbitals. The Δ N=2 matrix element estimated from these data is ˜80 keV, similar to values observed for the same two Nilsson states as neutron orbitals in the dysprosium isotopes.

Microwave-induced Bismuth Salts-mediated Synthesis of Molecules of Medicinal Interests.

PubMed

Bandyopadhyay, Debasish; Chavez, Ashlee; Banik, Bimal K

2017-01-01

Bismuth salts-mediated reactions have become a powerful tool for the synthesis of diverse medicinally-significant compounds because of their low-toxicity (non-toxic) and Lewis acidic capacity. In fact, LD50 of bismuth nitrate is lower than table salt. On the other hand, microwave-induced chemical synthesis is considered as a major greener route in modern chemistry. A total of 139 publications (including a few authentic web links) have been reviewed mainly to discuss bismuth salts-induced electrophilic aromatic substitution, protection-deprotection chemistry of carbonyl compounds, enamination, oxidation, carbohydrate chemistry, hydrolysis, addition-elimination route, Paal-Knorr reaction, Clauson-kaas synthesis, Michael addition, aza-Michael addition, Hantzsch reaction, Biginelli reaction, Ferrier rearrangement, Pechmann condensation, Diels-Alder and aza-Diels- Alder reactions, as well as effects of microwave irradiation in a wide range of chemical transformations. Bismuth salts-mediated reactions are developed for the synthesis of diverse organic molecules of medicinal significance. Reactions conducted with bismuth salts are environmentally benign, economical, rapid and high yielding. Microwave irradiation has accelerated these reactions significantly. It is believed that bismuth salts released corresponding acids in the media during the reaction. However, a coordination of bismuth salt to the electronegative atom is also observed in the NMR study. Bismuth has much less control (less attractive forces) over anions (for example, halides, nitrate, sulfate and triflates) compared to alkali metals. Therefore, it forms weak bond with electronegative atoms more readily and facilitates the reactions significantly. Many products obtained via bismuth salts-mediated reactions are medicinally active or intermediate for the synthesis of biologically active molecules including antifungal, anti-parasitic, anticancer and antibacterial agents, as well as agents to prevent Leishmaniosis and Chagas' diseases. Bismuth salts are able to (i) generate mineral acids in the reaction media and (ii) coordinate with electronegative atoms to facilitate the reaction. When the reagents and the catalyst (bismuth salt) are subjected to microwave irradiation, microwave passes through the (glass) walls of the reaction vessel and heat only the reactants avoiding local overheating at the wall of the vessel. Accordingly, the possibility of side reaction and subsequent by-product formation are reduced abruptly which in turn increases the yield of the desired product. The extreme rapidity with excellent yield of the product can be rationalized as a synergistic effect of the bismuth salts and microwave irradiation. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Particulate and gas-phase products from the atmospheric degradation of chlorpyrifos and chlorpyrifos-oxon

NASA Astrophysics Data System (ADS)

Borrás, Esther; Ródenas, Milagros; Vázquez, Mónica; Vera, Teresa; Muñoz, Amalia

2015-12-01

The phosphorothioate structure is highly present in several pesticides. However, there is a lack of information about its degradation process in air and the secondary pollutants formed. Herein, the atmospheric reactions of chlorpyrifos, one of the most world-used insecticide, and its main degradation product - chlorpyrifos-oxon - are described. The photo-oxidation under the presence of NOx was studied in a large outdoor simulation chamber for both chlorpyrifos and chlorpyrifos-oxon, observing a rapid degradation (Half lifetime < 3.5 h for both compounds). Also, the photolysis reactions of both were studied. The formation of particulate matter (aerosol mass yield ranged 6-59%) and gaseous products were monitored. The chemical composition of minor products was studied, identifying 15 multi-oxygenated derivatives. The most abundant products were ring-retaining molecules such as 3,5,6-trichloropyridin-2-ol and ethyl 3,5,6-trichloropyridin-2-yl hydrogen phosphate. An atmospheric degradation mechanism has been amplified based on an oxidation started with OH-nucleophilic attack to Pdbnd S bond.

The reduction of HNO3 by volatile organic compounds emitted by motor vehicles

NASA Astrophysics Data System (ADS)

Rutter, A. P.; Malloy, Q. G. J.; Leong, Y. J.; Gutierrez, C. V.; Calzada, M.; Scheuer, E.; Dibb, J. E.; Griffin, R. J.

2014-04-01

Nitric acid (HNO3) was reduced in a flow tube by volatile organic carbon compounds (VOCs) generated from engine oil vapor. The primary reaction product was believed to be HONO. The reaction was not enhanced when Teflon® Raschig rings were added to the flow tube to increase surface area, thereby showing the reaction to be homogeneous under the conditions studied. The HONO formation observed ranged between 0.1 and 0.6 ppb h-1, with a mean of 0.3 ± 0.1 ppb h-1, for typical HNO3 concentrations of 4-5 ppb and estimated concentrations of the reactive components in the engine oil vapor between 200 and 300 ppt. The observations in this study compare well to a recently published field study conducted in Houston that observed average formation rates of 0.6 ± 0.3 ppb h-1. Water vapor was found to decrease the HONO formation rate by ˜0.1 ppb h-1 for every 1% increase in the water mixing ratio.

Aerosol Fragmentation Driven by Coupling of Acid-Base and Free-Radical Chemistry in the Heterogeneous Oxidation of Aqueous Citric Acid by OH Radicals.

PubMed

Liu, Matthew J; Wiegel, Aaron A; Wilson, Kevin R; Houle, Frances A

2017-08-10

A key uncertainty in the heterogeneous oxidation of carboxylic acids by hydroxyl radicals (OH) in aqueous-phase aerosol is how the free-radical reaction pathways might be altered by acid-base chemistry. In particular, if acid-base reactions occur concurrently with acyloxy radical formation and unimolecular decomposition of alkoxy radicals, there is a possibility that differences in reaction pathways impact the partitioning of organic carbon between the gas and aqueous phases. To examine these questions, a kinetic model is developed for the OH-initiated oxidation of citric acid aerosol at high relative humidity. The reaction scheme, containing both free-radical and acid-base elementary reaction steps with physically validated rate coefficients, accurately predicts the experimentally observed molecular composition, particle size, and average elemental composition of the aerosol upon oxidation. The difference between the two reaction channels centers on the reactivity of carboxylic acid groups. Free-radical reactions mainly add functional groups to the carbon skeleton of neutral citric acid, because carboxylic acid moieties deactivate the unimolecular fragmentation of alkoxy radicals. In contrast, the conjugate carboxylate groups originating from acid-base equilibria activate both acyloxy radical formation and carbon-carbon bond scission of alkoxy radicals, leading to the formation of low molecular weight, highly oxidized products such as oxalic and mesoxalic acid. Subsequent hydration of carbonyl groups in the oxidized products increases the aerosol hygroscopicity and accelerates the substantial water uptake and volume growth that accompany oxidation. These results frame the oxidative lifecycle of atmospheric aerosol: it is governed by feedbacks between reactions that first increase the particle oxidation state, then eventually promote water uptake and acid-base chemistry. When coupled to free-radical reactions, acid-base channels lead to formation of low molecular weight gas-phase reaction products and decreasing particle size.

Aerosol Fragmentation Driven by Coupling of Acid–Base and Free-Radical Chemistry in the Heterogeneous Oxidation of Aqueous Citric Acid by OH Radicals

DOE PAGES

Liu, Matthew J.; Wiegel, Aaron A.; Wilson, Kevin R.; ...

2017-07-14

A key uncertainty in the heterogeneous oxidation of carboxylic acids by hydroxyl radicals (OH) in aqueous-phase aerosol is how the free-radical reaction pathways might be altered by acid-base chemistry. In particular, if acid-base reactions occur concurrently with acyloxy radical formation and unimolecular decomposition of alkoxy radicals, there is a possibility that differences in reaction pathways impact the partitioning of organic carbon between the gas and aqueous phases. To examine these questions, a kinetic model is developed for the OH-initiated oxidation of citric acid aerosol at high relative humidity. The reaction scheme, containing both free-radical and acid-base elementary reaction steps withmore » physically validated rate coefficients, accurately predicts the experimentally observed molecular composition, particle size, and average elemental composition of the aerosol upon oxidation. The difference between the two reaction channels centers on the reactivity of carboxylic acid groups. Free-radical reactions mainly add functional groups to the carbon skeleton of neutral citric acid, because carboxylic acid moieties deactivate the unimolecular fragmentation of alkoxy radicals. In contrast, the conjugate carboxylate groups originating from acid-base equilibria activate both acyloxy radical formation and carbon-carbon bond scission of alkoxy radicals, leading to the formation of low molecular weight, highly oxidized products such as oxalic and mesoxalic acid. Subsequent hydration of carbonyl groups in the oxidized products increases the aerosol hygroscopicity and accelerates the substantial water uptake and volume growth that accompany oxidation. These results frame the oxidative lifecycle of atmospheric aerosol: it is governed by feedbacks between reactions that first increase the particle oxidation state, then eventually promote water uptake and acid-base chemistry. When coupled to free-radical reactions, acid-base channels lead to formation of low molecular weight gas-phase reaction products and decreasing particle size.« less

Aerosol Fragmentation Driven by Coupling of Acid–Base and Free-Radical Chemistry in the Heterogeneous Oxidation of Aqueous Citric Acid by OH Radicals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Matthew J.; Wiegel, Aaron A.; Wilson, Kevin R.

A key uncertainty in the heterogeneous oxidation of carboxylic acids by hydroxyl radicals (OH) in aqueous-phase aerosol is how the free-radical reaction pathways might be altered by acid-base chemistry. In particular, if acid-base reactions occur concurrently with acyloxy radical formation and unimolecular decomposition of alkoxy radicals, there is a possibility that differences in reaction pathways impact the partitioning of organic carbon between the gas and aqueous phases. To examine these questions, a kinetic model is developed for the OH-initiated oxidation of citric acid aerosol at high relative humidity. The reaction scheme, containing both free-radical and acid-base elementary reaction steps withmore » physically validated rate coefficients, accurately predicts the experimentally observed molecular composition, particle size, and average elemental composition of the aerosol upon oxidation. The difference between the two reaction channels centers on the reactivity of carboxylic acid groups. Free-radical reactions mainly add functional groups to the carbon skeleton of neutral citric acid, because carboxylic acid moieties deactivate the unimolecular fragmentation of alkoxy radicals. In contrast, the conjugate carboxylate groups originating from acid-base equilibria activate both acyloxy radical formation and carbon-carbon bond scission of alkoxy radicals, leading to the formation of low molecular weight, highly oxidized products such as oxalic and mesoxalic acid. Subsequent hydration of carbonyl groups in the oxidized products increases the aerosol hygroscopicity and accelerates the substantial water uptake and volume growth that accompany oxidation. These results frame the oxidative lifecycle of atmospheric aerosol: it is governed by feedbacks between reactions that first increase the particle oxidation state, then eventually promote water uptake and acid-base chemistry. When coupled to free-radical reactions, acid-base channels lead to formation of low molecular weight gas-phase reaction products and decreasing particle size.« less

40 CFR 161.167 - Discussion of formation of impurities.

Code of Federal Regulations, 2011 CFR

2011-07-01

... reactions and side reactions which may occur in the production of the product, and the relative amounts of byproduct impurities produced by such reactions. (iv) The possible degradation of the ingredients in the product after its production but prior to its use. (v) Post-production reactions between the ingredients...

40 CFR 161.167 - Discussion of formation of impurities.

Code of Federal Regulations, 2010 CFR

2010-07-01

... reactions and side reactions which may occur in the production of the product, and the relative amounts of byproduct impurities produced by such reactions. (iv) The possible degradation of the ingredients in the product after its production but prior to its use. (v) Post-production reactions between the ingredients...

New Possibilities for Magnetic Control of Chemical and Biochemical Reactions.

PubMed

Buchachenko, Anatoly; Lawler, Ronald G

2017-04-18

Chemistry is controlled by Coulomb energy; magnetic energy is lower by many orders of magnitude and may be confidently ignored in the energy balance of chemical reactions. The situation becomes less clear, however, when reaction rates are considered. In this case, magnetic perturbations of nearly degenerate energy surface crossings may produce observable, and sometimes even dramatic, effects on reactions rates, product yields, and spectroscopic transitions. A case in point that has been studied for nearly five decades is electron spin-selective chemistry via the intermediacy of radical pairs. Magnetic fields, external (permanent or oscillating) and the internal magnetic fields of magnetic nuclei, have been shown to overcome electron spin selection rules for pairs of reactive paramagnetic intermediates, catalyzing or inhibiting chemical reaction pathways. The accelerating effects of magnetic stimulation may therefore be considered to be magnetic catalysis. This type of catalysis is most commonly observed for reactions of a relatively long-lived radical pair containing two weakly interacting electron spins formed by dissociation of molecules or by electron transfer. The pair may exist in singlet (total electron spin is zero) or triplet (total spin is unity) spin states. In virtually all cases, only the singlet state yields stable reaction products. Magnetic interactions with nuclear spins or applied fields may therefore affect the reactivity of radical pairs by changing the angular momentum of the pairs. Magnetic catalysis, first detected via its effect on spin state populations in nuclear and electron spin resonance, has been shown to function in a great variety of well-characterized reactions of organic free radicals. Considerably less well studied are examples suggesting that the basic mechanism may also explain magnetic effects that stimulate ATP synthesis, eliminating ATP deficiency in cardiac diseases, control cell proliferation, killing cancer cells, and control transcranial magnetic stimulation against cognitive deceases. Magnetic control has also been observed for some processes of importance in materials science and earth and environmental science and may play a role in animal navigation. In this Account, the radical pair mechanism is applied as a consistent explanation for several intriguing new magnetic phenomena. Specific examples include acceleration of solid state reactions of silicon by the magnetic isotope 29 Si, enrichment of 17 O during thermal decomposition of metal carbonates and magnetic effects on crystal plasticity. In each of these cases, the results are consistent with an initial one-electron transfer to generate a radical pair. Similar processes can account for mass-independent fractionation of isotopes of mercury, sulfur, germanium, tin, iron, and uranium in both naturally occurring samples and laboratory experiments. In the area of biochemistry, catalysis by magnetic isotopes has now been reported in several reactions of DNA and high energy phosphate. Possible medical applications of these observations are pointed out.

Kinetic study of the interaction of glutathione with four antitumor disulfides: possible mechanism for cellular glutathione depletion.

