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Sample records for h2o-3h exchange reaction

  1. Metal-containing ligands for mixed-metal polymers: novel Cu(II)-Ag(I) mixed-metal coordination polymers generated from [Cu(2-methylpyrazine-5-carboxylate)2(H2O)].3H2O and silver(I) salts.

    PubMed

    Dong, Y B; Smith, M D; zur Loye, H C

    2000-05-01

    One Cu(II)-containing ligand and two Cu(II)-Ag(I) mixed-metal coordination polymers have been synthesized. [Cu(2-methylpyrazine-5-carboxylate)2(H2O)].3H2O (1) was obtained as a molecular complex with two uncoordinated nitrogen donors by the reaction of 2-methylpyrazine-5-carboxylate sodium with CuCl(2).2H2O in water. Compound 1 crystallized in the triclinic space group P1, with a = 10.498(2) A, b = 11.000(2) A, c = 8.1424(16) A, alpha = 98.33(3) degrees, beta = 101.83(3) degrees, gamma = 66.68(3) degrees, and Z = 2. Reactions of 1 with silver(I) salts have been studied. Two Cu(II)-Ag(I) mixed-metal coordination polymers, namely, Ag[Cu(2-methylpyrazine-5-carboxylate)2.(H2O)2](BF4) (2) and Ag[Cu(2-methylpyrazine-5-carboxylate)2.(H2O)2](NO3) (3), have been generated by treating 1 with AgBF4 and AgNO3, respectively. Compound 2 crystallized in the monoclinic space group C2/c, with a = 25.827(5) A, b = 9.6430(19) A, c = 7.4525(15) A, beta = 94.74(3) degrees, and Z = 4. Compound 3 also crystallized in the monoclinic space group C2/c, with a = 25.855(5) A, b = 9.782(2) A, c = 7.1201(14) A, beta = 96.90(3) degrees, and Z = 4. The main structural feature in both 2 and 3 is a zigzag Cu(II)-Ag(I) mixed-metal chain, in which the alternating Cu(II) and Ag(I) centers are linked by 2-methylpyrazine-5-carboxylate spacers. The effect of the nitrate counterion was illustrated by compound 3, in which a novel [Ag+...NO3-] coordination chain has been found which acts as the connector to cross-link the one-dimensional zigzag chains into a three-dimensional network. In addition, an identical interchain O-H...O hydrogen bonding system has been found in both 2 and 3 and has been shown to play a significant role in directing the alignment of the one-dimensional mixed-metal polymer chains in the crystalline state. The magnetic susceptibilities of 2 and 3 were measured and found to follow the Curie law (mu eff = 1.85 for 2 and 1.83 for 3). PMID:11428114

  2. Multidimentional Normal Mode Calculations for the OH Vibrational Spectra of (H_2O)_3^+, (H_2O)_3^+Ar, H^+(H_2O)_3, and H^+(H_2O)_3Ar

    NASA Astrophysics Data System (ADS)

    Li, Ying-Cheng; Chuang, Hsiao-Han; Tan, Jake Acedera; Takahashi, Kaito; Kuo, Jer-Lai

    2014-06-01

    Recent experimental observations of (H_2O)_3^+, (H_2O)_3^+Ar, H^+(H_2O)_3, and H^+(H_2O)_3Ar clusters in the region 1400-3800 wn show that the OH stretching vibration has distinct characteristics. Multidimensional normal mode calculations were carried out for OH stretching vibrations in the 1200-4000 wn photon energy range. The potential energy and dipole surfaces were evaluated by using first-principles methods. By comparing the calculated frequencies and intensities of OH stretching vibration with experimental spectra, we found that the assignment of OH strecthing of H_3O^+ moiety and free OH strectching vibration have resonable agreement with experimental data. Jeffrey M. Headrick, Eric G. Diken, Richard S. Walters, Nathan I. Hammer, Richard A. Christie, Jun Cui, Evgeniy M. Myshakin, Michael A. Duncan, Mark A. Johnson, Kenneth D. Jordan, Science, 2005, 17, 1765. Kenta Mizuse, Jer-Lai Kuo and Asuka Fujii, Chem. Sci., 2011, 2, 868 Kenta Mizuse and Asuka Fujii, J. Phys. Chem. A, 2013, 117, 929.

  3. The Kinetics of Isotopic Exchange Reactions.

    ERIC Educational Resources Information Center

    Logan, S. R.

    1990-01-01

    Discussed are the kinetic interactions of these chemical processes and the determination of the actual order of such reactions. Included are multiple exchange, catalytic exchange with deuterium, and depletion of the original substrate. (CW)

  4. Multinucleon exchange in quasifission reactions

    NASA Astrophysics Data System (ADS)

    Ayik, S.; Yilmaz, B.; Yilmaz, O.

    2015-12-01

    The nucleon exchange mechanism is investigated in the central collisions of 40Ca+238U and 48Ca+238U systems near the quasifission regime in the framework of the stochastic mean-field (SMF) approach. Sufficiently below the fusion barrier, a dinuclear structure in the collisions is maintained to a large extent. Consequently, it is possible to describe nucleon exchange as a diffusion process familiar from deep-inelastic collisions. Diffusion coefficients for proton and neutron exchange are determined from the microscopic basis of the SMF approach in the semiclassical framework. Calculations show that after a fast charge equilibration the system drifts toward symmetry over a very long interaction time. Large dispersions of proton and neutron distributions of the produced fragments indicate that the diffusion mechanism may help to populate heavy transuranium elements near the quasifission regime in these collisions.

  5. Nucleon exchange in damped nuclear reactions

    SciTech Connect

    Randrup, J.

    1986-04-01

    Starting from the general context of one-body nuclear dynamics, the nucleon-exchange mechanism in damped nuclear reactions is discussed. Some of its characteristic effects on various dinuclear observables are highlighted and a few recent advances are described.

  6. Charge exchange reactions and applications to astrophysics

    NASA Astrophysics Data System (ADS)

    Cheoun, Myung-Ki; Ha, Eunja; Kajino, T.

    2012-11-01

    Neutrino-induced reactions have been known to play important roles as the neutrino process on the nucleosynthesis in core collapsing supernovae (SNe) explosions because expected neutrino flux and energy are sufficiently high enough to excite many relevant nuclei in spite of small cross sections of the weak interaction. However, we do not have enough data for the neutrino reaction to be exploited in the network calculation. Only a sparse data in the relevant energy range is known, in specific, for 12C. Therefore we have to rely on theoretical estimation of the reaction, which has two different modes, charge current (CC) and neutral current (NC). In particular, CC reactions are closely related to charge exchange reactions (CEXRs) which are feasible in the experiment, such as, (p,n) or (n,p) reactions. These CEXRs are usually dominated by the Gamow-Teller (GT) transition in the lower energy region. In this respect, any theoretical approaches for the neutrino reaction should be investigated for the CEXR because we have and expect more useful experimental data. After confirming our models to the GT strength deduced from the CEXR, we calculated neutrino-induced reactions in the energy range below the quasielastic region for nuclei of astrophysical importance. Our calculations are carried out with the Quasi-particle Random Phase Approximation (QRPA), which successfully described the nuclear beta decays of relevant nuclei. To describe neutrino-nucleus reactions, general multipole transitions by the weak interaction are considered for CC and NC reactions. Both reactions are described in a theoretical framework. Our results are shown to well reproduce the data from CEXRs and the sparse experimental data related to the neutrino-induced reaction, and further extended for neutrino reactions on various nuclear targets. Parts of the results are reported in this talk.

  7. PEP Carboxykinase Exchange Reaction in Photosynthetic Bacteria 1

    PubMed Central

    Cooper, T. G.; Benedict, C. R.

    1968-01-01

    This paper describes some new characteristics of the phosphoenolpyruvate carboxykinase CO2-oxaloacetate exchange reaction in purified preparations of Rhodospirillum rubrum. The enzymatic activity has been purified 169-fold. Nucleotide diphosphates substitute for nucleotide triphosphates in the exchange reaction. Nucleotide diphosphates will not support the synthesis of phosphoenolpyruvate from oxaloacetate. This reaction differs significantly from the CO2-oxaloacetate exchange reaction in higher plants and animals. PMID:5661493

  8. Heterogeneous Catalysis: Deuterium Exchange Reactions of Hydrogen and Methane

    ERIC Educational Resources Information Center

    Mirich, Anne; Miller, Trisha Hoette; Klotz, Elsbeth; Mattson, Bruce

    2015-01-01

    Two gas phase deuterium/hydrogen exchange reactions are described utilizing a simple inexpensive glass catalyst tube containing 0.5% Pd on alumina through which gas mixtures can be passed and products collected for analysis. The first of these exchange reactions involves H[subscript 2] + D[subscript 2], which proceeds at temperatures as low as 77…

  9. Using reactive artificial muscles to determine water exchange during reactions

    NASA Astrophysics Data System (ADS)

    Otero, T. F.; Martínez, J. G.; Zaifoglu, B.

    2013-10-01

    Artificial muscles based on films of conducting polymers translate film volume variations, driven by electrochemical reactions (Faradaic motors), into macroscopic movements with generation of mechanical energy. The reaction promotes exchange of counterions (anions here) and solvent molecules with the electrolyte. Attributing here both the film volume variation and the movement originated by these exchanges of ions and solvent, the described angles can be used to quantify the exchanged solvent. Different angles described by bending muscles consuming equal driving charges in electrolytes having the same cation and different anions were measured. The number of exchanged counterions is given by the consumed charge and the ion valence: this is a Faradaic reaction. The described angle fraction due to the exchanged anions is given by the number of anions and the crystallographic radius. Taking as reference the anion giving the shorter angle, whatever the consumed charge, the relative number of solvent molecules exchanged by the polymeric membrane during a reversible reaction was determined. Actuators and artificial muscles can be used as useful tools for, at least, an initial study of the solvent exchange during reactions in reactive gels.

  10. Phospholipid exchange reactions within the liver cell

    PubMed Central

    McMurray, W. C.; Dawson, R. M. C.

    1969-01-01

    1. Isolated rat liver mitochondria do not synthesize labelled phosphatidylcholine from CDP-[14C]choline or any phospholipid other than phosphatidic acid from [32P]phosphate. The minimal labelling of phosphatidylcholine and other phosphoglycerides can be attributed to microsomal contamination. However, when mitochondria and microsomes are incubated together with [32P]phosphate, the phosphatidylcholine, phosphatidylinositol and phosphatidylethanolamine of the reisolated mitochondria become labelled, suggesting a transfer of phospholipids between the two fractions. 2. When liver microsomes or mitochondria containing labelled phosphatidylcholine are independently incubated with the opposite un-labelled fraction, there is a substantial and rapid exchange of the phospholipid between the two membranes. Exchange of phosphatidylinositol also occurs rapidly, whereas phosphatidylethanolamine and phosphatidic acid exchange only slowly. There is no corresponding transfer of marker enzymes. The transfer of phosphatidylcholine does not occur at 0°, and there is no requirement for added substrate, ATP or Mg2+, but the omission of a heat-labile supernatant fraction markedly decreases the exchange. 3. After intravenous injection of [32P]phosphate, short-period labelling experiments of the individual phospholipids of rat liver microsomes and mitochondria in vivo give no evidence for a similar exchange process. However, the incubation of isolated microsomes and mitochondria with [32P]phosphate also fails on reisolation of the fractions to demonstrate a precursor–product relationship between the individual phospholipids of the two membranes. 4. The intraperitoneal injection of [32P]phosphate results in a far greater proportion of the dose entering the liver than does intravenous administration. After intraperitoneal administration of [32P]phosphate the specific radioactivities of the individual phospholipids are in the order microsomes > outer mitochondrial membrane > inner

  11. Cu Vacancies Boost Cation Exchange Reactions in Copper Selenide Nanocrystals

    PubMed Central

    2015-01-01

    We have investigated cation exchange reactions in copper selenide nanocrystals using two different divalent ions as guest cations (Zn2+ and Cd2+) and comparing the reactivity of close to stoichiometric (that is, Cu2Se) nanocrystals with that of nonstoichiometric (Cu2–xSe) nanocrystals, to gain insights into the mechanism of cation exchange at the nanoscale. We have found that the presence of a large density of copper vacancies significantly accelerated the exchange process at room temperature and corroborated vacancy diffusion as one of the main drivers in these reactions. Partially exchanged samples exhibited Janus-like heterostructures made of immiscible domains sharing epitaxial interfaces. No alloy or core–shell structures were observed. The role of phosphines, like tri-n-octylphosphine, in these reactions, is multifaceted: besides acting as selective solvating ligands for Cu+ ions exiting the nanoparticles during exchange, they also enable anion diffusion, by extracting an appreciable amount of selenium to the solution phase, which may further promote the exchange process. In reactions run at a higher temperature (150 °C), copper vacancies were quickly eliminated from the nanocrystals and major differences in Cu stoichiometries, as well as in reactivities, between the initial Cu2Se and Cu2–xSe samples were rapidly smoothed out. These experiments indicate that cation exchange, under the specific conditions of this work, is more efficient at room temperature than at higher temperature. PMID:26140622

  12. Cu Vacancies Boost Cation Exchange Reactions in Copper Selenide Nanocrystals.

    PubMed

    Lesnyak, Vladimir; Brescia, Rosaria; Messina, Gabriele C; Manna, Liberato

    2015-07-29

    We have investigated cation exchange reactions in copper selenide nanocrystals using two different divalent ions as guest cations (Zn(2+) and Cd(2+)) and comparing the reactivity of close to stoichiometric (that is, Cu2Se) nanocrystals with that of nonstoichiometric (Cu(2-x)Se) nanocrystals, to gain insights into the mechanism of cation exchange at the nanoscale. We have found that the presence of a large density of copper vacancies significantly accelerated the exchange process at room temperature and corroborated vacancy diffusion as one of the main drivers in these reactions. Partially exchanged samples exhibited Janus-like heterostructures made of immiscible domains sharing epitaxial interfaces. No alloy or core-shell structures were observed. The role of phosphines, like tri-n-octylphosphine, in these reactions, is multifaceted: besides acting as selective solvating ligands for Cu(+) ions exiting the nanoparticles during exchange, they also enable anion diffusion, by extracting an appreciable amount of selenium to the solution phase, which may further promote the exchange process. In reactions run at a higher temperature (150 °C), copper vacancies were quickly eliminated from the nanocrystals and major differences in Cu stoichiometries, as well as in reactivities, between the initial Cu2Se and Cu(2-x)Se samples were rapidly smoothed out. These experiments indicate that cation exchange, under the specific conditions of this work, is more efficient at room temperature than at higher temperature. PMID:26140622

  13. Heat exchanger development at Reaction Engines Ltd.

    NASA Astrophysics Data System (ADS)

    Varvill, Richard

    2010-05-01

    The SABRE engine for SKYLON has a sophisticated thermodynamic cycle with heat transfer between the fluid streams. The intake airflow is cooled in an efficient counterflow precooler, consisting of many thousand small bore thin wall tubes. Precooler manufacturing technology has been under investigation at REL for a number of years with the result that flightweight matrix modules can now be produced. A major difficulty with cooling the airflow to sub-zero temperatures at low altitude is the problem of frost formation. Frost control technology has been developed which enables steady state operation. The helium loop requires a top cycle heat exchanger (HX3) to deliver a constant inlet temperature to the main turbine. This is constructed in silicon carbide and the feasibility of manufacturing various matrix geometries has been investigated along with suitable joining techniques. A demonstration precooler will be made to run in front of a Viper jet engine at REL's B9 test facility in 2011. This precooler will incorporate full frost control and be built from full size SABRE engine modules. The facility will incorporate a high pressure helium loop that rejects the absorbed heat to a bath of liquid nitrogen.

  14. Pion double charge exchange reactions leading to double pionic atoms

    SciTech Connect

    Nieves, J.; Oset, E.; Vincente-Vacas, M.J. ); Hirenzaki, S.; Toki, H. )

    1992-10-20

    In this paper, the authors study theoretically pion double charge exchange reactions leading to double pionic atoms. The reaction cross-sections with two pions in the deeper bound pionic orbits in [sup 208]Pb are calculated with realistic pionic atom wave functions and distortion effects. The cross-sections are found to be d[sup 2] [sigma]/dEd[Omega] [approx] 10[sup [minus] 3] [minus] 10[sup [minus] 4] [mu]b/srMeV, which are only a small fraction of the double charge exchange.

  15. Individual breathing reactions measured in hemoglobin by hydrogen exchange methods

    SciTech Connect

    Englander, S.W.; Calhoun, D.B.; Englander, J.J.; Kallenbach, N.R.; Liem, R.K.H.; Malin, E.L.; Mandal, C.; Rogero, J.R.

    1980-10-01

    Protein hydrogen exchange is generally believed to register some aspect of internal protein dynamics, but the kind of motion at work is not clear. Experiments are being done to identify the determinants of protein hydrogen exchange and to distinguish between local unfolding and accessibility-penetration mechanisms. Results with small molecules, polynucleotides, and proteins demonstrate that solvent accessibility is by no means sufficient for fast exchange. H-exchange slowing is quite generally connected with intramolecular H-bonding, and the exchange process depends pivotally on transient H-bond cleavage. At least in ..cap alpha..-helical structures, the cooperative aspect of H-bond cleavage mut be expressed in local unfolding reactions. Results obtained by use of a difference hydrogen exchange method appear to provide a direct measurement of transient, cooperative, local unfolding reactions in hemoglobin. The reality of these supposed coherent breathing units is being tested by using the difference H-exchange approach to tritium label the units one at a time and then attempting to locate the tritium by fragmenting the protein, separating the fragments, and testing them for label. Early results demonstrate the feasibility of this approach.

  16. Cross-ligation and exchange reactions catalyzed by hairpin ribozymes.

    PubMed Central

    Komatsu, Y; Koizumi, M; Sekiguchi, A; Ohtsuka, E

    1993-01-01

    The negative strand of the satellite RNA of tobacco ringspot virus (sTobRV(-)) contains a hairpin catalytic domain that shows self-cleavage and self-ligation activities in the presence of magnesium ions. We describe here that the minimal catalytic domain can catalyze a cross-ligation reaction between two kinds of substrates in trans. The cross-ligated product increased when the reaction temperature was decreased during the reaction from 37 degrees C to 4 degrees C. A two-stranded hairpin ribozyme, divided into two fragments between G45 and U46 in a hairpin loop, showed higher ligation activity than the nondivided ribozyme. The two stranded ribozyme also catalyzed an exchange reaction of the 3'-portion of the cleavage site. Images PMID:8441626

  17. [Exchange reactions in brain tissue under chronic ethanol intoxication].

    PubMed

    Gil'miiarova, F N; Radomskaia, V M; Vinogradova, L N

    1982-01-01

    The paper deals with characterization of systems utilizing ethanol and reactions conjugated with its exchange in the brain tissue under chronic alcohol intoxication. The following is established: the absence of the alcoholdehydrogenase pathway of ethanol oxidation in rabbits, unbalanced splitting of carbohydrates under two-months ethanol load, disturbance of oxidative processes in the tricarboxylic acids cycle, a decrease in the pool of oxidized nicotin amide coenzymes. PMID:7036487

  18. Separation of the isotopes of boron by chemical exchange reactions

    DOEpatents

    McCandless, F.P.; Herbst, R.S.

    1995-05-30

    The isotopes of boron, {sup 10}B and {sup 11}B, are separated by means of a gas-liquid chemical exchange reaction involving the isotopic equilibrium between gaseous BF{sub 3} and a liquid BF{sub 3} donor molecular addition complex formed between BF{sub 3} gas and a donor chosen from the group consisting of: nitromethane, acetone, methyl isobutyl ketone, or diisobutyl ketone. 1 Fig.

  19. Momentum transfer in relativistic heavy ion charge-exchange reactions

    NASA Technical Reports Server (NTRS)

    Townsend, L. W.; Wilson, J. W.; Khan, F.; Khandelwal, G. S.

    1991-01-01

    Relativistic heavy ion charge-exchange reactions yield fragments (Delta-Z = + 1) whose longitudinal momentum distributions are downshifted by larger values than those associated with the remaining fragments (Delta-Z = 1, -2,...). Kinematics alone cannot account for the observed downshifts; therefore, an additional contribution from collision dynamics must be included. In this work, an optical model description of collision momentum transfer is used to estimate the additional dynamical momentum downshift. Good agreement between theoretical estimates and experimental data is obtained.

  20. EXFOR SYSTEMS MANUAL NUCLEAR REACTION DATA EXCHANGE FORMAT.

    SciTech Connect

    MCLANE,V.; NUCLEAR DATA CENTER NETWORK

    2000-05-19

    EXFOR is an exchange format designed to allow transmission of nuclear reaction data between the members of the Nuclear Data Centers Network. This document has been written for use by the members of the Network and includes matters of procedure and protocol, as well as detailed rules for the compilation of data. Users may prefer to consult EXFOR Basics' for a brief description of the format.

  1. Separation of the isotopes of boron by chemical exchange reactions

    DOEpatents

    McCandless, Frank P.; Herbst, Ronald S.

    1995-01-01

    The isotopes of boron, .sup.10 B and .sup.11 B, are separated by means of a gas-liquid chemical exchange reaction involving the isotopic equilibrium between gaseous BF.sub.3 and a liquid BF.sub.3 . donor molecular addition complex formed between BF.sub.3 gas and a donor chosen from the group consisting of: nitromethane, acetone, methyl isobutyl ketone, or diisobutyl ketone.

  2. Charge-exchange reactions with a radioactive triton beam

    SciTech Connect

    Jaenecke, J.

    1998-12-21

    A high-resolution (t, {sup 3}He) test experiment has been performed recently by making use of a secondary triton beam produced by fragmentation of {alpha}-particles. The purpose of this charge-exchange experiment was to achieve good energy resolution in an (n,p)-type reaction at intermediate bombarding energies. The experiment was carried out with the K1200 cyclotron at the National Superconducting Cyclotron Laboratory using the A1200 beam-analysis system and the S800 magnetic spectrometer. The beam-analysis system was used to transport the energy-dispersed radioactive triton beam from the production target to the target position, and the magnetic spectrometer was used to focus the dispersion-matched {sup 3}He particles from the (t, {sup 3}He) reaction at 0 degree sign onto the focal plane of the spectrometer. An energy resolution of 200-250 keV was achieved.

  3. Reactive Resonances in N+N2 Exchange Reaction

    NASA Technical Reports Server (NTRS)

    Wang, Dunyou; Huo, Winifred M.; Dateo, Christopher E.; Schwenke, David W.; Stallcop, James R.

    2003-01-01

    Rich reactive resonances are found in a 3D quantum dynamics study of the N + N2 exchange reaction using a recently developed ab initio potential energy surface. This surface is characterized by a feature in the interaction region called Lake Eyring , that is, two symmetric transition states with a shallow minimum between them. An L2 analysis of the quasibound states associated with the shallow minimum confirms that the quasibound states associated with oscillations in all three degrees of freedom in Lake Eyring are responsible for the reactive resonances in the state-to-state reaction probabilities. The quasibound states, mostly the bending motions, give rise to strong reasonance peaks, whereas other motions contribute to the bumps and shoulders in the resonance structure. The initial state reaction probability further proves that the bending motions are the dominating factors of the reaction probability and have longer life times than the stretching motions. This is the first observation of reactive resonances from a "Lake Eyring" feature in a potential energy surface.

  4. Epitactic ion-exchange reactions into vanadyl(IV) arsenate

    SciTech Connect

    Martinez-Lara, M.; Bruque, S.; Moreno, L.; Aranda, M.A.G. )

    1991-03-01

    The synthesis, structural characterization, thermal stability, and spectroscopic (IR, UV-vis-diffuse reflectance) properties of three vanadyl arsenates are described. Vanadyl(IV) bis(dihydrogenarsenate), (VO(H{sub 2}AsO{sub 4}){sub 2}) (1), lithium vanadyl arsenate, (Li{sub 4}VO(AsO{sub 4}){sub 2}{center dot}0.5H{sub 2}O) (2), and nickel(II) and lithium vanadyl arsenate, ((Li{sub 2.4}Ni){sub 0.8}VO(AsO{sub 4}){sub 2}{center dot}4H{sub 2}O) (3), have been prepared. (1) Tetragonal ({alpha} = 9.128 {angstrom}; c = 8.128 {angstrom}) is prepared by reduction with isobutanol or ethanol from vanadyl(V) arsenate. (2) Cubic (a = 9.024 {angstrom}) is obtained from (1) by lithium ion-exchange, and (3) tetragonal (a = 9.106 {angstrom}; c = 8.454 {angstrom}) is made from (2) by Ni{sup 2+} ion-exchange. These exchange reactions are epitactic and the overall result is a topotactic transformation.

  5. Mechanism of the Exchange Reaction in HRAS from Multiscale Modeling

    PubMed Central

    Kapoor, Abhijeet; Travesset, Alex

    2014-01-01

    HRAS regulates cell growth promoting signaling processes by cycling between active (GTP-bound) and inactive (GDP-bound) states. Understanding the transition mechanism is central for the design of small molecules to inhibit the formation of RAS-driven tumors. Using a multiscale approach involving coarse-grained (CG) simulations, all-atom classical molecular dynamics (CMD; total of 3.02 µs), and steered molecular dynamics (SMD) in combination with Principal Component Analysis (PCA), we identified the structural features that determine the nucleotide (GDP) exchange reaction. We show that weakening the coupling between the SwitchI (residues 25–40) and SwitchII (residues 59–75) accelerates the opening of SwitchI; however, an open conformation of SwitchI is unstable in the absence of guanine nucleotide exchange factors (GEFs) and rises up towards the bound nucleotide to close the nucleotide pocket. Both I21 and Y32, play a crucial role in SwitchI transition. We show that an open SwitchI conformation is not necessary for GDP destabilization but is required for GDP/Mg escape from the HRAS. Further, we present the first simulation study showing displacement of GDP/Mg away from the nucleotide pocket. Both SwitchI and SwitchII, delays the escape of displaced GDP/Mg in the absence of GEF. Based on these results, a model for the mechanism of GEF in accelerating the exchange process is hypothesized. PMID:25272152

  6. Alloyed Copper Chalcogenide Nanoplatelets via Partial Cation Exchange Reactions

    PubMed Central

    2014-01-01

    We report the synthesis of alloyed quaternary and quinary nanocrystals based on copper chalcogenides, namely, copper zinc selenide–sulfide (CZSeS), copper tin selenide–sulfide (CTSeS), and copper zinc tin selenide–sulfide (CZTSeS) nanoplatelets (NPLs) (∼20 nm wide) with tunable chemical composition. Our synthesis scheme consisted of two facile steps: i.e., the preparation of copper selenide–sulfide (Cu2–xSeyS1–y) platelet shaped nanocrystals via the colloidal route, followed by an in situ cation exchange reaction. During the latter step, the cation exchange proceeded through a partial replacement of copper ions by zinc or/and tin cations, yielding homogeneously alloyed nanocrystals with platelet shape. Overall, the chemical composition of the alloyed nanocrystals can easily be controlled by the amount of precursors that contain cations of interest (e.g., Zn, Sn) to be incorporated/alloyed. We have also optimized the reaction conditions that allow a complete preservation of the size, morphology, and crystal structure as that of the starting Cu2–xSeyS1–y NPLs. The alloyed NPLs were characterized by optical spectroscopy (UV–vis–NIR) and cyclic voltammetry (CV), which demonstrated tunability of their light absorption characteristics as well as their electrochemical band gaps. PMID:25050455

  7. Charge-exchange reaction by Reggeon exchange and W{sup +}W{sup −}-fusion

    SciTech Connect

    Schicker, R.

    2015-04-10

    Charge-exchange reactions at high energies are examined. The existing cross section data on the Reggeon induced reaction pp → n + Δ{sup ++} taken at the ZGS and ISR accelerators are extrapolated to the energies of the RHIC and LHC colliders. The interest in the charge-exchange reaction induced by W{sup ±}-fusion is presented, and the corresponding QCD-background is examined.

  8. Geometric Phase Appears in the Ultracold Hydrogen Exchange Reaction

    NASA Astrophysics Data System (ADS)

    Kendrick, B. K.; Hazra, Jisha; Balakrishnan, N.

    2015-10-01

    Quantum reactive scattering calculations for the hydrogen exchange reaction H +H2 (v =4 ,j =0 )→H +H2 (v', j') and its isotopic analogues are reported for ultracold collision energies. Because of the unique properties associated with ultracold collisions, it is shown that the geometric phase effectively controls the reactivity. The rotationally resolved rate coefficients computed with and without the geometric phase are shown to differ by up to 4 orders of magnitude. The effect is also significant in the vibrationally resolved and total rate coefficients. The dynamical origin of the effect is discussed and the large geometric phase effect reported here might be exploited to control the reactivity through the application of external fields or by the selection of a particular nuclear spin state.

  9. Population of 13Be with a Nucleon-Exchange Reaction

    NASA Astrophysics Data System (ADS)

    Marks, Bradon; Deyoung, Paul; Smith, Jenna; Thoennessen, Michael; MoNA Collaboration

    2015-10-01

    Neutron-unbound nuclei are traditionally formed by the removal of one or more nucleons from a fast beam of ions. This method often results in a background, which is difficult to separate from the particle of interest. Nucleon-removal entrance-channels also require the ion beam to be more massive than the particle of interest, which presents the additional challenges of the beam being difficult to make. The present work was done with a nucleon-exchange entrance channel. At the National Superconducting Cyclotron Laboratory, a 71 MeV/u 13B beam impinged on a 47 mg/cm2 thick target of 9Be. As a result numerous reactions occurred, including the population of 13Be through the nucleon-exchange entrance-channel. The 13Be nuclei decayed to 12Be and one neutron in approximately 10-21 seconds. The resulting neutrons were detected by either the Modular Neutron Array (MoNA) or the Large multi-Institution Scintillator Array (LISA), while the 12Be nuclei were directed through an array of charged particle detectors by a 4T superconducting sweeper magnet. The four-momentum vectors of the fragment nucleus and the neutron were calculated to determine the decay energy of 13Be. Monte-Carlo simulations consistent with results from previous analyses of 13Be were satisfactorily fit to the decay-energy spectrum. Additionally, the cross-section for the nucleon-exchange entrance-channel is consistent with a theoretical prediction. This material is based upon work supported by the National Science Foundation under Grant No. PHY-1306074.

  10. Spin-Isospin responses via charge exchange reactions of RI beams at SHARAQ

    SciTech Connect

    Shimoura, Susumu

    2012-11-12

    Nuclear spectroscopy via direct reactions of RI beams is discussed focusing on characteristics of charge-exchange reactions of RI beams. Recent experiments using the SHARAQ spectrometer at the RIBF are presented, where isovector spin monopole and spin-non-flip monopole responses are studied by charge exchange reaction of RI beams. Some experimental plans and perspectives are also presented.

  11. The formation of Kuiper-belt binaries through exchange reactions.

    PubMed

    Funato, Yoko; Makino, Junichiro; Hut, Piet; Kokubo, Eiichiro; Kinoshita, Daisuke

    2004-02-01

    Recent observations have revealed that an unexpectedly high fraction--a few per cent--of the trans-Neptunian objects (TNOs) that inhabit the Kuiper belt are binaries. The components have roughly equal masses, with very eccentric orbits that are wider than a hundred times the radius of the primary. Standard theories of binary asteroid formation tend to produce close binaries with circular orbits, so two models have been proposed to explain the unique characteristics of the TNOs. Both models, however, require extreme assumptions regarding the size distribution of the TNOs. Here we report a mechanism that is capable of producing binary TNOs with the observed properties during the early stages of their formation and growth. The only required assumption is that the TNOs were initially formed through gravitational instabilities in the protoplanetary dust disk. The basis of the mechanism is an exchange reaction in which a binary whose primary component is much more massive than the secondary interacts with a third body, whose mass is comparable to that of the primary. The low-mass secondary component is ejected and replaced by the third body in a wide but eccentric orbit. PMID:14765188

  12. Oxygen exchange reaction kinetics for cerium(IV) oxide at 1000 °C

    SciTech Connect

    Whiting, Christofer E. Douglas, John M.; Cremeans, Bethany M.; Barklay, Chadwick D.; Kramer, Daniel P.