PubMed

Kirkpatrick, D L

1989-01-01

The reactions between the cellular tripeptide, glutathione (GSH) and four disulfide derivatives of 6-mercaptopurine (6-MP) and 6-thioguanine (6-TG) (compounds 1-4) were studied kinetically. The decyl and phenyl derivatives of 6-MP and 6-TG were reacted with GSH in phosphate buffer (pH 7.4 or 6.0) at 25.0 degrees C and were monitored spectrophotometrically by observing the release of 6-MP and 6-TG. Second order kinetics were observed, with rate constants of 142, 564, 4174 and 429 M-1 s-1 being measured for compounds 1-4, respectively. When the reactions were carried out in the presence of GSH-S-transferase the rates were enhanced 1.3-5.4 times those observed in the absence of enzyme. Products of the reactions were isolated by chromatography and tentatively identified by TLC or fast atom bombardment mass spectrometry. It was observed that GSH reacted with each disulfide in a 1:1 manner, forming a mixed disulfide between GSH and decanethiol or thiophenol while releasing 6-MP or 6-TG. It was concluded that the reported depletion of GSH from EMT6 cells after exposure to these disulfides could be due to their reaction with GSH, and the formation of the mixed disulfides.

In situ gas fuel production during the treatment of textile wastewater at supercritical conditions.

PubMed

Kıpçak, Ekin; Akgün, Mesut

2013-01-01

Supercritical water gasification has recently received much attention as a potential alternative to energy conversion methods applied to aqueous/non-aqueous biomass sources, industrial wastes or fossil fuels such as coal because of the unique physical properties of water above its critical conditions (i.e. 374.8 °C and 22.1 MPa). This paper presents the results obtained for the hydrothermal gasification of textile wastewater at supercritical conditions. The experiments were carried out at five reaction temperatures (between 450 and 650 °C) and five reaction times (between 30 and 150 s), under a constant pressure of 25 MPa. It was found that the gaseous products contained considerable amounts of hydrogen, carbon monoxide, carbon dioxide, and C(1)-C(4) hydrocarbons, such as methane, ethane, propane and propylene. The maximum amount of the obtained gaseous product was 1.23 mL per mL textile wastewater, at a reaction temperature of 600 °C, with a reaction time of 150 s. At this state, the product comprised 13.02% hydrogen, 38.93% methane, 4.33% ethane, 0.10% propane, 0.01% propylene, 7.97% carbon monoxide, 27.22% carbon dioxide and 8.00% nitrogen. In addition, a 62.88% decrease in the total organic carbon (TOC) content was observed and the color of the wastewater was removed. Moreover, for the hydrothermal decomposition of the textile wastewater, a first-order reaction rate was designated with an activation energy of 50.42 (±2.33) kJ/mol and a pre-exponential factor of 13.29 (±0.41) s(-1).

Convergent synthesis of 13N-labelled Peptidic structures using aqueous [13N]NH3.

PubMed

Blower, Julia E; Cousin, Samuel F; Gee, Antony D

2017-01-01

Nitrogen-13 has a 10-min half-life which places time constraints on the complexity of viable synthetic methods for its incorporation into PET imaging agents. In exploring ways to overcome this limitation, we have used the Ugi reaction to develop a rapid one-pot method for radiolabelling peptidic molecules using [ 13 N]NH 3 as a synthetic precursor. Carrier-added [ 13 N]NH 3 (50 μL) was added to a solution of carboxylic acid, aldehyde, and isocyanide in 2,2,2-TFE (200 μL). The mixture was heated in a microwave synthesiser at 120 °C for 10 min. Reactions were analysed by radio-HPLC and radio-LCMS. Isolation of the target 13 N-labelled peptidic Ugi compound was achieved via semi-preparative radio-HPLC as demonstrated for Ugi 1. Radio-HPLC analysis of each reaction confirmed the formation of radioactive products co-eluting with their respective reference standards with radiochemical yields of the crude products ranging from 11% to 23%. Two cyclic γ-lactam structures were also achieved via intra-molecular reactions. Additional radioactive by-products observed in the radio-chromatogram were identified as 13 N-labelled di-imines formed from the reaction of [ 13 N]NH 3 with two isocyanide molecules. The desired 13 N-labelled Ugi product was isolated using semi-preparative HPLC. We have developed a one-pot method that opens up new routes to radiolabel complex, peptidic molecules with 13 N using aqueous [ 13 N]NH 3 as a synthetic precursor.

Gap junction systems in the rat vestibular labyrinth: immunohistochemical and ultrastructural analysis.

PubMed

Kikuchi, T; Adams, J C; Paul, D L; Kimura, R S

1994-09-01

The distribution of gap junctions within the vestibular labyrinth was investigated using immunohistochemistry and transmission electron microscopy. Connexin26-like immunoreactivity was observed among supporting cells in each vestibular sensory epithelium. Reaction product was also present in the transitional epithelium of each vestibular endorgan and in the planum semilunatum of crista ampullaris. No connexin26-like immunoreactivity was observed among thin wall epithelial cells or among vestibular dark cells. In addition, fibrocytes within vestibular connective tissue were positively immunostained. Reaction product was also detected in the melanocyte area just beneath dark cells. Ultrastructural observations indicated that a gap junction network of vestibular supporting cells extends to the transitional epithelium and planum semilunatum and forms an isolated epithelial cell gap junction system in each vestibular endorgan. In contrast, no gap junctions were found among wall epithelial cells or among dark cells. Fibrocytes and melanocytes were coupled by gap junctions and belong to the connective tissue cell gap junction system, which is continuous throughout the vestibular system and the cochlea. The possible functional significance of these gap junction systems is discussed.

SME observations of O2(1 Delta g) nightglow - An assessment of the chemical production mechanisms

NASA Technical Reports Server (NTRS)

Howell, Colin D.; Michelangeli, Diane V.; Allen, Mark; Yung, Yuk L.; Thomas, Ronald J.

1990-01-01

Solar Mesosphere Explorer (SME) observations of the 3 a.m. 1.27 micron nightglow at 45 N latitude are reported. From the deduced volume emission rates, the O2(a 1 Delta g) nighttime production rates for the 80-100 km altitude range are derived. Utilizing the mean SME-acquired 3 p.m. ozone profile for the same latitude and time period and an updated photochemical model, nighttime O, O3, H, OH, HO2, and H2O2 profiles are determined. These are used in calculating the rates of reactions which are sufficiently exothermic to produce O2(1 Delta) or excited states of OH or HO2, which could transfer their energy to O2 to form O2(1 Delta). Yields of O2(1 Delta) based on published laboratory and observational studies are used to find that the sum of two reaction sequences can approximate the SME measurements: (1) O + O + M and (2) H + O3 followed by OH-asterisk + O2.

Size-dependent chemical ageing of oleic acid aerosol under dry and humidified conditions

NASA Astrophysics Data System (ADS)

Al-Kindi, Suad S.; Pope, Francis D.; Beddows, David C.; Bloss, William J.; Harrison, Roy M.

2016-12-01

A chemical reaction chamber system has been developed for the processing of oleic acid aerosol particles with ozone under two relative humidity conditions: dry and humidified to 65 %. The apparatus consists of an aerosol flow tube, in which the ozonolysis occurs, coupled to a scanning mobility particle sizer (SMPS) and an aerosol time-of-flight mass spectrometer (ATOFMS) which measure the evolving particle size and composition. Under both relative humidity conditions, ozonolysis results in a significant decrease in particle size and mass which is consistent with the formation of volatile products that partition from the particle to the gas phase. Mass spectra derived from the ATOFMS reveal the presence of the typically observed reaction products: azelaic acid, nonanal, oxononanoic acid and nonanoic acid, as well as a range of higher molecular weight products deriving from the reactions of reaction intermediates with oleic acid and its oxidation products. These include octanoic acid and 9- and 10-oxooctadecanoic acid, as well as products of considerably higher molecular weight. Quantitative evaluation of product yields with the ATOFMS shows a marked dependence upon both particle size association (from 0.3 to 2.1 µm diameter) and relative humidity. Under both relative humidity conditions, the percentage residual of oleic acid increases with increasing particle size and the main lower molecular weight products are nonanal and oxononanoic acid. Under dry conditions, the percentage of higher molecular weight products increases with increasing particle size due to the poorer internal mixing of the larger particles. Under humidified conditions, the percentage of unreacted oleic acid is greater, except in the smallest particle fraction, with little formation of high molecular weight products relative to the dry particles. It is postulated that water reacts with reactive intermediates, competing with the processes which produce high molecular weight products. Whilst the oleic acid model aerosol system is of limited relevance to complex internally mixed atmospheric aerosol, the generic findings presented in this paper give useful insights into the nature of heterogeneous chemical processes.

Hydrothermal Reactivity of Amines

NASA Astrophysics Data System (ADS)

Robinson, K.; Shock, E.; Hartnett, H. E.; Williams, L. B.; Gould, I.

2013-12-01

The reactivity of aqueous amines depends on temperature, pH, and redox state [1], all of which are highly variable in hydrothermal systems. Temperature and pH affect the ratio of protonated to unprotonated amines (R-NH2 + H+ = R-NH3+), which act as nucleophiles and electrophiles, respectively. We hypothesize that this dual nature can explain the pH dependence of reaction rates, and predict that rates will approach a maximum at pH = pKa where the ratio of protonated and unprotonated amines approaches one and the two compounds are poised to react with one another. Higher temperatures in hydrothermal systems allow for more rapid reaction rates, readily reversible reactions, and unique carbon-nitrogen chemistry in which water acts as a reagent in addition to being the solvent. In this study, aqueous benzylamine was used as a model compound to explore the reaction mechanisms, kinetics, and equilibria of amines under hydrothermal conditions. Experiments were carried out in anoxic silica glass tubes at 250°C (Psat) using phosphate-buffered solutions to observe changes in reaction rates and product distributions as a function of pH. The rate of decomposition of benzylamine was much faster at pH 4 than at pH 9, consistent with the prediction that benzylamine acts as both nucleophile and an electrophile, and our estimate that the pKa of benzylamine is ~5 at 250°C and Psat. Accordingly, dibenzylamine is the primary product of the reaction of two benzylamine molecules, and this reaction is readily reversible under hydrothermal conditions. Extremely acidic or basic pH can be used to suppress dibenzylamine production, which also suppresses the formation of all other major products, including toluene, benzyl alcohol, dibenzylimine, and tribenzylamine. This suggests that dibenzylamine is the lone primary product that then itself reacts as a precursor to produce the above compounds. Analog experiments performed with ring-substituted benzylamine derivatives and chiral methylbenzylamine suggest an SN2 mechanism for the formation of dibenzylamine. These results show the interdependence of pH and speciation with amine reaction rates. We predict the distribution of primary, secondary, tertiary, and quaternary amines in hydrothermal solutions can be used to solve for the pH of subsurface reaction zones in hydrothermal systems. [1] McCollom, T.M. (2013) The influence of minerals on decomposition of the n-alkyl-α-amino acid norvaline under hydrothermal conditions. Geochim. Cosmochim. Acta, 104, 330-357.

Gas-phase ozonolysis of the monoterpenoids ( S)-(+)-carvone, ( R)-(-)-carvone, (-)-carveol, geraniol and citral

NASA Astrophysics Data System (ADS)

Nunes, Fabíola Maria N.; Veloso, M. C. C.; de P. Pereira, P. A.; de Andrade, J. B.

Biogenic emissions of volatile organic compounds (VOCs) play a fundamental role in atmospheric chemistry. Vegetation is the most abundant natural source of VOCs, while terpenoids, as limonene, α and β pinene and mircene, top the plants emission list. Much interest has been demonstrated in oxidation and photooxidation reactions of VOCs, particularly of monoterpenoids, owing to their diversity and to uncertainties regarding their mechanism of reaction. Quantification of primary carbonylic compounds, as well as of biradical reaction components, is highly relevant to the understanding of the major reactions. In this context, taking into account both structural factors and the fact that these compounds are found in the essential oils of plants typically found in Brazil and that they may be present in the atmosphere from emission by the plants, the monoterpenoids ( S)-(+)-carvone, ( R)-(-)-carvone, (-)-carveol, geraniol and citral (a mixture of the isomers geranial and neral) were selected for this study. The ozonolysis reactions of the monoterpenoids were carried out under dark conditions for all experiments, due to their photochemical reactivity. The analysis of the results lets us propose a mechanism by which these reactions occur. The observed results of the ozonolysis of S and R carvone suggest that the stereochemistry of asymmetric carbon does not affect either in the yields of both formaldehyde and of OH radicals produced in the reaction, or in the reactivity of these compounds, for which the rate constants were in the scale of 10 -6 s -1. We found that, in the (-)-carveol's cis and trans mixture, even though the hydroxyl in the axial position—in the case of trans-(C) and cis-(D') isomers—favors the attack by the ozone molecule on the external double bond, thus increasing the mixture's reactivity (k=2.0×10-4s), it affects the average production of formaldehyde. The presence of geraniol and citral led to the production of formaldehyde, propanone, glyoxal, methyl-glyoxal and cyclohexanone (OH radicals) as reaction products. The influence of an electron attractor group bonded to the carbon of the double bond, on the reactivity of the double bond, could not be observed in the case of citral, due to strong interference occurring in the instrument in all experiments with this monoterpenoid. For this reason, only the kinetics of geraniol was monitored (k=9.0×10-4s).

ESR evidence for radical production from the reaction of ozone with unsaturated lipids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Church, D.F.; McAdams, M.L..; Pryor, W.A.

1991-03-15

The authors report electron spin resonance (ESR) spin trapping evidence for radical production by the reaction of ozone with unsaturated compounds. Soy and egg phosphatidylcholine liposomes, fatty acid emulsions, and homogeneous aqueous solutions of 3-hexenoic acid were treated with ozone in the presence of the spin trap {alpha}-phenyl-N-tert-butyl nitrone (PBN). Under these conditions, they observe spin adducts resulting from the trapping of both organic carbon- and oxygen-centered radicals. When the lipid-soluble antioxidant alpha-tocopherol is included in the liposomal systems, the formation of spin adducts is completely inhibited. The authors suggest that radicals giving rise to these spin adducts arise formmore » the rapid decomposition of the 1,2,3-trioxolane intermediate that is initially formed when ozone reacts with the carbon-carbon double bonds of the substrates. These free radicals are not formed by the decomposition of the Criegee ozonide, since little of the ozonide is formed in the presence of water. Although hydrogen peroxide is the predominate peroxidic product of the ozone/alkene reaction, its decomposition is not responsible for the observed radical production since neither catalase nor iron chelators significantly affect the spin adduct yield. The radical yield is approximately 1%. Since a polyunsaturated fatty acid (PUFA) such as linoleic acid produces much higher concentrations of spin trappable radicals than does the monounsaturated fatty oleic acid, the results also suggest that sites in the lung containing higher levels of PUFA may be an important target for radical formation.« less

40 CFR 721.10126 - Alkyl amino substituted triazine amino substituted benezenesulfonic acid reaction product with...

Code of Federal Regulations, 2010 CFR

2010-07-01

... substituted benezenesulfonic acid reaction product with naphthalenesulfonato azo substituted phenyl azo... substituted triazine amino substituted benezenesulfonic acid reaction product with naphthalenesulfonato azo... substituted triazine amino substituted benezenesulfonic acid reaction product with naphthalenesulfonato azo...