    2014-10-15

    Bulk oxygen exchange rate kinetics on CeO{sub 2} at 1000 °C were observed to have a first order dependence on the fraction of reaction remaining and to be independent of oxygen partial pressure, total pressure, particle size, and specific surface area. This suggests that the exchange reaction is dominated by an internal chemical reaction that is occurring throughout the bulk of the material, and not at the material surface. Oxygen exchange rates were limited by this internal chemical reaction for all CeO{sub 2} powders studied (15 nm to −325 mesh), and had a rate constant of 1.19×10{sup −2} s{sup −1} with a time to completion of 617 s. These results are similar to the exchange rates observed previously on PuO{sub 2}, suggesting that oxygen exchange on PuO{sub 2} may also be dominated by an internal chemical reaction under similar conditions. This work will help guide future experiments on {sup 238}PuO{sub 2} oxygen exchange reactions. - Graphical abstract: Oxygen exchange kinetics on CeO{sub 2} at 1000 °C are independent of a wide range of experimental conditions and exhibit first-order chemical reaction kinetics. - Highlights: • Stable oxygen exchange rates obtained on a variety of CeO{sub 2} powders at 1000 °C. • Exchange rates are independent of atmospheric composition and specific surface area. • Exchange rates are limited by an internal chemical reaction, not a surface reaction. • CeO{sub 2} exchange rates appear similar to the rates observed on PuO{sub 2} at 1000 °C.

  13. Iron-copper cooperative catalysis in the reactions of alkyl Grignard reagents: exchange reaction with alkenes and carbometalation of alkynes.

    PubMed

    Shirakawa, Eiji; Ikeda, Daiji; Masui, Seiji; Yoshida, Masatoshi; Hayashi, Tamio

    2012-01-11

    Iron-copper cooperative catalysis is shown to be effective for an alkene-Grignard exchange reaction and alkylmagnesiation of alkynes. The Grignard exchange between terminal alkenes (RCH═CH(2)) and cyclopentylmagnesium bromide was catalyzed by FeCl(3) (2.5 mol %) and CuBr (5 mol %) in combination with PBu(3) (10 mol %) to give RCH(2)CH(2)MgBr in high yields. 1-Alkyl Grignard reagents add to alkynes in the presence of a catalyst system consisting of Fe(acac)(3), CuBr, PBu(3), and N,N,N',N'-tetramethylethylenediamine to give β-alkylvinyl Grignard reagents. The exchange reaction and carbometalation take place on iron, whereas copper assists with the exchange of organic groups between organoiron and organomagnesium species through transmetalation with these species. Sequential reactions consisting of the alkene-Grignard exchange and the alkylmagnesiation of alkynes were successfully conducted by adding an alkyne to a mixture of the first reaction. Isomerization of Grignard reagents from 2-alkyl to 1-alkyl catalyzed by Fe-Cu also is applicable as the first 1-alkyl Grignard formation step. PMID:22128888

  14. Invited Parallel Talk: Forward pion-nucleon charge exchange reaction and Regge constraints

    NASA Astrophysics Data System (ADS)

    Huang, Fei; Sibirtsev, A.; Krewald, S.; Hanhart, C.; Haidenbauer, J.; Meißner, U.-G.

    2009-12-01

    We present our recent study of pion-nucleon charge exchange amplitudes above 2 GeV. We analyze the forward pion-nucleon charge exchange reaction data in a Regge model and compare the resulting amplitudes with those from the Karlsruhe-Helsinki and George-Washington-University partial-wave analyses. We explore possible high-energy constraints for theoretical baryon resonance analyses in the energy region above 2 GeV. Our results show that for the pion-nucleon charge exchange reaction, the appropriate energy region for matching meson-nucleon dynamics to diffractive scattering should be around 3 GeV for the helicity flip amplitude.

  15. Electron and energy transfer as probes of interparticle ion-exchange reactions in zeolite Y

    SciTech Connect

    Brigham, E.S.; Snowden, P.T.; Kim, Y.I.; Mallouk, T.E. )

    1993-08-19

    Photoinduced electron transfer and energy transfer reactions of tris(2,2[prime]-bipyridyl)ruthenium(II) (Ru(bpy)[sub 3][sup 2+]) with methylviologen (MV[sup 2+]) and tris(2,2[prime]-bipyridyl)osmium(II) (Os(bpy)[sub 3][sup 2+]) ion-exchanged onto/into separate zeolite Y particles were studied by emission spectroscopy. The kinetics of interparticle exchange were probed by observing the quenching of the MLCT excited state of-Ru(bpy)[sub 3][sup 2+] by mobile MV[sup 2+] or OS(bpy)[sub 3][sup 2+] ions. The exchange reactions occur on time scales of seconds to hours, depending on the ionic strength of the surrounding medium. The time-dependent luminescence data were fitted to a dispersed kinetics model, from which average rate constants for the exchange reactions could be extracted. Time constants for interparticle exchange of MV[sup 2+] and Os(bpy)[sub 3][sup 2+] ions, in the range 10[sup 3]-10[sup 5] s at electrolyte concentrations of 0.1-3 mM, are significantly longer than the time scales (10[sup [minus]7]-10[sup 1] s) of most electrochemical and photochemical intrazeolitic reactions involving these and similar electroactive ions. These results argue for reaction mechanisms that invoke intrazeolite electron transfer, rather than exchange of electroactive ions followed by solution-phase electron transfer, in these systems. 25 refs., 6 figs., 1 tab.

  16. Sequential Anion and Cation Exchange Reactions for Complete Material Transformations of Nanoparticles with Morphological Retention.

    PubMed

    Hodges, James M; Kletetschka, Karel; Fenton, Julie L; Read, Carlos G; Schaak, Raymond E

    2015-07-20

    Ion exchange reactions of colloidal nanocrystals provide access to complex products that are synthetically challenging using traditional hot-injection methods. However, such reactions typically achieve only partial material transformations by employing either cation or anion exchange processes. It is now shown that anion and cation exchange reactions can be coupled together and applied sequentially in one integrated pathway that leads to complete material transformations of nanocrystal templates. Although the product nanocrystals do not contain any of the original constituent elements, the original morphology is retained, thereby fully decoupling morphology and composition control. The sequential anion/cation exchange process was applied to pseudo-spherical CdO nanocrystals and ZnO tetrapods, producing fully transformed and shape-controlled nanocrystals of copper and silver sulfides and selenides. Furthermore, hollow core-shell tetrapod ZnS@CdS heterostructures were readily accessible. PMID:26110653

  17. Proton exchange in acid-base complexes induced by reaction coordinates with heavy atom motions

    NASA Astrophysics Data System (ADS)

    Alavi, Saman; Taghikhani, Mahdi

    2012-06-01

    We extend previous work on nitric acid-ammonia and nitric acid-alkylamine complexes to illustrate that proton exchange reaction coordinates involve the rocking motion of the base moiety in many double hydrogen-bonded gas phase strong acid-strong base complexes. The complexes studied involve the biologically and atmospherically relevant glycine, formic, acetic, propionic, and sulfuric acids with ammonia/alkylamine bases. In these complexes, the magnitude of the imaginary frequencies associated with the proton exchange transition states are <400 cm-1. This contrasts with widely studied proton exchange reactions between symmetric carboxylic acid dimers or asymmetric DNA base pair and their analogs where the reaction coordinate is localized in proton motions and the magnitude of the imaginary frequencies for the transition states are >1100 cm-1. Calculations on complexes of these acids with water are performed for comparison. Variations of normal vibration modes along the reaction coordinate in the complexes are described.

  18. Determining Clumped Isotope (Δ47) Signatures of CO2 During Ion-Molecule Isotopic Exchange Reactions

    NASA Astrophysics Data System (ADS)

    Sarna, J.; Priyadarshi, A.; Pourmorady, P.; Tripati, A.; Estaris, J.

    2015-12-01

    The abundance of multiply-substituted isotopologues such as 13C16O18O can be used to understand fundamental mechanisms that controls isotopic fractionation in chemical reactions. Knowledge of the energy-dependent ion-molecule isotopic exchange rate for 13C16O18O may also provide important insights into the CO2 ion-molecular exchange that occurs in the source of the mass spectrometer. It may offer an explanation for the recently observed nonlinearities associated with clumped isotope measurements. We designed a controlled set of laboratory experiments to investigate variations in the abundance of 13C16O18O associated with different ion-molecular isotopic exchange reactions. In our experiments, we characterize the effects of changing ionization energy, reaction time, CO2 amount, the presence of different compounds, and reaction chamber temperature on the clumped isotopic composition of CO2.

  19. Acetic anhydride: an intermediate analogue in the acyl-exchange reaction of citramalate lyase.

    PubMed

    Buckel, W

    1976-04-15

    1. Reactivation of deacetyl citramalate lyase by acetic anhydride proceeds through an enzyme-anhydride complex prior to actual acetylation. The reaction is inhibited by citramalate which is competitive with acetic anhydride. 2. A corresponding complex is an intermediate in the carboxymethylation of deacetyl enzyme by iodoacetate. However, the inhibition of this reaction by S-citramalate appears to be non-competitive with iodoacetate. 3. The results lead to the conclusion that acetic anhydride can be regarded as a structural analogue of citramalic acetic anhydride, the proposed intermediate in the acyl exchange reaction on citramalate lyase. 4. The formation of 6-citryl thiolester from the 1-thiolester via the cyclic citric anhydride provides a chemicla model for enzymic acyl exchange. 5. The data suggest that anhydrides are of general importance in acyl exchange reactions of thiolesters. PMID:1278157

  20. Why Seemingly Trivial Events Sometimes Evoke Strong Emotional Reactions: The Role of Social Exchange Rule Violations

    PubMed Central

    Leary, Mark R.; Diebels, Kate J.; Jongman-Sereno, Katrina P.; Fernandez, Xuan Duong

    2015-01-01

    ABSTRACT People sometimes display strong emotional reactions to events that appear disproportionate to the tangible magnitude of the event. Although previous work has addressed the role that perceived disrespect and unfairness have on such reactions, this study examined the role of perceived social exchange rule violations more broadly. Participants (N = 179) rated the effects of another person’s behavior on important personal outcomes, the degree to which the other person had violated fundamental rules of social exchange, and their reactions to the event. Results showed that perceptions of social exchange rule violations accounted for more variance in participants’ reactions than the tangible consequences of the event. The findings support the hypothesis that responses that appear disproportionate to the seriousness of the eliciting event are often fueled by perceived rule violations that may not be obvious to others. PMID:26331429

  1. Hydrogen exchange in some coal-related reactions at 400C

    SciTech Connect

    Benjamin, B.M.; Michalczyk, M.J.; Woody, M.C.

    1980-01-01

    The source of hydrogen in cleavage reactions and the paths of internal hydrogen transfer reactions (''hydrogen shuttling'') during solvent refining of coal were studied with deuterium-labeled model compounds. The reactions of 1,2-diphenylethane (bibenzyl, BB) and diphenylmethane (DPM), in which the dimethylene and methylene linkages, respectively, were completely deuterated with tetralin showed that BB formed toluene by C-C cleavage and hydrogen abstraction from tetralin, that DPM was relatively stable to fragmentation, but that both underwent extensive hydrogen exchange at 400C. The kinetics and possible reaction paths were determined for the reactions BB and DPM with tetralin. Reactions of labeled DPM, which exchanged deuterium readily but was otherwise stable, with Illinois No. 6 coal and North Dakota lignite showed that deuterium exchange was much more rapid with coal than in the tetralin system, probably owing to the larger number of radicals present; and that the deuterium was mainly in the benzylic portions of the products. Separate tests with model compounds showed that some aromatic hydrogen, mainly from polynuclear compounds, also underwent exchange. Reaction paths are discussed.

  2. Cation Exchange Reactions for Improved Quality and Diversity of Semiconductor Nanocrystals

    NASA Astrophysics Data System (ADS)

    Beberwyck, Brandon James

    Observing the size and shape dependent physical properties of semiconductor nanocrystals requires synthetic methods capable of not only composition and crystalline phase control but also molecular scale uniformity for a particle consisting of tens to hundreds of thousands of atoms. The desire for synthetic methods that produce uniform nanocrystals of complex morphologies continues to increase as nanocrystals find roles in commercial applications, such as biolabeling and display technologies, that are simultaneously restricting material compositions. With these constraints, new synthetic strategies that decouple the nanocrystal's chemical composition from its morphology are necessary. This dissertation explores the cation exchange reaction of colloidal semiconductor nanocrystals, a template-based chemical transformation that enables the interconversion of nanocrystals between a variety of compositions while maintaining their size dispersity and morphology. Chapter 1 provides an introduction to the versatility of this replacement reaction as a synthetic method for semiconductor nanocrystals. An overview of the fundamentals of the cation exchange reaction and the diversity of products that are achievable is presented. Chapter 2 examines the optical properties of nanocrystal heterostructures produced through cation exchange reactions. The deleterious impact of exchange on the photoluminescence is correlated to residual impurities and a simple annealing protocol is demonstrated to achieve photoluminescence yields comparable to samples produced by conventional methods. Chapter 3 investigates the extension of the cation exchange reaction beyond ionic nanocrystals. Covalent III-V nanocrystal of high crystallinity and low size dispersity are synthesized by the cation exchange of cadmium pnictide nanocrystals with group 13 ions. Lastly, Chapter 4 highlights future studies to probe cation exchange reactions in colloidal semiconductor nanocrystals and progress that needs to be

  3. Excitation of Δ and N* resonances in isobaric charge-exchange reactions of heavy nuclei

    NASA Astrophysics Data System (ADS)

    Vidaña, I.; Benlliure, J.; Geissel, H.; Lenske, H.; Scheidenberger, C.; Vargas, J.

    2016-01-01

    We present a model for the study of the excitation of Δ(1232) and N*(1440) resonances in isobaric charge-exchange (AZ, A(Z ± 1)) reactions of heavy nuclei. Quasi-elastic and inelastic elementary processes contributing to the double differential cross sections of the reactions are described in terms of the exchange of virtual pions. The inelastic channel includes processes where the resonances are excited both in the target and in the projectile nucleus. We present results for reactions of 112Sn and 124Sn on different targets. Our results confirm that the position of the Δ peak is insensitive to targets with mass number A ≥ 12, and show that the origin of the Δ peak shift towards low excitation energies, with respect to its position in reactions with a proton target, can be easily explained in terms of the superposition of the different excitation mechanisms contributing to the reaction.

  4. Role of the aerosol phase state in ammonia/amines exchange reactions.

    PubMed

    Chan, Lap P; Chan, Chak K

    2013-06-01

    The exchange reaction of ammonia in (NH4)2SO4 with an amine and the corresponding reverse reaction of amines in aminium sulfates with ammonia were investigated using an electrodynamic balance coupled with a Raman spectrometer. The temporal changes in particle mass, chemical composition, and phase state were simultaneously monitored. When the salt particles were in an aqueous state at elevated relative humidities (RHs), the exchange of ammonia/amine vapors in the particle phase was reversible. The exchange rates of aqueous particles were in general higher than those of their corresponding solid counterparts. An aqueous phase was essential for the effective displacement of ammonia and amines. Aminium salts in different phase states and with different evaporation characteristics showed remarkably different reaction behaviors in ammonia vapor. The less compact amorphous aminium sulfate solids were more susceptible to ammonia exchange than the crystalline solids. The aminium salts in a liquid state exhibited substantial amine evaporation at <3% RH and formed acidic bisulfate. Under ammonia exposure, these acidic aminium droplets underwent both neutralization and displacement reactions. Stable solid salts containing ammonium, aminium, sulfate, and bisulfate were formed and hindered further reactions. The result suggests that ambient aminium sulfates may be acidic. Overall, the phase states of the ammonium and aminium salt particles crucially determine the heterogeneous reaction rates and final product properties and identities. PMID:23668831

  5. NN-->NNπ reaction near threshold in a covariant one-boson-exchange model

    NASA Astrophysics Data System (ADS)

    Shyam, R.; Mosel, U.

    1998-04-01

    We calculate the cross sections for the p(p,nπ+)p and p(p,pπ0)p reactions for proton beam energies near threshold in a covariant one-boson-exchange model, which incorporates the exchange of π, ρ, σ and ω mesons, treats both nucleon and delta isobar as intermediate states. The final state interaction effects are included within the Watson's theory. Within this model the ω and σ meson exchange terms contribute significantly at these energies, which, along with other meson exchanges, make it possible to reproduce the available experimental data for the total as well as differential cross sections for both the reactions. The cross sections at beam energies <=300 MeV are found to be almost free from the contributions of the Δ isobar excitation.

  6. EXFOR BASICS A SHORT GUIDE TO THE NEUTRON REACTION DATA EXCHANGE FORMAT.

    SciTech Connect

    MCLANE,V.; NUCLEAR DATA CENTER NETWORK

    2000-05-19

    This manual is intended as a guide to users of nuclear reaction data compiled in the EXFOR format, and is not intended as a complete guide to the EXFOR System. EXFOR is the exchange format designed to allow transmission of nuclear reaction data between the Nuclear Reaction Data Centers. In addition to storing the data and its' bibliographic information, experimental information is also compiled. The status (e.g., the source of the data) and history (e.g., date of last update) of the data set is also included. EXFOR is designed for flexibility in order to meet the diverse needs of the nuclear reaction data centers. It was originally conceived for the exchange of neutron data and was developed through discussions among personnel from centers situated in Saclay, Vienna, Livermore and Brookhaven. It was accepted as the official exchange format of the neutron data centers at Saclay, Vienna, Brookhaven and Obninsk, at a meeting held in November 1969. As a result of two meetings held in 1975 and 1976 and attended by several charged-particle data centers, the format was further developed and adapted to cover all nuclear reaction data. The exchange format should not be confused with a center-to-user format. Although users may obtain data from the centers in the EXFOR format, other center-to-user formats have been developed to meet the needs of the users within each center's own sphere of responsibility. The EXFOR format, as outlined, allows a large variety of numerical data tables with explanatory and bibliographic information to be transmitted in a format: that is machine-readable (for checking and indicating possible errors); that can be read by personnel (for passing judgment on and correcting errors). The data presently included in the EXFOR exchange file include: a complete compilation of experimental neutron-induced reaction data, a selected compilation of charged-particle-induced reaction data, a selected compilation of photon-induced reaction data.

  7. EXFOR BASICS A SHORT GUIDE TO THE NEUTRON REACTION DATA EXCHANGE FORMAT.

    SciTech Connect

    MCLANE,V.; NUCLEAR DATA CENTER NETWORK

    2000-05-19

    This manual is intended as a guide to users of nuclear reaction data compiled in the EXFOR format, and is not intended as a complete guide to the EXFOR System. EXFOR is the exchange format designed to allow transmission of nuclear reaction data between the Nuclear Reaction Data Centers. In addition to storing the data and its' bibliographic information, experimental information is also compiled. The status (e.g., the source of the data) and history (e.g., date of last update) of the data set is also included. EXFOR is designed for flexibility in order to meet the diverse needs of the nuclear reaction data centers. It was originally conceived for the exchange of neutron data and was developed through discussions among personnel from centers situated in Saclay, Vienna, Livermore and Brookhaven. It was accepted as the official exchange format of the neutron data centers at Saclay, Vienna, Brookhaven and Obninsk, at a meeting held in November 1969.3 As a result of two meetings held in 1975 and 1976 and attended by several charged-particle data centers, the format was further developed and adapted to cover all nuclear reaction data. The exchange format should not be confused with a center-to-user format. Although users may obtain data from the centers in the EXFOR format, other center-to-user formats have been developed to meet the needs of the users within each center's own sphere of responsibility. The EXFOR format, as outlined, allows a large variety of numerical data tables with explanatory and bibliographic information to be transmitted in a format: l that is machine-readable (for checking and indicating possible errors); l that can be read by personnel (for passing judgment on and correcting errors). The data presently included in the EXFOR exchange file include: a complete compilation of experimental neutron-induced reaction data, a selected compilation of charged-particle-induced reaction data, a selected compilation of photon-induced reaction data.

  8. Formation of pseudomorphic nanocages from Cu2O nanocrystals through anion exchange reactions.

    PubMed

    Wu, Hsin-Lun; Sato, Ryota; Yamaguchi, Atsushi; Kimura, Masato; Haruta, Mitsutaka; Kurata, Hiroki; Teranishi, Toshiharu

    2016-03-18

    The crystal structure of ionic nanocrystals (NCs) is usually controlled through reaction temperature, according to their phase diagram. We show that when ionic NCs with different shapes, but identical crystal structures, were subjected to anion exchange reactions under ambient conditions, pseudomorphic products with different crystal systems were obtained. The shape-dependent anionic framework (surface anion sublattice and stacking pattern) of Cu2O NCs determined the crystal system of anion-exchanged products of CuxS nanocages. This method enabled us to convert a body-centered cubic lattice into either a face-centered cubic or a hexagonally close-packed lattice to form crystallographically unusual, multiply twinned structures. Subsequent cation exchange reactions produced CdS nanocages while preserving the multiply-twinned structures. A high-temperature stable phase such as wurtzite ZnS was also obtained with this method at ambient conditions. PMID:26989249

  9. Arrhenius' law in turbulent media and an equivalent tunnel effect. [in binary exchange chemical reactions

    NASA Technical Reports Server (NTRS)

    Tsuge, S.; Sagara, K.

    1978-01-01

    The indeterminacy inherent to the formal extension of Arrhenius' law to reactions in turbulent flows is shown to be surmountable in the case of a binary exchange reaction with a sufficiently high activation energy. A preliminary calculation predicts that the turbulent reaction rate is invariant in the Arrhenius form except for an equivalently lowered activation energy. This is a reflection of turbulence-augmented molecular vigor, and causes an appreciable increase in the reaction rate. A similarity to the tunnel effect in quantum mechanics is indicated. The anomaly associated with the mild ignition of oxy-hydrogen mixtures is discussed in this light.

  10. Reaction chemistry and ligand exchange at cadmium selenide nanocrystal surfaces

    SciTech Connect

    Owen, Jonathan; Park, Jungwon; Trudeau, Paul-Emile; Alivisatos, A. Paul

    2008-12-02

    Chemical modification of nanocrystal surfaces is fundamentally important to their assembly, their implementation in biology and medicine, and greatly impacts their electrical and optical properties. However, it remains a major challenge owing to a lack of analytical tools to directly determine nanoparticle surface structure. Early nuclear magnetic resonance (NMR) and X-ray photoelectron spectroscopy (XPS) studies of CdSe nanocrystals prepared in tri-n-octylphosphine oxide (1) and tri-n-octylphosphine (2), suggested these coordinating solvents are datively bound to the particle surface. However, assigning the broad NMR resonances of surface-bound ligands is complicated by significant concentrations of phosphorus-containing impurities in commercial sources of 1, and XPS provides only limited information about the nature of the phosphorus containing molecules in the sample. More recent reports have shown the surface ligands of CdSe nanocrystals prepared in technical grade 1, and in the presence of alkylphosphonic acids, include phosphonic and phosphinic acids. These studies do not, however, distinguish whether these ligands are bound datively, as neutral, L-type ligands, or by X-type interaction of an anionic phosphonate/phosphinate moiety with a surface Cd{sup 2+} ion. Answering this question would help clarify why ligand exchange with such particles does not proceed generally as expected based on a L-type ligand model. By using reagents with reactive silicon-chalcogen and silicon-chlorine bonds to cleave the ligands from the nanocrystal surface, we show that our CdSe and CdSe/ZnS core-shell nanocrystal surfaces are likely terminated by X-type binding of alkylphosphonate ligands to a layer of Cd{sup 2+}/Zn{sup 2+} ions, rather than by dative interactions. Further, we provide spectroscopic evidence that 1 and 2 are not coordinated to our purified nanocrystals.

  11. Scaling Hydrologic Exchange Flows and Biogeochemical Reactions from Bedforms to Basins

    NASA Astrophysics Data System (ADS)

    Harvey, J. W.; Gomez-Velez, J. D.

    2015-12-01

    River water moves in and out of the main channel along pathways that are perpendicular to the channel's main axis that flow across or beneath the ground surface. These hydrologic exchange flows (HEFs) are difficult to measure, yet no less important than a river's downstream flow, or exchanges with the atmosphere and deeper groundwater (Harvey and Gooseff, 2015, WRR). There are very few comprehensive investigations of exchange fluxes to understand patterns with river size and relative importance of specific types of exchanges. We used the physically based model NEXSS to simulate multiple scales of hyporheic flow and their cumulative effects on solute reaction in large basins (on the order of Chesapeake Bay basin or larger). Our goal was to explain where and when particular types of hyporheic flow are important in enhancing key biogeochemical reactions, such as organic carbon respiration and denitrification. Results demonstrate that hyporheic flux (expressed per unit area of streambed) varies surprisingly little across the continuum of first-order streams to eighth-order rivers, and vertical exchange beneath small bedforms dominates in comparison with lateral flow beneath gravel bars and meanders. Also, the river's entire volume is exchanged many times with hyporheic flow within a basin, and the turnover length (after one entire river volume is exchanged) is strongly influenced by hydrogeomorphic differences between physiographic regions as well as by river size. The cumulative effects on biogeochemical reactions were assessed using a the reaction significance factor, RSF, which computes the cumulative potential for hyporheic reactions using a dimensionless index that balances reaction progress in a single hyporheic flow path against overall processing efficiency of river turnover through hyporheic flow paths of that type. Reaction significance appears to be strongly dominated by hydrologic factors rather than biogeochemical factors, and seems to be dominated by

  12. Competition between abstraction and exchange channels in H + HCN reaction: Full-dimensional quantum dynamics

    SciTech Connect

    Jiang, Bin; Guo, Hua

    2013-12-14

    Dynamics of the title reaction is investigated on an ab initio based potential energy surface using a full-dimensional quantum wave packet method within the centrifugal sudden approximation. It is shown that the reaction between H and HCN leads to both the hydrogen exchange and hydrogen abstraction channels. The exchange channel has a lower threshold and larger cross section than the abstraction channel. It also has more oscillations due apparently to quantum resonances. Both channels are affected by long-lived resonances supported by potential wells. Comparison with experimental cross sections indicates underestimation of the abstraction barrier height.

  13. Charge exchange and chemical reactions with trapped Th{sup 3+}

    SciTech Connect

    Churchill, L. R.; DePalatis, M. V.; Chapman, M. S.

    2011-01-15

    We have measured the reaction rates of trapped, buffer gas cooled Th{sup 3+} and various gases and have analyzed the reaction products using trapped ion mass spectrometry techniques. Ion trap lifetimes are usually limited by reactions with background molecules, and the high electron affinity of multiply charged ions such as Th{sup 3+} make them more prone to loss. Our results show that reactions of Th{sup 3+} with carbon dioxide, methane, and oxygen all occur near the classical Langevin rate, while reaction rates with argon, hydrogen, and nitrogen are orders of magnitude lower. Reactions of Th{sup 3+} with oxygen and methane proceed primarily via charge exchange, while simultaneous charge exchange and chemical reaction occurs between Th{sup 3+} and carbon dioxide. Loss rates of Th{sup 3+} in helium are consistent with reaction with impurities in the gas. Reaction rates of Th{sup 3+} with nitrogen and argon depend on the internal electronic configuration of the Th{sup 3+}.

  14. Energetics and Control of Ultracold Isotope-Exchange Reactions between Heteronuclear Dimers in External Fields

    NASA Astrophysics Data System (ADS)

    Tomza, Michał

    2015-08-01

    We show that isotope-exchange reactions between ground-state alkali-metal, alkaline-earth-metal, and lanthanide heteronuclear dimers consisting of two isotopes of the same atom are exothermic with an energy change in the range of 1-8000 MHz, thus resulting in cold or ultracold products. For these chemical reactions, there are only one rovibrational and at most several hyperfine possible product states. The number and energetics of open and closed reactive channels can be controlled by the laser and magnetic fields. We suggest a laser-induced isotope- and state-selective Stark shift control to tune the exothermic isotope-exchange reactions to become endothermic, thus providing the ground for testing models of the chemical reactivity. The present proposal opens the way for studying the state-to-state dynamics of ultracold chemical reactions beyond the universal limit with a meaningful control over the quantum states of both reactants and products.

  15. Energetics and Control of Ultracold Isotope-Exchange Reactions between Heteronuclear Dimers in External Fields.

    PubMed

    Tomza, Michał

    2015-08-01

    We show that isotope-exchange reactions between ground-state alkali-metal, alkaline-earth-metal, and lanthanide heteronuclear dimers consisting of two isotopes of the same atom are exothermic with an energy change in the range of 1-8000 MHz, thus resulting in cold or ultracold products. For these chemical reactions, there are only one rovibrational and at most several hyperfine possible product states. The number and energetics of open and closed reactive channels can be controlled by the laser and magnetic fields. We suggest a laser-induced isotope- and state-selective Stark shift control to tune the exothermic isotope-exchange reactions to become endothermic, thus providing the ground for testing models of the chemical reactivity. The present proposal opens the way for studying the state-to-state dynamics of ultracold chemical reactions beyond the universal limit with a meaningful control over the quantum states of both reactants and products. PMID:26296115

  16. Energy-loss cross sections for inclusive charge-exchange reactions at intermediate energies

    NASA Technical Reports Server (NTRS)

    Cucinotta, Francis A.; Townsend, Lawrence W.; Dubey, Rajendra R.

    1993-01-01

    Charge-exchange reactions for scattering to the continuum are considered in a high-energy multiple scattering model. Calculations for (p,n) and (He-3,H-3) reactions are made and compared with experimental results for C-12, O-16, and Al-27 targets. Coherent effects are shown to lead to an important role for inelastic multiple scattering terms when light projectiles are considered.

  17. (4B-3H) NADH-H2O exchange reaction of the mitochondrial NADH dehydrogenase

    SciTech Connect

    Chen, S.; Guillory, R.J.

    1985-06-14

    The purified mitochondrial NADH dehydrogenase enzyme has been shown to catalyze a rapid (4B-/sup 3/H) NADH-H/sub 2/O exchange reaction. When the enzyme is subjected to a single freeze-thaw cycle there is a complete loss of NADH dehydrogenation without a measurable decrease in the (4B-/sup 3/H) NADH-H/sub 2/O exchange. Complete loss of the (4B-/sup 3/H) NADH-H/sub 2/O exchange follows brief exposure to ultraviolet photoirradiation. The differential sensitivity of the water exchange reaction and the dehydrogenase activity suggests a direct involvement of the enzymes flavin cofactor in the catalysis of the (4B-/sup 3/H) NADH-H/sub 2/O exchange. Arylazido-beta-alanyl NAD+ (A3'-0-(3-(N-4-azido-2-nitrophenyl)amino) propionyl)NAD+) is shown to be a potent photodependent inhibitor of the (4B-3H) NADH-H/sub 2/O exchange activity following photoirradiation with visible light. This is consistent with the observed photodependent inhibition of the dehydrogenase activity by this photoprobe.

  18. Asymmetric ligand-exchange reaction of biphenol derivatives and chiral bis(oxazolinyl)phenyl-rhodium complex.

    PubMed

    Inoue, Hiroko; Ito, Jun-ichi; Kikuchi, Makoto; Nishiyama, Hisao

    2008-09-01

    Chiral bis(oxazolinyl)phenyl-rhodium acetate complex can enantioselectively capture 1,1'-binaphthol derivatives by ligand-exchange reaction. The structure of the bis(oxazolinyl)phenyl-rhodium biphenol and binaphthol complexes were confirmed by X-ray analysis. PMID:18496824

  19. Further studies on vinamidinium salt amine exchange reactions, borohydride reductions and subsequent transformations

    PubMed Central

    Gupton, John T.; Telang, Nakul; Jia, Xin; Giglio, Benjamin C.; Eaton, James E.; Barelli, Peter J.; Hovaizi, Mona; Hall, Kayleigh E.; Welden, R. Scott; Keough, Matthew J.; Worrall, Eric F.; Finzel, Kara L.; Kluball, Emily J.; Kanters, Rene P.F.; Smith, Timothy M.; Smith, Stanton Q.; Nunes, Shane R.; Wright, Mathew T.; Birnstihl, Jennifer M.

    2010-01-01

    Studies directed at the amine exchange reaction of vinamidinium salts followed by sodium borohydride reduction to secondary and tertiary allylic amines are described. The tertiary allylic amines were alkylated and subjected to base mediated rearrangement to yield a variety of highly functionalized tertiary homoallylic amines. PMID:21113324

  20. Immunoassay principle based on exchange reactions: investigations on agarose gel and silanized quartz.

    PubMed

    Weber, A; Ogendal, L H

    1992-01-01

    Preliminary studies of a new immunoassay principle based on exchange reactions is reported. Exchange of 125I-labelled insulin with unlabelled insulin from immobilized monoclonal antibodies was investigated. From antibody immobilized on a gel substrate the tagged insulin was exchanged according to a first-order process. With antibody immobilized on a quartz substrate by two different methods, the kinetics was changed dramatically, probably because of the non-specific interaction between the ligand and the surface. The recorded adsorption isotherms could not be described by the Langmuir adsorption equation, and a model allowing for non-specific adsorption of the ligand was developed. This model gave a satisfactory fit to the experimental data, allowing computation of adsorption parameters. It is concluded that even the best method used to immobilize receptors on quartz is not adequate for an exchange assay to be made. However, this coating method may lead to more sensitive receptor-based assays of more conventional type. PMID:1379052

  1. Competition between charge exchange and chemical reaction - The D2/+/ + H system

    NASA Technical Reports Server (NTRS)

    Preston, R. K.; Cross, R. J., Jr.

    1973-01-01

    Study of the special features of molecular charge exchange and its competition with chemical reaction in the case of the D2(+) + H system. The trajectory surface hopping (TSH) model proposed by Tully and Preston (1971) is used to study this competition for a number of reactions involving the above system. The diatomics-in-molecules zero-overlap approximation is used to calculate the three adiabatic surfaces - one triplet and two singlet - which are needed to describe this system. One of the significant results of this study is that the chemical reaction and charge exchange are strongly coupled. It is also found that the number of trajectories passing into the chemical regions of the three surfaces depends very strongly on the surface crossings.-

  2. Hydraulic controls of in-stream gravel bar hyporheic exchange and reactions

    NASA Astrophysics Data System (ADS)

    Trauth, Nico; Schmidt, Christian; Vieweg, Michael; Oswald, Sascha E.; Fleckenstein, Jan H.

    2015-04-01

    Hyporheic exchange transports solutes into the subsurface where they can undergo biogeochemical transformations, affecting fluvial water quality and ecology. A three-dimensional numerical model of a natural in-stream gravel bar (20 m × 6 m) is presented. Multiple steady state streamflow is simulated with a computational fluid dynamics code that is sequentially coupled to a reactive transport groundwater model via the hydraulic head distribution at the streambed. Ambient groundwater flow is considered by scenarios of neutral, gaining, and losing conditions. The transformation of oxygen, nitrate, and dissolved organic carbon by aerobic respiration and denitrification in the hyporheic zone are modeled, as is the denitrification of groundwater-borne nitrate when mixed with stream-sourced carbon. In contrast to fully submerged structures, hyporheic exchange flux decreases with increasing stream discharge, due to decreasing hydraulic head gradients across the partially submerged structure. Hyporheic residence time distributions are skewed in the log-space with medians of up to 8 h and shift to symmetric distributions with increasing level of submergence. Solute turnover is mainly controlled by residence times and the extent of the hyporheic exchange flow, which defines the potential reaction area. Although streamflow is the primary driver of hyporheic exchange, its impact on hyporheic exchange flux, residence times, and solute turnover is small, as these quantities exponentially decrease under losing and gaining conditions. Hence, highest reaction potential exists under neutral conditions, when the capacity for denitrification in the partially submerged structure can be orders of magnitude higher than in fully submerged structures.

  3. Neutrino nuclear responses for double beta decays and astro neutrinos by charge exchange reactions

    NASA Astrophysics Data System (ADS)

    Ejiri, Hiroyasu

    2014-09-01

    Neutrino nuclear responses are crucial for neutrino studies in nuclei. Charge exchange reactions (CER) are shown to be used to study charged current neutrino nuclear responses associated with double beta decays(DBD)and astro neutrino interactions. CERs to be used are high energy-resolution (He3 ,t) reactions at RCNP, photonuclear reactions via IAR at NewSUBARU and muon capture reactions at MUSIC RCNP and MLF J-PARC. The Gamow Teller (GT) strengths studied by CERs reproduce the observed 2 neutrino DBD matrix elements. The GT and spin dipole (SD) matrix elements are found to be reduced much due to the nucleon spin isospin correlations and the non-nucleonic (delta isobar) nuclear medium effects. Impacts of the reductions on the DBD matrix elements and astro neutrino interactions are discussed.

  4. Tuning the Optical Properties of Cesium Lead Halide Perovskite Nanocrystals by Anion Exchange Reactions

    PubMed Central

    2015-01-01

    We demonstrate that, via controlled anion exchange reactions using a range of different halide precursors, we can finely tune the chemical composition and the optical properties of presynthesized colloidal cesium lead halide perovskite nanocrystals (NCs), from green emitting CsPbBr3 to bright emitters in any other region of the visible spectrum, and back, by displacement of Cl– or I– ions and reinsertion of Br– ions. This approach gives access to perovskite semiconductor NCs with both structural and optical qualities comparable to those of directly synthesized NCs. We also show that anion exchange is a dynamic process that takes place in solution between NCs. Therefore, by mixing solutions containing perovskite NCs emitting in different spectral ranges (due to different halide compositions) their mutual fast exchange dynamics leads to homogenization in their composition, resulting in NCs emitting in a narrow spectral region that is intermediate between those of the parent nanoparticles. PMID:26214734

  5. Tuning the Optical Properties of Cesium Lead Halide Perovskite Nanocrystals by Anion Exchange Reactions.

    PubMed

    Akkerman, Quinten A; D'Innocenzo, Valerio; Accornero, Sara; Scarpellini, Alice; Petrozza, Annamaria; Prato, Mirko; Manna, Liberato

    2015-08-19

    We demonstrate that, via controlled anion exchange reactions using a range of different halide precursors, we can finely tune the chemical composition and the optical properties of presynthesized colloidal cesium lead halide perovskite nanocrystals (NCs), from green emitting CsPbBr3 to bright emitters in any other region of the visible spectrum, and back, by displacement of Cl(-) or I(-) ions and reinsertion of Br(-) ions. This approach gives access to perovskite semiconductor NCs with both structural and optical qualities comparable to those of directly synthesized NCs. We also show that anion exchange is a dynamic process that takes place in solution between NCs. Therefore, by mixing solutions containing perovskite NCs emitting in different spectral ranges (due to different halide compositions) their mutual fast exchange dynamics leads to homogenization in their composition, resulting in NCs emitting in a narrow spectral region that is intermediate between those of the parent nanoparticles. PMID:26214734

  6. Scaling hyporheic exchange and its influence on biogeochemical reactions in aquatic ecosystems

    USGS Publications Warehouse

    O'Connor, B.L.; Harvey, J.W.

    2008-01-01

    Hyporheic exchange and biogeochemical reactions are difficult to quantify because of the range in fluid-flow and sediment conditions inherent to streams, wetlands, and nearshore marine ecosystems. Field measurements of biogeochemical reactions in aquatic systems are impeded by the difficulty of measuring hyporheic flow simultaneously with chemical gradients in sediments. Simplified models of hyporheic exchange have been developed using Darcy's law generated by flow and bed topography at the sediment-water interface. However, many modes of transport are potentially involved (molecular diffusion, bioturbation, advection, shear, bed mobility, and turbulence) with even simple models being difficult to apply in complex natural systems characterized by variable sediment sizes and irregular bed geometries. In this study, we synthesize information from published hyporheic exchange investigations to develop a scaling relationship for estimating mass transfer in near-surface sediments across a range in fluid-flow and sediment conditions. Net hyporheic exchange was quantified using an effective diffusion coefficient (De) that integrates all of the various transport processes that occur simultaneously in sediments, and dimensional analysis was used to scale De to shear stress velocity, roughness height, and permeability that describe fluid-flow and sediment characteristics. We demonstrated the value of the derived scaling relationship by using it to quantify dissolved oxygen (DO) uptake rates on the basis of DO profiles in sediments and compared them to independent flux measurements. The results support a broad application of the De scaling relationship for quantifying coupled hyporheic exchange and biogeochemical reaction rates in streams and other aquatic ecosystems characterized by complex fluid-flow and sediment conditions.

  7. Charge Exchange Reaction in Dopant-Assisted Atmospheric Pressure Chemical Ionization and Atmospheric Pressure Photoionization

    NASA Astrophysics Data System (ADS)

    Vaikkinen, Anu; Kauppila, Tiina J.; Kostiainen, Risto

    2016-08-01

    The efficiencies of charge exchange reaction in dopant-assisted atmospheric pressure chemical ionization (DA-APCI) and dopant-assisted atmospheric pressure photoionization (DA-APPI) mass spectrometry (MS) were compared by flow injection analysis. Fourteen individual compounds and a commercial mixture of 16 polycyclic aromatic hydrocarbons were chosen as model analytes to cover a wide range of polarities, gas-phase ionization energies, and proton affinities. Chlorobenzene was used as the dopant, and methanol/water (80/20) as the solvent. In both techniques, analytes formed the same ions (radical cations, protonated molecules, and/or fragments). However, in DA-APCI, the relative efficiency of charge exchange versus proton transfer was lower than in DA-APPI. This is suggested to be because in DA-APCI both dopant and solvent clusters can be ionized, and the formed reagent ions can react with the analytes via competing charge exchange and proton transfer reactions. In DA-APPI, on the other hand, the main reagents are dopant-derived radical cations, which favor ionization of analytes via charge exchange. The efficiency of charge exchange in both DA-APPI and DA-APCI was shown to depend heavily on the solvent flow rate, with best efficiency seen at lowest flow rates studied (0.05 and 0.1 mL/min). Both DA-APCI and DA-APPI showed the radical cation of chlorobenzene at 0.05-0.1 mL/min flow rate, but at increasing flow rate, the abundance of chlorobenzene M+. decreased and reagent ion populations deriving from different gas-phase chemistry were recorded. The formation of these reagent ions explains the decreasing ionization efficiency and the differences in charge exchange between the techniques.

  8. Charge Exchange Reaction in Dopant-Assisted Atmospheric Pressure Chemical Ionization and Atmospheric Pressure Photoionization

    NASA Astrophysics Data System (ADS)

    Vaikkinen, Anu; Kauppila, Tiina J.; Kostiainen, Risto

    2016-04-01

    The efficiencies of charge exchange reaction in dopant-assisted atmospheric pressure chemical ionization (DA-APCI) and dopant-assisted atmospheric pressure photoionization (DA-APPI) mass spectrometry (MS) were compared by flow injection analysis. Fourteen individual compounds and a commercial mixture of 16 polycyclic aromatic hydrocarbons were chosen as model analytes to cover a wide range of polarities, gas-phase ionization energies, and proton affinities. Chlorobenzene was used as the dopant, and methanol/water (80/20) as the solvent. In both techniques, analytes formed the same ions (radical cations, protonated molecules, and/or fragments). However, in DA-APCI, the relative efficiency of charge exchange versus proton transfer was lower than in DA-APPI. This is suggested to be because in DA-APCI both dopant and solvent clusters can be ionized, and the formed reagent ions can react with the analytes via competing charge exchange and proton transfer reactions. In DA-APPI, on the other hand, the main reagents are dopant-derived radical cations, which favor ionization of analytes via charge exchange. The efficiency of charge exchange in both DA-APPI and DA-APCI was shown to depend heavily on the solvent flow rate, with best efficiency seen at lowest flow rates studied (0.05 and 0.1 mL/min). Both DA-APCI and DA-APPI showed the radical cation of chlorobenzene at 0.05-0.1 mL/min flow rate, but at increasing flow rate, the abundance of chlorobenzene M+. decreased and reagent ion populations deriving from different gas-phase chemistry were recorded. The formation of these reagent ions explains the decreasing ionization efficiency and the differences in charge exchange between the techniques.

  9. Charge Exchange Reaction in Dopant-Assisted Atmospheric Pressure Chemical Ionization and Atmospheric Pressure Photoionization.

    PubMed

    Vaikkinen, Anu; Kauppila, Tiina J; Kostiainen, Risto

    2016-08-01

    The efficiencies of charge exchange reaction in dopant-assisted atmospheric pressure chemical ionization (DA-APCI) and dopant-assisted atmospheric pressure photoionization (DA-APPI) mass spectrometry (MS) were compared by flow injection analysis. Fourteen individual compounds and a commercial mixture of 16 polycyclic aromatic hydrocarbons were chosen as model analytes to cover a wide range of polarities, gas-phase ionization energies, and proton affinities. Chlorobenzene was used as the dopant, and methanol/water (80/20) as the solvent. In both techniques, analytes formed the same ions (radical cations, protonated molecules, and/or fragments). However, in DA-APCI, the relative efficiency of charge exchange versus proton transfer was lower than in DA-APPI. This is suggested to be because in DA-APCI both dopant and solvent clusters can be ionized, and the formed reagent ions can react with the analytes via competing charge exchange and proton transfer reactions. In DA-APPI, on the other hand, the main reagents are dopant-derived radical cations, which favor ionization of analytes via charge exchange. The efficiency of charge exchange in both DA-APPI and DA-APCI was shown to depend heavily on the solvent flow rate, with best efficiency seen at lowest flow rates studied (0.05 and 0.1 mL/min). Both DA-APCI and DA-APPI showed the radical cation of chlorobenzene at 0.05-0.1 mL/min flow rate, but at increasing flow rate, the abundance of chlorobenzene M(+.) decreased and reagent ion populations deriving from different gas-phase chemistry were recorded. The formation of these reagent ions explains the decreasing ionization efficiency and the differences in charge exchange between the techniques. Graphical Abstract ᅟ. PMID:27126470

  10. Sn Cation Valency Dependence in Cation Exchange Reactions Involving Cu2-xSe Nanocrystals

    PubMed Central

    2014-01-01

    We studied cation exchange reactions in colloidal Cu2-xSe nanocrystals (NCs) involving the replacement of Cu+ cations with either Sn2+ or Sn4+ cations. This is a model system in several aspects: first, the +2 and +4 oxidation states for tin are relatively stable; in addition, the phase of the Cu2-xSe NCs remains cubic regardless of the degree of copper deficiency (that is, “x”) in the NC lattice. Also, Sn4+ ions are comparable in size to the Cu+ ions, while Sn2+ ones are much larger. We show here that the valency of the entering Sn ions dictates the structure and composition not only of the final products but also of the intermediate steps of the exchange. When Sn4+ cations are used, alloyed Cu2–4ySnySe NCs (with y ≤ 0.33) are formed as intermediates, with almost no distortion of the anion framework, apart from a small contraction. In this exchange reaction the final stoichiometry of the NCs cannot go beyond Cu0.66Sn0.33Se (that is Cu2SnSe3), as any further replacement of Cu+ cations with Sn4+ cations would require a drastic reorganization of the anion framework, which is not possible at the reaction conditions of the experiments. When instead Sn2+ cations are employed, SnSe NCs are formed, mostly in the orthorhombic phase, with significant, albeit not drastic, distortion of the anion framework. Intermediate steps in this exchange reaction are represented by Janus-type Cu2-xSe/SnSe heterostructures, with no Cu–Sn–Se alloys. PMID:25340627

  11. Modeling dune-induced hyporheic exchange and nutrient reactions in stream sediments

    NASA Astrophysics Data System (ADS)

    Bardini, L.; Boano, F.; Cardenas, M. B.; Revelli, R.; Ridolfi, L.

    2012-04-01

    The exchange of water across the streambed plays an important role in the ecology of fluvial environments, since it assures the connections of surface and subsurface waters, which have very different peculiarities. Water-borne chemicals are also involved in the process: they enter the sediments with the water and they are transformed into oxidized or reduced substances by biogeochemical reactions, mediated by the hyporheic microbiota. In particular, organic substances can be used as electron donors in a series of redox reactions, with different electron acceptors, e.g., oxygen and nitrate. Nitrification and other secondary reactions also occur as soon as water enters the streambed. These pore-scale transformations concur to affect subsurface solute concentrations and, consequently, the chemistry of upwelling water and the quality of the stream environment. The exchange with the hyporheic zone occurs in response to variations in bed topography, with a very wide range of spatial and temporal scales. For instance, small-scale exchanges are mainly induced by river bed forms, like ripples and dunes, while large-scale exchanges depend on larger geomorphological features. In this work we focus on small-scale exchange induced by the presence of dunes on the streambed, investigating the interplay of hydrological and biogeochemical processes and their effects on solute spatial distribution in the sediments. We numerically simulate the turbulent water flow and the pressure distribution on the streambed and then we evaluate the coupled flow field and biogeochemical reactions in the hyporheic zone in steady-state conditions. Four representative reactive compounds are taken into account: dissolved organic carbon (DOC), oxygen (O2), nitrate (NO3-) and ammonium (NH4+). Sensitivity analyses are also performed to analyze the influence of hydrological and chemical properties of the system on solute reaction rates. The results demonstrate that the stream water quality can strongly

  12. Hydrogen Isotope Exchange of Chlorinated Ethylenes in Aqueous Solution: Possibly a Termolecular Liquid Phase Reaction.

    PubMed

    Gabričević, Mario; Lente, Gábor; Fábián, István

    2015-12-24

    This work reports an experimental study of the hydrogen/deuterium exchange in the basic aqueous solutions of trichloroethylene, trans-1,2-dichloroethylene, and cis-1,2-dichloroethylene using (1)H NMR as a monitoring method. 1,1-Dichlorethylene was also investigated but found not to exchange hydrogen isotopes with water. The kinetics of isotope exchange features two different pathways, the first is first order with respect to hydroxide ion, whereas the second is second order. The first pathway is interpreted as a straightforward bimolecular reaction between chloroethylene and hydroxide ion, which leads to the deprotonation of chloroethylene. The second pathway involves a transition state with the association of one molecule of the chloroethylene and two hydroxide ions. It is shown that the second pathway could involve the formation of a precursor complex composed of one chloroethylene molecule and one hydroxide ion, but a direct termolecular elementary reaction is also feasible, which is shown by deriving a theoretical highest limit for the rate constants of termolecular reactions in solution. PMID:26618984

  13. EXFOR basics: A short guide to the nuclear reaction data exchange format

    SciTech Connect

    McLane, V.

    1996-07-01

    This manual is intended as a guide to users of nuclear reaction data compiled in the EXFOR format, and is not intended as a complete guide to the EXFOR System. EXFOR is the exchange format designed to allow transmission of nuclear data between the Nuclear Reaction Data Centers. In addition to storing the data and its` bibliographic information, experimental information, including source of uncertainties, is also compiled. The status and history of the data set is also included, e.g., the source of the data, any updates which have been made, and correlations to other data sets. EXFOR is designed for flexibility in order to meet the diverse needs of the nuclear data compilation centers. This format should not be confused with a center-to-user format. Although users may obtain data from the centers in the EXFOR format, other center-to-user formats have been developed to meet the needs of the users within each center`s own sphere of responsibility. The exchange format, as outlined, allows a large variety of numerical data tables with explanatory and bibliographic information to be transmitted in an easily machine-readable format (for checking and indicating possible errors) and a format that can be read by personnel (for passing judgment on and correcting any errors indicated by the machine). The data presently included in the EXFOR exchange include: a complete compilation of experimental neutron-induced reaction data, a selected compilation of charged-particle induced reaction data, a selected compilation of photon-induced reaction data.

  14. Towards rotationally state-resolved differential cross sections for the hydrogen exchange reaction

    SciTech Connect

    Vrakking, M.J.J.

    1992-11-01

    The hydrogen exchange reaction H + H[sub 2] [yields] H[sub 2] + H (and its isotopic variants) plays a pivotal role in chemical reaction dynamics. It is the only chemical reaction for which fully converged quantum scattering calculations have been carried out using a potential energy surface which is considered to be chemically accurate. To improve our ability to test the theory, a 'perfect experiment', measuring differential cross sections with complete specification of the reactant and product states, is called for. In this thesis, the design of an experiment is described that aims at achieving this goal for the D + H[sub 2] reaction. A crossed molecular beam arrangement is used, in which a photolytic D atom beam is crossed by a pulsed beam of H[sub 2] molecules. DH molecules formed in the D + H[sub 2] reaction are state-specifically ionized using Doppler-free (2+1) Resonance-Enhanced Multi-Photon Ionization (REMPI) and detected using a Position-sensitive microchannel plate detector. This detection technique has an unprecedented single shot detection sensitivity of 6.8 10[sup 3] molecules/cc. This thesis does not contain experimental results for the D + H[sub 2] reaction yet, but progress that has been made towards achieving this goal is reported. In addition, results are reported for a study of the Rydberg spectroscopy of the water molecule.

  15. Towards rotationally state-resolved differential cross sections for the hydrogen exchange reaction

    SciTech Connect

    Vrakking, M.J.J.

    1992-11-01

    The hydrogen exchange reaction H + H{sub 2} {yields} H{sub 2} + H (and its isotopic variants) plays a pivotal role in chemical reaction dynamics. It is the only chemical reaction for which fully converged quantum scattering calculations have been carried out using a potential energy surface which is considered to be chemically accurate. To improve our ability to test the theory, a `perfect experiment`, measuring differential cross sections with complete specification of the reactant and product states, is called for. In this thesis, the design of an experiment is described that aims at achieving this goal for the D + H{sub 2} reaction. A crossed molecular beam arrangement is used, in which a photolytic D atom beam is crossed by a pulsed beam of H{sub 2} molecules. DH molecules formed in the D + H{sub 2} reaction are state-specifically ionized using Doppler-free (2+1) Resonance-Enhanced Multi-Photon Ionization (REMPI) and detected using a Position-sensitive microchannel plate detector. This detection technique has an unprecedented single shot detection sensitivity of 6.8 10{sup 3} molecules/cc. This thesis does not contain experimental results for the D + H{sub 2} reaction yet, but progress that has been made towards achieving this goal is reported. In addition, results are reported for a study of the Rydberg spectroscopy of the water molecule.

  16. Double-Regge exchange limit for the γ p →K+K-p reaction

    NASA Astrophysics Data System (ADS)

    Shi, M.; Danilkin, I. V.; Fernández-Ramírez, C.; Mathieu, V.; Pennington, M. R.; Schott, D.; Szczepaniak, A. P.

    2015-02-01

    We apply the generalized Veneziano model (B5 model) in the double-Regge exchange limit to the γ p →K+K-p reaction. Four different cases defined by the possible combinations of the signature factors of leading Regge exchanges [(K*,a2/f2 ) , (K*,ρ /ω ) , (K2*,a2/f2) , and (K2*,ρ /ω ) ] have been simulated through the Monte Carlo method. Suitable event candidates for the double-Regge exchange high-energy limit were selected employing Van Hove plots as a better alternative to kinematical cuts in the K+K-p Dalitz plot. In this way we predict and analyze the double-Regge contribution to the K+K-p Dalitz plot, which constitutes one of the major backgrounds in the search for strangeonia, hybrids and exotics using γ p →K+K-p reaction. We expect that data currently under analysis, and those to come in the future, will allow verification of the double-Regge behavior and a better assessment of this component of the amplitude.

  17. Double-regge exchange limit for the γp→ K⁺K⁻p reaction

    DOE PAGESBeta

    Shi, M.; Danilkin, I. V.; Fernández-Ramírez, C.; Mathieu, V.; Pennington, M. R.; Schott, D.; Szczepaniak, A. P.

    2015-02-01

    We apply the generalized Veneziano model (B₅ model) in the double-Regge exchange limit to the γp→K⁺K⁻p reaction. Four different cases defined by the possible combinations of the signature factors of leading Regge exchanges ((K*,a₂/f₂), (K*,ρ/ω), (K*₂,a₂/f₂), and (K*₂,ρ/ω)) have been simulated through the Monte Carlo method. Suitable event candidates for the double-Regge exchange high-energy limit were selected employing Van Hove plots as a better alternative to kinematical cuts in the K⁺K⁻p Dalitz plot. In this way we predict and analyze the double-Regge contribution to the K⁺K⁻p Dalitz plot, which constitutes one of the major backgrounds in the search for strangeonia,more » hybrids and exotics using γp→K⁺K⁻p reaction. We expect that data currently under analysis, and that to come in the future, will allow verification of the double-Regge behavior and a better assessment of this component of the amplitude.« less

  18. Double-regge exchange limit for the γp→ K⁺K⁻p reaction

    SciTech Connect

    Shi, M.; Danilkin, I. V.; Fernández-Ramírez, C.; Mathieu, V.; Pennington, M. R.; Schott, D.; Szczepaniak, A. P.

    2015-02-01

    We apply the generalized Veneziano model (B₅ model) in the double-Regge exchange limit to the γp→K⁺K⁻p reaction. Four different cases defined by the possible combinations of the signature factors of leading Regge exchanges ((K*,a₂/f₂), (K*,ρ/ω), (K*₂,a₂/f₂), and (K*₂,ρ/ω)) have been simulated through the Monte Carlo method. Suitable event candidates for the double-Regge exchange high-energy limit were selected employing Van Hove plots as a better alternative to kinematical cuts in the K⁺K⁻p Dalitz plot. In this way we predict and analyze the double-Regge contribution to the K⁺K⁻p Dalitz plot, which constitutes one of the major backgrounds in the search for strangeonia, hybrids and exotics using γp→K⁺K⁻p reaction. We expect that data currently under analysis, and that to come in the future, will allow verification of the double-Regge behavior and a better assessment of this component of the amplitude.

  19. Influence of the Ion Coordination Number on Cation Exchange Reactions with Copper Telluride Nanocrystals.

    PubMed

    Tu, Renyong; Xie, Yi; Bertoni, Giovanni; Lak, Aidin; Gaspari, Roberto; Rapallo, Arnaldo; Cavalli, Andrea; Trizio, Luca De; Manna, Liberato

    2016-06-01

    Cu2-xTe nanocubes were used as starting seeds to access metal telluride nanocrystals by cation exchanges at room temperature. The coordination number of the entering cations was found to play an important role in dictating the reaction pathways. The exchanges with tetrahedrally coordinated cations (i.e., with coordination number 4), such as Cd(2+) or Hg(2+), yielded monocrystalline CdTe or HgTe nanocrystals with Cu2-xTe/CdTe or Cu2-xTe/HgTe Janus-like heterostructures as intermediates. The formation of Janus-like architectures was attributed to the high diffusion rate of the relatively small tetrahedrally coordinated cations, which could rapidly diffuse in the Cu2-xTe NCs and nucleate the CdTe (or HgTe) phase in a preferred region of the host structure. Also, with both Cd(2+) and Hg(2+) ions the exchange led to wurtzite CdTe and HgTe phases rather than the more stable zinc-blende ones, indicating that the anion framework of the starting Cu2-xTe particles could be more easily deformed to match the anion framework of the metastable wurtzite structures. As hexagonal HgTe had never been reported to date, this represents another case of metastable new phases that can only be accessed by cation exchange. On the other hand, the exchanges involving octahedrally coordinated ions (i.e., with coordination number 6), such as Pb(2+) or Sn(2+), yielded rock-salt polycrystalline PbTe or SnTe nanocrystals with Cu2-xTe@PbTe or Cu2-xTe@SnTe core@shell architectures at the early stages of the exchange process. In this case, the octahedrally coordinated ions are probably too large to diffuse easily through the Cu2-xTe structure: their limited diffusion rate restricts their initial reaction to the surface of the nanocrystals, where cation exchange is initiated unselectively, leading to core@shell architectures. Interestingly, these heterostructures were found to be metastable as they evolved to stable Janus-like architectures if annealed at 200 °C under vacuum. PMID:27177274

  20. Fluctuational opening-closing reactions in DNA and mononucleosome cores of chromatin probed by H-exchange and ligand binding reactions

    SciTech Connect

    Mandal, C.; Englander, S.W.; Young, P.R.; Kallenbach, N.R.

    1980-10-01

    The DNA double helix represents a dynamic structure in solution that undergoes a spectrum of conformational opening and closing reactions under conditions remote from onset of denaturation. Two kinds of opening reactions of the double helix are manifested by: (a) the ability of base and solvent protons to exchange; and (b) the access of the duplex interior to intercalating agents such as ethidium bromide.

  1. The analysis of reactions {pi}N {yields} two mesons + N within reggeon exchanges. Basic formulas for fit

    SciTech Connect

    Anisovich, V. V. Sarantsev, A. V.

    2009-11-15

    We present technical aspects of the fitting procedure given in the paper by V.V. Anisovich and A.V. Sarantsev 'The analysis of reactions {pi}N {yields} two mesons + N within reggeon exchanges. Fit and results.'

  2. Barrier Height for the Exchange Reaction F + HF → FH + F

    PubMed Central

    O'Neil, Stephen V.; Schaefer, Henry F.; Bender, Charles F.

    1974-01-01

    There exists a body of conflicting data as to the existence or nonexistence of FHF, ClHCl, BrHBr, and IHI as chemically bound molecular species. Ab initio quantum mechanical electronic structure calculations are presented which predict linear symmetric FHF to be unstable. The barrier height for the F + HF exchange reaction is suggested to be no less than 18 kcal/mol, much larger than expected either intuitively or on the basis of certain experiments on related systems. The expected reliability of the calculations is based upon comparable results for diatomic molecules and the F + H2 and H + F2 potential energy surfaces. PMID:16592128

  3. Weak interaction processes in supernovae: New probes using charge exchange reaction at intermediate energies

    NASA Astrophysics Data System (ADS)

    Frekers, Dieter

    2005-04-01

    Spin-isospin-flip excitations in nuclei at vanishing momentum transfer are generally referred to as Gamov-Teller (GT) transitions. They are being studied because the simplicity of the excitation makes them an ideal probe for testing nuclear structure models. In astrophysics, GT transitions provide an important input for model calculations and element formation during the explosive phase of a massive star at the end of its life-time. GT transitions in the β- direction (also referred to as isospin lowering T< transitions) have extensively been studied through (p,n) and (3He,t) charge-exchange reactions [B.D. Anderson et al., Phys. Rev. C 36 (1987) 2195, B.D. Anderson et al., Phys. Rev. C 43 (1991) 50, J. Rapaport et al., Phys. Rev. C 24 (1981) 335, H. Akimune et al., Nucl. Phys. A 569 (1994) 245c, Y. Fujita et al., Phys. Lett. B 365 (1996) 29]. The generally good resolution allows easy extraction of the GT distribution and the total B(GT-) strength in the final nucleus. On the other hand, determination of B(GT+) strength through a charge-exchange reaction in the T> direction were mostly done with secondary neutron beams, and as such, they come with significant experimental difficulties. TRIUMF has pioneered this field in the late 80's and early 90's with a rich and highly successful (n,p) program using a several hundred MeV neutron beam from a 7Li(p,n)7Be reaction [R. Helmer, Can. J. Phys. 65 (1987) 588]. In this paper we present the (d,2He) reaction at intermediate energies as another and potentially even more powerful tool for charge-exchange reactions in the T>, resp. β+ direction. The key issue here will be the high resolution of order 100 keV, which provides new and sometimes unexpected insight into nuclear structure phenomena. This program has been launched at the AGOR Superconducting Cyclotron Facility at the KVI Groningen. By now, it covers a wide field of physics questions ranging from few-body physics, the structure of halo-nuclei, to questions pertaining

  4. Time-Resolved Structural Analysis of Cation Exchange Reactions in Birnessite Using Synchrotron XRD

    NASA Astrophysics Data System (ADS)

    Lopano, C. L.; Heaney, P. J.; Post, J. E.; Hanson, J. C.; Lee, Y.; Komarneni, S.