40 CFR 721.10126 - Alkyl amino substituted triazine amino substituted benezenesulfonic acid reaction product with...

Code of Federal Regulations, 2011 CFR

2011-07-01

... substituted benezenesulfonic acid reaction product with naphthalenesulfonato azo substituted phenyl azo... substituted triazine amino substituted benezenesulfonic acid reaction product with naphthalenesulfonato azo... substituted triazine amino substituted benezenesulfonic acid reaction product with naphthalenesulfonato azo...

UV/chlorine treatment of carbamazepine: Transformation products and their formation kinetics.

PubMed

Pan, Yanheng; Cheng, ShuangShuang; Yang, Xin; Ren, Jingyue; Fang, Jingyun; Shang, Chii; Song, Weihua; Lian, Lushi; Zhang, Xinran

2017-06-01

Carbamazepine (CBZ) is one of the pharmaceuticals most frequently detected in the aqueous environment. This study investigated the transformation products when CBZ is degraded by chlorine under ultraviolet (UV) irradiation (the UV/chlorine process). Detailed pathways for the degradation of CBZ were elucidated using ultra-high performance liquid chromatography (UHPLC)-quadrupole time-of-flight mass spectrometry (QTOF-MS). CBZ is readily degraded by hydroxyl radicals (HO) and chlorine radicals (Cl) in the UV/chlorine process, and 24 transformation products were identified. The products indicate that the 10,11-double bond and aromatic ring in CBZ are the sites most susceptible to attack by HO and Cl. Subsequent reaction produces hydroxylated and chlorinated aromatic ring products. Four specific products were quantified and their evolution was related with the chlorine dose, pH, and natural organic matter concentration. Their yields showed an increase followed by a decreasing trend with prolonged reaction time. CBZ-10,11-epoxide (I), the main quantified transformation product from HO oxidation, was observed with a peak transformation yield of 3-32% depending on the conditions. The more toxic acridine (IV) was formed involving both HO and Cl with peak transformation yields of 0.4-1%. All four quantified products together amounted to a peak transformation yield of 34.5%. The potential toxicity of the transformation products was assayed by evaluating their inhibition of the bioluminescence of the bacterium Vibrio Fischeri. The inhibition increased at first and the decreased at longer reaction times, which was in parallel with the evolution of transformation products. Copyright © 2017 Elsevier Ltd. All rights reserved.

Distinct roles of two anaplerotic pathways in glutamate production induced by biotin limitation in Corynebacterium glutamicum.

PubMed

Sato, Hiroki; Orishimo, Keita; Shirai, Tomokazu; Hirasawa, Takashi; Nagahisa, Keisuke; Shimizu, Hiroshi; Wachi, Masaaki

2008-07-01

Corynebacterium glutamicum is a biotin auxotrophic bacterium in which glutamate production is induced under biotin-limited conditions. During glutamate production, anaplerotic reactions catalyzed by phosphoenolpyruvate carboxylase (PEPC) and a biotin-containing enzyme pyruvate carboxylase (PC) are believed to play an important role in supplying oxaloacetate in the tricarboxylic acid cycle. To understand the distinct roles of PEPC and PC on glutamate production by C. glutamicum, we observed glutamate production induced under biotin-limited conditions in the disruptants of the genes encoding PEPC (ppc) and PC (pyc), respectively. The pyc disruptant retained the ability to produce high amounts of glutamate, and lactate was simultaneously produced probably due to the increased intracellular pyruvate levels. On the other hand, the ppc knockout mutant could not produce glutamate. Additionally, glutamate production in the pyc disruptant was enhanced by overexpression of ppc rather than disruption of the lactate dehydrogenase gene (ldh), which is involved in lactate production. Metabolic flux analysis based on the 13C-labeling experiment and measurement of 13C-enrichment in glutamate using nuclear magnetic resonance spectroscopy revealed that the flux for anaplerotic reactions in the pyc disruptant was lower than that in the wild type, concomitantly increasing the flux for lactate formation. Moreover, overexpression of ppc increased this flux in both the pyc disruptant and the wild type. Our results suggest that the PEPC-catalyzed anaplerotic reaction is necessary for glutamate production induced under biotin-limited conditions, because PC is not active during glutamate production, and overexpression of ppc effectively enhances glutamate production under biotin-limited conditions.

Clay-catalyzed reactions of coagulant polymers during water chlorination

USGS Publications Warehouse

Lee, J.-F.; Liao, P.-M.; Lee, C.-K.; Chao, H.-P.; Peng, C.-L.; Chiou, C.T.

2004-01-01

The influence of suspended clay/solid particles on organic-coagulant reactions during water chlorination was investigated by analyses of total product formation potential (TPFP) and disinfection by-product (DBP) distribution as a function of exchanged clay cation, coagulant organic polymer, and reaction time. Montmorillonite clays appeared to act as a catalytic center where the reaction between adsorbed polymer and disinfectant (chlorine) was mediated closely by the exchanged clay cation. The transition-metal cations in clays catalyzed more effectively than other cations the reactions between a coagulant polymer and chlorine, forming a large number of volatile DBPs. The relative catalytic effects of clays/solids followed the order Ti-Mont > Fe-Mont > Cu-Mont > Mn-Mont > Ca-Mont > Na-Mont > quartz > talc. The effects of coagulant polymers on TPFP follow the order nonionic polymer > anionic polymer > cationic polymer. The catalytic role of the clay cation was further confirmed by the observed inhibition in DBP formation when strong chelating agents (o-phenanthroline and ethylenediamine) were added to the clay suspension. Moreover, in the presence of clays, total DBPs increased appreciably when either the reaction time or the amount of the added clay or coagulant polymer increased. For volatile DBPs, the formation of halogenated methanes was usually time-dependent, with chloroform and dichloromethane showing the greatest dependence. ?? 2003 Elsevier Inc. All rights reserved.

Analysis of Reaction between α-Lipoic Acid and 2-Chloro-1-methylquinolinium Tetrafluoroborate Used as a Precolumn Derivatization Technique in Chromatographic Determination of α-Lipoic Acid.

PubMed

Godlewska, Magdalena; Odachowska, Angelika; Turkowicz, Monika; Karpinska, Joanna

2015-01-01

The present study offers results of analysis concerning the course of reaction between reduced α-lipoic acid (LA) and 2-chloro-1-methylquinolinium tetrafluoroborate (CMQT). In water environments, the reaction between CMQT and hydrophilic thiols proceeds very rapidly and the resultant products are stable. For the described analysis, optimum reaction conditions, such as concentration of the reducing agent, environment pH, and concentration of the reagent were carefully selected. The spectrophotometric assay was carried out measuring absorbance at λ = 348 nm (i.e., the spectral band of the obtained reaction product). Furthermore, the calibration curve of lipoic acid was registered. It was concluded that the Lambert-Beer law was observed within the range 1-10 μmol L(-1). Later, the reaction between LA and CMQT was used as precolumn derivatization in a chromatographic determination of the lipoic acid in the range 2.5-50 μmol L(-1). Practical applicability of the designed methods was evaluated by determining lipoic acid in Revitanerv pharmaceutical preparation which contains 300 mg LA in a single capsule. The error of the determination did not exceed 0.5% in relation to the declared value.

Analysis of Reaction between α-Lipoic Acid and 2-Chloro-1-methylquinolinium Tetrafluoroborate Used as a Precolumn Derivatization Technique in Chromatographic Determination of α-Lipoic Acid

PubMed Central

Godlewska, Magdalena; Odachowska, Angelika; Turkowicz, Monika; Karpinska, Joanna

2015-01-01

The present study offers results of analysis concerning the course of reaction between reduced α-lipoic acid (LA) and 2-chloro-1-methylquinolinium tetrafluoroborate (CMQT). In water environments, the reaction between CMQT and hydrophilic thiols proceeds very rapidly and the resultant products are stable. For the described analysis, optimum reaction conditions, such as concentration of the reducing agent, environment pH, and concentration of the reagent were carefully selected. The spectrophotometric assay was carried out measuring absorbance at λ = 348 nm (i.e., the spectral band of the obtained reaction product). Furthermore, the calibration curve of lipoic acid was registered. It was concluded that the Lambert-Beer law was observed within the range 1–10 μmol L−1. Later, the reaction between LA and CMQT was used as precolumn derivatization in a chromatographic determination of the lipoic acid in the range 2.5–50 μmol L−1. Practical applicability of the designed methods was evaluated by determining lipoic acid in Revitanerv pharmaceutical preparation which contains 300 mg LA in a single capsule. The error of the determination did not exceed 0.5% in relation to the declared value. PMID:26504616

Nonequiatomic NiTi Alloy Produced by Self Propagating High Temperature Synthesis

NASA Astrophysics Data System (ADS)

Bassani, P.; Bassani, E.; Tuissi, A.; Giuliani, P.; Zanotti, C.

2014-07-01

Shape memory alloy NiTi in porous form is of high interest as implantable material, as low apparent elastic modulus, comparable to that of bone, can be achieved. This condition, combined with proper pore size, allows good osteointegration. Porous NiTi can be produced by self propagating high temperature synthesis (SHS), starting from mixed powders of pure Ni and Ti. Process parameters, among which powder compaction degree and preheating temperature, strongly influence the reaction temperature and the resulting product: at low reaction temperatures, high quantity of secondary phases are formed, which are generally considered detrimental for biocompatibility. On the contrary, at higher reaction temperatures, the powders melt and crystallize in ingots. The porous structure is lost and huge pores are formed. Mechanical activation of powders through ball milling and addition of TiH x are investigated as means to reduce reaction temperature and overheating, in order to preserve high porosity and limit secondary phases content. Both processes affect SHS reaction, and require adjustment of parameters such as heating rate. Changes in porous shape and size were observed especially for TiH x additions: the latter could be a promising route to obtain shaped porous products of improved quality.

Unexpected dependence on pH of NO release from Paracoccus pantotrophus cytochrome cd1.

PubMed

Sam, Katharine A; Tolland, John D; Fairhurst, Shirley A; Higham, Christopher W; Lowe, David J; Thorneley, Roger N F; Allen, James W A; Ferguson, Stuart J

2008-07-11

A previous study of nitrite reduction by Paracoccus pantotrophus cytochrome cd(1) at pH 7.0 identified early reaction intermediates. The c-heme rapidly oxidised and nitrite was reduced to NO at the d(1)-heme. A slower equilibration of electrons followed, forming a stable complex assigned as 55% cFe(III)d(1)Fe(II)-NO and 45% cFe(II)d(1)Fe(II)-NO(+). No catalytically competent NO release was observed. Here we show that at pH 6.0, a significant proportion of the enzyme undergoes turnover and releases NO. An early intermediate, which was previously overlooked, is also identified; enzyme immediately following product release is a candidate. However, even at pH 6.0 a considerable fraction of the enzyme remains bound to NO so another component is required for full product release. The kinetically stable product formed at the end of the reaction differs significantly at pH 6.0 and 7.0, as does its rate of formation; thus the reaction is critically dependent on pH.

A stimuli-responsive fluorescence platform for simultaneous determination of D-isoascorbic acid and Tartaric acid based on Maillard reaction product

NASA Astrophysics Data System (ADS)

Zhao, Yanmei; Yuan, Haiyan; Zhang, Xinling; Yang, Jidong

2018-05-01

An activatable fluorescence monitoring platform based on a novel Maillard reaction product from D-glucose and L-arginine was prepared through a facile one-pot approach and applied for simultaneous detection of D-isoascorbic acid and tartaric acid. In this work, the new Maillard reaction product GLA was first obtained, and its fluorescence intensity can be effectively quenched by KMnO4, resulting from a new complex (GLA-KMnO4) formation between GLA and KMnO4. Upon addition of D-isoascorbic acid or tartaric acid, an enhanced fluorescence was observed under the optimumed experimental conditions, indicating a stimuli-responsive fluorescence turn on platform for D-isoascorbic acid or tartaric acid can be developed. The corresponding experimental results showed that this turn on fluorescence sensing platform has a high sensitivity for D-isoascorbic acid or tartaric acid, because the detection limits were 5.9 μM and 21.5 μM, respectively. Additionally, this proposed sensing platform was applied to simultaneously detection of D-isoascorbic acid and tartaric acid in real tap water samples with satisfactory results.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Zhe-Chen; Bierbaum, Veronica M.

The likely existence of aromatic anions in many important extraterrestrial environments, from the atmosphere of Titan to the interstellar medium (ISM), is attracting increasing attention. Nitrogen and oxygen atoms are also widely observed in the ISM and in the ionospheres of planets and moons. In the current work, we extend previous studies to explore the reactivity of prototypical aromatic anions (deprotonated toluene, aniline, and phenol) with N and O atoms both experimentally and computationally. The benzyl and anilinide anions both exhibit slow associative electron detachment (AED) processes with N atom, and moderate reactivity with O atom in which AED dominatesmore » but ionic products are also formed. The reactivity of phenoxide is dramatically different; there is no measurable reaction with N atom, and the moderate reactivity with O atom produces almost exclusively ionic products. The reaction mechanisms are studied theoretically by employing density functional theory calculations, and spin conversion is found to be critical for understanding some product distributions. This work provides insight into the rich gas-phase chemistry of aromatic ion-atom reactions and their relevance to ionospheric and interstellar chemistry.« less

Chemo-selective high yield microwave assisted reaction turns cellulose to green chemicals.

PubMed

Hassanzadeh, Salman; Aminlashgari, Nina; Hakkarainen, Minna

2014-11-04

Exceptionally high cellulose liquefaction yields, up to 87% as calculated from the amount of solid residue, were obtained under mild conditions by utilizing the synergistic effect of microwave radiation and acid catalysis. The effect of processing conditions on degradation products was fingerprinted by rapid laser desorption ionization-mass spectrometry (LDI-MS) method. The reaction was chemo-tunable, enabling production of glucose (Glc) or levulinic acid (LeA) at significantly high selectivity and yields, the relative molar yields being up to 50 and 69%, respectively. A turning point from pure depolymerization to glucose to further degradation to levulinic acid and formic acid was observed at approximately 50% liquefaction or above 140 °C. This was accompanied by the formation of small amounts of solid spherical carbonized residues. The reaction was monitored by multiple analytical techniques. The high yields were connected to the ability of the process to break the strong secondary interactions in cellulose. The developed method has great potential for future production of green platform chemicals. Copyright © 2014 Elsevier Ltd. All rights reserved.