    2002-12-01

    Birnessite ((Na,Ca,Mn2+) Mn7O142.8H2O) is a layered Mn-oxide with a 7.2Å spacing between the Mn octahedral sheets. Since birnessite is an abundant phase in soils, desert varnishes, and ocean nodules, it plays a significant role in soil and groundwater chemistry. Experiments by Golden et al. (1986,1987) have demonstrated that Na-buserite (hydrated birnessite) readily exchanges Na+ for a variety of other cations, including K+, Mg2+, Ca2+, Ba2+, Ni2+, and Sr2+. In light of its high cation exchange capacity, birnessite is industrially important for ion and molecular sieves and cathodic materials. In addition, birnessite serves as a precursor in the synthesis of todorokite, which has a 3x3 tunnel structure and is used as an octahedral sieve. We monitored cation-exchange reactions in birnessite by time-resolved X-ray powder diffraction with a simple flow-through cell at the National Synchrotron Light Source. The flow-through cell was developed by Lee and Parise at SUNY-Stony Brook, and this work represents its first application to Mn oxides. A series of synthetic Na-birnessite samples were saturated with chloride solutions containing dissolved K+, Mg2+, and Ba2+, ranging from 0.1M to 0.001M. Powder X-ray diffraction patterns were collected every ~ 3 minutes. The synchrotron experiments revealed that complete cation exchange occurs within three hours, and significant modifications of the arrangements of interlayer cations and water molecules accompany the exchange. Specifically, the replacement of Na by Mg resulted in the continuous growth of a discrete buserite-like phase with a 10Å layer spacing, while replacement of Na by K and Ba retained the 7Å spacing. K replacement of Na resulted in gradually decreasing peak intensity and peak merging. The Ba exchange yielded an abrupt decrease in diffraction intensities followed by a more gradual lattice change over the last 2 hours. Rietveld analysis led to the first determination of the structure of Ba-birnessite in space

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

    NASA Astrophysics Data System (ADS)

    Chen, Peng; Solomon, Edward I.

    2004-09-01

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

  6. Independent control of the shape and composition of ionic nanocrystals through sequential cation exchange reactions

    SciTech Connect

    Luther, Joseph Matthew; Zheng, Haimei; Sadtler, Bryce; Alivisatos, A. Paul

    2009-07-06

    Size- and shape-controlled nanocrystal growth is intensely researched for applications including electro-optic, catalytic, and medical devices. Chemical transformations such as cation exchange overcome the limitation of traditional colloidal synthesis, where the nanocrystal shape often reflects the inherent symmetry of the underlying lattice. Here we show that nanocrystals, with established synthetic protocols for high monodispersity, can be templates for independent composition control. Specifically, controlled interconversion between wurtzite CdS, chalcocite Cu2S, and rock salt PbS occurs while preserving the anisotropic dimensions unique to the as-synthesized materials. Sequential exchange reactions between the three sulfide compositions are driven by the disparate solubilites of the metal ion exchange pair in specific coordinating molecules. Starting with CdS, highly anisotropic PbS nanorods are created, which serve as an important material for studying strong 2-dimensional quantum confinement, as well as for optoelectronic applications. Furthermore, interesting nanoheterostructures of CdS|PbS are obtained by precise control over ion insertion and removal.

  7. The neutron-proton charge-exchange amplitudes measured in the dp → ppn reaction

    NASA Astrophysics Data System (ADS)

    Mchedlishvili, D.; Barsov, S.; Carbonell, J.; Chiladze, D.; Dymov, S.; Dzyuba, A.; Engels, R.; Gebel, R.; Glagolev, V.; Grigoryev, K.; Goslawski, P.; Hartmann, M.; Kacharava, A.; Kamerdzhiev, V.; Keshelashvili, I.; Khoukaz, A.; Komarov, V.; Kulessa, P.; Kulikov, A.; Lehrach, A.; Lomidze, N.; Lorentz, B.; Macharashvili, G.; Maier, R.; Merzliakov, S.; Mielke, M.; Mikirtychyants, M.; Mikirtychyants, S.; Nioradze, M.; Ohm, H.; Papenbrock, M.; Prasuhn, D.; Rathmann, F.; Serdyuk, V.; Seyfarth, H.; Stein, H. J.; Steffens, E.; Stockhorst, H.; Ströher, H.; Tabidze, M.; Trusov, S.; Uzikov, Yu.; Valdau, Yu.; Wilkin, C.

    2013-04-01

    The unpolarised differential cross section and the two deuteron tensor analysing powers A xx and A yy of the ěc dp to \\{ pp\\} _s n charge-exchange reaction have been measured with the ANKE spectrometer at the COSY storage ring. Using deuteron beams with energies 1.2, 1.6, 1.8, and 2.27GeV, data were obtained for small momentum transfers to a { pp} s system with low excitation energy. The results at the three lower energies are consistent with impulse approximation predictions based upon the current knowledge of the neutron-proton amplitudes. However, at 2.27GeV, where these amplitudes are far more uncertain, agreement requires a reduction in the overall double-spin-flip contribution, with an especially significant effect in the longitudinal direction. These conclusions are supported by measurements of the deuteron-proton spin-correlation parameters C x,x and C y,y that were carried out in the ěc děc p to \\{ pp\\} _s n reaction at 1.2 and 2.27GeV. The values obtained for the proton analysing power A {/y p } also suggest the need for a radical re-evaluation of the neutron-proton elastic scattering amplitudes at the higher energy. It is therefore clear that such measurements can provide a valuable addition to the neutron-proton database in the charge-exchange region.

  8. Oxygen exchange reactions catalyzed by vacuolar H(+)-translocating pyrophosphatase. Evidence for reversible formation of enzyme-bound pyrophosphate.

    PubMed

    Baykov, A A; Kasho, V N; Bakuleva, N P; Rea, P A

    1994-08-22

    Vacuolar membrane-derived vesicles isolated from Vigna radiata catalyze oxygen exchange between medium phosphate and water. On the basis of the inhibitor sensitivity and cation requirements of the exchange activity, it is almost exclusively attributable to the vacuolar H(+)-pyrophosphatase (V-PPase). The invariance of the partition coefficient and the results of kinetic modeling indicate that exchange proceeds via a single reaction pathway and results from the reversal of enzyme-bound pyrophosphate synthesis. Comparison of the exchange reactions catalyzed by V-PPase and soluble PPases suggests that the two classes of enzyme mediate P(i)-HOH exchange by the same mechanism and that the intrinsic reversibility of the V-PPase is no greater than that of soluble PPases. PMID:8070586

  9. Hydrogen exchange in some coal-related reactions at 400/sup 0/C

    SciTech Connect

    Benjamin, B.M.; Michalczyk, M.J.; Woody, M.C.

    1980-01-01

    Data are available for kinetics of the transfer of hydrogen from tetralin and other hydrogen-rich solvents, but not much is known about the detailed mechanism involving individual linkages or groups in coal. In order to obtain some of this information, we have chosen to work with the pure compounds, 1,2-diphenylethane (bibenzyl), and diphenylmethane as models for certain linkages in coal. Because the thermolysis of the compound gives some different products when heated alone or when heated in the presence of a good hydrogen donor, such as tetralin, it was of interest to know where the cleavage fragments derive their hydrogen to give the final product. While the source of hydrogen needed to cap off the thermolysis fragments is obvious when bibenzyl is heated alone, its origin is ambiguous when tetralin is present. In order to resolve this aspect of the reaction, we prepared bibenzyl completely deuterated (99.8%) in the dimethylene linkage, and pyrolyzed it in the presence of ordinary tetralin. The products were isolated and their hydrogen and deuterium content were determined. From the data we conclude that the benzyl radical, formed by cleavage of bibenzyl, gives toluene by abstracting hydrogen from tetralin. The product after 1 percent conversion was PhCD/sub 2/H. Further, it was observed that, upon heating the mixture for eight hours, deuterium appeared in all the compounds. A considerable amount of deuterium exchange had taken place. In fact, in this mixture, tetralin-bibenzyl-d/sub 4/ at 400/sup 0/C, deuterium is lost from bibenzyl by exchange 3 to 4 times faster than it undergoes carbon-carbon bond scission. Thus, the chemistry of bibenzyl at 400/sup 0/ is dominated by hydrogen exchange reactions.

  10. EXCHANGE

    SciTech Connect

    Boltz, J.C.

    1992-09-01

    EXCHANGE is published monthly by the Idaho National Engineering Laboratory (INEL), a multidisciplinary facility operated for the US Department of Energy (DOE). The purpose of EXCHANGE is to inform computer users about about recent changes and innovations in both the mainframe and personal computer environments and how these changes can affect work being performed at DOE facilities.

  11. Synthesis of ordered mesoporous crystalline CuS and Ag2S materials via cation exchange reaction

    NASA Astrophysics Data System (ADS)

    Wang, Jun; Xu, Weiming; Bao, Haifeng; Shi, Yifeng

    2015-02-01

    Cation exchange reaction is a strong tool for the synthesis of new ionic nanomaterials. Most of them are isolated nanoparticles with simple geometric features, such as nanodots, nanorods and nanospheres. In this work, we demonstrated that ordered mesoporous CdS with a complex cubic Ia3d gyroidal 3D bicontinuous porous structure and large particle size can be successfully converted to crystalline CuS and Ag2S materials via cation exchange reaction without destroying the well-defined nanostructure. The change in crystal structure is an important factor for a successful conversion when the reaction is carried out without the presence of a silica template. In addition, the cation exchange reaction is sufficient for a complete compositional conversion, even when the mesostructured CdS precursor is embedded inside a mesoporous silica matrix. Our results indicate that cation exchange reaction may be applied to highly complex nanostructures with extremely large particle sizes.Cation exchange reaction is a strong tool for the synthesis of new ionic nanomaterials. Most of them are isolated nanoparticles with simple geometric features, such as nanodots, nanorods and nanospheres. In this work, we demonstrated that ordered mesoporous CdS with a complex cubic Ia3d gyroidal 3D bicontinuous porous structure and large particle size can be successfully converted to crystalline CuS and Ag2S materials via cation exchange reaction without destroying the well-defined nanostructure. The change in crystal structure is an important factor for a successful conversion when the reaction is carried out without the presence of a silica template. In addition, the cation exchange reaction is sufficient for a complete compositional conversion, even when the mesostructured CdS precursor is embedded inside a mesoporous silica matrix. Our results indicate that cation exchange reaction may be applied to highly complex nanostructures with extremely large particle sizes. Electronic supplementary

  12. Effect of chelate dynamics on water exchange reactions of paramagnetic aminopolycarboxylate complexes.

    PubMed

    Maigut, Joachim; Meier, Roland; Zahl, Achim; van Eldik, Rudi

    2008-07-01

    Because of our interest in evaluating a possible relationship between complex dynamics and water exchange reactivity, we performed (1)H NMR studies on the paramagnetic aminopolycarboxylate complexes Fe (II)-TMDTA and Fe (II)-CyDTA and their diamagnetic analogues Zn (II)-TMDTA and Zn (II)-CyDTA. Whereas a fast Delta-Lambda isomerization was observed for the TMDTA species, no acetate scrambling between in-plane and out-of-plane positions is accessible for any of the CyDTA complexes because the rigid ligand backbone prevents any configurational changes in the chelate system. In variable-temperature (1)H NMR studies, no evidence of spectral coalescence due to nitrogen inversion was found for any of the complexes in the available temperature range. The TMDTA complexes exhibit the known solution behavior of EDTA, whereas the CyDTA complexes adopt static solution structures. Comparing the exchange kinetics of flexible EDTA-type complexes and static CyDTA complexes appears to be a suitable method for evaluating the effect of ligand dynamics on the overall reactivity. In order to assess information concerning the rates and mechanism of water exchange, we performed variable-temperature and -pressure (17)O NMR studies of Ni (II)-CyDTA, Fe (II)-CyDTA, and Mn (II)-CyDTA. For Ni (II)-CyDTA, no significant effects on line widths or chemical shifts were apparent, indicating either the absence of any chemical exchange or the existence of a very small amount of the water-coordinated complex in solution. For [Fe (II)(CyDTA)(H 2O)] (2-) and [Mn (II)(CyDTA)(H 2O)] (2-), exchange rate constant values of (1.1 +/- 0.3) x 10 (6) and (1.4 +/- 0.2) x 10 (8) s (-1), respectively, at 298 K were determined from fits to resonance-shift and line-broadening data. A relationship between chelate dynamics and reactivity seems to be operative, since the CyDTA complexes exhibited significantly slower reactions than their EDTA counterparts. The variable-pressure (17)O NMR measurements for [Mn (II

  13. Pion nucleus single charge exchange reactions above the. delta. (1232) resonance

    SciTech Connect

    Rokni, S.H.

    1987-06-01

    Forward-angle differential cross sections for the (..pi../sup +/, ..pi../sup 0/) reaction leading to the Isobaric Analog State in the residual nuclei at 300, 425, 500 and 550 MeV have been measured. Targets ranged in mass from /sup 7/Li to /sup 208/Pb. A description of the experimental setup and the analysis is presented. The 0/sup 0/ cross sections are found to rise markedly between 300 and 425 MeV, contrary to the extrapolation from the lower energy data and to the behavior of the free pion-nucleon single charge exchange process. The angular distributions are sharply forward peaked. Systematics of the data indicate increased volume penetration with increasing pion beam energy. The cross sections are compared with the results of Glauber model calculations indicating the significance of higher order processes even at these energies. 67 refs., 40 figs., 22 tabs.

  14. Pion-induced double-charge exchange reactions in the {delta} resonance region

    SciTech Connect

    Buss, O.; Alvarez-Ruso, L.; Larionov, A. B.; Mosel, U.

    2006-10-15

    We have applied the Giessen BUU (GiBUU) transport model to the description of the double-charge exchange (DCX) reaction of pions with different nuclear targets at incident kinetic energies of 120-180 MeV. The DCX process is highly sensitive to details of the interactions of pions with the nuclear medium and, therefore, represents a major benchmark for any model of pion scattering off nuclei at low and intermediate energies. The impact of surface effects, such as the neutron skins of heavy nuclei, is investigated. The dependence of the total cross section on the nuclear mass number is also discussed. We achieve a good quantitative agreement with the extensive data set obtained at LAMPF. Furthermore, we compare the solutions of the transport equations obtained in the test-particle ansatz using two different schemes: the full and the parallel ensemble methods.

  15. Ligand Exchange Reaction of Au(I) R-N-Heterocyclic Carbene Complexes with Cysteine.

    PubMed

    Dos Santos, H F; Vieira, M A; Sánchez Delgado, G Y; Paschoal, D

    2016-04-14

    The chemotherapy with gold complexes has been attempted since the 90s after the clinical success of auranofin, a gold(I) coordination complex. Currently, the organometallics compounds have shown promise in cancer therapy, mainly in those complexes containing N-heterocylic carbenes (NHC) as a ligand. The present study shows a kinetic analysis of the reaction of six alkyl-substituted NHC with cysteine (Cys), which is taken as an important bionucleophile representative. The first and second ligand exchange processes were analyzed with the complete description of the mechanism and energy profiles. For the first reaction step, which is the rate-limiting step of the whole substitution reaction, the activation enthalpy follows the order 1/Me2 < 2/Me,Et < 4/n-Bu2 < 3/i-Pr2 < 6/Cy2 < 5/t-Bu2, which is fully explained by steric and electronic features. From a steric point of view, the previous reactivity order is correlated with the r(Au-S) calculated for the transition state structures where S is the sulfur ligand from the Cys entering group. This means that longer r(Au-S) leads to higher activation enthalpy and is consistent with the effectiveness of gold shielding from nucleophile attack by bulkier alkyl-substituted NHC ligand. When electronic effect was addressed we found that higher activation barrier was predicted for strongly electron-donating NHC ligand, represented by the eigenvalue of σ-HOMO orbital of the free ligands. The molecular interpretation of the electronic effects is that strong donating NHC forms strong metal-ligand bond. For the second reaction step, similar structure-reactivity relationships were obtained, however the activation energies are less sensitive to the structure. PMID:27010796

  16. Effect of ADP on Na+-Na+ Exchange Reaction Kinetics of Na,K-ATPase

    PubMed Central

    Peluffo, R. Daniel

    2004-01-01

    The whole-cell voltage-clamp technique was used in rat cardiac myocytes to investigate the kinetics of ADP binding to phosphorylated states of Na,K-ATPase and its effects on presteady-state Na+-dependent charge movements by this enzyme. Ouabain-sensitive transient currents generated by Na,K-ATPase functioning in electroneutral Na+-Na+ exchange mode were measured at 23°C with pipette ADP concentrations ([ADP]) of up to 4.3 mM and extracellular Na+ concentrations ([Na]o) between 36 and 145 mM at membrane potentials (VM) from −160 to +80 mV. Analysis of charge-VM curves showed that the midpoint potential of charge distribution was shifted toward more positive VM both by increasing [ADP] at constant Na+o and by increasing [Na]o at constant ADP. The total quantity of mobile charge, on the other hand, was found to be independent of changes in [ADP] or [Na]o. The presence of ADP increased the apparent rate constant for current relaxation at hyperpolarizing VM but decreased it at depolarizing VM as compared to control (no added ADP), an indication that ADP binding facilitates backward reaction steps during Na+-Na+ exchange while slowing forward reactions. Data analysis using a pseudo three-state model yielded an apparent Kd of ∼6 mM for ADP binding to and release from the Na,K-ATPase phosphoenzyme; a value of 130 s−1 for k2, a rate constant that groups Na+ deocclusion/release and the enzyme conformational transition E1∼P → E2-P; a value of 162 s−1M−1 for k−2, a lumped second-order VM-independent rate constant describing the reverse reactions; and a Hill coefficient of ∼1 for Na+o binding to E2-P. The results are consistent with electroneutral release of ADP before Na+ is deoccluded and released through an ion well. The same approach can be used to study additional charge-moving reactions and associated electrically silent steps of the Na,K-pump and other transporters. PMID:15298896

  17. Charge-exchange reactions and electron-capture rates for presupernova stellar evolution

    NASA Astrophysics Data System (ADS)

    Zegers, Remco

    2015-04-01

    Weak reaction rates such as electron captures and beta decays play major roles in a variety of astrophysical phenomena, such as core-collapse and thermonuclear supernovae and accreting neutron stars. Consequently, the use of accurate weak reaction rates in astrophysical simulations to understand these phenomena is important. Unfortunately, the number of relevant nuclei is typically very large, and, except for a few special cases, it is impossible to rely on experimental results only: theoretical models must be used to estimate the weak reaction rates. These models can then be benchmarked and improved on the basis of a limited number of experimental data. The most important nuclear structure input that is required for calculating weak reaction rates are Gamow-Teller transition strengths. Although these can be extracted from beta and electron-capture decay data, the energy window accessible by such experiments is limited, if accessible at all. However, at the high temperatures and densities that occur in massive stars prior to the cataclysmic demise, transitions to final states at high excitation energies are important. In addition, to properly test theory, full Gamow-Teller transition strength distributions are very valuable. Fortunately, nature is kind: charge-exchange experiments at intermediate energies can provide the relevant strength distributions over a wide energy window and a variety of charge-exchange probes, such as (p,n), (n,p), (d,2 He) and (t,3 He) have been used to extract strengths of relevance for astrophysics (and for other purposes). This presentation will focus on efforts to validate electron capture rates calculated based on nuclear structure models for nuclei with masses ranging from A ~ 40-65, and on studies aimed at testing astrophysical sensitivities to uncertainties/deviations in the theoretical rates. These efforts include experiments with unstable isotopes, and special gamma-ray coincidence techniques to localize very weak, but

  18. Reprint of: A numerical modelling of gas exchange mechanisms between air and turbulent water with an aquarium chemical reaction

    NASA Astrophysics Data System (ADS)

    Nagaosa, Ryuichi S.

    2014-08-01

    This paper proposes a new numerical modelling to examine environmental chemodynamics of a gaseous material exchanged between the air and turbulent water phases across a gas-liquid interface, followed by an aquarium chemical reaction. This study uses an extended concept of a two-compartment model, and assumes two physicochemical substeps to approximate the gas exchange processes. The first substep is the gas-liquid equilibrium between the air and water phases, A(g)⇌A(aq), with Henry's law constant H. The second is a first-order irreversible chemical reaction in turbulent water, A(aq)+H2O→B(aq)+H+ with a chemical reaction rate κA. A direct numerical simulation (DNS) technique has been employed to obtain details of the gas exchange mechanisms and the chemical reaction in the water compartment, while zero velocity and uniform concentration of A is considered in the air compartment. The study uses the different Schmidt numbers between 1 and 8, and six nondimensional chemical reaction rates between 10(≈0) to 101 at a fixed Reynolds number. It focuses on the effects of the Schmidt number and the chemical reaction rate on fundamental mechanisms of the gas exchange processes across the interface.

  19. A numerical modelling of gas exchange mechanisms between air and turbulent water with an aquarium chemical reaction

    NASA Astrophysics Data System (ADS)

    Nagaosa, Ryuichi S.

    2014-01-01

    This paper proposes a new numerical modelling to examine environmental chemodynamics of a gaseous material exchanged between the air and turbulent water phases across a gas-liquid interface, followed by an aquarium chemical reaction. This study uses an extended concept of a two-compartment model, and assumes two physicochemical substeps to approximate the gas exchange processes. The first substep is the gas-liquid equilibrium between the air and water phases, A(g)⇌A(aq), with Henry's law constant H. The second is a first-order irreversible chemical reaction in turbulent water, A(aq)+H2O→B(aq)+H+ with a chemical reaction rate κA. A direct numerical simulation (DNS) technique has been employed to obtain details of the gas exchange mechanisms and the chemical reaction in the water compartment, while zero velocity and uniform concentration of A is considered in the air compartment. The study uses the different Schmidt numbers between 1 and 8, and six nondimensional chemical reaction rates between 10(≈0) to 101 at a fixed Reynolds number. It focuses on the effects of the Schmidt number and the chemical reaction rate on fundamental mechanisms of the gas exchange processes across the interface.

  20. Photo-induced hydrogen exchange reaction between methanol and glyoxal: formation of hydroxyketene.

    PubMed

    Mielke, Zofia; Mucha, Małgorzata; Bil, Andrzej; Golec, Barbara; Coussan, Stephane; Roubin, Pascale

    2008-08-25

    We study the structure and photochemistry of the glyoxal-methanol system (G-MeOH) by means of FTIR matrix isolation spectroscopy and ab initio calculations. The FTIR spectra show that the non-hydrogen-bonded complex, G-MeOH-1, is present in an inert environment of solid argon. MP2/aug-cc-pVDZ calculations indicate that G-MeOH-1 is the most stable complex among the five optimized structures. The interaction energy partitioned according to the symmetry-adapted perturbation theory (SAPT) scheme demonstrates that the dispersion energy gives a larger contribution to the stabilization of a non-hydrogen-bonded G-MeOH-1 complex than compared to the hydrogen-bonded ones. The irradiation of G-MeOH-1 with the filtered output of a mercury lamp (lambda>370 nm) leads to its photo-conversion into the hydroxyketene-methanol complex HK-MeOH-1. The identity of HK-MeOH-1 is confirmed by both FTIR spectroscopy and MP2/aug-cc-pVDZ calculations. An experiment with deuterated methanol (CH(3)OD) evidences that hydroxyketene is formed in a photo-induced hydrogen exchange reaction between glyoxal and methanol. The pathway for the photo-conversion of G-MeOH-1 to HK-MeOH-1 is studied by a coupled-cluster method [CR-CC(2,3)]. The calculations confirm our experimental findings that the reaction proceeds via hydrogen atom exchange between the OH group of methanol and CH group of glyoxal. PMID:18613199

  1. Metastable structures and isotope exchange reactions in polyoxometalate ions provide a molecular view of oxide dissolution.

    PubMed

    Rustad, James R; Casey, William H

    2012-03-01

    Reactions involving minerals and glasses in water are slow and difficult to probe spectroscopically but are fundamental to the performance of oxide materials in green technologies such as automotive thermoelectric power generation, CO2 capture and storage and water-oxidation catalysis; these must be made from geochemically common elements and operate in hydrous environments. Polyoxometalate ions (POMs) have structures similar to condensed oxide phases and can be used as molecular models of the oxide/water interface. Oxygen atoms in POM exchange isotopes at different rates, but, at present, there is no basis for predicting how the coordination environment and metal substitution influences rates and mechanisms. Here we identify low-energy metastable configurations that form from the breaking of weak bonds between metals and underlying highly coordinated oxygen atoms, followed by facile hydroxide, hydronium or water addition. The mediation of oxygen exchange by these stuffed structures suggests a new view of the relationship between structure and reactivity at the oxide/solution interface. PMID:22231599

  2. Fluorescent metal ion chemosensors via cation exchange reactions of complexes, quantum dots, and metal-organic frameworks.

    PubMed

    Cheng, Jinghui; Zhou, Xiangge; Xiang, Haifeng

    2015-11-01

    Due to their wide range of applications and biological significance, fluorescent sensors have been an active research area in the past few years. In the present review, recent research developments on fluorescent chemosensors that detect metal ions via cation exchange reactions (transmetalation, metal displacement, or metal exchange reactions) of complexes, quantum dots, and metal-organic frameworks are described. These complex-based chemosensors might have a much better selectivity than the corresponding free ligands/receptors because of the shielding function of the filled-in metal ions. Moreover, not only the chemical structure of the ligands/receptors but also the identity of the central metal ions have a tremendous impact on the sensing performances. Therefore, sensing via cation exchange reactions potentially provides a new, simple, and powerful way to design fluorescent chemosensors. PMID:26375420

  3. Bidirectional exchange of biogenic volatiles with vegetation: emission sources, reactions, breakdown and deposition

    PubMed Central

    Niinemets, Ülo; Fares, Silvano; Harley, Peter; Jardine, Kolby J.

    2014-01-01

    Biogenic volatile organic compound (BVOC) emissions are widely modeled as inputs to atmospheric chemistry simulations. However, BVOC may interact with cellular structures and neighboring leaves in a complex manner during volatile diffusion from the sites of release to leaf boundary layer and during turbulent transport to the atmospheric boundary layer. Furthermore, recent observations demonstrate that the BVOC emissions are bidirectional, and uptake and deposition of BVOC and their oxidation products are the rule rather than the exception. This review summarizes current knowledge of within-leaf reactions of synthesized volatiles with reactive oxygen species (ROS), uptake, deposition and storage of volatiles and their oxidation products as driven by adsorption on leaf surface and solubilization and enzymatic detoxification inside leaves. The available evidence indicates that due to reactions with ROS and enzymatic metabolism, the BVOC gross production rates are much larger than previously thought. The degree to which volatiles react within leaves and can be potentially taken up by vegetation depends on compound reactivity, physicochemical characteristics, as well as their participation in leaf metabolism. We argue that future models should be based on the concept of bidirectional BVOC exchange and consider modification of BVOC sink/source strengths by within-leaf metabolism and storage. PMID:24635661

  4. Influence of matrix diffusion and exchange reactions on radiocarbon ages in fissured carbonate aquifers

    SciTech Connect

    Maloszewski, P. ); Zuber, A. )

    1991-08-01

    The parallel fissure model coupled with the equation of diffusion into the matrix and with exchange reaction equations has been used to derive a simple formula for estimating the influence of matrix porosity and reaction parameters on the determination of radiocarbon ages in fissured carbonate rocks. Examples of evidently too great radiocarbon ages in carbonate formations, which are not explainable by models for the initial {sup 14}C corrections, can easily be explained by this formula. Parameters obtained for a chalk formation from a known multitracer experiment combined with a pumping test suggest a possibility of {sup 14}C ages more than three orders of magnitude greater than the ages which would be observed if the radiocarbon transport took place only in the mobile water in the fissures. It is shown that contrary to the solute movement on a small scale and with a variable input, the large-scale movement, characteristic for the {sup 14}C dating, does not necessarily require the knowledge of kinetic parameters, because they may be replaced by the distribution coefficient. Discordant tritium and {sup 14}C concentrations are commonly interpreted as a proof of mixing either in the aquifer or at the discharge site. For fissured carbonate formations, however, an alternative explanation is given by the derived model showing a considerable delay of {sup 14}C with respect to nonsorbable tracers.

  5. Neutrino and antineutrino charge-exchange reactions on {sup 12}C

    SciTech Connect

    Samana, A. R.; Krmpotic, F.; Paar, N.; Bertulani, C. A.

    2011-02-15

    We extend the formalism of weak interaction processes, obtaining new expressions for the transition rates, which greatly facilitate numerical calculations, for both neutrino-nucleus reactions and muon capture. Explicit violation of the conserved vector current hypothesis by the Coulomb field, as well as development of a sum-rule approach for inclusive cross sections, has been worked out. We have done a thorough study of exclusive (ground-state) properties of {sup 12}B and {sup 12}N within the projected quasiparticle random phase approximation (PQRPA). Good agreement with experimental data achieved in this way put into evidence the limitations of the standard RPA and QRPA models, which come from the inability of the RPA to open the p{sub 3/2} shell and from the nonconservation of the number of particles in the QRPA. The inclusive neutrino/antineutrino ({nu}/{nu}-tilde) reactions {sup 12}C({nu},e{sup -}){sup 12}N and {sup 12}C({nu}-tilde,e{sup +}){sup 12}B are calculated within both the PQRPA and the relativistic QRPA. It is found that (i) the magnitudes of the resulting cross sections are close to the sum-rule limit at low energy, but significantly smaller than this limit at high energies, for both {nu} and {nu}-tilde; (ii) they increase steadily when the size of the configuration space is augmented, particularly for {nu}/{nu}-tilde energies >200 MeV; and (iii) they converge for sufficiently large configuration space and final-state spin. The quasi-elastic {sup 12}C({nu},{mu}{sup -}){sup 12}N cross section recently measured in the MiniBooNE experiment is briefly discussed. We study the decomposition of the inclusive cross section based on the degree of forbiddenness of different multipoles. A few words are dedicated to the {nu}/{nu}-tilde-{sup 12}C charge-exchange reactions related to astrophysical applications.

  6. Reversible Dissociation and Ligand-Glutathione Exchange Reaction in Binuclear Cationic Tetranitrosyl Iron Complex with Penicillamine

    PubMed Central

    Syrtsova, Lidia; Sanina, Natalia; Lyssenko, Konstantin; Kabachkov, Evgeniy; Psikha, Boris; Shkondina, Natal'ja; Pokidova, Olesia; Kotelnikov, Alexander; Aldoshin, Sergey

    2014-01-01

    This paper describes a comparative study of the decomposition of two nitrosyl iron complexes (NICs) with penicillamine thiolic ligands [Fe2(SC5H11NO2)2(NO)4]SO4·5H2O (I) and glutathione- (GSH-) ligands [Fe2(SC10H17N3O6)2(NO)4]SO4·2H2O (II), which spontaneously evolve to NO in aqueous medium. NO formation was measured by a sensor electrode and by spectrophotometric methods by measuring the formation of a hemoglobin- (Hb-) NO complex. The NO evolution reaction rate from (I)  k1 = (4.6 ± 0.1)·10−3 s−1 and the elimination rate constant of the penicillamine ligand k2 = (1.8 ± 0.2)·10−3 s−1 at 25°C in 0.05 M phosphate buffer,  pH 7.0, was calculated using kinetic modeling based on the experimental data. Both reactions are reversible. Spectrophotometry and mass-spectrometry methods have firmly shown that the penicillamine ligand is exchanged for GS− during decomposition of 1.5·10−4 M (I) in the presence of 10−3 M GSH, with 76% yield in 24 h. As has been established, such behaviour is caused by the resistance of (II) to decomposition due to the higher affinity of iron to GSH in the complex. The discovered reaction may impede S-glutathionylation of the essential enzyme systems in the presence of (I) and is important for metabolism of NIC, connected with its antitumor activity. PMID:24790592

  7. Reversible dissociation and ligand-glutathione exchange reaction in binuclear cationic tetranitrosyl iron complex with penicillamine.

    PubMed

    Syrtsova, Lidia; Sanina, Natalia; Lyssenko, Konstantin; Kabachkov, Evgeniy; Psikha, Boris; Shkondina, Natal'ja; Pokidova, Olesia; Kotelnikov, Alexander; Aldoshin, Sergey

    2014-01-01

    This paper describes a comparative study of the decomposition of two nitrosyl iron complexes (NICs) with penicillamine thiolic ligands [Fe2(SC5H11NO2)2(NO)4]SO4 ·5H2O (I) and glutathione- (GSH-) ligands [Fe2(SC10H17N3O6)2(NO)4]SO4 ·2H2O (II), which spontaneously evolve to NO in aqueous medium. NO formation was measured by a sensor electrode and by spectrophotometric methods by measuring the formation of a hemoglobin- (Hb-) NO complex. The NO evolution reaction rate from (I)  k 1 = (4.6 ± 0.1)·10(-3) s(-1) and the elimination rate constant of the penicillamine ligand k 2 = (1.8 ± 0.2)·10(-3) s(-1) at 25°C in 0.05 M phosphate buffer,  pH 7.0, was calculated using kinetic modeling based on the experimental data. Both reactions are reversible. Spectrophotometry and mass-spectrometry methods have firmly shown that the penicillamine ligand is exchanged for GS(-) during decomposition of 1.5·10(-4) M (I) in the presence of 10(-3) M GSH, with 76% yield in 24 h. As has been established, such behaviour is caused by the resistance of (II) to decomposition due to the higher affinity of iron to GSH in the complex. The discovered reaction may impede S-glutathionylation of the essential enzyme systems in the presence of (I) and is important for metabolism of NIC, connected with its antitumor activity. PMID:24790592

  8. Hydrogen and oxygen isotope exchange reactions between clay minerals and water

    USGS Publications Warehouse

    O'Neil, J.R.; Kharaka, Y.K.

    1976-01-01

    The extent of hydrogen and oxygen isotope exchange between clay minerals and water has been measured in the temperature range 100-350?? for bomb runs of up to almost 2 years. Hydrogen isotope exchange between water and the clays was demonstrable at 100??. Exchange rates were 3-5 times greater for montmorillonite than for kaolinite or illite and this is attributed to the presence of interlayer water in the montmorillonite structure. Negligible oxygen isotope exchange occurred at these low temperatures. The great disparity in D and O18 exchange rates observed in every experiment demonstrates that hydrogen isotope exchange occurred by a mechanism of proton exchange independent of the slower process of O18 exchange. At 350?? kaolinite reacted to form pyrophyllite and diaspore. This was accompanied by essentially complete D exchange but minor O18 exchange and implies that intact structural units in the pyrophyllite were inherited from the kaolinite precursor. ?? 1976.

  9. Cation exchange reactions controlling desorption of 90Sr 2+ from coarse-grained contaminated sediments at the Hanford site, Washington

    NASA Astrophysics Data System (ADS)

    McKinley, J. P.; Zachara, J. M.; Smith, S. C.; Liu, C.

    2007-01-01

    Nuclear waste that bore 90Sr 2+ was accidentally leaked into the vadose zone at the Hanford site, and was immobilized at relatively shallow depths in sediments containing little apparent clay or silt-sized components. Sr 2+, 90Sr 2+, Mg 2+, and Ca 2+ was desorbed and total inorganic carbon concentration was monitored during the equilibration of this sediment with varying concentrations of Na +, Ca 2+. A cation exchange model previously developed for similar sediments was applied to these results as a predictor of final solution compositions. The model included binary exchange reactions for the four operant cations and an equilibrium dissolution/precipitation reaction for calcite. The model successfully predicted the desorption data. The contaminated sediment was also examined using digital autoradiography, a sensitive tool for imaging the distribution of radioactivity. The exchanger phase containing 90Sr was found to consist of smectite formed from weathering of mesostasis glass in basaltic lithic fragments. These clasts are a significant component of Hanford formation sands. The relatively small but significant cation exchange capacity of these sediments was thus a consequence of reaction with physically sequestered clays in sediment that contained essentially no fine-grained material. The nature of this exchange component explained the relatively slow (scale of days) evolution of desorption solutions. The experimental and model results indicated that there is little risk of migration of 90Sr 2+ to the water table.

  10. Cation Exchange Reactions Controlling Desorption of 90Sr2+ From Coarse-Grained Contaminated Sediments at the Hanford Site, Washington

    NASA Astrophysics Data System (ADS)

    McKinley, J. P.; Zachara, J. M.; Smith, S. C.; Liu, C.

    2005-12-01

    Nuclear waste that bore 90Sr2+ was accidentally leaked into the vadose zone at the Hanford site, and was immobilized at relatively shallow depths in sediments containing little apparent clay or silt-sized components. We desorbed Sr2+, 90Sr2+, Mg2+, and Ca2+, and monitored total inorganic carbon concentration during the equilibration of this sediment with varying concentrations of Na+ and Ca2+. A cation exchange model previously developed for similar sediments was applied to these results as a predictor of final solution compositions. The model included binary exchange reactions for the four operant cations and an equilibrium dissolution/precipitation reaction for calcite. The model produced an excellent prediction for desorption data. We also examined the contaminated sediment using digital autoradiography, a sensitive tool for imaging the distribution of radioactivity. The exchanger phase containing 90Sr was found to consist of smectite formed from weathering of mesostasis glass in basaltic lithic fragments. These clasts are a significant component of Hanford formation sands. The relatively small but significant cation exchange capacity of these sediments was thus a consequence of reaction with physically sequestered clays in a sediment that contained essentially no fine-grained material. The nature of this exchange component explains the relatively slow (scale of days) evolution of desorption solutions. The experimental and model results indicate that there is little risk of migration of 90Sr2+ to the water table.

  11. Photochemical Synthesis and Ligand Exchange Reactions of Ru(CO)[subscript 4] (Eta[superscript 2]-Alkene) Compounds

    ERIC Educational Resources Information Center

    Cooke, Jason; Berry, David E.; Fawkes, Kelli L.

    2007-01-01

    The photochemical synthesis and subsequent ligand exchange reactions of Ru(CO)[subscript 4] (eta[superscript2]-alkene) compounds has provided a novel experiment for upper-level inorganic chemistry laboratory courses. The experiment is designed to provide a system in which the changing electronic properties of the alkene ligands could be easily…

  12. Prospects for Thermal Atomic Layer Etching Using Sequential, Self-Limiting Fluorination and Ligand-Exchange Reactions.

    PubMed

    George, Steven M; Lee, Younghee

    2016-05-24

    Thermal atomic layer etching (ALE) of Al2O3 and HfO2 using sequential, self-limiting fluorination and ligand-exchange reactions was recently demonstrated using HF and tin acetylacetonate (Sn(acac)2) as the reactants. This new thermal pathway for ALE represents the reverse of atomic layer deposition (ALD) and should lead to isotropic etching. Atomic layer deposition and ALE can together define the atomic layer growth and removal steps required for advanced semiconductor fabrication. The thermal ALE of many materials should be possible using fluorination and ligand-exchange reactions. The chemical details of ligand-exchange can lead to selective ALE between various materials. Thermal ALE could produce conformal etching in high-aspect-ratio structures. Thermal ALE could also yield ultrasmooth thin films based on deposit/etch-back methods. Enhancement of ALE rates and possible anisotropic ALE could be achieved using radicals or ions together with thermal ALE. PMID:27216115

  13. Presolvated Electron Reaction with Methylacetoacetate: Electron Localization, Proton-Deuteron Exchange, and H-atom Abstraction

    PubMed Central

    Petrovici, Alex; Adhikary, Amitava; Kumar, Anil; Sevilla, Michael D.

    2015-01-01

    Radiation-produced electrons initiate various reaction processes that are important to radiation damage to biomolecules. In this work, the site of attachment of the prehydrated electrons with methylacetoacetate (MAA, CH3-CO-CH2-CO-OCH3) at 77 K and subsequent reactions of the anion radical (CH3-CO•−-CH2-CO-OCH3) in the temperature range (77 to ca. 170 K) have been investigated in homogeneous H2O and D2O aqueous glasses by electron spin resonance (ESR) spectroscopy. At 77 K, the prehydrated electron attaches to MAA forming the anion radical in which the electron is delocalized over the two carbonyl groups. This species readily protonates to produce the protonated electron adduct radical CH3-C(•)OH-CH2-CO-OCH3. The ESR spectrum of CH3-C(•)OH-CH2-CO-OCH3 in H2O shows line components due to proton hyperfine couplings of the methyl and methylene groups. Whereas, the ESR spectrum of CH3-C(•)OH-CH2-CO-OCH3 in D2O glass shows only the line components due to proton hyperfine couplings of CH3 group. This is expected since the methylen protons in MAA are readily exchangeable in D2O. On stepwise annealing to higher temperatures (ca. 150 to 170 K), CH3-C(•)OH-CH2-CO-OCH3 undergoes bimolecular H-atom abstraction from MAA to form the more stable radical, CH3-CO-CH•-CO-OCH3. Theoretical calculations using density functional theory (DFT) support the radical assignments. PMID:25255751

  14. Exchange repulsive potential adaptable for electronic structure changes during chemical reactions

    SciTech Connect

    Yokogawa, D.

    2015-04-28

    Hybrid methods combining quantum mechanical (QM) and classical calculations are becoming important tools in chemistry. The popular approach to calculate the interaction between QM and classical calculations employs interatomic potentials. In most cases, the interatomic potential is constructed of an electrostatic (ES) potential and a non-ES potential. Because QM treatment is employed in the calculation of the ES potential, the electronic change can be considered in this ES potential. However, QM treatment of the non-ES potential is difficult because of high computational cost. To overcome this difficulty of evaluating the non-ES potential, we proposed an exchange repulsive potential as the main part of the non-ES potential on the basis of a QM approach. This potential is independent of empirical parameters and adaptable for electronic structure. We combined this potential with the reference interaction site model self-consistent field explicitly including spatial electron density distribution and successfully applied it to the chemical reactions in aqueous phase.

  15. Supportless silver nanowires as oxygen reduction reaction catalysts for hydroxide-exchange membrane fuel cells.

    PubMed

    Alia, Shaun M; Duong, Kathlynne; Liu, Toby; Jensen, Kurt; Yan, Yushan

    2012-08-01

    Silver nanowires (AgNWs) and nanoparticles (AgNPs) have been synthesized to facilitate hydroxide-exchange membrane fuel cell development and commercialization. AgNWs and AgNPs with variable diameters (25-60 nm AgNWs, 2.4-30 nm AgNPs) have been studied with rotating-disk electrode experiments to examine the impact of size and morphology on the oxygen reduction reaction (ORR). Although a detrimental particle size effect is observed, AgNWs exceed the specific activity of bulk polycrystalline Ag. AgNWs with a diameter of 25 nm further exceed the ORR specific and mass activity of 2.4 nm AgNPs 5.3 times and by 16 %, respectively. Rotating ring-disk electrode testing demonstrates minimal peroxide formation on AgNWs; peroxide production increases with the use of AgNPs by as much as an order of magnitude and further increases with particle size reduction. Silver catalysts demonstrate alcohol tolerance for ORR, illustrating the benefit of silver and AgNWs as catalysts in hydroxide and alcohol hydroxide-based fuel cells. PMID:22887923

  16. Synthesis of Composition Tunable and Highly Luminescent Cesium Lead Halide Nanowires through Anion-Exchange Reactions.

    PubMed

    Zhang, Dandan; Yang, Yiming; Bekenstein, Yehonadav; Yu, Yi; Gibson, Natalie A; Wong, Andrew B; Eaton, Samuel W; Kornienko, Nikolay; Kong, Qiao; Lai, Minliang; Alivisatos, A Paul; Leone, Stephen R; Yang, Peidong

    2016-06-15

    Here, we demonstrate the successful synthesis of brightly emitting colloidal cesium lead halide (CsPbX3, X = Cl, Br, I) nanowires (NWs) with uniform diameters and tunable compositions. By using highly monodisperse CsPbBr3 NWs as templates, the NW composition can be independently controlled through anion-exchange reactions. CsPbX3 alloy NWs with a wide range of alloy compositions can be achieved with well-preserved morphology and crystal structure. The NWs are highly luminescent with photoluminescence quantum yields (PLQY) ranging from 20% to 80%. The bright photoluminescence can be tuned over nearly the entire visible spectrum. The high PLQYs together with charge transport measurements exemplify the efficient alloying of the anionic sublattice in a one-dimensional CsPbX3 system. The wires increased functionality in the form of fast photoresponse rates and the low defect density suggest CsPbX3 NWs as prospective materials for optoelectronic applications. PMID:27213511

  17. Preparation of poly(aniline-co-o-anisidine)-intercalated mesostructured manganese oxide composites by exchange reaction

    SciTech Connect

    Wang Gengchao Yang Zhenyu; Li Xingwei; Li Chunzhong; Yuan Weikang

    2008-08-04

    Layered mesostructured manganese oxide (mesostructured MnO{sub 2}) was synthesized using manganese chloride and lithium hydroxide as the raw materials and cetyltrimethylammonium bromide (CTAB) as the structure-directing agent. Poly(aniline-co-o-anisidine)-intercalated mesostructured MnO{sub 2} composites (P(An-co-oAs)/MnO{sub 2}) were synthesized in an organic solvent through the exchange reaction between the CTAB in MnO{sub 2} gallery and the P(An-co-oAs). The interlayer spacing (I{sub c} values) of mesostructured MnO{sub 2} enlarged from 2.52 to 4.41 nm as the added amount of P(An-co-oAs) increased from 0 to 0.5 g per 0.5 g of mesostructured MnO{sub 2}. The regularity of the layered structure of the composites was firstly decreased due to intercalation of low amounts of P(An-co-oAs). However, with increasing the intercalated amount of P(An-co-oAs) the layered structure of the composites becomes more regular. The electrical conductivity of the composites is 10{sup 2} to 10{sup 3} times higher than that of the mesostructured MnO{sub 2}.

  18. Heavy-ion double charge exchange reactions: A tool toward 0 νββ nuclear matrix elements

    NASA Astrophysics Data System (ADS)

    Cappuzzello, F.; Cavallaro, M.; Agodi, C.; Bondì, M.; Carbone, D.; Cunsolo, A.; Foti, A.

    2015-11-01

    The knowledge of the nuclear matrix elements for the neutrinoless double beta decay is fundamental for neutrino physics. In this paper, an innovative technique to extract information on the nuclear matrix elements by measuring the cross section of a double charge exchange nuclear reaction is proposed. The basic point is that the initial- and final-state wave functions in the two processes are the same and the transition operators are similar. The double charge exchange cross sections can be factorized in a nuclear structure term containing the matrix elements and a nuclear reaction factor. First pioneering experimental results for the 40Ca(18O,18Ne)40Ar reaction at 270 MeV incident energy show that such cross section factorization reasonably holds for the crucial 0+ → 0+ transition to 40Args, at least at very forward angles.

  19. Electrocatalytic reduction of acetone in a proton-exchange-membrane reactor: a model reaction for the electrocatalytic reduction of biomass.

    PubMed

    Green, Sara K; Tompsett, Geoffrey A; Kim, Hyung Ju; Bae Kim, Won; Huber, George W

    2012-12-01

    Acetone was electrocatalytically reduced to isopropanol in a proton-exchange-membrane (PEM) reactor on an unsupported platinum cathode. Protons needed for the reduction were produced on the unsupported Pt-Ru anode from either hydrogen gas or electrolysis of water. The current efficiency (the ratio of current contributing to the desired chemical reaction to the overall current) and reaction rate for acetone conversion increased with increasing temperature or applied voltage for the electrocatalytic acetone/water system. The reaction rate and current efficiency went through a maximum with respect to acetone concentration. The reaction rate for acetone conversion increased with increasing temperature for the electrocatalytic acetone/hydrogen system. Increasing the applied voltage for the electrocatalytic acetone/hydrogen system decreased the current efficiency due to production of hydrogen gas. Results from this study demonstrate the commercial feasibility of using PEM reactors to electrocatalytically reduce biomass-derived oxygenates into renewable fuels and chemicals. PMID:22961747

  20. Effect of grossular on garnet-biotite, Fe Mg exchange reactions: evidence from garnet with mixed growth and diffusion zoning

    NASA Astrophysics Data System (ADS)

    Alcock, J.

    1996-07-01

    Garnets that exhibit mixed growth and diffusion zoning are used to evaluate the effect of grossular content on garnet Fe Mg exchange reactions. These garnets from the uppermost amphibolite-facies to granulite-facies gneiss of the Wissahickon Group, southeastern Pennsylvania, show variation in grossular content (0.035< X Ca<0.14) but nearly constant Mg? ( X Mg/( X Mg+ X Fe) and X Mn through the interior indicating re-equilibration of garnet and matrix minerals with respect to iron, magnesium, and manganese. Mg? is not correlated with calcium content, evidence that the effect of calcium on garnet Fe Mg exchange reactions is small or is offset by other interactions in almandine-rich garnets. In either case, the data presented here indicate that correction for calcium content of garnets in the application of garnet-biotite geothermometry to high-grade metapelites is unnecessary and may lead to an overestimate of peak temperature.

  1. Synthesis of N=127 isotones through (p,n) charge-exchange reactions induced by relativistic {sup 208}Pb projectiles

    SciTech Connect

    Morales, A. I.; Benlliure, J.; Alvarez-Pol, H.; Casarejos, E.; Dragosavac, D.; Perez-Loureiro, D.; Verma, S.; Agramunt, J.; Molina, F.; Rubio, B.; Algora, A.; Alkhomashi, N.; Farrelly, G.; Gelletly, W.; Pietri, S.; Podolyak, Z.; Regan, P. H.; Steer, S. J.; Boutachkov, P.; Caceres, L. S.

    2011-07-15

    The production cross sections of four N=127 isotones ({sup 207}Hg, {sup 206}Au, {sup 205}Pt, and {sup 204}Ir) have been measured using (p,n) charge-exchange reactions, induced in collisions of a {sup 208}Pb primary beam at 1 A GeV with a Be target. These data allow one to investigate the use of a reaction mechanism to extend the limits of the chart of nuclides toward the important r-process nuclei in the region of the third peak of elemental abundance distribution.

  2. Kinetic and Mechanistic Studies of the Deuterium Exchange in Classical Keto-Enol Tautomeric Equilibrium Reactions

    ERIC Educational Resources Information Center

    Nichols, Michael A.; Waner, Mark J.

    2010-01-01

    An extension of the classic keto-enol tautomerization of beta-dicarbonyl compounds into a kinetic analysis of deuterium exchange is presented. It is shown that acetylacetone and ethyl acetoacetate undergo nearly complete deuterium exchange of the alpha-methylene carbon when dissolved in methanol-d[subscript 4]. The extent of deuteration may be…

  3. Detecting 5-methylcytosine using an enzyme-free DNA strand exchange reaction without pretreatment under physiological conditions.

    PubMed

    Xu, Chen; Wu, Jinjun; Liu, Wenting; Hong, Tingting; Wang, Tianlu; Zhang, Xiaoe; Fu, Boshi; Wu, Fan; Wu, Zhiguo; Zhou, Xiang

    2016-05-21

    We present here a novel and efficient method for 5mC detection using a DNA strand exchange reaction (SER) strategy. This enzyme-free method needs no pre-treatment of target DNAs and can be adapted to most of the target duplexes under physiological conditions. The high sequence selectivity of this method can distinguish 5mC from normal cytosine in an accurate manner. PMID:27139156

  4. Balance between the physical diffusion and the exchange reaction on binary ionic liquid electrolyte for dye-sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Hao, Feng; Lin, Hong; Zhang, Jing; Li, Jianbao

    A comprehensive characterizations of viscosities, conductivities, triiodide diffusion coefficients, charge-transfer resistances and photovoltaic performance of a potential dye-sensitized solar cell (DSC) electrolyte systems based on binary ionic liquid (IL) mixtures, namely, 1-ethyl-3-methylimidazolium dicyanamide (EMIDCA)/1-methyl-3-propylimidazolium iodide (PMII) with a fixed iodine concentration at varying EMIDCA volume fraction are investigated in the present study. Viscosity and conductivity values are accurately correlated with regard to temperature and EMIDCA volume fraction. The triiodide diffusion coefficients, the predominant electrolyte parameter for limitation of DSC efficiency, are determined by symmetrical cell methods. The physical diffusion and exchange reactions between the iodide and triiodide dominate the apparent triiodide diffusion coefficients at different range of EMIDCA volume fraction. A balance between the viscosity-dependent physical diffusion and the exchange reactions can get at an optimal volume percents of EMIDCA. Impedance spectroscopy and photovoltaic results both support the existence of an optimized binary IL electrolyte composition. Hence, for optimizing an IL-based electrolyte in regards to triiodide transport, a low viscosity is not the exclusive crucial factor since exchange reactions transport effects also play an important role to resolve the diffusion limitation of DSC efficiency.

  5. The loss rates of O{sup +} in the inner magnetosphere caused by both magnetic field line curvature scattering and charge exchange reactions

    SciTech Connect

    Ji, Y.; Shen, C.

    2014-03-15

    With consideration of magnetic field line curvature (FLC) pitch angle scattering and charge exchange reactions, the O{sup +} (>300 keV) in the inner magnetosphere loss rates are investigated by using an eigenfunction analysis. The FLC scattering provides a mechanism for the ring current O{sup +} to enter the loss cone and influence the loss rates caused by charge exchange reactions. Assuming that the pitch angle change is small for each scattering event, the diffusion equation including a charge exchange term is constructed and solved; the eigenvalues of the equation are identified. The resultant loss rates of O{sup +} are approximately equal to the linear superposition of the loss rate without considering the charge exchange reactions and the loss rate associated with charge exchange reactions alone. The loss time is consistent with the observations from the early recovery phases of magnetic storms.

  6. Reaction Engineering International and Pacific Northwest Laboratory staff exchange: Addressing computational fluid dynamics needs of the chemical process industry

    SciTech Connect

    Fort, J.A.

    1995-07-01

    Staff exchanges, such as the one described in this report, are intended to facilitate communications and collaboration among scientists and engineers at Department of Energy (DOE) laboratories, in US industry, and academia. Funding support for these exchanges is provided by the DOE, Office of Energy Research, Laboratory Technology Transfer Program. Funding levels for each exchange typically range from $20,000 to $40,000. The exchanges offer the opportunity for the laboratories to transfer technology and expertise to industry, gain a perspective to industry`s problems, and develop the basis for further cooperative efforts through Cooperative Research and Development Agreements (CRADAS) or other mechanisms. Information in this report on the staff exchange of the Pacific Northwest Laboratory (PNL) staff with Reaction Engineering International (REI) includes the significant accomplishments, significant problems, industry benefits realized, recommended follow-on work and potential benefit of that work. The objectives of this project were as follows: Work with REI to develop an understanding of the computational fluid dynamics (CFD) needs of the chemical process industry; assess the combined capabilities of the PNL and REI software analysis tools to address these needs; and establish a strategy for a future programmatically funded, joint effort to develop a new CFD tool for the chemical process industry.

  7. Quantal Study of the Exchange Reaction for N + N2 using an ab initio Potential Energy Surface

    NASA Technical Reports Server (NTRS)

    Wang, Dunyou; Stallcop, James R.; Huo, Winifred M.; Dateo, Christopher E.; Schwenke, David W.; Partridge, Harry; Kwak, Dochan (Technical Monitor)

    2002-01-01

    The N + N2 exchange rate is calculated using a time-dependent quantum dynamics method on a newly determined ab initio potential energy surface (PES) for the ground A" state. This ab initio PES shows a double barrier feature in the interaction region with the barrier height at 47.2 kcal/mol, and a shallow well between these two barriers, with the minimum at 43.7 kcal/mol. A quantum dynamics wave packet calculation has been carried out using the fitted PES to compute the cumulative reaction probability for the exchange reaction of N + N2(J=O). The J - K shift method is then employed to obtain the rate constant for this reaction. The calculated rate constant is compared with experimental data and a recent quasi-classical calculation using a LEPS PES. Significant differences are found between the present and quasiclassical results. The present rate calculation is the first accurate 3D quantal dynamics study for N + N2 reaction system and the ab initio PES reported here is the first such surface for N3.

  8. Declines in Soil pH due to Anthropogenic Nitrogen Inputs Alter Buffering and Exchange Reactions in Tropical Forest Soils

    NASA Astrophysics Data System (ADS)

    Lohse, K. A.

    2003-12-01

    Anthropogenic nitrogen (N) inputs may alter tropical soil buffering and exchange reactions that have important implications for nutrient cycling, forest productivity, and downstream ecosystems. In contrast to relatively young temperate soils that are typically buffered from N inputs by base cation reactions, aluminum reactions may serve to buffer highly weathered tropical soils and result in immediate increases in aluminum mobility and toxicity. Increased nitrate losses due to chronic N inputs may also deplete residual base cations in already weathered base cation-poor soils, further acidify soils, and thereby reduce nitrate mobility through pH-dependent anion exchange reactions. To test these hypotheses, I determined soil pH and cation and anion exchange capacity (CEC and AEC) and measured base cation and aluminum soil solution losses following first-time and long-term experimental N additions from two Hawaiian tropical forest soils, a 300 year old Andisol and a 4.1 million year old Oxisol. I found that elevated base cation losses accompanied increased nitrate losses after first time N additions to the young Andisol whereas immediate and large aluminum losses were associated with increased nitrate losses from the Oxisol. In the long-term, base cation and aluminum losses increased in proportion to nitrate losses. Long-term N additions at both sites resulted in significant declines in soil pH, decreased CEC and increased AEC. These results suggest that even chronic N inputs resulting in small but elevated nitrate losses may deplete residual base cations, increase mobility and toxicity of aluminum, and potentially lead to declines in forest productivity and acidification of downstream ecosystems. These findings also suggest that AEC may provide a long-term mechanism to delay nitrate losses in tropical forests with significant variable charge that are experiencing chronic anthropogenic N inputs.

  9. Functionalized Mesoporous Silica via an Aminosilane Surfactant Ion Exchange Reaction: Controlled Scaffold Design and Nitric Oxide Release

    PubMed Central

    2015-01-01

    Nitric oxide-releasing mesoporous silica nanoparticles (MSNs) were prepared using an aminosilane-template surfactant ion exchange reaction. Initially, bare silica particles were synthesized under basic conditions in the presence of cetyltrimethylammonium bromide (CTAB). These particles were functionalized with nitric oxide (NO) donor precursors (i.e., secondary amines) via the addition of aminosilane directly to the particle sol and a commensurate ion exchange reaction between the cationic aminosilanes and CTAB. N-Diazeniumdiolate NO donors were formed at the secondary amines to yield NO-releasing MSNs. Tuning of the ion exchange-based MSN modification approach allowed for the preparation of monodisperse particles ranging from 30 to 1100 nm. Regardless of size, the MSNs stored appreciable levels of NO (0.4–1.5 μmol mg–1) with tunable NO release durations (1–33 h) dependent on the aminosilane modification. Independent control of NO release properties and particle size was achieved, demonstrating the flexibility of this novel MSN synthesis over conventional co-condensation and surface grafting strategies. PMID:26717238

  10. Studies in the reaction-separation method for the preparation of barium chloride from barite using ion exchange

    SciTech Connect

    Gokarn, A.N.; Gaikwad, A.G.; Phalak, C.A.; Bhandari, V.M.

    1999-06-01

    The authors report the application of an ion-exchange process as a reaction-separation strategy for the preparation of barium chloride from barite ore and sodium chloride. Experimental studies were carried out to evaluate the process efficiency and purity/yield of barium chloride using a strong acid cation-exchange resin, Tulsion T-42. The effects of various process parameters such as concentration of barium sulfide and concentration of sodium chloride were investigated, and optimization of the experimental variables was attempted. The results indicate the developed strategy to be attractive and an alternative route to existing processes. The methodology developed has large potential for the inorganic chemical process industry in general.

  11. Inclusive measurement of (p,. pi. /sup -/xn) double charge exchange reactions on bismuth from threshold to 800 MeV

    SciTech Connect

    Dombsky, M.; D'Auria, J.M.; Kelson, I.; Yavin, A.I.; Ward, T.E.; Clark, J.L.; Ruth, T.; Sheffer, G.

    1985-07-01

    The energy dependence of the total angle-integrated cross section for the production of astatine isotopes from (p,..pi../sup -/xn) double charge exchange reactions on bismuth (/sup 209/Bi) was measured from 120 to 800 MeV using activation and radiochemical techniques. Chemical yields were estimated by direct radioassaying of /sup 211/At activity in thin (approx.1 mg/cm/sup 2/), irradiated bismuth targets. Calculations of the contributions of secondary (two-step) reactions to these measured astatine yields were performed, based partially upon the observed /sup 211/At activity although even at the highest energies, the contribution to products lighter than /sup 207/At was negligible. These data for products with as many as seven neutrons removed from the doubly coherent product (/sup 210/At) display nearly Gaussian shapes for the mass distributions of the astatine residues, with the maximum occurring for about /sup 204/At. The most probable momentum transfer deduced from these distributions for the initial ..pi../sup -/ production step was 335 MeV/c. The observed excitation functions display a behavior similar to that observed for the yield of /sup 210/Po from a (p,..pi../sup 0/) reaction on /sup 209/Bi, but radically different from that observed for inclusive ..pi../sup -/ reactions on a heavy nucleus. These data are discussed in terms of recent theoretical approaches to negative pion production from bismuth. In addition, a simple, schematic model is developed to treat the rapidly decreasing percentage of the total inclusive ..pi../sup -/ emission which is observed for this double charge exchange reaction. This model reflects the opacity of a nucleus to a source of internal energetic protons.

  12. Cu3-xP Nanocrystals as a Material Platform for Near-Infrared Plasmonics and Cation Exchange Reactions

    PubMed Central

    2015-01-01

    Synthesis approaches to colloidal Cu3P nanocrystals (NCs) have been recently developed, and their optical absorption features in the near-infrared (NIR) have been interpreted as arising from a localized surface plasmon resonance (LSPR). Our pump–probe measurements on platelet-shaped Cu3-xP NCs corroborate the plasmonic character of this absorption. In accordance with studies on crystal structure analysis of Cu3P dating back to the 1970s, our density functional calculations indicate that this material is substoichiometric in copper, since the energy of formation of Cu vacancies in certain crystallographic sites is negative, that is, they are thermodynamically favored. Also, thermoelectric measurements point to a p-type behavior of the majority carriers from films of Cu3-xP NCs. It is likely that both the LSPR and the p-type character of our Cu3-xP NCs arise from the presence of a large number of Cu vacancies in such NCs. Motivated by the presence of Cu vacancies that facilitate the ion diffusion, we have additionally exploited Cu3-xP NCs as a starting material on which to probe cation exchange reactions. We demonstrate here that Cu3-xP NCs can be easily cation-exchanged to hexagonal wurtzite InP NCs, with preservation of the anion framework (the anion framework in Cu3-xP is very close to that of wurtzite InP). Intermediate steps in this reaction are represented by Cu3-xP/InP heterostructures, as a consequence of the fact that the exchange between Cu+ and In3+ ions starts from the peripheral corners of each NC and gradually evolves toward the center. The feasibility of this transformation makes Cu3-xP NCs an interesting material platform from which to access other metal phosphides by cation exchange. PMID:25960605

  13. Exchange Effects in the Radiative Capture Reactions 3H(α, γ)7Li and 3He(α, γ)7Be

    NASA Astrophysics Data System (ADS)

    Solovyev, A. S.; Igashov, S. Yu.; Tchuvil'sky, Yu. M.

    2016-05-01

    The mirror 3H(α, γ)7Li and 3He(α, γ)7Be reactions have been considered using the algebraic versions of the resonating group model and of the orthogonality conditions model. Exchange effects in interaction of the colliding nuclei and influence of the corresponding exchange terms in matrix elements of the interaction potential on calculated astrophysical S-factors for the reactions have been studied.

  14. NUMEN Project @ LNS : Heavy ions double charge exchange reactions towards the 0νββ nuclear matrix element determination

    SciTech Connect

    Agodi, C. Calabretta, L.; Calanna, A.; Carbone, D.; Cavallaro, M.; Colonna, M.; Cuttone, G.; Finocchiaro, P.; Pandola, L.; Rifuggiato, D.; Tudisco, S.; Cappuzzello, F.; Greco, V.; Bonanno, D. L.; Bongiovanni, D. G.; Longhitano, F.; Branchina, V.; Foti, A.; Lo Presti, D.; Lanzalone, G.; and others

    2015-10-28

    In the NUMEN Project it is proposed an innovative technique to access the nuclear matrix elements entering in the expression of the life-time of the neutrinoless double beta decay, using relevant cross sections of double charge exchange reactions. A key aspect is the use of MAGNEX large acceptance magnetic spectrometer, for the detection of the ejectiles, and of the INFN Laboratori Nazionali del Sud (LNS) K800 Superconducting Cyclotron (CS), for the acceleration of the required high resolution and low emittance heavy-ion beams.

  15. NUMEN Project @ LNS : Heavy ions double charge exchange reactions towards the 0νββ nuclear matrix element determination

    NASA Astrophysics Data System (ADS)

    Agodi, C.; Cappuzzello, F.; Bonanno, D. L.; Bongiovanni, D. G.; Branchina, V.; Calabretta, L.; Calanna, A.; Carbone, D.; Cavallaro, M.; Colonna, M.; Cuttone, G.; Foti, A.; Finocchiaro, P.; Greco, V.; Lanzalone, G.; Lo Presti, D.; Longhitano, F.; Muoio, A.; Pandola, L.; Rifuggiato, D.; Tudisco, S.