Anomalous regioselective four-member multicomponent Biginelli reaction II: one-pot parallel synthesis of spiro heterobicyclic aliphatic rings.

PubMed

Byk, Gerardo; Kabha, Eihab

2004-01-01

In a previous preliminary study, we found that a cyclic five-member ring beta-keto ester (lactone) reacts with one molecule of urea and two of aldehyde to give a new family of spiro heterobicyclic aliphatic rings in good yields with no traces of the expected dihydropyrimidine (Biginelli) products. The reaction is driven by a regiospecific condensation of two molecules of aldehyde with urea and beta-keto-gamma-lactone to afford only products harboring substitutions exclusively in a syn configuration (Byk, G.; Gottlieb, H. E.; Herscovici, J.; Mirkin, F. J. Comb. Chem. 2000, 2, 732-735). In the present work ((a) Presented in part at ISCT Combitech, October 15, 2002, Israel, and Eurocombi-2, Copenhagen 2003 (oral and poster presentation). (b) Also in American Peptide Society Symposium, Boston, 2003 (poster presentation). (c) Abstract in Biopolymers 2003, 71 (3), 354-355), we report a large and exciting extension of this new reaction utilizing parallel organic synthesis arrays, as demonstrated by the use of chiral beta-keto-gamma-lactams, derived from natural amino acids, instead of tetronic acid (beta-keto-gamma-lactone) and the potential of the spirobicyclic products for generating "libraries from libraries". Interestingly, we note an unusual and important anisotropy effect induced by perpendicular interactions between rigid pi systems and different groups placed at the alpha position of the obtained spirobicyclic system. Stereo/regioselectivity of the aldehyde condensation is driven by the nature of the substitutions on the starting beta-keto-gamma-lactam. Aromatic aldehydes can be used as starting reagents with good yields; however, when aliphatic aldehydes are used, the desired products are obtained in poor yields, as observed in the classical Biginelli reaction. The possible reasons for these poor yields are addressed and clarify, to some extent, the complexity of the Biginelli multicomponent reaction mechanism and, in particular, the mechanism of the present reaction. Finally, we have investigated and proposed a mechanism for this new reaction by intercepting several intermediates.

Kinetic and mechanistic study of the gas-phase reaction of CxF2x+1CHCH2 (x=1, 2, 3, 4 and 6) with O3 under atmospheric conditions.

PubMed

Soto, A; Ballesteros, B; Jiménez, E; Antiñolo, M; Martínez, E; Albaladejo, J

2018-06-01

The relative-rate technique has been used to determine the rate coefficient for the reaction of C x F 2x+1 CHCH 2 (x = 1, 2, 3, 4 and 6) with ozone at (298 ± 2) K and (720 ± 5) Torr of air by FTIR (Fourier Transform Infrared Spectroscopy) and by GC-MS/SPME (Gas Chromatography-Mass Spectroscopy with Solid Phase Micro Extraction) in two different atmospheric simulation chambers. The following rate coefficients, in units of 10 -19  cm 3 molecule -1 s -1 , were obtained: (3.01 ± 0.10) for CF 3 CHCH 2 , (2.11 ± 0.35) for C 2 F 5 CHCH 2 , (2.34 ± 0.42) for C 3 F 7 CHCH 2 , (2.05 ± 0.31) for C 4 F 9 CHCH 2 and (2.07 ± 0.39) for C 6 F 13 CHCH 2 , where uncertainties represent ±2σ statistical error. The atmospheric lifetime of C x F 2x+1 CHCH 2 due to reaction with ozone was estimated from the reported rate coefficients. Additionally, the gaseous products formed in these reactions were investigated in the presence of synthetic air simulating a clean atmosphere. Perfluoroaldehydes, C x F 2x+1 C(O)H (PFALs), formaldehyde, formic acid and CF 2 O were identified as reaction products in the investigated reactions. The identified products made possible to propose a reaction mechanism that justifies the observed products. The atmospheric implications of these results are discussed in terms of the potential contribution of the atmospheric degradation of these species to PFAL and PFCA burden. Copyright © 2018 Elsevier Ltd. All rights reserved.

78 FR 78748 - 2,5-Furandione, polymer With ethenylbenzene, Reaction Products With polyethylene-polypropylene...

Federal Register 2010, 2011, 2012, 2013, 2014

2013-12-27

..., polymer With ethenylbenzene, Reaction Products With polyethylene-polypropylene glycol 2-aminopropyl Me...-furandione, polymer with ethenylbenzene, reaction products with polyethylene-polypropylene glycol 2... residues of 2,5-furandione, polymer with ethenylbenzene, reaction products with polyethylene-polypropylene...

Imino Acids in the Murchison Meteorite: Evidence of Strecker Reactions

NASA Technical Reports Server (NTRS)

Lerner, N. R.; Cooper, G. W.

2003-01-01

Both alpha-amino acids and alpha-hydroxy acids occur in aqueous extracts of the Murchison carbonaceous meteorite. The Strecker-cyanohydrin reaction, the reaction of carbonyl compounds, cyanide, and ammonia to produce amino and hydroxy acids, has been proposed as a source of such organic acids in meteorites. Such syntheses are consistent with the suggestion that interstellar precursors of meteoritic organic compounds accreted on the meteorite parent body together with other ices. Subsequent internal heating of the parent body melted these ices and led to the formation of larger compounds in synthetic reactions during aqueous alteration, which probably occurred at temperatures between 273K and 298K. In the laboratory, imino acids are observed as important by-products of the Strecker synthesis.

Spin differences in the Zr 90 compound nucleus induced by ( p , p ' ) , ( p , d ) , and ( p , t ) surrogate reactions

DOE PAGES

Ota, S.; Burke, J. T.; Casperson, R. J.; ...

2015-11-04

Here, the effect of the production mechanism on the decay of a compound nucleus is investigated. The nucleus 90Zr was produced by three different reactions, namely 90Zr (p,p') 90Zr, 91Zr (p,d) 90Zr, and 92Zr (p,t) 90Zr , which served as surrogate reactions for 89Zr (n,γ). The spin-parity (J π) distributions of the states populated by these reactions were studied to investigate the surrogate reaction approach, which aims at indirectly determining cross sections for compound-nuclear reactions involving unstable targets such as 89Zr. Discrete γ rays, associated with transitions in 90Zr and 89Zr, were measured in coincidence with light ions for scatteringmore » angles of 25°–60° and 90Zr excitation energies extending above the neutron separation energy. The measured transition systematics were used to gain insights into the J π distributions of 90Zr. The 90Zr (p,p') reaction was found to produce fewer γ rays associated with transitions involving high spin states (J = 6–8 ℏ) than the other two reactions, suggesting that inelastic scattering preferentially populates states in 90Zr that have lower spins than those populated in the transfer reactions investigated. The γ-ray production was also observed to vary by factors of 2–3 with the angle at which the outgoing particle was detected. These findings are relevant to the application of the surrogate reaction approach.« less

Hydrogen-Bonding Catalysis and Inhibition by Simple Solvents in the Stereoselective Kinetic Epoxide-Opening Spirocyclization of Glycal Epoxides to Form Spiroketals

PubMed Central

Wurst, Jacqueline M.; Liu, Guodong; Tan, Derek S.

2011-01-01

Mechanistic investigations of a MeOH-induced kinetic epoxide-opening spirocyclization of glycal epoxides have revealed dramatic, specific roles for simple solvents in hydrogen-bonding catalysis of this reaction to form spiroketal products stereoselectively with inversion of configuration at the anomeric carbon. A series of electronically-tuned C1-aryl glycal epoxides was used to study the mechanism of this reaction based on differential reaction rates and inherent preferences for SN2 versus SN1 reaction manifolds. Hammett analysis of reaction kinetics with these substrates is consistent with an SN2 or SN2-like mechanism (ρ = −1.3 vs. ρ = −5.1 for corresponding SN1 reactions of these substrates). Notably, the spirocyclization reaction is second-order dependent on MeOH and the glycal ring oxygen is required for second-order MeOH catalysis. However, acetone cosolvent is a first-order inhibitor of the reaction. A transition state consistent with the experimental data is proposed in which one equivalent of MeOH activates the epoxide electrophile via a hydrogen bond while a second equivalent of MeOH chelates the sidechain nucleophile and glycal ring oxygen. A paradoxical previous observation that decreased MeOH concentration leads to increased competing intermolecular methyl glycoside formation is resolved by the finding that this side reaction is only first-order dependent on MeOH. This study highlights the unusual abilities of simple solvents to act as hydrogen-bonding catalysts and inhibitors in epoxide-opening reactions, providing both stereoselectivity and discrimination between competing reaction manifolds. This spirocyclization reaction provides efficient, stereocontrolled access to spiroketals that are key structural motifs in natural products. PMID:21539313

The Heterogeneous Oxidation of Organic Droplets -Temperature and Physical Phase Effects

NASA Astrophysics Data System (ADS)

Hung, H.; Tang, C.; Lin, L.

2008-12-01

The heterogeneous reactions of oleic acid droplets with ozone are studied at different temperatures to imitating the atmospheric condition. The reactions are monitored concomitantly by using attenuated total reflectance Fourier Transform infrared spectroscopy (ATR-FT-IR) for the organic species and UV-VIS spectrometry for the ozone concentration, in order to investigate reaction rate discrepancies reported in literature as well as the oxidation mechanism, temperature and physical phase effects. The less and semi- volatile products are identified and resolved by a liquid chromatography and a gas chromatography mass spectrometer, respectively. The identified products are predominantly composed by nananoic acid and azelaic acid and might be due to propagation reactions possibly initiated by a secondary reaction such as the stabilized Criegee intermediates reacting with oleic acid. For temperature effect, the oxidation rate decreases with temperature when the oleic acid droplets are in the same physical phases. As oleic acid turns into the solid phase, the oxidation mechanism is observed to be different from the liquid phase. Furthermore, the concentration of ozone was monitored to examine the kinetics of the oxidation reaction. The integrated ozone profile recorded by UV-VIS spectrometry shows that the consumed ozone represents only approximately 12% of total oleic acid for the solid cases at 4°C in contrast to 30% for the liquid cases at 25°C, and hence confirmed the existence of secondary reactions.

Integral and differential cross section measurements at low collision energies for the N2++CH4/CD4 reactions

NASA Astrophysics Data System (ADS)

Nicolas, Christophe; Torrents, Raquel; Gerlich, Dieter

2003-02-01

Absolute integral cross sections are measured in the collision energy range between 0.1 to 3.5 eV for the N2++CH4 and N2++CD4 reactions using the universal guided ion beam apparatus. The reaction branching ratio, CX3+:CX2+:N2X+ (X=H or D), is found to be 0.86:0.09:0.05 and 0.88:0.07:0.05 for the N2++CH4 and N2++CD4 reactions, respectively. The CH3+/CH2+ ratio is constant over the whole collision energy range and very similar to the one obtained for the almost isoenergetic Ar++CH4 reaction. Axial velocity distributions of the product ions are measured by time of flight at collision energies between 0.1 and 3.5 eV. The results provide direct insight into the reaction dynamics. The dissociative charge transfer channels, leading to CH3+ and CH2+ product ions, occur via an electron jump combined with some exchange of momentum between the colliding partners. The H (D) transfer leading to N2H+ can be described as a direct process, similar to a spectator stripping mechanism. Various isotope effects are observed, the dominant being that the cross sections for reaction with CH4 are up to 20% bigger than the corresponding ones for CD4.

Things fall apart: Fragmentation reactions in the oxidative aging of organic species

NASA Astrophysics Data System (ADS)

Kroll, J. H.; Isaacman-VanWertz, G. A.; Wilson, K. R.; Daumit, K. E.; Kessler, S. H.; Lim, C. Y.; Worsnop, D. R.

2016-12-01

The atmospheric oxidation of organic compounds involves a wide array of chemical transformations, including functionalization reactions (addition of polar functional groups to the carbon skeleton), fragmentation reactions (formation of lower carbon-number products via C-C bond scission), and accretion reactions (increases in molecular weight by the combination of two chemical species). Each of these reaction classes can lead to large changes in volatility, and hence can have major implications for atmospheric organic aerosol (OA). For example, the formation of OA is predominantly driven by functionalization and accretion reactions, which generally lead to decreases in volatility. Here we describe a series of laboratory studies of the subsequent organic "aging", the multiday oxidation processes that occur after the initial OA formation and growth. In these studies, the multigenerational oxidation of organic compounds in various phases (the gas phase, the condensed OA phase, and the aqueous phase) is carried out within either an environmental chamber or a flow reactor, and monitored using various high-resolution mass spectrometric techniques. In all cases it is found that fragmentation reactions play a major role in the observed aging chemistry, dominated by the formation of small, volatile oxidation products. These results suggest that multi-day oxidative aging processes do not lead to sustained aerosol growth, but rather may serve as a chemical sink for atmospheric OA.

Real-time monitoring of the oxalate decarboxylase reaction and probing hydron exchange in the product, formate, using fourier transform infrared spectroscopy.

PubMed

Muthusamy, Mylrajan; Burrell, Matthew R; Thorneley, Roger N F; Bornemann, Stephen

2006-09-05

Oxalate decarboxylase converts oxalate to formate and carbon dioxide and uses dioxygen as a cofactor despite the reaction involving no net redox change. We have successfully used Fourier transform infrared spectroscopy to monitor in real time both substrate consumption and product formation for the first time. The assignment of the peaks was confirmed using [(13)C]oxalate as the substrate. The K(m) for oxalate determined using this assay was 3.8-fold lower than that estimated from a stopped assay. The infrared assay was also capable of distinguishing between oxalate decarboxylase and oxalate oxidase activity by the lack of formate being produced by the latter. In D(2)O, the product with oxalate decarboxylase was C-deuterio formate rather than formate, showing that the source of the hydron was solvent as expected. Large solvent deuterium kinetic isotope effects were observed on V(max) (7.1 +/- 0.3), K(m) for oxalate (3.9 +/- 0.9), and k(cat)/K(m) (1.8 +/- 0.4) indicative of a proton transfer event during a rate-limiting step. Semiempirical quantum mechanical calculations on the stability of formate-derived species gave an indication of the stability and nature of a likely enzyme-bound formyl radical catalytic intermediate. The capability of the enzyme to bind formate under conditions in which the enzyme is known to be active was determined by electron paramagnetic resonance. However, no enzyme-catalyzed exchange of the C-hydron of formate was observed using the infrared assay, suggesting that a formyl radical intermediate is not accessible in the reverse reaction. This restricts the formation of potentially harmful radical intermediates to the forward reaction.