    2015-10-01

    In the NUMEN Project it is proposed an innovative technique to access the nuclear matrix elements entering in the expression of the life-time of the neutrinoless double beta decay, using relevant cross sections of double charge exchange reactions. A key aspect is the use of MAGNEX large acceptance magnetic spectrometer, for the detection of the ejectiles, and of the INFN Laboratori Nazionali del Sud (LNS) K800 Superconducting Cyclotron (CS), for the acceleration of the required high resolution and low emittance heavy-ion beams.

  16. Nuclear magnetic resonance study of the kinetics of ligand-exchange reactions in uranyl complexes. Part 5. Exchange reaction of acetylacetonate in bis(acetylacetonato)(dimethyl sulfoxide)dioxouranium(VI)

    SciTech Connect

    Ikeda, Y.; Tomiyasu, H.; Fukutomi, H.

    1984-09-26

    The kinetics of the exchange reaction of acac in UO/sub 2/(acac)/sub 2/Me/sub 2/SO (acac = acetylacetonate, Me/sub 2/SO = dimethyl sulfoxide) has been studied in o-C/sub 6/H/sub 4/Cl/sub 2/ by means of /sup 1/H NMR. The exchange rate depends on the concentration of the enol isomer of acetylacetone in its low region and approaches to the limiting value in its high region. The rate-determining step seems to be ring opening for one of two coordinated acac ions. The kinetic parameters of this step at 25/sup 0/C were found to be: equilibrium constant = 2.04 sec/sup -1/, enthalpy = 66.4 +/- 8.4 kJ mol/sup -1/, and entropy = 17.1 +/- 28.6 J K/sup -1/ mol/sup -1/. It was found that the exchange rate is decreased by addition of free Me/sub 2/SO. This is explained by considering the competition of Me/sub 2/SO with the enol isomer in attacking the four-coordinated intermediate in the equatorial plane or the outer-sphere complex formation between UO/sub 2/(acac)/sub 2/Me/sub 2/SO and free Me/sub 2/SO.

  17. Charge-exchange and fusion reaction measurements during compression experiments with neutral beam heating in the Tokamak Fusion Test Reactor

    SciTech Connect

    Kaita, R.; Heidbrink, W.W.; Hammett, G.W.; Chan, A.A.; England, A.C.; Hendel, H.W.; Medley, S.S.; Nieschmidt, E.; Roquemore, A.L.; Scott, S.D.

    1986-04-01

    Adiabatic toroidal compression experiments were performed in conjunction with high power neutral beam injection in the Tokamak Fusion Test Reactor (TFTR). Acceleration of beam ions to energies nearly twice the injection energy was measured with a charge-exchange neutral particle analyzer. Measurements were also made of 2.5 MeV neutrons and 15 MeV protons produced in fusion reactions between the deuterium beam ions and the thermal deuterium and /sup 3/He ions, respectively. When the plasma was compressed, the d(d,n)/sup 3/He fusion reaction rate increased a factor of five, and the /sup 3/He(d,p)/sup 4/He rate by a factor of twenty. These data were simulated with a bounce-averaged Fokker-Planck program, which assumed conservation of angular momentum and magnetic moment during compression. The results indicate that the beam ion acceleration was consistent with adiabatic scaling.

  18. [Comparative analysis of gas exchange and cardiorespiratory systems reactions to increasing normobaric hypoxia and physical load of swimmers and skiers].

    PubMed

    Krivoshchekin, S G; Divert, V E; Mel'nikov, V N; Vodianitskiĭ, S N; Girenko, L A

    2013-01-01

    Qualification comparable groups of young men engaged in cyclic kinds of sports were tested with stepwise accruing loads on bicycle ergometer and 25-minute exponential increasing normobaric hypoxia to final concentration of 10% oxygen. Group of skiers, having the greatest values of the maximal oxygen consumption at muscular work, show the relaxed cardiorespiratory reactions and more falling of blood oxygen in the hypoxia. The swimmers, having restrictions of ventilatory function in the course of trainings, form preadaptation to hypoxia with changes of external respiration and gas exchange functions that allows at hypoxia to better oxygen sate the blood in lungs. The joint assessment of aerobic capacity at physical work and physiological reactions to hypoxia shows the direct relation between individual maximal oxygen consumption and the descent rate of blood oxygen saturation at accruing hypoxia that can be useful at an assessment of a sportsman functional state and its correction at training processes. PMID:23668078

  19. Charge exchange dp → (pp)n reaction study at 1.75 A GeV/c by the STRELA spectrometer

    NASA Astrophysics Data System (ADS)

    Basilev, S. N.; Bushuev, Yu. P.; Glagolev, V. V.; Dolgiy, S. A.; Kirillov, D. A.; Kostyaeva, N. V.; Kovalenko, A. D.; Livanov, A. N.; Manyakov, P. K.; Martinská, G.; Mušinský, J.; Piskunov, N. M.; Povtoreiko, A. A.; Rukoyatkin, P. A.; Shindin, R. A.; Sitnik, I. M.; Slepnev, V. M.; Slepnev, I. V.; Urbán, J.

    2016-02-01

    The differential cross sections of the charge exchange reaction dp → (pp)n has been measured at 1.75 GeV/c momentum per nucleon for small transferred momenta using the one arm magnetic spectrometer STRELA at the Nuclotron accelerator. The ratio of the differential cross section of the charge exchange reaction dp → (pp)n to that of the np → pn elementary process is discussed in order to estimate the spin-dependent part of the np → pn charge exchange amplitude on the basis of dp → (pp)n data. The np → pn amplitude turned out to be predominantly spin-dependent.

  20. Reduced-Dimensionality Semiclassical Transition State Theory: Application to Hydrogen Atom Abstraction and Exchange Reactions of Hydrocarbons.

    PubMed

    Greene, Samuel M; Shan, Xiao; Clary, David C

    2015-12-17

    Quantum mechanical methods for calculating rate constants are often intractable for reactions involving many atoms. Semiclassical transition state theory (SCTST) offers computational advantages over these methods but nonetheless scales exponentially with the number of degrees of freedom (DOFs) of the system. Here we present a method with more favorable scaling, reduced-dimensionality SCTST (RD SCTST), that treats only a subset of DOFs of the system explicitly. We apply it to three H abstraction and exchange reactions for which two-dimensional potential energy surfaces (PESs) have previously been constructed and evaluated using RD quantum scattering calculations. We differentiated these PESs to calculate harmonic frequencies and anharmonic constants, which were then used to calculate cumulative reaction probabilities and rate constants by RD SCTST. This method yielded rate constants in good agreement with quantum scattering results. Notably, it performed well for a heavy-light-heavy reaction, even though it does not explicitly account for corner-cutting effects. Recent extensions to SCTST that improve its treatment of deep tunneling were also evaluated within the reduced-dimensionality framework. The success of RD SCTST in this study suggests its potential applicability to larger systems. PMID:26090556

  1. Imidazole C-2 Hydrogen/Deuterium Exchange Reaction at Histidine for Probing Protein Structure and Function with MALDI Mass Spectrometry

    PubMed Central

    Hayashi, Naoka; Kuyama, Hiroki; Nakajima, Chihiro; Kawahara, Kazuki; Miyagi, Masaru; Nishimura, Osamu; Matsuo, Hisayuki; Nakazawa, Takashi

    2015-01-01

    We present a mass spectrometric method for analyzing protein structure and function, based on the imidazole C-2 or histidine Cε1 hydrogen/deuterium (H/D) exchange reaction, which is intrinsically second order with respect to the concentrations of the imidazolium cation and OD− in D2O. The second-order rate constant (k2) of this reaction was calculated from the pH-dependency of the pseudo-first-order rate constant (kφ) obtained from the change of average mass ΔMr (0 ≤ ΔMr < 1) of a peptide fragment containing a defined histidine residue at incubation time (t) such that kφ = − [ln(1−ΔMr)]/t. We preferred using k2 rather than kφ because k2max (maximal value of k2) was empirically related to pKa as illustrated with a Brønsted plot: logk2max=-0.7pKa+α (α is an arbitrary constant), so that we could analyze the effect of structure on the H/D-exchange rate in terms of log(k2max/k2) representing the deviation of k2 from k2max. In the catalytic site of bovine ribonuclease A, His12 showed much larger change in log(k2max/k2) compared with His119 upon binding with cytidine 3′-monophosphate, as anticipated from the X-ray structures and the possible change in solvent accessibility. However, there is a need of considering the hydrogen bonds of the imidazole group with non-dissociable groups to interpret an extremely slow H/D exchange rate of His48 in partially solvent-exposed situation. PMID:24606199

  2. Room Temperature Cation Exchange Reaction in Nanocrystals for Ultrasensitive Speciation Analysis of Silver Ions and Silver Nanoparticles.

    PubMed

    Huang, Ke; Xu, Kailai; Tang, Jie; Yang, Lu; Zhou, Jingrong; Hou, Xiandeng; Zheng, Chengbin

    2015-07-01

    To evaluate the toxicity of silver nanoparticles (AgNPs) and Ag(+) and gain deep insight into the transformation of AgNPs in the environment or organisms, ultrasensitive analytical methods are needed for their speciation analysis. About 40-fold of Cd(2+) in CdTe ionic nanocrystals can be "bombarded-and-exploded" (exchanged) in less than 1 min simply by mixing the nanocrystals with Ag(+) solution at room temperature, while this cation exchange reaction did not occur when only silver nanoparticles were present. On the basis of this striking difference, an ultrasensitive method was developed for speciation analysis of Ag(+) and AgNPs in complex matrices. The released Cd(2+) was reduced to its volatile species by sodium tetrahydroborate, which was separated and swept to an inductively coupled plasma mass spectrometer (ICPMS) or an atomic fluorescence spectrometer (AFS) for the indirect but ultrasensitive detection of Ag(+). Owing to the remarkable signal amplification via the cation exchange reaction and the advantages of chemical vapor generation for sampling, the limit of detection was 0.0003 μg L(-1) for Ag(+) by ICPMS, which was improved by 100-fold compared to the conventional method. Relative standard deviations are better than 2.5% at a concentration of 0.5 μg L(-1) Ag(+) or AgNPs regardless of the detector. The proposed method retains several unique advantages, including ultrahigh sensitivity, speciation analysis, simplicity and being organic reagent-free, and has been successfully utilized for speciation analysis of Ag(+) and AgNPs in environmental water samples and paramecium cells. PMID:26017198

  3. Quantum dynamics of {sup 16}O + {sup 36}O{sub 2} and {sup 18}O + {sup 32}O{sub 2} exchange reactions

    SciTech Connect

    Rajagopala Rao, T.; Mahapatra, S.; Guillon, G.; Honvault, P.

    2015-05-07

    We present quantum dynamical investigations of {sup 16}O + {sup 36}O{sub 2} and {sup 18}O + {sup 32}O{sub 2} exchange reactions using a time-independent quantum mechanical method and an accurate global potential energy surface of ozone [Dawes et al., J. Chem. Phys. 135, 081102 (2011)]. Initial state-selected integral cross sections, rate constants, and Boltzmann averaged thermal rate constants are obtained and compared with earlier experimental and theoretical results. The computed thermal rate constants for the oxygen exchange reactions exhibit a negative temperature dependence, as found experimentally. They are in better agreement with the experiments than the previous studies on the same reactions.

  4. Ab initio study of the H + HONO reaction: Direct abstraction versus indirect exchange processes

    SciTech Connect

    Hsu, C.C.; Lin, M.C.; Mebel, A.M.; Melius, C.F.

    1997-01-02

    The mechanism of the H + HONO reaction (for which no experimental data are available) has been elucidated by ab initio molecular orbital calculations using modified G2 and BAC-MP4 methods. These results indicate that the reaction occurs predominantly by two indirect metathetical processes. One produces OH + HNO and H{sub 2}O + NO from the decomposition of vibrationally excited hydroxyl nitroxide, HN(O)OH, formed by H atom addition to the N atom of HONO. The other produces H{sub 2}O + NO from the decomposition of vibrationally excited dihydroxylamino radical, N(OH){sub 2}, formed by H atom addition to the terminal O atom. These indirect displacement processes are much more efficient than the commonly assumed, direct H-abstraction reaction producing H{sub 2} + NO{sub 2}. A transition-state theory calculation for the direct abstraction reaction and RRKM calculations for the two indirect displacement processes give rise to the following rate constants, in units of cm{sup 3} molecule{sup -1} s{sup -1} for the 300-3500 K temperature range under atmospheric conditions: k{sub H(2)} = 3.33 x 10{sup -16}T{sup 1.55} exp(-3328.5/T), k{sub OH} = 9.36 x 10{sup -14}T{sup 0.86} exp(-2500.8/T), k{sub H(2)O} = 1.35 x 10{sup -17}T{sup 1.89} exp-(-1935.7/T), where the rate constant for H{sub 2}O production represents the sum from both indirect displacement reactions. 32 refs., 3 figs., 7 tabs.

  5. Quasiclassical dynamics for the H + HS abstraction and exchange reactions on the 3A" and the 3A' states.

    PubMed

    Duan, Zhi Xin; Li, Wen Liang; Xu, Wen Wu; Lv, Shuang Jiang

    2013-09-01

    A detailed quasiclassical trajectory study of the H + HS reaction yielding an exchange (H + HS) and an abstraction (H2 + S) channel has been performed by employing the new triplet (3)A" and (3)A' surfaces developed by our group. The cross sections for both channels are presented and found to be in good agreement with previous quantum wave packet results. The thermal rate coefficients for abstraction channel at the temperature between 200 and 1000 K have been evaluated by averaging over a Boltzmann distribution of rotational states and compared with the available experimental values. It is found that the thermal rate coefficients exhibit a conventional Arrhenius-type dependence on temperature, which agrees well with the experimental data. Average fractions, vibration and rotation distributions of the products H2 and HS at different collision energies have been also fully investigated. Furthermore, influence of the collision energy on the total and product-state-resolved differential cross sections (DCSs) for both channels are calculated and discussed. Some observations on the mechanism of the title reaction have been made; in particular it was discovered that reactive collisions along the collinear pathway cause the H2 product to scatter backward, while the reactive collisions with large impact parameters b, which are favored deviating from the minimum energy path, produced mainly forward scattering. For the exchange channel, the discrepancies in the DCS are also distinguished through an analysis of individual trajectories and found a double microscopic mechanism, migration or non-migration. The state-to-state DCSs provide a global perspective of the reaction mechanisms and their contribution to the final product internal energy states. The theoretical findings are discussed and compared with a kinematic constraint model. PMID:24028117

  6. A delayed hemolytic transfusion reaction after partial exchange transfusion for sickle cell disease in pregnancy: a case report and review of the literature.

    PubMed

    Brumfield, C G; Huddleston, J F; DuBois, L B; Harris, B A

    1984-03-01

    A delayed hemolytic transfusion reaction that occurred after a prophylactic partial exchange transfusion for sickle-cell disease in pregnancy is described. The clinical presentation and laboratory findings of delayed transfusion reactions are discussed, with special emphasis on problems associated in the sickle-cell disease patient. Suggestions on how to minimize the risk of transfusion reactions in the pregnant sickle-cell disease patient are given. PMID:6700873

  7. Density functional theory studies on the structures and water-exchange reactions of aqueous Al(III)-oxalate complexes.

    PubMed

    Jin, Xiaoyan; Yan, Yu; Shi, Wenjing; Bi, Shuping

    2011-12-01

    The structures and water-exchange reactions of aqueous aluminum-oxalate complexes are investigated using density functional theory. The present work includes (1) The structures of Al(C(2)O(4))(H(2)O)(4)(+) and Al(C(2)O(4))(2)(H(2)O)(2)(-) were optimized at the level of B3LYP/6-311+G(d,p). The geometries obtained suggest that the Al-OH(2) bond lengths trans to C(2)O(4)(2-) ligand in Al(C(2)O(4))(H(2)O)(4)(+) are much longer than the Al-OH(2) bond lengths cis to C(2)O(4)(2-). For Al(C(2)O(4))(2)(H(2)O)(2)(-), the close energies between cis and trans isomers imply the coexistence in aqueous solution. The (27)Al NMR and (13)C NMR chemical shifts computed with the consideration of sufficient solvent effect using HF GIAO method and 6-311+G(d,p) basis set are in agreement with the experimental values available, indicating the appropriateness of the applied models; (2) The water-exchange reactions of Al(III)-oxalate complexes were simulated at the same computational level. The results show that water exchange proceeds via dissociative pathway and the activation energy barriers are sensitive to the solvent effect. The energy barriers obtained indicate that the coordinated H(2)O cis to C(2)O(4)(2-) in Al(C(2)O(4))(H(2)O)(4)(+) is more labile than trans H(2)O. The water-exchange rate constants (k(ex)) of trans- and cis-Al(C(2)O(4))(2)(H(2)O)(2)(-) were estimated by four methods and their respective characteristics were explored; (3) The significance of the study on the aqueous aluminum-oxalate complexes to environmental chemistry is discussed. The influences of ubiquitous organic ligands in environment on aluminum chemistry behavior can be elucidated by extending this study to a series of Al(III)-organic system. PMID:21973197

  8. Viking gas exchange reaction - Simulation on UV-irradiated manganese dioxide substrate

    NASA Technical Reports Server (NTRS)

    Blackburn, T. R.; Holland, H. D.; Ceasar, G. P.

    1979-01-01

    The exchange of O2 for H2O, analogous to that recorded on Mars by the Viking GEX experiment, has been observed on humidifying powdered beta-MnO2 (pyrolusite) which had been irradiated by UV in a humidified analog of the Martian atmosphere. Pyrolusite irradiated in a dry atmosphere did not release O2 on humidification. The XPS spectra of Mn and O of the reactive pyrolusite were shifted toward higher binding energies during UV irradiation. These shifts are consistent with the creation of a surface layer of a Mn(V) or Mn(VI) compound. The destruction of such a layer on humidification could account for the observed O2 release. Although manganese has not been identified in the Martian regolith, the upper limit of the Mn concentration is sufficiently high that O2 release from pyrolusite could have been responsible for the results of the Viking GEX experiment.

  9. Determination of alkanolamines in cattails (Typha latifolia) utilizing electrospray ionization with selected reaction monitoring and ion-exchange chromatography.

    PubMed

    Peru, Kerry M; Headley, John V; Doucette, William J

    2004-01-01

    Selected reaction monitoring (SRM) with electrospray ionization was used as a specific detection technique for the analysis of alkanolamines in plant tissue extracts. Ion-exchange chromatography was used as the method of separation. Quantification was based on monitoring the loss of either H2O or 2(H2O) from the protonated molecule [M+H]+. The method provided increased selectivity for all analytes and better detection limits for three of the six analytes investigated compared with an earlier method using selected ion monitoring with liquid chromatography. Instrumental detection limits ranged from 6-300 pg injected for monoethanolamine (MEA), monoisopropanolamine (MIPA), diethanolamine (DEA), methyldiethanolamine (MDEA), diisopropanolamine (DIPA), and triethanolamine (TEA). Method robustness and selectivity were demonstrated by the determination of DIPA and a known transformation product MIPA in over 35 plant extract samples derived from a laboratory study of plant uptake mechanisms. PMID:15282789

  10. The T{sub z} = -1{yields}T{sub z} =0 beta decays and comparison with Charge Exchange reactions

    SciTech Connect

    Molina, F.; Rubio, B.; Fujita, Y.; Gelletly, W.; Collaboration: Santiago Collaboration

    2011-11-30

    Gamow-Teller (GT) transitions can be studied in both {beta} decay and charge exchange (CE) reactions. If isospin is a good quantum number, then the Tz = -1{yields}0 and Tz = +1{yields}0GT mirror transitions, are identical. Therefore, a comparison of the results from studies of {beta} decay and CE should shed light on this assumption. Accordingly we have studied the {beta} decay of the Tz = -1 fp-shell nuclei, {sup 54}Ni, {sup 50}Fe, {sup 46}Cr, and {sup 42}Ti, produced in fragmentation and we have compared our results with the spectra from ({sup 3}He, t) measurements on the mirror Tz = +1 target nuclei studied in high resolution at RCNP, Osaka. The {beta} decay experiments were performed as part of the STOPPED beam RISING campaign at GSI.

  11. Exploring the limits of ultrafast polymerase chain reaction using liquid for thermal heat exchange: A proof of principle

    NASA Astrophysics Data System (ADS)

    Maltezos, George; Johnston, Matthew; Taganov, Konstantin; Srichantaratsamee, Chutatip; Gorman, John; Baltimore, David; Chantratita, Wasun; Scherer, Axel

    2010-12-01

    Thermal ramp rate is a major limiting factor in using real-time polymerase chain reaction (PCR) for routine diagnostics. We explored the limits of speed by using liquid for thermal exchange rather than metal as in traditional devices, and by testing different polymerases. In a clinical setting, our system equaled or surpassed state-of-the-art devices for accuracy in amplifying DNA/RNA of avian influenza, cytomegalovirus, and human immunodeficiency virus. Using Thermococcus kodakaraensis polymerase and optimizing both electrical and chemical systems, we obtained an accurate, 35 cycle amplification of an 85-base pair fragment of E. coli O157:H7 Shiga toxin gene in as little as 94.1 s, a significant improvement over a typical 1 h PCR amplification.

  12. An assay for ribonucleotide reductase based on ion-exchange chromatography of the reaction product.

    PubMed

    Narine, D R; Bacchetti, S; Chan, W W

    1985-03-01

    A rapid and convenient assay for ribonucleotide reductase has been developed in which the reaction product, deoxycytidine diphosphate (dCDP), is isolated without further conversion. The enzymatic reaction is terminated by the addition of ethanol and the sample is chromatographed on a single, small, and disposable column of polyethylenimine cellulose. A two-step elution is conducted with buffers containing 25% ethanol. First, contaminants and byproducts such as cytidine and its monophosphate are removed at low ionic strength while the diphosphates are retained. Then dCDP is selectively eluted as a sharp peak with a strong borate buffer. Under these conditions, the excess substrate, cytidine diphosphate, remains on the column, presumably as the borate complex. The assay is linear with time for 15 min at 25 degrees C and linear with the amount of enzyme even at very low concentrations. With slight modifications, the assay seems applicable to the use of UDP or ADP as substrates. The method is not suitable for samples which contain nucleotide kinase or other interfering enzymes which convert a significant amount of dCDP into byproducts. However, another chromatographic system based on similar principles has been found which could be used to measure any dCTP produced in this way. PMID:2990252

  13. Simple ligand exchange reactions enabling excellent dispersibility and stability of magnetic nanoparticles in polar organic, aromatic, and protic solvents.

    PubMed

    Wang, Xinyu; Tilley, Richard D; Watkins, James J

    2014-02-18

    The use of magnetic nanoparticles (MNPs) in real-world applications is often limited by the lack of stable solutions of monodisperse NPs in appropriate solvents. We report a facile one-pot ligand exchange reaction that is fast, efficient, and thorough for the synthesis of hydrophilic MNPs that are readily dispersed in polar organic and protic solvents (polarity index = 3.9-7.2) including alcohols, THF, DMF, and DMSO for years without precipitation. We emphasize the rational selection of small-molecule ligands such as 4-hydroxybenzoic acid (HBA), 3-(4-hydroxyphenyl)propionic acid (HPP), and gallic acid (GAL) that provide strong bonding with the MNP (FePt and FeOx) surfaces, hydrophilic termini to match the polarity of target solvents, and offer the potential for hydrogen-bonding interactions to facilitate incorporation into polymers and other media. Areal ligand densities (Σ) calculated based on the NP core size from transmission electron microscopy (TEM) images, and the inorganic fractions of NPs derived from thermogravimetric analysis (TGA) indicated a significant (2-4 times) increase in the ligand coverage after the exchange reactions. Fourier transform infrared spectrometry (FTIR) and (1)H nuclear magnetic resonance (NMR) studies also confirmed anchoring of carboxyl groups on NP surfaces. In addition, we demonstrate a facile one-step in situ synthesis of FePt NPs with aromatic ligands for better dispersibility in solvents of intermediate polarity (polarity index = 1.0-3.5) such as toluene, chlorobenzene, and dichloromethane. The creation of stable dispersions of NPs in solvents across the polarity spectrum opens up new applications and new processing widows for creating NP composites in a variety of host materials. PMID:24460074

  14. Does Size Really Matter? The Steric Isotope Effect in a Supramolecular Host?Guest Exchange Reaction

    SciTech Connect

    Mugridge, Jeffrey; Bergman, Robert; Raymond, Kenneth

    2010-01-29

    Isotope effects (IEs), which arise from differences in zero point energies (ZPEs) between a parent and isotopically substituted bond, have been used extensively by chemists to probe molecular interactions and reactivity. Due to the anharmonicity of the C-H/D vibrational potential energy function and the lower ZPE of a C-D bond, the average C-D bond length is typically {approx}0.005 {angstrom} shorter than an equivalent C-H bond. It is this difference in size that is often invoked to explain the observation of secondary, inverse kinetic isotope effects (KIEs) in chemical processes which proceed through a sterically strained transition state. This so-called 'steric isotope effect' (SIE) has been observed in processes such as the racemization of ortho-substituted biphenyls[6] and phenanthrenes, ring flipping of cyclophanes, and more recently in the deslipping of rotaxanes, where substitution of the sterically less demanding deuterium for protium results in rate accelerations for these processes. Herein, we use deuterium substitution in a cationic guest molecule to probe the sensitivity limits of the guest exchange process from a highly-charged supramolecular host.

  15. Oxygen evolution reaction characteristics of synthetic nickel-cobalt-oxide electrodes for alkaline anion-exchange membrane water electrolysis

    NASA Astrophysics Data System (ADS)

    Koo, Tae Woo; Park, ChanSu; Kim, Yang Do; Lee, Dooyong; Park, Sungkyun; Lee, Jae Ho; Choi, Sung Mook; Choi, Chul Young

    2015-11-01

    A polymer electrolyte membrane water electrolysis system can produce high-purity hydrogen gases in a highly efficient manner. However, the level of hydrogen gas production is still small. In addition, noble-metal catalysts for the reaction in acidic environments, as well as an additional drying step to remove water contained in the hydrogen, are required. Therefore, water electrolysis system with high efficiency and lower cost, an alkaline anion-exchange membrane system that can produce high-purity hydrogen without a noble-metal catalyst, is needed. Nano-size NiCo2O4 powders were prepared by using a sol-gel method to achieve an efficient and economical water electrolysis system. When the powder was calcined at 450 °C, the crystallinity and the cyclic voltammogram measurement showed the best values. In addition, the 15-wt.% polytetrafluoroethylene mixed NiCo2O4 powders exhibited the largest cyclic voltammetry active area and the highest oxygen evolution reaction activity with the appropriate stability.

  16. Self-assembled monolayer exchange reactions as a tool for channel interface engineering in low-voltage organic thin-film transistors.

    PubMed

    Lenz, Thomas; Schmaltz, Thomas; Novak, Michael; Halik, Marcus

    2012-10-01

    In this work, we compared the kinetics of monolayer self-assembly long-chained carboxylic acids and phosphonic acids on thin aluminum oxide surfaces and investigated their dielectric properties in capacitors and low-voltage organic thin-film transistors. Phosphonic acid anchor groups tend to substitute carboxylic acid molecules on aluminum oxide surfaces and thus allow the formation of mixed or fully exchanged monolayers. With different alkyl chain substituents (n-alkyl or fluorinated alkyl chains), the exchange reaction can be monitored as a function of time by static contact angle measurements. The threshold voltage in α,α'-dihexyl-sexithiophene thin-film transistors composed of such mixed layer dielectrics correlates with the exchange progress and can be tuned from negative to positive values or vice versa depending on the dipole moment of the alkyl chain substituents. The change in the dipole moment with increasing exchange time also shifts the capacitance of these devices. The rate constants for exchange reactions determined by the time-dependent shift of static contact angle, threshold voltage, and capacitance exhibit virtually the same value thus proving the exchange kinetics to be highly controllable. In general, the exchange approach is a powerful tool in interface engineering, displaying a great potential for tailoring of device characteristics. PMID:22963322

  17. Demonstration of Synaptic Behaviors and Resistive Switching Characterizations by Proton Exchange Reactions in Silicon Oxide

    PubMed Central

    Chang, Yao-Feng; Fowler, Burt; Chen, Ying-Chen; Zhou, Fei; Pan, Chih-Hung; Chang, Ting-Chang; Lee, Jack C.

    2016-01-01

    We realize a device with biological synaptic behaviors by integrating silicon oxide (SiOx) resistive switching memory with Si diodes. Minimal synaptic power consumption due to sneak-path current is achieved and the capability for spike-induced synaptic behaviors is demonstrated, representing critical milestones for the use of SiO2–based materials in future neuromorphic computing applications. Biological synaptic behaviors such as long-term potentiation (LTP), long-term depression (LTD) and spike-timing dependent plasticity (STDP) are demonstrated systematically using a comprehensive analysis of spike-induced waveforms, and represent interesting potential applications for SiOx-based resistive switching materials. The resistive switching SET transition is modeled as hydrogen (proton) release from (SiH)2 to generate the hydrogen bridge defect, and the RESET transition is modeled as an electrochemical reaction (proton capture) that re-forms (SiH)2. The experimental results suggest a simple, robust approach to realize programmable neuromorphic chips compatible with large-scale CMOS manufacturing technology. PMID:26880381

  18. Demonstration of Synaptic Behaviors and Resistive Switching Characterizations by Proton Exchange Reactions in Silicon Oxide

    NASA Astrophysics Data System (ADS)

    Chang, Yao-Feng; Fowler, Burt; Chen, Ying-Chen; Zhou, Fei; Pan, Chih-Hung; Chang, Ting-Chang; Lee, Jack C.

    2016-02-01

    We realize a device with biological synaptic behaviors by integrating silicon oxide (SiOx) resistive switching memory with Si diodes. Minimal synaptic power consumption due to sneak-path current is achieved and the capability for spike-induced synaptic behaviors is demonstrated, representing critical milestones for the use of SiO2-based materials in future neuromorphic computing applications. Biological synaptic behaviors such as long-term potentiation (LTP), long-term depression (LTD) and spike-timing dependent plasticity (STDP) are demonstrated systematically using a comprehensive analysis of spike-induced waveforms, and represent interesting potential applications for SiOx-based resistive switching materials. The resistive switching SET transition is modeled as hydrogen (proton) release from (SiH)2 to generate the hydrogen bridge defect, and the RESET transition is modeled as an electrochemical reaction (proton capture) that re-forms (SiH)2. The experimental results suggest a simple, robust approach to realize programmable neuromorphic chips compatible with large-scale CMOS manufacturing technology.

  19. Quasiclassical trajectory study of Li2 (v ≤ 100)-Na exchange reaction

    NASA Astrophysics Data System (ADS)

    Rubahn, H.-G.; Sathyamurthy, N.

    The effect of high initial vibrational (v = 0-25) and rotational (j = 0-100) excitation of the reactant molecule on the cross-section σR for the reaction Li2 + Na → LiNa + Li at a relative translational energy (Etrans) of 0·5 eV has been investigated using the three-dimensional quasiclassical trajectory method on the recently proposed Varandas-Morais-Pais (VMP) potential. σR increases almost linearly with increase in v, but it remains unaltered, within the statistical error, with increase in j for j = 0-30. For the higher j states, there is an increase in σR with increase in j, and the rotational enhancement gets larger with increase in v, becoming comparable to the vibrational enhancement at v = 20. The dependence of σR on Etrans over the range 0·18 - 0·85 eV has been examined for v = 0, j = 0. For Etrans ≤ 0·25 eV, all trajectories get trapped. For higher Etrans, σR rises to a maximum and then levels off. Comparison of our results with those on the Whitehead-Grice (WG) potential reveals that the reactivity is larger on the VMP potential than on the WG for the low v while the opposite is true for the higher v.

  20. Demonstration of Synaptic Behaviors and Resistive Switching Characterizations by Proton Exchange Reactions in Silicon Oxide.