Groundwater nitrate reduction versus dissolved gas production: A tale of two catchments.

PubMed

McAleer, E B; Coxon, C E; Richards, K G; Jahangir, M M R; Grant, J; Mellander, Per E

2017-05-15

At the catchment scale, a complex mosaic of environmental, hydrogeological and physicochemical characteristics combine to regulate the distribution of groundwater and stream nitrate (NO 3 - ). The efficiency of NO 3 - removal (via denitrification) versus the ratio of accumulated reaction products, dinitrogen (excess N 2 ) & nitrous oxide (N 2 O), remains poorly understood. Groundwater was investigated in two well drained agricultural catchments (10km 2 ) in Ireland with contrasting subsurface lithologies (sandstone vs. slate) and landuse. Denitrification capacity was assessed by measuring concentration and distribution patterns of nitrogen (N) species, aquifer hydrogeochemistry, stable isotope signatures and aquifer hydraulic properties. A hierarchy of scale whereby physical factors including agronomy, water table elevation and permeability determined the hydrogeochemical signature of the aquifers was observed. This hydrogeochemical signature acted as the dominant control on denitrification reaction progress. High permeability, aerobic conditions and a lack of bacterial energy sources in the slate catchment resulted in low denitrification reaction progress (0-32%), high NO 3 - and comparatively low N 2 O emission factors (EF 5g 1). In the sandstone catchment denitrification progress ranged from 4 to 94% and was highly dependent on permeability, water table elevation, dissolved oxygen concentration solid phase bacterial energy sources. Denitrification of NO 3 - to N 2 occurred in anaerobic conditions, while at intermediate dissolved oxygen; N 2 O was the dominant reaction product. EF 5g 1 (mean: 0.0018) in the denitrifying sandstone catchment was 32% less than the IPCC default. The denitrification observations across catchments were supported by stable isotope signatures. Stream NO 3 - occurrence was 32% lower in the sandstone catchment even though N loading was substantially higher than the slate catchment. Copyright © 2016 The Authors. Published by Elsevier B.V. All rights reserved.

High performance microbiological transformation of L-tyrosine to L-dopa by Yarrowia lipolytica NRRL-143

PubMed Central

Ali, Sikander; Shultz, Jeffry L; Ikram-ul-Haq

2007-01-01

Background The 3,4-dihydroxy phenyl L-alanine (L-dopa) is a drug of choice for Parkinson's disease, controlling changes in energy metabolism enzymes of the myocardium following neurogenic injury. Aspergillus oryzae is commonly used for L-dopa production; however, potential improvements in ease of handling, growth rate and environmental impact have led to an interest in exploiting alternative yeasts. The two important elements required for L-dopa production are intracellular tyrosinases (thus pre-grown yeast cells are required for the transformation of L-tyrosine to L-dopa) and L-ascorbate, which acts as a reducing agent. Results Pre-grown cells of Yarrowia lipolytica NRRL-143 were used for the microbiological transformation of L-tyrosine to L-dopa. Different diatomite concentrations (0.5–3.0 mg/ml) were added to the acidic (pH 3.5) reaction mixture. Maximum L-dopa biosynthesis (2.96 mg/ml L-dopa from 2.68 mg/ml L-tyrosine) was obtained when 2.0 mg/ml diatomite was added 15 min after the start of the reaction. After optimizing reaction time (30 min), and yeast cell concentration (2.5 mg/ml), an overall 12.5 fold higher L-dopa production rate was observed when compared to the control. Significant enhancements in Yp/s, Qs and qs over the control were observed. Conclusion Diatomite (2.0 mg/ml) addition 15 min after reaction commencement improved microbiological transformation of L-tyrosine to L-dopa (3.48 mg/ml; p ≤ 0.05) by Y. lipolytica NRRL-143. A 35% higher substrate conversion rate was achieved when compared to the control. PMID:17705832

Infrared identification of the {sigma}-complex of Cl-C{sub 6}H{sub 6} in the reaction of chlorine atom and benzene in solid para-hydrogen

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bahou, Mohammed; Witek, Henryk; Lee, Yuan-Pern

2013-02-21

The reaction of a chlorine atom with benzene (C{sub 6}H{sub 6}) is important in organic chemistry, especially in site-selective chlorination reactions, but its product has been a subject of debate for five decades. Previous experimental and theoretical studies provide no concrete conclusion on whether the product is a {pi}- or {sigma}-form of the Cl-C{sub 6}H{sub 6} complex. We took advantage of the diminished cage effect of para-hydrogen (p-H{sub 2}) to produce Cl in situ to react with C{sub 6}H{sub 6} (or C{sub 6}D{sub 6}) upon photolysis of a Cl{sub 2}/C{sub 6}H{sub 6} (or C{sub 6}D{sub 6})/p-H{sub 2} matrix at 3.2more » K. The infrared spectrum, showing intense lines at 1430.5, 833.6, 719.8, 617.0, and 577.4 cm{sup -1}, and several weaker ones for Cl-C{sub 6}H{sub 6}, and the deuterium shifts of observed new lines unambiguously indicate that the product is a 6-chlorocyclohexadienyl radical, i.e., the {sigma}-complex of Cl-C{sub 6}H{sub 6}. Observation of the {sigma}-complex rather than the {pi}-complex indicates that the {sigma}-complex is more stable in solid p-H{sub 2} at 3.2 K. The spectral information is crucial for further investigations of the Cl + C{sub 6}H{sub 6} reaction either in the gaseous or solution phase.« less

40 CFR 721.9485 - Dimer acid/polymerized rosin amidoamine reaction product (generic).

Code of Federal Regulations, 2011 CFR

2011-07-01

... amidoamine reaction product (generic). 721.9485 Section 721.9485 Protection of Environment ENVIRONMENTAL... reaction product (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as Dimer acid/polymerized rosin amidoamine reaction product (PMN...

40 CFR 721.10058 - Reaction product of alkylphenol, aromatic cyclicamine, alkyl diglycidyl dibenzene, and...

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Reaction product of alkylphenol... Reaction product of alkylphenol, aromatic cyclicamine, alkyl diglycidyl dibenzene, and formaldehyde... identified generically as reaction product of alkylphenol, aromatic cyclicamine, alkyl diglycidyl dibenzene...

40 CFR 721.10059 - Reaction product of alkylphenyl glycidyl ether, polyalkylenepolyamine, and alkyl diglycidyl...

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Reaction product of alkylphenyl... Reaction product of alkylphenyl glycidyl ether, polyalkylenepolyamine, and alkyl diglycidyl dibenzene... identified generically as reaction product of alkylphenyl glycidyl ether, polyalkylenepolyamine, and alkyl...

40 CFR 721.10059 - Reaction product of alkylphenyl glycidyl ether, polyalkylenepolyamine, and alkyl diglycidyl...

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Reaction product of alkylphenyl... Reaction product of alkylphenyl glycidyl ether, polyalkylenepolyamine, and alkyl diglycidyl dibenzene... identified generically as reaction product of alkylphenyl glycidyl ether, polyalkylenepolyamine, and alkyl...

40 CFR 721.9485 - Dimer acid/polymerized rosin amidoamine reaction product (generic).

Code of Federal Regulations, 2010 CFR

2010-07-01

... amidoamine reaction product (generic). 721.9485 Section 721.9485 Protection of Environment ENVIRONMENTAL... reaction product (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as Dimer acid/polymerized rosin amidoamine reaction product (PMN...

40 CFR 721.10058 - Reaction product of alkylphenol, aromatic cyclicamine, alkyl diglycidyl dibenzene, and...

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Reaction product of alkylphenol... Reaction product of alkylphenol, aromatic cyclicamine, alkyl diglycidyl dibenzene, and formaldehyde... identified generically as reaction product of alkylphenol, aromatic cyclicamine, alkyl diglycidyl dibenzene...

Generation of Hydrogen and Methane during Experimental Low-Temperature Reaction of Ultramafic Rocks with Water

NASA Astrophysics Data System (ADS)

McCollom, Thomas M.; Donaldson, Christopher

2016-06-01

Serpentinization of ultramafic rocks is widely recognized as a source of molecular hydrogen (H2) and methane (CH4) to support microbial activity, but the extent and rates of formation of these compounds in low-temperature, near-surface environments are poorly understood. Laboratory experiments were conducted to examine the production of H2 and CH4 during low-temperature reaction of water with ultramafic rocks and minerals. Experiments were performed by heating olivine or harzburgite with aqueous solutions at 90°C for up to 213 days in glass bottles sealed with butyl rubber stoppers. Although H2 and CH4 increased steadily throughout the experiments, the levels were very similar to those found in mineral-free controls, indicating that the rubber stoppers were the predominant source of these compounds. Levels of H2 above background were observed only during the first few days of reaction of harzburgite when CO2 was added to the headspace, with no detectable production of H2 or CH4 above background during further heating of the harzburgite or in experiments with other mineral reactants. Consequently, our results indicate that production of H2 and CH4 during low-temperature alteration of ultramafic rocks may be much more limited than some recent experimental studies have suggested. We also found no evidence to support a recent report suggesting that spinels in ultramafic rocks may stimulate H2 production. While secondary silicates were observed to precipitate during the experiments, formation of these deposits was dominated by Si released by dissolution of the glass bottles, and reaction of the primary silicate minerals appeared to be very limited. While use of glass bottles and rubber stoppers has become commonplace in experiments intended to study processes that occur during serpentinization of ultramafic rocks at low temperatures, the high levels of H2, CH4, and SiO2 released during heating indicate that these reactor materials are unsuitable for this purpose.

A STUDY OF THE INDIGOGENIC PRINCIPLE AND IN VITRO MACROPHAGE DIFFERENTIATION

DTIC Science & Technology

and beta- glucuronidase activities. Moreover, there was a progressive increase in the densities of enzyme reactive centers. Indigo reaction product was...not observed over nuclei; lipid droplets and cell background were free from spurious precipitations. Both galactosidase and glucuronidase were

Mixed quantum-classical studies of energy partitioning in unimolecular chemical reactions

NASA Astrophysics Data System (ADS)

Bladow, Landon Lowell

A mixed quantum-classical reaction path Hamiltonian method is utilized to study the dynamics of unimolecular reactions. The method treats motion along the reaction path classically and treats the transverse vibrations quantum mechanically. The theory leads to equations that predict the disposai of the exit-channel potential energy to product translation and vibration. In addition, vibrational state distributions are obtained for the product normal modes. Vibrational excitation results from the curvature of the minimum energy reaction path. The method is applied to six unimolecular reactions: HF elimination from fluoroethane, 1,1-difluoroethane, 1,1-difluoroethene, and trifluoromethane; and HCl elimination from chloroethane and acetyl chloride. The minimum energy paths were calculated at either the MP2 or B3LYP level of theory. In all cases, the majority of the vibrational excitation of the products occurs in the HX fragment. The results are compared to experimental data and other theoretical results, where available. The best agreement between the experimental and calculated HX vibrational distributions is found for the halogenated ethanes, and the experimental deduction that the majority of the HX vibrational excitation arises from the potential energy release is supported. It is believed that the excess energy provided in experiments contributes to the poorer agreement between experiment and theory observed for HF elimination from 1,1-difluoroethene and trifluoromethane. An attempt is described to incorporate a treatment of the excess energy into the present method. However, the sign of the curvature coupling elements is then found to affect the dynamics. Overall, the method appears to be an efficient dynamical tool for modeling the disposal of the exit-channel potential energy in unimolecular reactions.

Effect of additives on mineral trioxide aggregate setting reaction product formation.

PubMed

Zapf, Angela M; Chedella, Sharath C V; Berzins, David W

2015-01-01

Mineral trioxide aggregate (MTA) sets via hydration of calcium silicates to yield calcium silicate hydrates and calcium hydroxide (Ca[OH]2). However, a drawback of MTA is its long setting time. Therefore, many additives have been suggested to reduce the setting time. The effect those additives have on setting reaction product formation has been ignored. The objective was to examine the effect additives have on MTA's setting time and setting reaction using differential scanning calorimetry (DSC). MTA powder was prepared with distilled water (control), phosphate buffered saline, 5% calcium chloride (CaCl2), 3% sodium hypochlorite (NaOCl), or lidocaine in a 3:1 mixture and placed in crucibles for DSC evaluation. The setting exothermic reactions were evaluated at 37°C for 8 hours to determine the setting time. Separate samples were stored and evaluated using dynamic DSC scans (37°C→640°C at10°C/min) at 1 day, 1 week, 1 month, and 3 months (n = 9/group/time). Dynamic DSC quantifies the reaction product formed from the amount of heat required to decompose it. Thermographic peaks were integrated to determine enthalpy, which was analyzed with analysis of variance/Tukey test (α = 0.05). Isothermal DSC identified 2 main exothermal peaks occurring at 44 ± 12 and 343 ± 57 minutes for the control. Only the CaCl2 additive was an accelerant, which was observed by a greater exothermic peak at 101 ± 11 minutes, indicating a decreased setting time. The dynamic DSC scans produced an endothermic peak around 450°C-550°C attributed to Ca(OH)2 decomposition. The use of a few additives (NaOCl and lidocaine) resulted in significantly less Ca(OH)2 product formation. DSC was used to discriminate calcium hydroxide formation in MTA mixed with various additives and showed NaOCl and lidocaine are detrimental to MTA reaction product formation, whereas CaCl2 accelerated the reaction. Copyright © 2015 American Association of Endodontists. Published by Elsevier Inc. All rights reserved.

Trimolecular reactions of uranium hexafluoride with water.

PubMed

Lind, Maria C; Garrison, Stephen L; Becnel, James M

2010-04-08

The hydrolysis reaction of uranium hexafluoride (UF(6)) is a key step in the synthesis of uranium dioxide (UO(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(6) molecule with a water molecule in the gas phase has been previously predicted to proceed over a relatively sizable barrier of 78.2 kJ x mol(-1), indicating this reaction is only feasible at elevated temperatures. Given the observed formation of a second morphology for the UO(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(6) molecules and one water molecule, and (2) the reaction of two water molecules with a single UF(6) molecule. The predicted reaction of two UF(6) molecules with one water molecule displays an interesting "fluorine-shuttle" mechanism, a significant energy barrier of 69.0 kJ x mol(-1) to the formation of UF(5)OH, and an enthalpy of reaction (DeltaH(298)) of +17.9 kJ x mol(-1). The reaction of a single UF(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 x mol(-1) and an exothermic enthalpy of reaction (DeltaH(298)) of -13.9 kJ x mol(-1). The exothermic nature of the overall UF(6) + 2H(2)O trimolecular reaction and the lowering of the barrier height with respect to the bimolecular reaction are encouraging.