    PubMed

    Chang, Yao-Feng; Fowler, Burt; Chen, Ying-Chen; Zhou, Fei; Pan, Chih-Hung; Chang, Ting-Chang; Lee, Jack C

    2016-01-01

    We realize a device with biological synaptic behaviors by integrating silicon oxide (SiO(x)) resistive switching memory with Si diodes. Minimal synaptic power consumption due to sneak-path current is achieved and the capability for spike-induced synaptic behaviors is demonstrated, representing critical milestones for the use of SiO2-based materials in future neuromorphic computing applications. Biological synaptic behaviors such as long-term potentiation (LTP), long-term depression (LTD) and spike-timing dependent plasticity (STDP) are demonstrated systematically using a comprehensive analysis of spike-induced waveforms, and represent interesting potential applications for SiO(x)-based resistive switching materials. The resistive switching SET transition is modeled as hydrogen (proton) release from (SiH)2 to generate the hydrogen bridge defect, and the RESET transition is modeled as an electrochemical reaction (proton capture) that re-forms (SiH)2. The experimental results suggest a simple, robust approach to realize programmable neuromorphic chips compatible with large-scale CMOS manufacturing technology. PMID:26880381

  1. Methane to acetic acid over Cu-exchanged zeolites: mechanistic insights from a site-specific carbonylation reaction.

    PubMed

    Narsimhan, Karthik; Michaelis, Vladimir K; Mathies, Guinevere; Gunther, William R; Griffin, Robert G; Román-Leshkov, Yuriy

    2015-02-11

    The selective low temperature oxidation of methane is an attractive yet challenging pathway to convert abundant natural gas into value added chemicals. Copper-exchanged ZSM-5 and mordenite (MOR) zeolites have received attention due to their ability to oxidize methane into methanol using molecular oxygen. In this work, the conversion of methane into acetic acid is demonstrated using Cu-MOR by coupling oxidation with carbonylation reactions. The carbonylation reaction, known to occur predominantly in the 8-membered ring (8MR) pockets of MOR, is used as a site-specific probe to gain insight into important mechanistic differences existing between Cu-MOR and Cu-ZSM-5 during methane oxidation. For the tandem reaction sequence, Cu-MOR generated drastically higher amounts of acetic acid when compared to Cu-ZSM-5 (22 vs 4 μmol/g). Preferential titration with sodium showed a direct correlation between the number of acid sites in the 8MR pockets in MOR and acetic acid yield, indicating that methoxy species present in the MOR side pockets undergo carbonylation. Coupled spectroscopic and reactivity measurements were used to identify the genesis of the oxidation sites and to validate the migration of methoxy species from the oxidation site to the carbonylation site. Our results indicate that the Cu(II)-O-Cu(II) sites previously associated with methane oxidation in both Cu-MOR and Cu-ZSM-5 are oxidation active but carbonylation inactive. In turn, combined UV-vis and EPR spectroscopic studies showed that a novel Cu(2+) site is formed at Cu/Al <0.2 in MOR. These sites oxidize methane and promote the migration of the product to a Brønsted acid site in the 8MR to undergo carbonylation. PMID:25562431

  2. Core-shell self-assembly triggered via a thiol-disulfide exchange reaction for reduced glutathione detection and single cells monitoring.

    PubMed

    Zhang, Zhen; Jiao, Yuting; Wang, Yuanyuan; Zhang, Shusheng

    2016-01-01

    A novel core-shell DNA self-assembly catalyzed by thiol-disulfide exchange reactions was proposed, which could realize GSH-initiated hybridization chain reaction (HCR) for signal amplification and molecules gathering. Significantly, these self-assembled products via electrostatic interaction could accumulate into prominent and clustered fluorescence-bright spots in single cancer cells for reduced glutathione monitoring, which will effectively drive cell monitoring into a new era. PMID:27412605

  3. Time dependent three-dimensional body frame quantal wave packet treatment of the H + H2 exchange reaction on the Liu-Siegbahn-Truhlar-Horowitz (LSTH) surface

    NASA Technical Reports Server (NTRS)

    Neuhauser, Daniel; Baer, Michael; Judson, Richard S.; Kouri, Donald J.

    1989-01-01

    The first successful application of the three-dimensional quantum body frame wave packet approach to reactive scattering is reported for the H + H2 exchange reaction on the LSTH potential surface. The method used is based on a procedure for calculating total reaction probabilities from wave packets. It is found that converged, vibrationally resolved reactive probabilities can be calculated with a grid that is not much larger than required for the pure inelastic calculation. Tabular results are presented for several energies.

  4. Core-shell self-assembly triggered via a thiol-disulfide exchange reaction for reduced glutathione detection and single cells monitoring

    PubMed Central

    Zhang, Zhen; Jiao, Yuting; Wang, Yuanyuan; Zhang, Shusheng

    2016-01-01

    A novel core-shell DNA self-assembly catalyzed by thiol-disulfide exchange reactions was proposed, which could realize GSH-initiated hybridization chain reaction (HCR) for signal amplification and molecules gathering. Significantly, these self-assembled products via electrostatic interaction could accumulate into prominent and clustered fluorescence-bright spots in single cancer cells for reduced glutathione monitoring, which will effectively drive cell monitoring into a new era. PMID:27412605

  5. Cation exchange reactions controlling desorption of Sr-90(2+) from coarse-grained contaminated sediments at the Hanford site, Washington

    SciTech Connect

    McKinley, James P.; Zachara, John M.; Smith, Steven C.; Liu, Chongxuan

    2007-01-15

    Nuclear waste that bore 90Sr2+ was accidentally leaked into the vadose zone at the Hanford site, and was immobilized at relatively shallow depths in sediments containing little apparent clay or silt-sized components. Sr2+, 90Sr2+, Mg2+, and Ca2+ was desorbed and total inorganic carbon concentration was monitored during the equilibration of this sediment with varying concentrations of Na+, Ca2+. A cation exchange model previously developed for similar sediments was applied to these results as a predictor of final solution compositions. The model included binary exchange reactions for the four operant cations and an equilibrium dissolution/precipitation reaction for calcite. The model successfully predicted the desorption data. The contaminated sediment was also examined using digital autoradiography, a sensitive tool for imaging the distribution of radioactivity. The exchanger phase containing 90Sr was found to consist of smectite formed from weathering of mesostasis glass in basaltic lithic fragments. These clasts are a significant component of Hanford formation sands. The relatively small but significant cation exchange capacity of these sediments was thus a consequence of reaction with physically sequestered clays in sediment that contained essentially no fine-grained material. The nature of this exchange component explained the relatively slow (scale of days) evolution of desorption solutions. The experimental and model results indicated that there is little risk of migration of 90Sr2+ to the water table.

  6. H/D exchange in reactions of OH(-) with D2 and of OD(-) with H2 at low temperatures.

    PubMed

    Mulin, Dmytro; Roučka, Štěpán; Jusko, Pavol; Zymak, Illia; Plašil, Radek; Gerlich, Dieter; Wester, Roland; Glosík, Juraj

    2015-04-14

    Using a cryogenic linear 22-pole rf ion trap, rate coefficients for H/D exchange reactions of OH(-) with D2 (1) and OD(-) with H2 (2) have been measured at temperatures between 11 K and 300 K with normal hydrogen. Below 60 K, we obtained k1 = 5.5 × 10(-10) cm(3) s(-1) for the exoergic . Upon increasing the temperature above 60 K, the data decrease with a power law, k1(T) ∼T(-2.7), reaching ≈1 × 10(-10) cm(3) s(-1) at 200 K. This observation is tentatively explained with a decrease of the lifetime of the intermediate complex as well as with the assumption that scrambling of the three hydrogen atoms is restricted by the topology of the potential energy surface. The rate coefficient for the endoergic increases with temperature from 12 K up to 300 K, following the Arrhenius equation, k2 = 7.5 × 10(-11) exp(-92 K/T) cm(3) s(-1) over two orders of magnitude. The fitted activation energy, EA-Exp = 7.9 meV, is in perfect accordance with the endothermicity of 24.0 meV, if one accounts for the thermal population of the rotational states of both reactants. The low mean activation energy in comparison with the enthalpy change in the reaction is mainly due to the rotational energy of 14.7 meV contributed by ortho-H2 (J = 1). Nonetheless, one should not ignore the reactivity of pure para-H2 because, according to our model, it already reaches 43% of that of ortho-H2 at 100 K. PMID:25738934

  7. Nanosized IrxRu1-xO2 electrocatalysts for oxygen evolution reaction in proton exchange membrane water electrolyzer

    NASA Astrophysics Data System (ADS)

    Hanh Pham, Hong; Nguyen, Ngoc Phong; Linh Do, Chi; Thang Le, Ba

    2015-01-01

    Normally in proton exchange membrane water electrolysis (PEMWE), the anode has the largest overpotential at typical operating current densities. By development of the electrocatalytic material used for the oxygen evolving electrode, great improvements in efficiency can be performed. In electrochemistry, rare metallic oxides RuO2 and IrO2 exhibit the best catalytic properties for the oxygen evolution reaction (OER) in acid electrolytes compared to other noble metals. RuO2 is the most active catalyst and IrO2 is the most stable catalyst. An oxide containing both elements is therefore expected to be a good catalyst for the OER. In this study IrxRu1-xO2 nanosized powder electrocatalysts for oxygen evolution reaction is synthesized by hydrolysis method. Cyclic voltammetry, anodic polarization and galvanostatic measurements were conducted in solution of 0.5 M H2SO4 to investigate electrocatalytic behavior and stability of the electrocatalyst. The mechanisms of the thermal decomposition process of RuCl3.nH2O and IrCl3.mH2O precursors to form oxide powders were studied by means of thermal gravity analysis (TGA). X-ray diffraction (XRD) and scanning electron microscopy (SEM) were used analysis for determination of the crystallographic structure, morphology and catalysts particle size. Based on the given results, the IrxRu1-xO2 (x = 0.5 0.7) compounds were found to be more active than pure IrO2 and more stable than pure RuO2.

  8. Quasielastic charge-exchange reaction p/sup 3/ He. -->. n/sub F/ ppp at intermediate energies

    SciTech Connect

    Blinov, A.V.; Vanyushin, I.A.; Grechko, V.E.; Zombkovskii, S.M.; Kondratyuk, L.A.; Korolev, Y.V.; Selektor, Y.M.; Solov'ev, V.V.; Turov, V.F.; Chuvilo, I.V.; and others

    1988-04-01

    The principal characteristics of the quasielastic-charge-exchange reaction p/sup 3/He..-->..n/sub F/ppp are investigated by means of the liquid-hydrogen bubble chamber at our institute of diameter 80 cm, exposed in beams of /sup 3/He nuclei with momenta 2.5 and 5 GeV/c (the kinetic energy of the primary protons T/sub p/ in the rest system of the nucleus is respectively 0.318 and 0.978 GeV). The experimental data are compared with the predictions of the Glauber-Sitenko multiple-scattering theory and with the pole model taking into account the interaction of spectator nucleons in the final state. In the mass spectrum of the 3p system at 3.05 GeV a well expressed structure is observed which is not described in the framework of the pole model. A possible resonance occurrence of this structure is discussed.

  9. tetra neutron system studied by exothermic double-charge exchange reaction 4He(8He, 8Be)4n

    NASA Astrophysics Data System (ADS)

    Kisamori, Keiichi; Sharaq06 Collaboration

    2014-09-01

    A possible existence of the tetra-neutron system as a resonance state is still an open and fascinating question, while theoretical papers using ab-initio calculation suggests that the bound tetra-neutron does not exist. We have performed a missing-mass spectroscopy of the 4n system via the exothermic double-charge exchange reaction 4He(8He,8Be)4n. The experiment was carried out at the RIBF at RIKEN using the SHARAQ spectrometer and the liquid He target system. Since the secondary beam, 8He at 190A MeV, has a large internal energy, it is possible to produce the 4n system in small momentum transfers of less than 20 MeV/c. In the present analysis, a new analytical framework to treat multi-particles under high beam rate condition (2 MHz) was developed for good statistics. At the SHARAQ spectrometer, 8Be can be identified by measuring the invariant mass of the coincident two-alpha particle with a good signal-to-noise ratio. About several tens of candidate events are obtained above the 4n threshold. We will show the preliminary result of missing-msss spectrum and discuss the shape of spectrum.

  10. Hyporheic exchange and fulvic acid redox reactions in an Alpine stream/wetland ecosystem, Colorado Front Range.

    PubMed

    Miller, Matthew P; McKnight, Diane M; Cory, Rose M; Williams, Mark W; Runkel, Robert L

    2006-10-01

    The influence of hyporheic zone interactions on the redox state of fulvic acids and other redox active species was investigated in an alpine stream and adjacent wetland, which is a more reducing environment. A tracer injection experiment using bromide (Br-) was conducted in the stream system. Simulations with a transport model showed that rates of exchange between the stream and hyporheic zone were rapid (alpha approximately 10(-3) s(-1)). Parallel factor analysis of fluorescence spectra was used to quantifythe redox state of dissolved fulvic acids. The rate coefficient for oxidation of reduced fulvic acids (lambda = 6.5 x 10(-3) s(-1)) in the stream indicates that electron-transfer reactions occur over short time scales. The rate coefficients for decay of ammonium (lambda = 1.2 x 10(-3) s(-1)) and production of nitrate (lambda = -1.0 x 10(-3) s(-1)) were opposite in sign but almost equal in magnitude. Our results suggest that fulvic acids are involved in rapid electron-transfer processes in and near the stream channel and may be important in determining ecological energy flow at the catchment scale. PMID:17051783

  11. Hyporheic exchange and fulvic acid redox reactions in an alpine stream/wetland ecosystem, Colorado front range

    USGS Publications Warehouse

    Miller, M.P.; McKnight, Diane M.; Cory, R.M.; Williams, M.W.; Runkel, R.L.

    2006-01-01

    The influence of hyporheic zone interactions on the redox state of fulvic acids and other redox active species was investigated in an alpine stream and adjacent wetland, which is a more reducing environment. A tracer injection experiment using bromide (Br-) was conducted in the stream system. Simulations with a transport model showed that rates of exchange between the stream and hyporheic zone were rapid (?? ??? 10-3 s -1). Parallel factor analysis of fluorescence spectra was used to quantify the redox state of dissolved fulvic acids. The rate coefficient for oxidation of reduced fulvic acids (?? = 6.5 ?? 10-3 s -1) in the stream indicates that electron-transfer reactions occur over short time scales. The rate coefficients for decay of ammonium (?? = 1.2 ?? 10-3 s-1) and production of nitrate (?? = -1.0 ?? 10-3 s-1) were opposite in sign but almost equal in magnitude. Our results suggest that fulvic acids are involved in rapid electron-transfer processes in and near the stream channel and may be important in determining ecological energy flow at the catchment scale. ?? 2006 American Chemical Society.

  12. (16) O/(18) O Exchange of Aldehydes and Ketones caused by H2 (18) O in the Mechanistic Investigation of Organocatalyzed Michael, Mannich, and Aldol Reactions.

    PubMed

    Hayashi, Yujiro; Mukaiyama, Takasuke; Benohoud, Meryem; Gupta, Nishant R; Ono, Tsuyoshi; Toda, Shunsuke

    2016-04-18

    Organocatalyzed Michael, Mannich, and aldol reactions of aldehydes or ketones, as nucleophiles, have triggered several discussions regarding their reaction mechanism. H2 (18) O has been utilized to determine if the reaction proceeds through an enamine or enol mechanism by monitoring the ratio of (18) O incorporated into the final product. In this communication, we describe the risk of H2 (18) O as an evaluation tool for this mechanistic investigation. We have demonstrated that exchange of (16) O/(18) O occurs in the aldehyde or ketone starting material, caused by the presence of H2 (18) O and amine catalysts, before the Michael, Mannich, and aldol reactions proceed. Because the newly generated (18) O starting aldehydes or ketones and (16) O water affect the incorporation ratio of (18) O in the final product, the use of H2 (18) O would not be appropriate to distinguish the mechanism of these organocatalyzed reactions. PMID:26841358

  13. Simple (17) O NMR method for studying electron self-exchange reaction between UO2 (2+) and U(4+) aqua ions in acidic solution.

    PubMed

    Bányai, István; Farkas, Ildikó; Tóth, Imre

    2016-06-01

    (17) O NMR spectroscopy is proven to be suitable and convenient method for studying the electron exchange by following the decrease of (17) O-enrichment in U(17) OO(2+) ion in the presence of U(4+) ion in aqueous solution. The reactions have been performed at room temperature using I = 5 M ClO4 (-) ionic medium in acidic solutions in order to determine the kinetics of electron exchange between the U(4+) and UO2 (2+) aqua ions. The rate equation is given as R = a[H(+) ](-2)  + R', where R' is an acid independent parallel path. R' depends on the concentration of the uranium species according to the following empirical rate equation: R' = k1 [UO(2 +) ](1/2) [U(4 +) ](1/2)  + k2 [UO(2 +) ](3/2) [U(4 +) ](1/2) . The mechanism of the inverse H(+) concentration-dependent path is interpreted as equilibrium formation of reactive UO2 (+) species from UO2 (2+) and U(4+) aqua ions and its electron exchange with UO2 (2+) . The determined rate constant of this reaction path is in agreement with the rate constant of UO2 (2+) -UO2 (+) , one electron exchange step calculated by Marcus theory, match the range given experimentally of it in an early study. Our value lies in the same order of magnitude as the recently calculated ones by quantum chemical methods. The acid independent part is attributed to the formation of less hydrolyzed U(V) species, i.e. UO(3+) , which loses enrichment mainly by electron exchange with UO2 (2+) ions. One can also conclude that (17) O NMR spectroscopy, or in general NMR spectroscopy with careful kinetic analysis, is a powerful tool for studying isotope exchange reactions without the use of sophisticated separation processes. Copyright © 2015 John Wiley & Sons, Ltd. PMID:25854521

  14. The interaction of quinone and detergent with reaction centers of purple bacteria. I. Slow quinone exchange between reaction center micelles and pure detergent micelles.

    PubMed Central

    Shinkarev, V P; Wraight, C A

    1997-01-01

    The kinetics of light-induced electron transfer in reaction centers (RCs) from the purple photosynthetic bacterium Rhodobacter sphaeroides were studied in the presence of the detergent lauryldimethylamine-N-oxide (LDAO). After the light-induced electron transfer from the primary donor (P) to the acceptor quinone complex, the dark re-reduction of P+ reflects recombination from the reduced acceptor quinones, QA- or QB-. The secondary quinone, QB, which is loosely bound to the RC, determines the rate of this process. Electron transfer to QB slows down the return of the electron to P+, giving rise to a slow phase of the recovery kinetics with time tau P approximately 1 s, whereas charge recombination in RCs lacking QB generates a fast phase with time tau AP approximately 0.1 s. The amount of quinone bound to RC micelles can be reduced by increasing the detergent concentration. The characteristic time of the slow component of P+ dark relaxation, observed at low quinone content per RC micelle (at high detergent concentration), is about 1.2-1.5 s, in sharp contrast to expectations from previous models, according to which the time of the slow component should approach the time of the fast component (about 0.1 s) when the quinone concentration approaches zero. To account for this large discrepancy, a new quantitative approach has been developed to analyze the kinetics of electron transfer in isolated RCs with the following key features: 1) The exchange of quinone between different micelles (RC and detergent micelles) occurs more slowly than electron transfer from QB- to P+; 2) The exchange of quinone between the detergent "phase" and the QB binding site within the same RC micelle is much faster than electron transfer between QA- and P+; 3) The time of the slow component of P+ dark relaxation is determined by (n) > or = 1, the average number of quinones in RC micelles, calculated only for those RC micelles that have at least one quinone per RC (in excess of QA). An

  15. A facile route to synthesize CdZnSe core–shell-like alloyed quantum dots via cation exchange reaction in aqueous system

    SciTech Connect

    Sheng, Yingzhuo; Wei, Jumeng; Liu, Bitao; Peng, Lingling

    2014-09-15

    Highlights: • Water-soluble CdZnSe alloyed QDs synthesized by cation exchange reaction. • The as-prepared CdZnSe QDs have fairly good luminescence properties. • The surface defects of obtained QDs were removed due to the alloyed structure. - Abstract: Water-soluble CdZnSe alloyed nanocrystals have been successfully prepared via “green” cation exchange reaction in aqueous system. The X-ray diffraction (XRD) patterns indicate that the as-prepared nanocrystals had high crystallinity and small particle size of 4–5 nm. The absorption spectra of CdZnSe show red shift of 100 nm from 375 to 475 nm. Moreover, the band-gap photoluminescent (PL) emission has a red shift of 50 nm from 430 to 480 nm with the increase of the reaction time. On the basis of the PL properties and transmission electron microscopy (TEM) images, one kind of core–shell-like structure model was proposed, which resulted from the different cation exchange reaction rates. This structure could greatly improve the luminescence properties by the removal of surface defect of quantum dots. This work would support potential applications in optoelectronic devices, and biomedical tags fields.

  16. The non-statistical dynamics of the 18O + 32O2 isotope exchange reaction at two energies

    NASA Astrophysics Data System (ADS)

    Van Wyngarden, Annalise L.; Mar, Kathleen A.; Quach, Jim; Nguyen, Anh P. Q.; Wiegel, Aaron A.; Lin, Shi-Ying; Lendvay, Gyorgy; Guo, Hua; Lin, Jim J.; Lee, Yuan T.; Boering, Kristie A.

    2014-08-01

    The dynamics of the 18O(3P) + 32O2 isotope exchange reaction were studied using crossed atomic and molecular beams at collision energies (Ecoll) of 5.7 and 7.3 kcal/mol, and experimental results were compared with quantum statistical (QS) and quasi-classical trajectory (QCT) calculations on the O3(X1A') potential energy surface (PES) of Babikov et al. [D. Babikov, B. K. Kendrick, R. B. Walker, R. T. Pack, P. Fleurat-Lesard, and R. Schinke, J. Chem. Phys. 118, 6298 (2003)]. In both QS and QCT calculations, agreement with experiment was markedly improved by performing calculations with the experimental distribution of collision energies instead of fixed at the average collision energy. At both collision energies, the scattering displayed a forward bias, with a smaller bias at the lower Ecoll. Comparisons with the QS calculations suggest that 34O2 is produced with a non-statistical rovibrational distribution that is hotter than predicted, and the discrepancy is larger at the lower Ecoll. If this underprediction of rovibrational excitation by the QS method is not due to PES errors and/or to non-adiabatic effects not included in the calculations, then this collision energy dependence is opposite to what might be expected based on collision complex lifetime arguments and opposite to that measured for the forward bias. While the QCT calculations captured the experimental product vibrational energy distribution better than the QS method, the QCT results underpredicted rotationally excited products, overpredicted forward-bias and predicted a trend in the strength of forward-bias with collision energy opposite to that measured, indicating that it does not completely capture the dynamic behavior measured in the experiment. Thus, these results further underscore the need for improvement in theoretical treatments of dynamics on the O3(X1A') PES and perhaps of the PES itself in order to better understand and predict non-statistical effects in this reaction and in the formation

  17. Ion-exchange reactions on clay minerals coupled with advection/dispersion processes. Application to Na+/Ca2+ exchange on vermiculite: Reactive-transport modeling, batch and stirred flow-through reactor experiments

    NASA Astrophysics Data System (ADS)

    Tertre, E.; Hubert, F.; Bruzac, S.; Pacreau, M.; Ferrage, E.; Prêt, D.

    2013-07-01

    The present study aims at testing the validity of using an Na+/Ca2+ ion-exchange model, derived from batch data to interpret experimental Ca2+-for-Na+ exchange breakthrough curves obtained on vermiculite (a common swelling clay mineral in surface environments). The ion-exchange model was constructed considering the multi-site nature of the vermiculite surface as well as the exchange of all aqueous species (Mg2+ derived from the dissolution of the solid and H+). The proposed ion-exchange model was then coupled with a transport model, and the predicted breakthrough curves were compared with the experimental ones obtained using a well stirred flow-through reactor. For a given solute residence time in the reactor (typically 50 min), our thermodynamic model based on instantaneous equilibrium was found to accurately reproduce several of the experimental breakthrough curves, depending on the Na+ and Ca2+ concentrations of the influents pumped through the reactor. However the model failed to reproduce experimental breakthrough curves obtained at high flow rates and low chemical gradient between the exchanger phase and the solution. An alternative model based on a hybrid equilibrium/kinetic approach was thus used and allowed predicting experimental data. Based on these results, we show that a simple parameter can be used to differentiate between thermodynamic and kinetic control of the exchange reaction with water flow. The results of this study are relevant for natural systems where two aquatic environments having contrasted chemistries interact. Indeed, the question regarding the attainment of a full equilibrium in such a system during the contact time of the aqueous phase with the particle/colloid remains most often open. In this context, we show that when a river (a flow of fresh water) encounters marine colloids, a systematic full equilibrium can be assumed (i.e., the absence of kinetic effects) when the residence time of the solute in 1 m3 of the system is ⩾6200 h.

  18. Single-Crystal to Single-Crystal Linker Substitution, Linker Place Exchange, and Transmetalation Reactions in Interpenetrated Pillared-Bilayer Zinc(II) Metal-Organic Frameworks.

    PubMed

    De, Dinesh; Neogi, Subhadip; Sañudo, E Carolina; Bharadwaj, Parimal K

    2015-11-23

    A twofold interpenetrated pillared-bilayer framework, {[Zn3 (L)2 (L2 )(DMF)]⋅(18DMF)(6H2 O)}n (1), has been synthesized from the ligands tris(4'-carboxybiphenyl)amine (H3 L) and 1,2-bis(4-pyridyl)ethylene (L2 ). The structure contains [Zn3 (COO)6 ] secondary building units (SBUs), in which three Zn(II) ions are almost linear with carboxylate bridging. This framework undergoes reversible pillar linker substitution reactions at the terminal Zn(II) centers with three different dipyridyl linkers of different lengths to afford three daughter frameworks, 2-4. Frameworks 2-4 are interconvertible through reversible linker substitution reactions. Also, competitive linker-exchange experiments show preferential incorporation of linker L3 in the parent framework 1. The larger linker L5 does not undergo such substitution reactions and framework 5, which contains this linker, can be synthesized solvothermally as a twofold interpenetrated structure. Interestingly, when framework 5 is dipped in a solution of L3 in DMF, linker substitution takes place as before, but linker L5 now moves and diagonally binds two Zn(II) centers to afford 6 as a nonpenetrated single framework. This linker place exchange reaction is unprecedented. All of these reactions take place in a single-crystal to single-crystal (SC-SC) manner, and have been observed directly through X-ray crystallography. In addition, each 3D framework undergoes complete copper(II) transmetalation. PMID:26462612

  19. Hydrogen-deuterium exchange reactions of cis- and trans-cyclopropane derivatives with D(2)O and CD(3)OD in the gas phase

    PubMed

    Li; Liu

    2000-01-01

    Gas-phase hydrogen-deuterium (H/D) exchange reactions involving four isomeric cyclopropane derivatives were investigated under chemical ionization (CI) conditions, using D(2)O and CD(3)OD as reagent gases. There are abundant ions at [M + 1](+), [M + 2](+) and [M + 3](+) in the D(2)O and CD(3)OD positive-ion CI mass spectra of the two isomer pairs 1, 2 and 3, 4. Their CI mass spectra are identical with each pair, and so are the collision-induced dissociation (CID) spectra of ions [M + 1](+), [M + 2](+) and [M + 3](+) of each of the two isomer pairs. The CID spectra of [M + 1](+) ions indicate that they have common D/H exchange reactions within each pair, which take place between molecular ions and deuterium-labeling reagents to form the [M - H + D](+) ions. Those of their [M + 2](+) ions show that they have common D/H exchange reactions within each pair, which form the [M(d1) + H](+) ions. Those of their [M + 3](+) ions show that they have common D/H exchange reactions within each pair, which take place between the [M(d1)] and deuterium-labeling reagents to produce [M(d2) + H](+) for the isomer pair 1, 2 and [M(d1) + D](+) for the isomer pair 3, 4. The number and position, and active order of the active hydrogen atoms of the isomer pairs 1, 2 and 3, 4 were determined. Copyright 2000 John Wiley & Sons, Ltd. PMID:10637425

  20. Metal chalcogenide nanoparticle gel networks: Their formation mechanism and application for novel material generation and heavy metal water remediation via cation exchange reactions

    NASA Astrophysics Data System (ADS)

    Palhares, Leticia F.

    The dissertation research is focused on (1) uncovering the mechanism of metal chalcogenide nanoparticle gel formation; (2) extending the cation exchange reaction protocol to zinc sulfide gel networks, with the goal of accessing new aerogel chemistries and understanding the factors that drive the process; and (3) conducting a quantitative analysis of the ability of ZnS aerogels to remove heavy metal ions from aqueous solutions. The mechanism of metal chalcogenide nanoparticle gel formation was investigated using Raman spectroscopy and X-ray Photoelectron Spectroscopy to probe the chemical changes that occur during the gelation process. These techniques suggest that the bonding between the particles in the CdSe nanoparticle gels is due to the oxidation of surface selenide species, forming covalent Se--Se bonds. Treating the gel networks with a suitable reducing agent, such as a thiol, breaks the covalent bond and disperses the gel network. The addition of sodium borohydride, a "pure" reducing agent, also breaks down the gel network, strengthening the hypothesis that the reducing character of the thiols, not their ligation ability, is responsible for the gel network breakdown. UV-Vis spectroscopy, Transmission Electron Microscopy and Powder X-ray Diffraction were used to analyze the particles after successive gelation-dispersion cycles. The primary particle size decreases after repeated oxidation-reduction cycles, due to nanoparticle surface etching. This trend is observed for CdSe and CdS gel networks, allowing for the proposition that the oxidative-reductive mechanism responsible for the formation-dispersion of the gels is general, applying to other metal chalcogenide nanocrystals as well. The cation exchange reaction previously demonstrated for CdSe gels was extended to ZnS gel networks. The exchange occurs under mild reaction conditions (room temperature, methanol solvent) with exchanging ions of different size, charge and mobility (Ag+, Pb2+, Cd2+ , Cu2+). The

  1. Radiochemical study of the medium energy pion double charge exchange reactions: /sup 209/Bi(pi/sup +/pi/sup -/)/sup 209-x/At

    SciTech Connect

    Clark, J.L.

    1980-01-01

    Carrier-free radiochemical techniques have been used to measure cross sections for the double charge exchange reactions of the type /sup 209/Bi(pi/sup +/, pi/sup -/xn)/sup 209-x/At for 100, 180, and 300 MeV incident pions. The observed formation of astatine products with mass numbers ranging from 208 to 205 is interpreted as evidence of processes in which energy deposited in the initial double charge exchange interaction is subsequently dissipated through neutron evaporation. The excitation functions for these reactions are seen to rise rapidly with decreasing incident pion energy with the maximum results for this study at 100 MeV. The astatine production cross secions measured for these positive pion irradiations of thick bismuth targets must be corrected for secondary processes, particularly the pion induced production of fast alpha particles which can contribute to the total cross sections through reactions like /sup 209/Bi(alpha,xn)/sup 213-x/At. The importance of these secondary contributions was studied through a series of negative pion irradiations of bismuth in which secondary pathways furnish the only means of producing astatine. The failure of evaporation calculations to reproduce the astatine product mass yields observed in these secondary studies suggests that direct mechanisms for energetic complex particle formation are quite important. Values for the alpha decay branches of /sup 207/At, /sup 208/At, and /sup 209/At were determined through a study of the electron capture and alpha decay characteristics of chemically purified astatine fractions.

  2. Multivalency in the gas phase: H/D exchange reactions unravel the dynamic "rock 'n' roll" motion in dendrimer-dendrimer complexes.

    PubMed

    Qi, Zhenhui; Schlaich, Christoph; Schalley, Christoph A

    2013-10-25

    Noncovalent dendrimer-dendrimer complexes were successfully ionized by electrospray ionization of partly protonated amino-terminated polypropylene amine (POPAM) and POPAM dendrimers fully functionalized with benzo[21]crown-7 on all branches. Hydrogen/deuterium exchange (HDX) experiments conducted on dendrimer-dendrimer complexes in the high vacuum of a mass spectrometer give rise to a complete exchange of all labile NH hydrogen atoms. As crown ethers represent noncovalent protective groups against HDX reactions on the ammonium group to which they are coordinated, this result provides evidence for a very dynamic binding situation: each crown is mobile enough to move from one ammonium binding site to another. Schematically, one might compare this motion with two rock 'n' roll dancers that swirl around each other without completely losing all contact at any time. Although the multivalent attachment certainly increases the overall affinity, the "microdynamics" of individual site binding and dissociation remains fast. PMID:24105808

  3. Protonolysis and amide exchange reactions of a three-coordinate cobalt amide complex supported by an N-heterocyclic carbene ligand.