Thermal decomposition of the solid phase of nitromethane: ab initio molecular dynamics simulations.

PubMed

Chang, Jing; Lian, Peng; Wei, Dong-Qing; Chen, Xiang-Rong; Zhang, Qing-Ming; Gong, Zi-Zheng

2010-10-29

The Car-Parrinello molecular dynamics simulations were employed to investigate thermal decomposition of the solid nitromethane. It is found that it undergoes chemical decomposition at about 2200 K under ambient pressure. The initiation of reactions involves both proton transfer and commonly known C-N bond cleavage. About 75 species and 100 elementary reactions were observed with the final products being H2O, CO2, N2, and CNCNC. It represents the first complete simulation of solid-phase explosive reactions reported to date, which is of far-reaching implication for design and development of new energetic materials.

[Pulmonary reaction after furazidin (Furagin). Case report].

PubMed

Zielonka, T M; Demkow, U; Kuś, J

1997-05-01

For the first time in Poland we present the case of pulmonary reaction to furazidin which is by chemical structure closely related to nitrofurantoin. 63 years old woman presented generalized symptoms of acute hypersensitivity reaction induced by furazidin as well as features of chronic pulmonary fibrosis. After few months of treatment with this drug patients complained of weight loss, dyspnea on effort, non-productive cough, chills and fever. Radiological and functional evaluation of respiratory system confirmed features of lung fibrosis. Drug provocation test was positive. In vitro furazidin in low concentrations stimulated proliferation of patient's lymphocytes. After cessation of treatment we have observed rapid improvement of clinical, radiological, biochemical and functional parameters.

Indium-catalyzed direct chlorination of alcohols using chlorodimethylsilane-benzil as a selective and mild system.

PubMed

Yasuda, Makoto; Yamasaki, Satoshi; Onishi, Yoshiyuki; Baba, Akio

2004-06-16

The InCl3-catalyzed reaction of alcohols with chlorodimethylsilane (HSiMe2Cl) in the presence of benzil gave the corresponding organic chlorides under mild conditions. Benzil significantly changes the reaction course because the reducing product through dehydroxyhydration was obtained in the absence of benzil. The secondary or tertiary alcohols were effectively chlorinated. The substrates bearing acid-sensitive functional groups were also applied to this system. The highly selective chlorination of the tertiary site was observed in the competitive reaction between tertiary and primary alcohols. The highly coordinated hydrosilane generated from benzil and HSiMe2Cl is an important intermediate.

Rhodium-catalyzed asymmetric aqueous Pauson-Khand-type reaction.

PubMed

Kwong, Fuk Yee; Li, Yue Ming; Lam, Wai Har; Qiu, Liqin; Lee, Hang Wai; Yeung, Chi Hung; Chan, Kin Shing; Chan, Albert S C

2005-06-20

An interesting rhodium-catalyzed asymmetric aqueous Pauson-Khand-type reaction was developed. A chiral atropisomeric dipyridyldiphosphane ligand was found to be highly effective in this system. This operationally simple protocol allows both catalyst and reactants to be handled under air without precautions. Various enynes were transformed to the corresponding bicyclic cyclopentenones in good yield and enantiomeric excess (up to 95 % ee). A study of the electronic effects of the enyne substrates revealed a correlation between the electronic properties of the substrates and the ee value obtained in the product of the Pauson-Khand-type reaction. A linear free-energy relationship was observed from a Hammett study.

Inside out: Speed-dependent barriers to reactive mixing

NASA Astrophysics Data System (ADS)

Kelley, Douglas; Nevins, Thomas

2015-11-01

Reactive mixing occurs wherever fluid flow and chemical or biological growth interact over time and space. Those interactions often lead to steep gradients in reactant and product concentration, arranged in complex spatial structures that can cause wide variation in the global reaction rate and concentrations. By simultaneously measuring fluid velocity and reaction front locations in laboratory experiments with the Belousov-Zhabotinsky reaction, we find that the barriers defining those structures vary dramatically with speed. In particular, we find that increasing flow speed causes reacted regions to move from vortex edges to vortex cores, thus turning the barriers ``inside out''. This observation has implications for reactive mixing of phytoplankton in global oceans.

77 FR 21676 - Silicic Acid, Sodium Salt etc.; Tolerance Exemption

Federal Register 2010, 2011, 2012, 2013, 2014

2012-04-11

... Silicic acid, sodium salt, reaction products with chlorotrimethylsilane and iso-propyl alcohol, reaction..., reaction products with chlorotrimethylsilane and iso-propyl alcohol, reaction with poly(oxypropylene)-poly... from the requirement of a tolerance for residues of Silicic acid, sodium salt, reaction products with...

Combustion dynamics in liquid rocket engines

NASA Technical Reports Server (NTRS)

Mclain, W. H.

1971-01-01

A chemical analysis of the emission and absorption spectra in the combustion chamber of a nitrogen tetroxide/aerozine-50 rocket engine was conducted. Measurements were made under conditions of preignition, ignition, and post combustion operating periods. The cause of severe ignition overpressures sporadically observed during the vacuum startup of the Apollo reaction control system engine was investigated. The extent to which residual propellants or condensed intermediate reaction products remain after the engine has been operated in a pulse mode duty cycle was determined.

Quantifying risk: the role of absolute and relative measures in interpreting risk of adverse reactions from product labels of antipsychotic medications.

PubMed

Citrome, Leslie

2009-09-01

Pharmaceutical product labeling as approved by regulatory agencies include statements of adverse event risk. Product labels include descriptive statements such as whether events are uncommon or rare, as well as percentage occurrence for more common events. In addition tables are provided with the frequencies of the latter events for both product and placebo as observed in clinical trials. Competing products are not mentioned in a specific drug's product labeling but indirect comparisons can be made using the corresponding label information for the alternate product. Two types of tools are easily used for this purpose: absolute measures such as number needed to harm (NNH), and relative measures such as relative risk increase (RRI). The calculations for both of these types of quantitative measures are presented using as examples the oral first-line second-generation antipsychotic medications. Among three sample outcomes selected a priori, akathisia, weight gain, and discontinuation from a clinical trial because of an adverse reaction, there appears to be differences among the different antipsychotics versus placebo. Aripiprazole was associated with the highest risk for akathisia, particularly when used as adjunctive treatment of major depressive disorder (NNH 5, 95% CI 4-7; RRI 525%, 95% CI 267%-964%). Although insufficient information was available in product labeling to calculate the CI, olanzapine was associated with the highest risk for weight gain of at least 7% from baseline (NNH 6, RRI 640% for adults; NNH 4, RRI 314% for adolescents), and quetiapine for the indication of bipolar depression was associated with the highest risk of discontinuation from a clinical trial because of an adverse reaction (NNH 8, RRI 265% for 600 mg/d; NNH 15, RRI 137% for 300 mg/d). In conclusion, with certain limitations, it is possible for the clinician to extract information from medication product labeling regarding the frequency with which certain adverse reactions can be expected. This supplements, but does not replace, information reported directly in clinical trial reports.

Stereoselectivity in ene reactions with 1O2: matrix effects in polymer supports, photo-oxygenation of organic salts and asymmetric synthesis.

PubMed

Griesbeck, Axel G; Bartoschek, Anna; Neudörfl, Jörg; Miara, Claus

2006-01-01

The ene reaction of chiral allylic alcohols is applied as a tool for the investigation of intrapolymer effects by means of the stereoselectivity of the singlet-oxygen addition. The diastereo selectivity strongly depends on the structure of the polymer, the substrate loading degree and also on the degree of conversion demonstrating additional supramolecular effects evolving during the reaction. The efficiency and the stability of polymer-bound sensitizers were evaluated by the ene reaction of singlet oxygen with citronellol. The ene reaction with chiral ammonium salts of tiglic acid was conducted under solution phase conditions or in polystyrene beads under chiral contact ion-pair conditions. The products thus obtained precipitate during the photoreaction as ammonium salts. Moderate asymmetric induction was observed for this procedure for the first time.

Communication: Charge transfer dominates over proton transfer in the reaction of nitric acid with gas-phase hydrated electrons

NASA Astrophysics Data System (ADS)

Lengyel, Jozef; Med, Jakub; Slavíček, Petr; Beyer, Martin K.

2017-09-01

The reaction of HNO3 with hydrated electrons (H2O)n- (n = 35-65) in the gas phase was studied using Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry and ab initio molecular dynamics simulations. Kinetic analysis of the experimental data shows that OH-(H2O)m is formed primarily via a reaction of the hydrated electron with HNO3 inside the cluster, while proton transfer is not observed and NO3-(H2O)m is just a secondary product. The reaction enthalpy was determined using nanocalorimetry, revealing a quite exothermic charge transfer with -241 ± 69 kJ mol-1. Ab initio molecular dynamics simulations indicate that proton transfer is an allowed reaction pathway, but the overall thermochemistry favors charge transfer.

Determination of Double Bond Positions in Polyunsaturated Fatty Acids Using the Photochemical Paternò-Büchi Reaction with Acetone and Tandem Mass Spectrometry.

PubMed

Murphy, Robert C; Okuno, Toshiaki; Johnson, Christopher A; Barkley, Robert M

2017-08-15

The positions of double bonds along the carbon chain of methylene interrupted polyunsaturated fatty acids are unique identifiers of specific fatty acids derived from biochemical reactions that occur in cells. It is possible to obtain direct structural information as to these double bond positions using tandem mass spectrometry after collisional activation of the carboxylate anions of an acetone adduct at each of the double bond positions formed by the photochemical Paternò-Büchi reaction with acetone. This reaction can be carried out by exposing a small portion of an inline fused silica capillary to UV photons from a mercury vapor lamp as the sample is infused into the electrospray ion source of a mass spectrometer. Collisional activation of [M - H] - yields a series of reverse Paternò-Büchi reaction product ions that essentially are derived from cleavage of the original carbon-carbon double bonds that yield an isopropenyl carboxylate anion corresponding to each double bond location. Aldehydic reverse Paternò-Büchi product ions are much less abundant as the carbon chain length and number of double bonds increase. The use of a mixture of D 0 /D 6 -acetone facilitates identification of these double bonds indicating product ions as shown for arachidonic acid. If oxygen is present in the solvent stream undergoing UV photoactivation, ozone cleavage ions are also observed without prior collisional activation. This reaction was used to determine the double bond positions in a 20:3 fatty acid that accumulated in phospholipids of RAW 264.7 cells cultured for 3 days.

Validated spectrophotometric methods for determination of sodium valproate based on charge transfer complexation reactions.

PubMed

Belal, Tarek S; El-Kafrawy, Dina S; Mahrous, Mohamed S; Abdel-Khalek, Magdi M; Abo-Gharam, Amira H

2016-02-15

This work presents the development, validation and application of four simple and direct spectrophotometric methods for determination of sodium valproate (VP) through charge transfer complexation reactions. The first method is based on the reaction of the drug with p-chloranilic acid (p-CA) in acetone to give a purple colored product with maximum absorbance at 524nm. The second method depends on the reaction of VP with dichlone (DC) in dimethylformamide forming a reddish orange product measured at 490nm. The third method is based upon the interaction of VP and picric acid (PA) in chloroform resulting in the formation of a yellow complex measured at 415nm. The fourth method involves the formation of a yellow complex peaking at 361nm upon the reaction of the drug with iodine in chloroform. Experimental conditions affecting the color development were studied and optimized. Stoichiometry of the reactions was determined. The proposed spectrophotometric procedures were effectively validated with respect to linearity, ranges, precision, accuracy, specificity, robustness, detection and quantification limits. Calibration curves of the formed color products with p-CA, DC, PA and iodine showed good linear relationships over the concentration ranges 24-144, 40-200, 2-20 and 1-8μg/mL respectively. The proposed methods were successfully applied to the assay of sodium valproate in tablets and oral solution dosage forms with good accuracy and precision. Assay results were statistically compared to a reference pharmacopoeial HPLC method where no significant differences were observed between the proposed methods and reference method. Copyright © 2015 Elsevier B.V. All rights reserved.

Validated spectrophotometric methods for determination of sodium valproate based on charge transfer complexation reactions

NASA Astrophysics Data System (ADS)

Belal, Tarek S.; El-Kafrawy, Dina S.; Mahrous, Mohamed S.; Abdel-Khalek, Magdi M.; Abo-Gharam, Amira H.

2016-02-01

This work presents the development, validation and application of four simple and direct spectrophotometric methods for determination of sodium valproate (VP) through charge transfer complexation reactions. The first method is based on the reaction of the drug with p-chloranilic acid (p-CA) in acetone to give a purple colored product with maximum absorbance at 524 nm. The second method depends on the reaction of VP with dichlone (DC) in dimethylformamide forming a reddish orange product measured at 490 nm. The third method is based upon the interaction of VP and picric acid (PA) in chloroform resulting in the formation of a yellow complex measured at 415 nm. The fourth method involves the formation of a yellow complex peaking at 361 nm upon the reaction of the drug with iodine in chloroform. Experimental conditions affecting the color development were studied and optimized. Stoichiometry of the reactions was determined. The proposed spectrophotometric procedures were effectively validated with respect to linearity, ranges, precision, accuracy, specificity, robustness, detection and quantification limits. Calibration curves of the formed color products with p-CA, DC, PA and iodine showed good linear relationships over the concentration ranges 24-144, 40-200, 2-20 and 1-8 μg/mL respectively. The proposed methods were successfully applied to the assay of sodium valproate in tablets and oral solution dosage forms with good accuracy and precision. Assay results were statistically compared to a reference pharmacopoeial HPLC method where no significant differences were observed between the proposed methods and reference method.

40 CFR 721.8085 - Reaction product of substituted aromatic diol, formaldehyde and alkanolamine, propoxylated...

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Reaction product of substituted... Reaction product of substituted aromatic diol, formaldehyde and alkanolamine, propoxylated (generic). (a... generically as reaction product of substituted aromatic diol, formaldehyde and alkanolamine, propoxylated (PMN...

40 CFR 721.8085 - Reaction product of substituted aromatic diol, formaldehyde and alkanolamine, propoxylated...

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Reaction product of substituted... Reaction product of substituted aromatic diol, formaldehyde and alkanolamine, propoxylated (generic). (a... generically as reaction product of substituted aromatic diol, formaldehyde and alkanolamine, propoxylated (PMN...

40 CFR 721.9265 - Reaction product of dichlorobenzidine and substituted alkylamide.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Reaction product of dichlorobenzidine... Significant New Uses for Specific Chemical Substances § 721.9265 Reaction product of dichlorobenzidine and... substance identified generically as a reaction product of dichlorobenzidine and substituted alkylamide (PMN...

40 CFR 721.9265 - Reaction product of dichlorobenzidine and substituted alkylamide.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Reaction product of dichlorobenzidine... Significant New Uses for Specific Chemical Substances § 721.9265 Reaction product of dichlorobenzidine and... substance identified generically as a reaction product of dichlorobenzidine and substituted alkylamide (PMN...

Product ion distributions for the reactions of NO+ with some physiologically significant volatile organosulfur and organoselenium compounds obtained using a selective reagent ionization time-of-flight mass spectrometer

PubMed Central

Mochalski, Paweł; Unterkofler, Karl; Španěl, Patrik; Smith, David; Amann, Anton

2014-01-01

RATIONALE The reactions of NO+ with volatile organic compounds (VOCs) in Selective Reagent Ionization Time-of-Flight Mass Spectrometry (SRI-TOF-MS) reactors are relatively poorly known, inhibiting their use for trace gas analysis. The rationale for this product ion distribution study was to identify the major product ions of the reactions of NO+ ions with 13 organosulfur compounds and 2 organoselenium compounds in an SRI-TOF-MS instrument and thus to prepare the way for their analysis in exhaled breath, in skin emanations and in the headspace of urine, blood and cell and bacterial cultures. METHODS Product ion distributions have been investigated by a SRI-TOF-MS instrument at an E/N in the drift tube reactor of 130 Td for both dry air and humid air (4.9% absolute humidity) used as the matrix gas. The investigated species were five monosulfides (dimethyl sulfide, ethyl methyl sulfide, methyl propyl sulfide, allyl methyl sulfide and methyl 5-methyl-2-furyl sulfide), dimethyl disulfide, dimethyl trisulfide, thiophene, 2-methylthiophene, 3-methylthiophene, methanethiol, allyl isothiocyanate, dimethyl sulfoxide, and two selenium compounds – dimethyl selenide and dimethyl diselenide. RESULTS Charge transfer was seen to be the dominant reaction mechanism in all reactions under study forming the M+ cations. For methanethiol and allyl isothiocyanate significant fractions were also observed of the stable adduct ions NO+M, formed by ion-molecule association, and [M–H]+ ions, formed by hydride ion transfer. Several other minor product channels are seen for most reactions indicating that the nascent excited intermediate (NOM)+* adduct ions partially fragment along other channels, most commonly by the elimination of neutral CH3, CH4 and/or C2H4 species that are probably bound to an NO molecule. Humidity had little effect on the product ion distributions. CONCLUSIONS The findings of this study are of particular importance for data interpretation in studies of volatile organosulfur and volatile organoselenium compounds employing SRI-TOF-MS in the NO+ mode. © 2014 The Authors. Rapid Communications in Mass Spectrometry published by John Wiley & Sons Ltd. PMID:24975248

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ding, Ling; Song, Yu, E-mail: songyu@dlpu.edu.cn; Yang, Wei

Open-framework zinc phosphates were synthesized by microwave-assisted technique, and it was shown that the morphology of as-prepared materials could be easily tailored by changing synthesis temperature, reaction time and pH value. During the synthesis, when the reaction temperature increases from 130 °C to 220 °C, the products transformed from hexagonal prisms to polyhedron along with the disappearance of the hexagonal prisms vertical plane. Simultaneously, both the reaction time and pH value could promote the nucleation and growth of crystal particles. More interestingly, the target products with different morphologies could be obtained by varying the usage of NaOH or NH{sub 3}·H{submore » 2}O at 130 °C during the microwave synthesis process. - Graphical abstract: Zinc phosphates with variable morphologies can be obtained by simply tuning the microwave-heating temperatures. Display Omitted - Highlights: • Synthesis of open-framework Zn{sub 4} (H{sub 3}O) (NH{sub 4}){sub 3}(PO{sub 4}){sub 4} compounds employing microwave technique. • Dependence of morphology on the reaction conditions. • Morphology transformation from hexagonal prisms to polyhedron was observed.« less

Experimental and DFT study of cyclodehydration and acetylation of ferrocenyl diols

NASA Astrophysics Data System (ADS)

Lapić, Jasmina; Višnjevac, Aleksandar; Cetina, Mario; Djaković, Senka; Vrček, Valerije; Rapić, Vladimir

2012-07-01

Racemic ferrocenyl diols, i.e. ferrocenyl(2-hydroxymethylphenyl)methanol (2), ferrocenyl-2-(2-hydroxymethylphenyl)ethanol (7), and ferrocenyl(2-(2-hydroxyethyl)phenyl)methanol (9) have been prepared by reduction of corresponding ketoesters using NaBH4 in a mixture EtOH and Et2O. In the course of these reactions new cyclic ethers 1-ferrocenyl-2-oxaindane (3), 3-ferrocenylisochromane (8), and 1-ferrocenylisochromane (10) have been isolated as side-products. Intramolecular cyclizations of ferrocenyl diols occur in both acidic and neutral medium. Density functional theory (BP86) calculations were used to explain the mechanism of these cyclodehydrations. Acid catalyzed reaction follows the classical SN1 mechanism, whereas the cyclodehydration in neutral medium is described as an SN2 reaction. X-ray diffraction analysis of new cyclic ether products has been performed. Monoacetates 11, 13 and 15 have been obtained in the reaction of ferrocenyl diols 2, 7, and 9, respectively, and acetic anhydride. Stereoselective acylation of racemic diols by vinyl acetate have been catalyzed by various lipases, and the best stereoselectivity has been observed for the diol 2 in the presence of Penicillium camembertii lipase.

Studying interfacial reactions of cholesterol sulfate in an unsaturated phosphatidylglycerol layer with ozone using field induced droplet ionization mass spectrometry.

PubMed

Ko, Jae Yoon; Choi, Sun Mi; Rhee, Young Min; Beauchamp, J L; Kim, Hugh I

2012-01-01

Field-induced droplet ionization (FIDI) is a recently developed ionization technique that can transfer ions from the surface of microliter droplets to the gas phase intact. The air-liquid interfacial reactions of cholesterol sulfate (CholSO(4)) in a 1-palmitoyl-2-oleoyl-sn-phosphatidylglycerol (POPG) surfactant layer with ozone (O(3)) are investigated using field-induced droplet ionization mass spectrometry (FIDI-MS). Time-resolved studies of interfacial ozonolysis of CholSO(4) reveal that water plays an important role in forming oxygenated products. An epoxide derivative is observed as a major product of CholSO(4) oxidation in the FIDI-MS spectrum after exposure of the droplet to O(3) for 5 s. The abundance of the epoxide product then decreases with continued O(3) exposure as the finite number of water molecules at the air-liquid interface becomes exhausted. Competitive oxidation of CholSO(4) and POPG is observed when they are present together in a lipid surfactant layer at the air-liquid interface. Competitive reactions of CholSO(4) and POPG with O(3) suggest that CholSO(4) is present with POPG as a well-mixed interfacial layer. Compared with CholSO(4) and POPG alone, the overall ozonolysis rates of both CholSO(4) and POPG are reduced in a mixed layer, suggesting the double bonds of both molecules are shielded by additional hydrocarbons from one another. Molecular dynamics simulations of a monolayer comprising POPG and CholSO(4) correlate well with experimental observations and provide a detailed picture of the interactions between CholSO(4), lipids, and water molecules in the interfacial region. © American Society for Mass Spectrometry, 2011

Unraveling the mysteries of microwave chemistry using silicon carbide reactor technology.

PubMed

Kappe, C Oliver

2013-07-16

In the past few years, the use of microwave energy to heat chemical reactions has become an increasingly popular theme in the scientific community. This nonclassical heating technique has slowly progressed from a laboratory curiosity to an established method commonly used both in academia and in industry. Because of its efficiency, microwave heating dramatically reduces reaction times (from days and hours to minutes and seconds) and improves product purities or material properties among other advantages. Since the early days of microwave chemistry, researchers have observed rate-accelerations and, in some cases, altered product distributions as compared with reactions carried out using classical oil-bath heating. As a result, researchers have speculated that so-called specific or nonthermal microwave effects could be responsible for these differences. Much of the debate has centered on the question of whether the electromagnetic field can exert a direct influence on a chemical transformation outside of the simple macroscopic change in bulk reaction temperature. In 2009, our group developed a relatively simple "trick" that allows us to rapidly evaluate whether an observed effect seen in a microwave-assisted reaction results from a purely thermal phenomenon, or involves specific or nonthermal microwave effects. We use a microwave reaction vessel made from silicon carbide (SiC) ceramic. Because of its high microwave absorptivity, the vessel shields its contents from the electromagnetic field. As a result, we can easily mimic a conventionally heated autoclave experiment inside a microwave reactor under carefully controlled reaction conditions. The switch from an almost microwave transparent glass (Pyrex) to a strongly microwave absorbing SiC reaction vial under otherwise identical reaction conditions (temperature profiles, pressure, stirring speed) then allows us to carefully evaluate the influence of the electromagnetic field on the particular chemical transformation. Over the past five years we have subjected a wide variety of chemical transformations, including organic reactions, preparations of inorganic nanoparticles, and the hydrolysis of proteins, to the "SiC test." In nearly all of the studied examples, we obtained identical results from reactions carried out in Pyrex vials and those carried out in SiC vials. The data obtained from these investigations confirm that in the overwhelming majority of cases a bulk temperature phenomenon drives the enhancements in microwave chemistry and that the electromagnetic field has no direct influence on the reaction pathway.

Gas-phase ozonolysis of β-ocimene: Temperature dependent rate coefficients and product distribution

NASA Astrophysics Data System (ADS)

Gaona-Colmán, Elizabeth; Blanco, María B.; Barnes, Ian; Teruel, Mariano A.

2016-12-01

Rate coefficients for the reaction of β-ocimene with O3 molecules have been determined over the temperature range 288-311 K at 750 Torr total pressure of nitrogen using the relative rate technique. The investigations were performed in a large volume reaction vessel using long-path in-situ Fourier transformed infrared (FTIR) spectroscopy to monitor the reactants and products. A value of k(β-ocimene + O3) = (3.74 ± 0.92) × 10-16 cm3 molecule-1 s-1 has been obtained for the reaction at 298 K. The temperature dependence of the reaction is best described by the Arrhenius expression k = (1.94 ± 0.02) × 10-14 exp [(-1181 ± 51)/T] cm3 molecule-1 s-1. In addition, a product study has been carried out at 298 K in 750 Torr of synthetic air and the following products with yields in molar % were observed: formaldehyde (36 ± 2), acetone (15 ± 1), methylglyoxal (9.5 ± 0.4) and hydroxyacetone (19 ± 1). The formation of formaldehyde can be explained by the addition of O3 to the C1sbnd C2 double bond of the β-ocimene. Addition of O3 to the C6sbnd C7 double bond leads to the formation of acetone and the CH3C·(OO·)CH3 biradical, which can through isomerization/stabilization form methylglyoxal (hydroperoxide channel) and hydroxyacetone. The formed products will contribute to the formation of PAN and derivatives in polluted environments and also the oxidation capacity of the atmosphere.

Conversion of 1,3-Propylene Glycol on Rutile TiO2(110)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Long; Li, Zhenjun; Smith, R. Scott

2014-10-09

The adsorption of 1,3-propylene glycol (1,3-PG) on partially reduced TiO2(110) and its conversion to products have been studied by a combination of molecular beam dosing and temperature programmed desorption (TPD). When the Ti surface sites are saturated by 1,3-PG, ~80% of the molecules undergo further reactions to yield products that are liberated during the TPD ramp. In contrast to ethylene glycol (EG) and 1,2- propylene glycol (1,2-PG) that yield only alkenes and water at very low coverages (< 0.05 ML), two additional products, HCHO and C2H4, along with propylene (CH3CHCH2) and water are observed for 1,3-PG. Identical TPD line shapesmore » and desorption yields for HCHO and C2H4 suggest that these products result from C-C bond cleavage and are coupled. At higher 1,3-PG coverages (> 0.1 ML), propanal (CH3CH2CHO) and two additional products, 1-propanol (CH3CH2CH2OH) and acrolein (CH2CHCHO), are observed. The desorption of 1-propanol is found to be coupled with the desorption of acrolein, suggesting that these products are formed by the disproportionation of two 1,3-PG molecules. The coverage dependent TPD results further show that propylene formation dominates at low coverages (< 0.3 ML), while the decomposition and disproportionation channels increase rapidly at higher coverages and reach yields comparable to that of propylene at the 1,3-PG saturation coverage of 0.5 ML. The observed surface chemistry clearly shows how the molecular structure of glycols influences their reaction pathways on oxide surfaces.« less

Putrescine Aminopropyltransferase Is Responsible for Biosynthesis of Spermidine, Spermine, and Multiple Uncommon Polyamines in Osmotic Stress-Tolerant Alfalfa.

PubMed Central

Bagga, S.; Rochford, J.; Klaene, Z.; Kuehn, G. D.; Phillips, G. C.

1997-01-01

The biosynthesis of polyamines from the diamine putrescine is not fully understood in higher plants. A putrescine aminopropyltransferase (PAPT) enzyme activity was characterized in alfalfa (Medicago sativa L.). This enzyme activity was highly specific for putrescine as the initial substrate and did not recognize another common diamine, 1,3-diaminopropane, or higher-molecular-weight polyamines such as spermidine and spermine as alternative initial substrates. The enzyme activity was inhibited by a general inhibitor of aminopropyltransferases, 5[prime]-methylthioadenosine, and by a specific inhibitor of PAPTs, cyclohexylammonium sulfate. The initial substrate specificity and inhibition characteristics of the enzyme activity suggested that it is a classical example of a PAPT. However, this enzyme activity yielded multiple polyamine products, which is uncharacteristic of PAPTs. The major reaction product of PAPT activity in alfalfa was spermidine. The next most abundant products of the enzyme reaction using putrescine as the initial substrate included the tetramines spermine and thermospermine. These two tetramines were distinguished by thin-layer chromatography to be distinct reaction products exhibiting differential rates of formation. In addition, the uncommon polyamines homocaldopentamine and homocaldohexamine were tentatively identified as minor enzymatic reaction products but only in extracts prepared from osmotic stresstolerant alfalfa cultivars. PAPT activity from alfalfa was highest in meristematic shoot tip and floral bud tissues and was not detected in older, nonmeristematic tissues. Product inhibition of the enzyme activity was observed after spermidine was added into the in vitro assay for alfalfa PAPT activity. A biosynthetic pathway is proposed that accounts for the characteristics of this PAPT activity and accommodates a novel scheme by which certain uncommon polyamines are produced in plants. PMID:12223719

Structural basis for regioisomerization in the alkali-metal-mediated zincation (AMMZn) of trifluoromethyl benzene by isolation of kinetic and thermodynamic intermediates.

PubMed

Armstrong, David R; Blair, Victoria L; Clegg, William; Dale, Sophie H; Garcia-Alvarez, Joaquin; Honeyman, Gordon W; Hevia, Eva; Mulvey, Robert E; Russo, Luca

2010-07-14

Performed with a desire to advance knowledge of the structures and mechanisms governing alkali-metal-mediated zincation, this study monitors the reaction between the TMP-dialkylzincate reagent [(TMEDA)Na(TMP)((t)Bu)Zn((t)Bu)] 1 and trifluoromethyl benzene C(6)H(5)CF(3) 2. A complicated mixture of products is observed at room temperature. X-ray crystallography has identified two of these products as ortho- and meta-regioisomers of heterotrianionic [(TMEDA)Na(TMP)(C(6)H(4)-CF(3))Zn((t)Bu)], 3-ortho and 3-meta, respectively. Multinuclear NMR data of the bulk crystalline product confirm the presence of these two regioisomers as well as a third isomer, 3-para, in a respective ratio of 20:11:1, and an additional product 4, which also exhibits ortho-zincation of the aryl substrate. Repeating the reaction at 0 degrees C gave exclusively 4, which was crystallographically characterized as [{(TMEDA)(2)Na}(+){Zn(C(6)H(4)-CF(3))((t)Bu)(2)}(-)]. Mimicking the original room-temperature reaction, this kinetic product was subsequently reacted with TMP(H) to afford a complicated mixture of products, including significantly the three regioisomers of 3. Surprisingly, 4 adopts a solvent-separated ion pair arrangement in contrast to the contacted ion variants of 3-ortho and 3-meta. Aided by DFT calculations on model systems, discussion focuses on the different basicities, amido or alkyl, and steps, exhibited in these reactions, and how the structures and bonding within these isolated key metallic intermediates (prior to any electrophilic interception step), specifically the interactions involving the alkali metal, influence the regioselectivity of the Zn-H exchange process.

Phase, composition, and growth mechanism for secondary organic aerosol from the ozonolysis of α-cedrene

NASA Astrophysics Data System (ADS)

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

2016-03-01

Sesquiterpenes are an important class of biogenic volatile organic compounds (BVOCs) and have a high secondary organic aerosol (SOA) forming potential. However, SOA formation from sesquiterpene oxidation has received less attention compared to other BVOCs such as monoterpenes, and the underlying mechanisms remain poorly understood. In this work, we present a comprehensive experimental investigation of the ozonolysis of α-cedrene both in a glass flow reactor (27-44 s reaction times) and in static Teflon chambers (30-60 min reaction times). The SOA was collected by impaction or filters, followed by analysis using attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy and electrospray ionization mass spectrometry (ESI-MS), or measured online using direct analysis in real-time mass spectrometry (DART-MS) and aerosol mass spectrometry (AMS). The slow evaporation of 2-ethylhexyl nitrate that was incorporated into the SOA during its formation and growth gives an estimated diffusion coefficient of 3 × 10-15 cm2 s-1 and shows that SOA is a highly viscous semisolid. Possible structures of four newly observed low molecular weight (MW ≤ 300 Da) reaction products with higher oxygen content than those previously reported were identified. High molecular weight (HMW) products formed in the early stages of the oxidation have structures consistent with aldol condensation products, peroxyhemiacetals, and esters. The size-dependent distributions of HMW products in the SOA, as well as the effects of stabilized Criegee intermediate (SCI) scavengers on HMW products and particle formation, confirm that HMW products and reactions of SCI play a crucial role in early stages of particle formation. Our studies provide new insights into mechanisms of SOA formation and growth in α-cedrene ozonolysis and the important role of sesquiterpenes in new particle formation as suggested by field measurements.

Phase, composition and growth mechanism for secondary organic aerosol from the ozonolysis of α-cedrene

NASA Astrophysics Data System (ADS)

Zhao, Y.; Wingen, L. M.; Perraud, V.; Finlayson-Pitts, B. J.

2015-12-01

Sesquiterpenes are an important class of biogenic volatile organic compounds (BVOCs) and have a high secondary organic aerosol (SOA) forming potential. However, SOA formation from sesquiterpene oxidation has received less attention compared to other BVOCs such as monoterpenes, and the underlying mechanisms remain poorly understood. In this work, we present a comprehensive experimental investigation of the ozonolysis of α-cedrene both in a glass flow reactor (27-44 s reaction times) and in static Teflon chambers (30-60 min reaction times). The SOA was collected by impaction or filters, followed by analysis using attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) and electrospray ionization mass spectrometry (ESI-MS), or measured on line using direct analysis in real time (DART-MS) and aerosol mass spectrometry (AMS). The slow evaporation of 2-ethylhexyl nitrate that was incorporated into the SOA during its formation and growth gives an estimated diffusion coefficient of 3 × 10-15 cm2 s-1 and shows that SOA is a highly viscous semi-solid. Possible structures of four newly observed low molecular weight (MW ≤ 300 Da) reaction products with higher oxygen content than those previously reported were identified. High molecular weight (HMW) products formed in the early stages of the oxidation have structures consistent with aldol condensation products, peroxyhemiacetals, and esters. The size-dependent distributions of HMW products in the SOA, as well as the effects of stabilized Criegee intermediate (SCI) scavengers on HMW products and particle formation, confirm that HMW products and reactions of Criegee intermediates play a crucial role in early stages of particle formation. Our studies provide new insights into mechanisms of SOA formation and growth in α-cedrene ozonolysis and the important role of sesquiterpenes in new particle formation as suggested by field measurements.

Observation of the hc(1P1) state of charmonium.

PubMed

Rosner, J L; Adam, N E; Alexander, J P; Berkelman, K; Cassel, D G; Crede, V; Duboscq, J E; Ecklund, K M; Ehrlich, R; Fields, L; Galik, R S; Gibbons, L; Gittelman, B; Gray, R; Gray, S W; Hartill, D L; Heltsley, B K; Hertz, D; Jones, C D; Kandaswamy, J; Kreinick, D L; Kuznetsov, V E; Mahlke-Krüger, H; Meyer, T O; Onyisi, P U E; Patterson, J R; Peterson, D; Phillips, E A; Pivarski, J; Riley, D; Ryd, A; Sadoff, A J; Schwarthoff, H; Shi, X; Shepherd, M R; Stroiney, S; Sun, W M; Urner, D; Wilksen, T; Weaver, K M; Weinberger, M; Athar, S B; Avery, P; Breva-Newell, L; Patel, R; Potlia, V; Stoeck, H; Yelton, J; Rubin, P; Cawlfield, C; Eisenstein, B I; Gollin, G D; Karliner, I; Kim, D; Lowrey, N; Naik, P; Sedlack, C; Selen, M; White, E J; Williams, J; Wiss, J; Edwards, K W; Besson, D; Pedlar, T K; Cronin-Hennessy, D; Gao, K Y; Gong, D T; Hietala, J; Kubota, Y; Klein, T; Lang, B W; Li, S Z; Poling, R; Scott, A W; Smith, A; Dobbs, S; Metreveli, Z; Seth, K K; Tomaradze, A; Zweber, P; Ernst, J; Mahmood, A H; Severini, H; Asner, D M; Dytman, S A; Love, W; Mehrabyan, S; Mueller, J A; Savinov, V; Li, Z; Lopez, A; Mendez, H; Ramirez, J; Huang, G S; Miller, D H; Pavlunin, V; Sanghi, B; Shipsey, I P J; Adams, G S; Cravey, M; Cummings, J P; Danko, I; Napolitano, J; He, Q; Muramatsu, H; Park, C S; Park, W; Thorndike, E H; Coan, T E; Gao, Y S; Liu, F; Artuso, M; Boulahouache, C; Blusk, S; Butt, J; Dorjkhaidav, O; Li, J; Menaa, N; Mountain, R; Nandakumar, R; Randrianarivony, K; Redjimi, R; Sia, R; Skwarnicki, T; Stone, S; Wang, J C; Zhang, K; Csorna, S E; Bonvicini, G; Cinabro, D; Dubrovin, M; Briere, R A; Chen, G P; Chen, J; Ferguson, T; Tatishvili, G; Vogel, H; Watkins, M E

2005-09-02

The h(c)((1)P(1)) state of charmonium has been observed in the reaction psi(2S) --> pi(0)h(c) --> (gammagamma)(gammaeta(c)) using 3.08 x10(6) psi(2S) decays recorded in the CLEO detector. Data have been analyzed both for the inclusive reaction, where the decay products of the eta(c) are not identified, and for exclusive reactions, in which eta(c) decays are reconstructed in seven hadronic decay channels. We find M(h(c)) = 3524.4 +/- 0.6 +/- 0.4 MeV which corresponds to a hyperfine splitting DeltaM(hf)(1P) triple-bond pi(0)h(c)) x B(h(c) --> gammaeta(c)) = (4.0 +/- 0.8 +/- 0.7) x 10(-4).

Evaluation of resonances above the proton threshold in 26Si

NASA Astrophysics Data System (ADS)

Chipps, K. A.

2016-09-01

26Al remains an intriguing target for observational gamma-ray astronomy, thanks to its characteristic decay. The 25Al(p, γ)26Si reaction is the crucial link in a sequence that bypasses the production of the observable 26Alg . s . in favor of the isomeric state, and as such has been the focus of many studies. Considerable confusion in this regard has arisen from the use of outdated excitation energies and masses in reaction studies and rate evaluations. Recalibration of existing data from the literature has resulted in updated excitation and resonance energies, but open questions remain, particularly with regard to spin assignments and partial widths/resonance strengths. A discussion of the levels just above the proton threshold in 26Si relevant to the astrophysical 25Al(p, γ)26Si reaction rate will be presented. This work is funded by the US Department of Energy, Office of Science, Office of Nuclear Physics.

Cascade Cyclizations of Acyclic and Macrocyclic Alkynones: Studies toward the Synthesis of Phomactin A

PubMed Central

Ciesielski, Jennifer; Gandon, Vincent; Frontier, Alison J.

2013-01-01

A study of the reactivity and diastereoselectivity of the Lewis acid-promoted cascade cyclizations of both acyclic and macrocyclic alkynones is described. In these reactions, a β-iodoallenolate intermediate is generated via conjugate addition of iodide to an alkynone, followed by an intramolecular aldol reaction with a tethered aldehyde to afford a cyclohexenyl alcohol. The Lewis acid magnesium iodide (MgI2) was found to promote irreversible ring closure, while cyclizations using BF3·OEt2 as promoter occurred reversibly. For both acyclic and macrocyclic ynones, high diastereoselectivity was observed in the intramolecular aldol reaction. The MgI2 protocol for cyclization was applied to the synthesis of advanced intermediates relevant to the synthesis of phomactin natural products, during which a novel transannular cation-olefin cyclization was observed. DFT calculations were conducted to analyze the mechanism of this unusual MgI2-promoted process. PMID:23724905

A quantum protective mechanism in photosynthesis

NASA Astrophysics Data System (ADS)

Marais, Adriana; Sinayskiy, Ilya; Petruccione, Francesco; van Grondelle, Rienk

2015-03-01

Since the emergence of oxygenic photosynthesis, living systems have developed protective mechanisms against reactive oxygen species. During charge separation in photosynthetic reaction centres, triplet states can react with molecular oxygen generating destructive singlet oxygen. The triplet product yield in bacteria is observed to be reduced by weak magnetic fields. Reaction centres from plants' photosystem II share many features with bacterial reaction centres, including a high-spin iron whose function has remained obscure. To explain observations that the magnetic field effect is reduced by the iron, we propose that its fast-relaxing spin plays a protective role in photosynthesis by generating an effective magnetic field. We consider a simple model of the system, derive an analytical expression for the effective magnetic field and analyse the resulting triplet yield reduction. The protective mechanism is robust for realistic parameter ranges, constituting a clear example of a quantum effect playing a macroscopic role vital for life.

A quantum protective mechanism in photosynthesis.

PubMed

Marais, Adriana; Sinayskiy, Ilya; Petruccione, Francesco; van Grondelle, Rienk

2015-03-03

Since the emergence of oxygenic photosynthesis, living systems have developed protective mechanisms against reactive oxygen species. During charge separation in photosynthetic reaction centres, triplet states can react with molecular oxygen generating destructive singlet oxygen. The triplet product yield in bacteria is observed to be reduced by weak magnetic fields. Reaction centres from plants' photosystem II share many features with bacterial reaction centres, including a high-spin iron whose function has remained obscure. To explain observations that the magnetic field effect is reduced by the iron, we propose that its fast-relaxing spin plays a protective role in photosynthesis by generating an effective magnetic field. We consider a simple model of the system, derive an analytical expression for the effective magnetic field and analyse the resulting triplet yield reduction. The protective mechanism is robust for realistic parameter ranges, constituting a clear example of a quantum effect playing a macroscopic role vital for life.

Method for production of magnesium

DOEpatents

Diaz, Alexander F.; Howard, Jack B.; Modestino, Anthony J.; Peters, William A.

1998-01-01

A continuous process for the production of elemental magnesium is described. Magnesium is made from magnesium oxide and a light hydrocarbon gas. In the process, a feed stream of the magnesium oxide and gas is continuously fed into a reaction zone. There the magnesium oxide and gas are reacted at a temperature of about 1400.degree. C. or greater in the reaction zone to provide a continuous product stream of reaction products, which include elemental magnesium. The product stream is continuously quenched after leaving the reaction zone, and the elemental magnesium is separated from other reaction products.

Method for production of magnesium

DOEpatents

Diaz, A.F.; Howard, J.B.; Modestino, A.J.; Peters, W.A.

1998-07-21

A continuous process for the production of elemental magnesium is described. Magnesium is made from magnesium oxide and a light hydrocarbon gas. In the process, a feed stream of the magnesium oxide and gas is continuously fed into a reaction zone. There the magnesium oxide and gas are reacted at a temperature of about 1400 C or greater in the reaction zone to provide a continuous product stream of reaction products, which include elemental magnesium. The product stream is continuously quenched after leaving the reaction zone, and the elemental magnesium is separated from other reaction products. 12 figs.