    PubMed

    Hansen, Christopher B; Jordan, Richard F; Hillhouse, Gregory L

    2015-05-18

    A three-coordinate cobalt species, IPrCoCl{N(SiMe3)2} [1; IPr = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene], was synthesized by the reaction of {IPrCoCl2}2 with NaN(SiMe3)2. Compound 1 is a useful starting material for low-coordinate (IPr)Co species. 1 reacts with 2,6-di-tert-butyl-4-methylphenol (BHT-H) via aminolysis of the Co-N bond to generate a three-coordinate phenoxide complex, IPrCoCl(O-2,6-(t)Bu2-4-MeC6H2) (2). The reaction of 1 with 2,6-diisopropylaniline (NH2DIPP) generates IPrCoCl(NHDIPP) (4), which undergoes disproportionation to form a mixture of 4, {IPrCoCl2}2, and IPrCo(NHDIPP)2 (3). The same product mixture is formed by the reaction of 1 with Li[NH(DIPP)], which unexpectedly proceeds by amide exchange. Compound 3 was synthesized independently by the reaction of {IPrCoCl2}2 with 4 equiv of Li[NH(DIPP)]. The reaction of 1 with the bulkier lithium 2,6-dimesitylanilide (LiNHDMP) also proceeds by amide exchange to generate IPrCoCl(NHDMP) (5), which is stable toward disproportionation. Compounds 1 and 2 exhibit trigonal-planar geometries at cobalt in the solid state. The solid-state structure of 3 also contains a trigonal-planar cobalt center and exhibits close Co---H contacts involving the methine hydrogen atoms of the NH(DIPP) groups in the axial positions. The solid-state structure of 5 features an interaction between cobalt and a flanking aryl group of the anilide ligand, resulting in pyramidalization of the cobalt center. PMID:25938547

  4. Ab initio calculation of transition state normal mode properties and rate constants for the H(T)+CH4(CD4) abstraction and exchange reactions

    NASA Astrophysics Data System (ADS)

    Schatz, George C.; Walch, Stephen P.; Wagner, Albert F.

    1980-11-01

    We present ab initio (GVB-POL-CI) calculations for enough of the region about the abstraction and exchange saddle points for H(T)+CH4(CD4) to perform a full normal mode analysis of the transition states. The resulting normal mode frequencies are compared to four other published surfaces: an ab initio UHF-SCF calculation by Carsky and Zahradnik, a semiempirical surface by Raff, and two semiempirical surfaces by Kurylo, Hollinden, and Timmons. Significant quantitative and qualitative differences exist between the POL-CI results and those of the other surfaces. Transition state theory rate constants and vibrationally adiabatic reaction threshold energies were computed for all surfaces and compared to available experimental values. For abstraction, the POL-CI rates are in good agreement with experimental rates and in better agreement than are the rates of any of the other surfaces. For exchange, uncertainties in the experimental values and in the importance of vibrationally nonadiabatic effects cloud the comparison of theory to experiment. Tentative conclusions are that the POL-CI barrier is too low by several kcal. Unless vibrationaly nonadiabatic effects are severe, the POL-CI surface is still in better agreement with experiment than are the other surfaces. The rates for a simple 3-atom transition state theory model (where CH3 is treated as an atom) are compared to the rates for the full 6-atom model. The kinetic energy coupling of reaction coordinate modes to methyl group modes is identified as being of primary importance in determining the accuracy of the 3-atom model for this system. Substantial coupling in abstraction, but not exchange, causes the model to fail for abstraction but succeed for exchange.

  5. Role of associated defects in oxygen ion conduction and surface exchange reaction for epitaxial samaria-doped ceria thin films as catalytic coatings

    DOE PAGESBeta

    Yang, Nan; Shi, Yanuo; Schweiger, Sebastian; Strelcov, Evgheni; Foglietti, Vittorio; Orgiani, Pasquale; Balestrino, Giuseppe; Kalinin, Sergei V.; Jennifer L. M. Rupp; Aruta, Carmela; et al

    2016-05-18

    Samaria-doped ceria (SDC) thin films are particularly important for energy and electronic applications such as micro-solid oxide fuel cells, electrolysers, sensors and memristors. In this paper we report a comparative study investigating ionic conductivity and surface reactions for well-grown epitaxial SDC films varying the samaria doping concentration. With increasing doping above 20 mol% of samaria, an enhancement in the defect association was observed by Raman spectroscopy. The role of such defect associates on the films` oxygen ion transport and exchange was investigated by electrochemical impedance spectroscopy and electrochemical strain microscopy (ESM). The measurements reveal that the ionic transport has amore » sharp maximum in ionic conductivity and drop in its activation energy down to 0.6 eV for 20 mol% doping. Increasing the doping concentration further up to 40 mol%, raises the activation energy substantially by a factor of two. We ascribe the sluggish transport kinetics to the "bulk" ionic-near ordering in case of the heavily doped epitaxial films. Analysis of the ESM first order reversal curve measurements indicate that these associated defects may have a beneficial role by lowering the activation of the oxygen exchange "surface" reaction for heavily doped 40 mol% of samaria. We reveal in a model experiment through a solid solution series of samaria doped ceria epitaxial films that the occurrence of associate defects in the bulk affects the surface charging state of the films to increase the exchange rates. Lastly, the implication of these findings are the design of coatings with tuned oxygen surface exchange by control of bulk associate clusters for future electro-catalytic applications.« less

  6. Role of Associated Defects in Oxygen Ion Conduction and Surface Exchange Reaction for Epitaxial Samaria-Doped Ceria Thin Films as Catalytic Coatings.

    PubMed

    Yang, Nan; Shi, Yanuo; Schweiger, Sebastian; Strelcov, Evgheni; Belianinov, Alex; Foglietti, Vittorio; Orgiani, Pasquale; Balestrino, Giuseppe; Kalinin, Sergei V; Rupp, Jennifer L M; Aruta, Carmela

    2016-06-15

    Samaria-doped ceria (SDC) thin films are particularly important for energy and electronic applications such as microsolid oxide fuel cells, electrolyzers, sensors, and memristors. In this paper, we report a comparative study investigating ionic conductivity and surface reactions for well-grown epitaxial SDC films varying the samaria doping concentration. With increasing doping above 20 mol % of samaria, an enhancement in the defect association is observed by Raman spectroscopy. The role of such associated defects on the films̀ oxygen ion transport and exchange is investigated by electrochemical impedance spectroscopy and electrochemical strain microscopy (ESM). The measurements reveal that the ionic transport has a sharp maximum in ionic conductivity and drops in its activation energy down to 0.6 eV for 20 mol % doping. Increasing the doping concentration further up to 40 mol %, it raises the activation energy substantially by a factor of 2. We ascribe the sluggish transport kinetics to the "bulk" ionic-near ordering in case of the heavily doped epitaxial films. Analysis of the ESM first-order reversal curve measurements indicates that these associated defects may have a beneficial role by lowering the activation of the oxygen exchange "surface" reaction for heavily doped 40 mol % of samaria. In a model experiment, through a solid solution series of samaria doped ceria epitaxial films, we reveal that the occurrence of associated defects in the bulk affects the surface charging state of the SDC films to increase the exchange rates. The implication of these findings is the design of coatings with tuned oxygen surface exchange by controlling the bulk associated clusters for future electrocatalytic applications. PMID:27192540

  7. Formation of gypsum and bassanite by cation exchange reactions in the absence of free-liquid H2O: Implications for Mars

    NASA Astrophysics Data System (ADS)

    Wilson, Siobhan A.; Bish, David L.

    2011-09-01

    Smectites and hydrated Mg sulfate minerals have been identified in close association at various locations on the Martian surface. The hydration states of sulfates and smectites are dependent on temperature and relative humidity (RH), and therefore these minerals have the potential to affect cycling and bioavailability of H2O on Mars. We have conducted X-ray powder diffraction experiments to investigate cycling of H2O within mixtures of Ca-bearing smectites and hydrated Mg sulfate minerals under conditions of varying RH similar to those that exist at or just beneath the Martian surface. Our experiments show that under conditions of varying RH, cation-exchange reactions occur between these two potential components of the Martian regolith, producing gypsum [CaSO4·2H2O] and bassanite [CaSO4·˜0.5H2O] in the absence of free-liquid H2O. Cation-exchange reactions were accompanied by significant loss of porosity, warping of the sample surface and, in some cases, volume expansion. The formation of Ca sulfate minerals in these experiments provides evidence for the development of thin films of H2O at mineral surfaces and suggests that similar processes may operate at the arid surface of Mars. Humidity-driven cation-exchange reactions between smectites and hydrated Mg sulfate minerals may therefore play a role in shaping the present-day Martian surface and could have provided a transient source of H2O and nutrients (e.g., major and trace elements and possibly organic micro/macronutrients) for putative microorganisms.

  8. Modeling and experiment reveal an unexpected stereoelectronic effect on conformation and scalar couplings of alpha-aminoorganostannanes, with possible relevance to the tin-lithium exchange reaction.

    PubMed

    Santiago, Marcelina; Low, Eddy; Chambournier, Gilles; Gawley, Robert E

    2003-10-31

    The solution conformation of N-methyl-2-(tributylstannyl)piperidines has been determined through the use of vicinal 119Sn-13C coupling constants, revealing a conformational distortion caused by an unexpected stereoelectronic effect in some cases. Specifically, the "equatorial" conformer is distorted into a half-chair, in which the nitrogen lone pair eclipses the C-Sn bond. This distortion, which "costs" approximately 1 kcal/mol, correlates with a conformational dependence of geminal 119Sn-15N couplings and a possible correlation with reactivity in the tin-lithium exchange reaction. PMID:14575474

  9. Impact of transient stream flow on water exchange and reactions in the hyporheic zone of an in-stream gravel bar

    NASA Astrophysics Data System (ADS)

    Trauth, Nico; Schmidt, Christian; Fleckenstein, Jan H.

    2015-04-01

    Groundwater-surface water exchange is an important process that can facilitate the degradation of critical substances like nitrogen-species and contaminants, supporting a healthy status of the aquatic ecosystem. In our study, we simulate water exchange, solute transport and reactions within a natural in-stream gravel bar using a coupled surface and subsurface numerical model. Stream water flow is simulated by computational fluid dynamics software that provides hydraulic head distributions at the streambed, which are used as an upper boundary condition for a groundwater model. In the groundwater model water exchange, solute transport, aerobic respiration and denitrification in the subsurface are simulated. Ambient groundwater flow is introduced by lateral upstream and downstream hydraulic head boundaries that generate neutral, losing or gaining stream conditions. Stream water transports dissolved oxygen, organic carbon (as the dominant electron donor) and nitrate into the subsurface, whereas an additional nitrate source exists in the ambient groundwater. Scenarios of stream flow events varying in duration and stream stage are simulated and compared with steady state scenarios with respect to water fluxes, residence times and the solute turn-over rates. Results show, that water exchange and solute turn-over rates highly depend on the interplay between event characteristics and ambient groundwater levels. For scenarios, where the stream flow event shifts the hydraulic system to a net-neutral hydraulic gradient between the average stream stage and the ambient groundwater level (minimal exchange between ground- and surface water), solute consumption is higher, compared to the steady losing or gaining case. In contrast, events that induce strong losing conditions lead to a lower potential of solute consumption.

  10. Production of the neutron-rich hypernucleus 10LambdaLi in the (pi-,K+) double charge-exchange reaction.

    PubMed

    Saha, P K; Fukuda, T; Imoto, W; Ahn, J K; Ajimura, S; Aoki, K; Bhang, H C; Fujioka, H; Hotchi, H; Hwang, J I; Itabashi, T; Kang, B H; Kim, H D; Kim, M J; Kishimoto, T; Krutenkova, A; Maruta, T; Miura, Y; Miwa, K; Nagae, T; Noumi, H; Outa, H; Ohtaki, T; Sakaguchi, A; Sato, Y; Sekimoto, M; Shimizu, Y; Tamura, H; Tanida, K; Toyoda, A; Ukai, M; Yim, H J

    2005-02-11

    In order to produce a neutron-rich Lambda hypernucleus for the first time, we carried out an experiment by utilizing the (pi-,K+) double charge-exchange reaction on a 10B target. We observed the production of a 10LambdaLi hypernucleus. The cross section for the Lambda bound region was found to be 11.3+/-1.9 nb/sr with the 1.2 GeV/c incident momentum, which is compared with the 10LambdaB hypernucleus production cross section, 7.8+/-0.3 microb/sr, in the (pi+,K+) reaction with a 1.05 GeV/c incident momentum beam. PMID:15783631

  11. High-yield cell-free synthesis of human EGFR by IRES-mediated protein translation in a continuous exchange cell-free reaction format

    PubMed Central

    Quast, Robert B.; Sonnabend, Andrei; Stech, Marlitt; Wüstenhagen, Doreen A.; Kubick, Stefan

    2016-01-01

    Cell-free protein synthesis systems derived from eukaryotic sources often provide comparatively low amounts of several μg per ml of de novo synthesized membrane protein. In order to overcome this, we herein demonstrate the high-yield cell-free synthesis of the human EGFR in a microsome-containing system derived from cultured Sf21 cells. Yields were increased more than 100-fold to more than 285 μg/ml by combination of IRES-mediated protein translation with a continuous exchange cell-free reaction format that allowed for prolonged reaction lifetimes exceeding 24 hours. In addition, an orthogonal cell-free translation system is presented that enabled the site-directed incorporation of p-Azido-L-phenylalanine by amber suppression. Functionality of cell-free synthesized receptor molecules is demonstrated by investigation of autophosphorylation activity in the absence of ligand and interaction with the cell-free synthesized adapter molecule Grb2. PMID:27456041

  12. Estimation of free energy barriers in the cytoplasmic and mitochondrial aspartate aminotransferase reactions probed by hydrogen-exchange kinetics of C alpha-labeled amino acids with solvent

    SciTech Connect

    Julin, D.A.; Wiesinger, H.; Toney, M.D.; Kirsch, J.F. )

    1989-05-02

    The existence of the postulated quinonoid intermediate in the cytoplasmic aspartate amino-transferase catalyzed transamination of aspartate to oxaloacetate was probed by determining the extent of transfer of tritium from the C alpha position of tritiated L-aspartate to pyridoxamine 5'-phosphate in single turnover experiments in which washout from the back-reaction was obviated by product trapping. The maximum amount of transferred tritium observed was 0.7%, consistent either with a mechanism in which a fraction of the net transamination reaction proceeds through a quinonoid intermediate or with a mechanism in which this intermediate is formed off the main reaction pathway. It is shown that transfer of labeled hydrogen from the amino acid to cofactor cannot be used to differentiate a stepwise from a concerted transamination mechanism. The amount of tritium transferred is a function of the rate constant for torsional equilibration about the epsilon-amino group of Lys-258, the presumptive abstractor of the C alpha proton; the relative rate constants for hydrogen exchange with solvent versus cofactor protonation; and the tritium isotope effect on this ratio. The free energy barriers facing the covalent intermediate between aldimine and keto acid product (i.e., ketimine and possibly quinonoid) were evaluated relatively by comparing the rates of C alpha-hydrogen exchange in starting amino acid with the rates of keto acid formation. The value of theta (= kexge/kprod) was found to be 2.6 for the reaction of cytoplasmic isozyme with aspartate and ca. 0.5 for that of the mitochondrial form with glutamate.

  13. Pt nanoparticle-dispersed graphene-wrapped MWNT composites as oxygen reduction reaction electrocatalyst in proton exchange membrane fuel cell.

    PubMed

    Aravind, S S Jyothirmayee; Ramaprabhu, Sundara

    2012-08-01

    Chemical and electrical synergies between graphite oxide and multiwalled carbon nanotube (MWNT) for processing graphene wrapped-MWNT hybrids has been realized by chemical vapor deposition without any chemical functionalization. Potential of the hybrid composites have been demonstrated by employing them as electrocatalyst supports in proton exchange membrane fuel cells. The defects present in the polyelectrolyte, which have been wrapped over highly dispersed MWNT, act as anchoring sites for the homogeneous deposition of platinum nanoparticles. Single-cell proton exchange membrane fuel cells show that the power density of the hybrid composite-based fuel cells is higher compared to the pure catalyst-support-based fuel cells, because of enhanced electrochemical reactivity and good surface area of the nanocomposites. PMID:22850438

  14. Two-dimensional free-energy surface on the exchange reaction of alkyl chloride/chloride using the QM/MM-MC method

    SciTech Connect

    Ohisa, M.; Yamataka, H.; Dupuis, Michel; Aida, Misako

    2007-12-05

    Two-dimensional free-energy surfaces are calculated for alkyl chloride/chloride exchange/inversion reactions: Cl- + RCl (R = Me and t-Bu) surrounded by one hundred H2O molecules as a model of solvent. The methodology of free-energy calculation by perturbation theory based on a mixed-Hamiltonian model (QM/MM) combined with Monte Carlo sampling of the solvent configurations was used to obtain the changes in solvation free energy. We devised a special procedure to analyze the two-dimensional free-energy surfaces to gain unique insight into the differences in the reaction mechanisms between the two systems. The inversion reaction path for R = t-Bu on the free-energy surface is found to proceed in an asynchronous way within a concerted framework via the ion-pair region. This is in contrast to the R = Me system that proceeds as a typical SN2 reaction. This work was supported by the U.S. Department of Energy's (DOE) Office of Basic Energy Sciences, Chemical Sciences program. The Pacific Northwest National Laboratory is operated by Battelle for DOE.

  15. Uniformly microsized luminescent materials obtained through a solid state reaction of WO{sub 3} with Ln{sup 3+}-exchanged zeolite L at 700 °C

    SciTech Connect

    Wang, Yige; Fang, Yi; Zhang, Wenjun; Zhang, Li; Chen, Yuhuan; Yu, Xiaoyan

    2013-06-01

    Graphical abstract: We have reported the modification of Ln3+/ZL microcrystals by the tungstate-oxygen species via a solid state reaction of WO{sub 3} and Ln{sup 3+}-exchanged zeolite L at 700 °C. Highlights: ► Luminescent materials were obtained from zeolite L crystals. ► The materials show characteristic luminescence of Eu{sup 3+} and Tb{sup 3+} ions. ► The framework of zeolite L crystals has been kept during the annealing process. ► Energy transfer from tungstate-oxygen species to lanthanide was confirmed. - Abstract: In this work, we report the uniformly microsized luminescent materials prepared by a solid state reaction of WO{sub 3} and Ln{sup 3+}-exchanged zeolite L at 700 °C. The obtained materials were investigated by SEM, XRD and photoluminescence spectroscopy. The influence of tungstate-oxygen species on the morphology and luminescence of the materials were discussed in detail. Energy transfer from the tungstate-oxygen species to Eu{sup 3+} and Tb{sup 3+} ions have been demonstrated by the photoluminescence spectra, implying the loading of tungstate-oxygen species into the nanochannels of the crystals and the close proximity of which to Eu{sup 3+} ions.

  16. Absolute level-to-level rate constants for inelastic collisions and exchange reactions in lithium + gaseous lithium(v,j) going to gaseous lithium(v',j') + lithium

    NASA Astrophysics Data System (ADS)

    Coppage, Steven Danforth

    We report 644 absolute level-to-level inelastic and reactive constants for the L7i*2 A1S+u (nui, ji) + 7Li → L7i*2 A1S+u (nu', j') + 7Li system with initial molecular quantum numbers nui = 2 and ji = 3, 11, and 19. We collected 87 rate constants for rotationally inelastic and vibrationally elastic collisions, 281 rate constants for vibrationally inelastic collisions, and 276 constants for exchange reactions with final vibrational levels from nu f = 0 to nuf = 3. Inelastic collisions are characterized by even changes in rotational quantum number, j , and exchange reactions are identified by odd Deltaj. Level-to-level rate constants for even Deltaj inelastic collisions show distributions similar to those in rare gas collisions with the excited Li2 molecule. The ECS (energy corrected sudden) scaling law of DePristo, et al., fit the vibrationally elastic data well. Reactive rate constant results are characterized by a statistical distribution for Deltanu of 0, -1, and -2 at a substantially reduced effective temperature consistent with a kinematic model proposed by Picconatto et al. Fitting quasiclassical trajectory studies to the data using a modified LEPS potential surface provide first insights into the parameters of the excited-state Li3* three-body potential.

  17. A study of the interfacial resistive switching mechanism by proton exchange reactions on the SiO(x) layer.

    PubMed

    Zhou, Fei; Chang, Yao-Feng; Chen, Ying-Chen; Wu, Xiaohan; Zhang, Ye; Fowler, Burt; Lee, Jack C

    2016-01-14

    In this work, we investigated SiO(x)-based interfacial resistive switching in planar metal-insulator-metal structures using physical/chemical/electrical analyses. This work helps clarify the interfacial reaction process and mechanism in SiO(x), and also shows the potential for high temperature operation in future nonvolatile memory applications. PMID:26659556

  18. /sup 31/P NMR saturation-transfer measurements in Saccharomyces cerevisiae: characterization of phosphate exchange reactions by iodoacetate and antimycin A inhibition

    SciTech Connect

    Campbell-Burk, S.L.; Jones, K.A.; Shulman, R.G.

    1987-11-17

    /sup 31/P nuclear magnetic resonance (NMR) saturation-transfer (ST) techniques have been used to measure steady-state flows through phosphate-adenosine 5'-triphosphate (ATP) exchange reactions in glucose-grown derepressed yeast. The results have revealed that the reactions catalyzed by glyceraldehyde-3-phosphate dehydrogenase/phosphoglycerate kinase (GAPDH/PGK) and by the mitochondrial ATPase contribute to the observed ST. Contributions from these reactions were evaluated by performing ST studies under various metabolic conditions in the presence and absence of either iodoacetate, a specific inhibitor of GAPDH, or the respiratory chain inhibitor antimycin A. Intracellular phosphate (P/sub i/) longitudinal relaxation times were determined by performing inversion recovery experiments during steady-state ATP/sub lambda/ saturation and were used in combination with ST data to determine P/sub i/ consumption rates. /sup 13/C NMR and O/sub 2/ electrode measurements were also conducted to monitor changes in rates of glucose consumption and O/sub 2/ consumption, respectively, under the various metabolic conditions examined. The results suggest that GAPDH/PGK-catalyzed P/sub i/-ATP exchange is responsible for antimycin-resistant saturation transfer observed in anaerobic and aerobic glucose-fed yeast. Kinetics through GAPDH/PGK were found to depend on metabolic conditions. The coupled system appears to operate in a unidirectional manner during anaerobic glucose metabolism and bidirectionally when the cells are respiring on exogenously supplied ethanol. Additionally, mitochondrial ATPase activity appears to be responsible for the transfer observed in iodoacetate-treated aerobic cells supplied with either glucose or ethanol, with synthesis of ATP occurring unidirectionally.

  19. Anion-exchange reactions on a robust phosphonium photopolymer for the controlled deposition of ionic gold nanoclusters.

    PubMed

    Guterman, Ryan; Hesari, Mahdi; Ragogna, Paul J; Workentin, Mark S

    2013-05-28

    UV curing (photopolymerization) is ubiquitous in many facets of industry ranging from the application of paints, pigments, and barrier coatings all the way to fiber optic cable production. To date no reports have focused on polymerizable phosphonium salts under UV irradiation, and despite this dearth of examples, they potentially offer numerous substantial advantages to traditional UV formulation components. We have generated a highly novel coating based on UV-curable trialkylacryloylphosphonium salts that allow for the fast (seconds) and straightforward preparation of ion-exchange surfaces amenable to a roll-to-roll process. We have quantified the surface charges and exploited their accessibility by employing these surfaces in an anion exchange experiment by which [Au25L18](-) (L = SCH2CH2Ph) nanocrystals can be assembled into the solid state. This unprecedented application of such surfaces offers a paradigm shift in the emerging chemistry of Au25 research where the nanocrystals remain single and intact and where the integrity of the cluster and its solution photophysical properties are resilient in the solid state. The specific loading of [Au25L18](-) on the substrates has been determined and the completely reversible loading and unloading of intact nanocrystals to and from the surface has been established. In the solid state, the assembly has an incredible mechanical resiliency, where the surface remains undamaged even when subjected to repeated Scotch tests. PMID:23472738

  20. Weak-interaction strength from charge-exchange reactions versus {beta} decay in the A=40 isoquintet

    SciTech Connect

    Bhattacharya, M.; Goodman, C. D.; Garcia, A.

    2009-11-15

    We report a measurement of the Gamow-Teller (GT) strength distribution for {sup 40}Ar{yields}{sup 40}K using the 0 deg. (p,n) reaction. The measurement extends observed GT strength distribution in the A=40 system up to an excitation energy of {approx}8 MeV. In comparing our results with those from the {beta} decay of the isospin mirror nucleus {sup 40}Ti, we find that, within the excitation energy region probed by the {beta}-decay experiment, we observe a total GT strength that is in fair agreement with the {beta}-decay measurement. However, we find that the relative strength of the two strongest transitions differs by a factor of {approx}1.8 in comparing our results from (p,n) reactions with the {beta} decay of {sup 40}Ti. Using our results we present the neutrino-capture cross section for {sup 40}Ar.

  1. Influence of varying hydraulic conditions on hyporheic exchange and reactions in an in-stream gravel bar

    NASA Astrophysics Data System (ADS)

    Trauth, Nico; Schmidt, Christian; Maier, Uli; Fleckenstein, Jan H.

    2014-05-01

    In the hyporheic zone (HZ) important biogeochemical transformations occur with crucial impact on nutrient cycling in fluvial systems. Here we investigate the interplay between stream flow and HZ exchange of a natural in-stream gravel bar (ISGB), by using three-dimensional steady state simulations of a coupled surface and subsurface numerical model. Stream flow is simulated by the open source computational fluid dynamics (CFD) software OpenFOAM. It is sequentially coupled by the hydraulic head distribution to the top boundary of the groundwater model code MIN3P, simulating flow, solute transport, aerobic respiration (AR) and denitrification (DN) in the HZ. The modelling approach is validated to the stream rating curve and the subsurface travel times in the ISGB based on field measurements. Hydraulic conditions are varied by stream discharge, ranging from low discharge, sufficient to allow stream water flow through both stream channels surrounding the ISGB (0.1 m³/s), to conditions where the ISGB is completely submerged (5.0 m³/s). Ambient groundwater flow is assigned by constant head boundaries upstream and downstream of the ISGB. By varying stream discharge or ambient groundwater heads the general flow field of the ISGB can be adjusted from losing via neutral to gaining conditions. Reactive transport scenarios consider stream water as the primary source of dissolved oxygen and dissolved organic carbon. Furthermore, two nitrate sources originated from the stream water and ambient groundwater are included in the model. Results show that highest hyporheic exchange and longest residence times occur under neutral conditions, where the extent of the hyporheic flow cell is at a maximum. Hence, the stronger the system is gaining and losing, the smaller is the hyporheic exchange flux and the shorter are the residence times in the HZ of the ISGB. AR and DN efficiencies of the ISGB are lowest under gaining conditions because infiltrating solutes are restriced to the

  2. MAX phase - Alumina composites via elemental and exchange reactions in the Tin+1ACn systems (A=Al, Si, Ga, Ge, In and Sn)

    NASA Astrophysics Data System (ADS)

    Cuskelly, Dylan; Richards, Erin; Kisi, Erich

    2016-05-01

    Extension of the aluminothermal exchange reaction synthesis of Mn+1AXn phases to systems where the element 'A' is not the reducing agent was investigated in systems TiO2-A-Al-C for A=Al, Si, Ga, Ge, In and Sn as well as Cr2O3-Ga-Al-C. MAX phase-Al2O3 composites were made in all systems except those with A=Ga or In. The effectiveness of conversion to MAX phases was generally in the range 63-96% without optimisation of starting ratios. Optimisation in the Ti-Si-C system gave a MAX phase component with >98% Ti3SiC2.

  3. Exploring the ester-exchange reactions of diester-diterpenoid alkaloids in the aconite decoction process by electrospray ionization tandem mass spectrometry.

    PubMed

    Wang, Yong; Shi, Lei; Song, Fengrui; Liu, Zhiqiang; Liu, Shuying

    2003-01-01

    The chemical components in the decoctions of Chinese herbal medicines are not always the same as those in the crude herbs because of the insolubility or instability of some compounds. In this work electrospray ionization tandem mass spectrometry was used to explore the ester-exchange reactions for aconitine-type diester-diterpenoid alkaloids occurring during the process of decocting aconite root. The aconitines were screened in a diverse range of samples, including crude aconite, decoction of crude aconite, residues from decoction of crude aconite, prepared aconite, decoction of prepared aconite, decoction of prepared aconite with added palmitic acid, and decoction of a mixture of mesaconitine and hypaconitine standards with liquorice root. It was found that diester-diterpenoid aconitines were converted into lipo-alkaloids as well as monoester alkaloids by the decoction of aconite. PMID:12569436

  4. Expressions for Form Factors for Inelastic Scattering and Charge Exchange in Plane-Wave, Distorted-Wave, and Coupled-Channels Reaction Formalisms

    SciTech Connect

    Dietrich, F S

    2006-09-25

    This document is intended to facilitate calculation of inelastic scattering and charge-exchange cross sections in a variety of reaction models, including the plane-wave and distorted-wave approximations and the full coupled-channels treatments. Expressions are given for the coupling potentials between the relevant channels in both coordinate and momentum space. In particular, it is expected that the plane-wave calculations should be useful as a check on the correctness of coupled-channels calculations. The Fourier transform methods used to calculate the plane-wave approximation cross sections are also intended to be used to generate the transition potentials for coupled-channels codes, using a folding model with local effective interactions. Specific expressions are given for calculating transition densities for the folding model in the random phase approximation (RPA).

  5. On-Demand Dissolution of a Dendritic Hydrogel-based Dressing for Second-Degree Burn Wounds through Thiol-Thioester Exchange Reaction.

    PubMed

    Konieczynska, Marlena D; Villa-Camacho, Juan C; Ghobril, Cynthia; Perez-Viloria, Miguel; Tevis, Kristie M; Blessing, William A; Nazarian, Ara; Rodriguez, Edward K; Grinstaff, Mark W

    2016-08-16

    An adhesive yet easily removable burn wound dressing represents a breakthrough in second-degree burn wound care. Current second-degree burn wound dressings absorb wound exudate, reduce bacterial infections, and maintain a moist environment for healing, but are surgically or mechanically debrided from the wound, causing additional trauma to the newly formed tissues. We have developed an on-demand dissolvable dendritic thioester hydrogel burn dressing for second-degree burn care. The hydrogel is composed of a lysine-based dendron and a PEG-based crosslinker, which are synthesized in high yields. The hydrogel burn dressing covers the wound and acts as a barrier to bacterial infection in an in vivo second-degree burn wound model. A unique feature of the hydrogel is its capability to be dissolved on-demand, via a thiol-thioester exchange reaction, allowing for a facile burn dressing removal. PMID:27410669

  6. Communication: Rigorous quantum dynamics of O + O{sub 2} exchange reactions on an ab initio potential energy surface substantiate the negative temperature dependence of rate coefficients

    SciTech Connect

    Li, Yaqin; Sun, Zhigang E-mail: dawesr@mst.edu; Jiang, Bin; Guo, Hua E-mail: dawesr@mst.edu; Xie, Daiqian; Dawes, Richard E-mail: dawesr@mst.edu

    2014-08-28

    The kinetics and dynamics of several O + O{sub 2} isotope exchange reactions have been investigated on a recently determined accurate global O{sub 3} potential energy surface using a time-dependent wave packet method. The agreement between calculated and measured rate coefficients is significantly improved over previous work. More importantly, the experimentally observed negative temperature dependence of the rate coefficients is for the first time rigorously reproduced theoretically. This negative temperature dependence can be attributed to the absence in the new potential energy surface of a submerged “reef” structure, which was present in all previous potential energy surfaces. In addition, contributions of rotational excited states of the diatomic reactant further accentuate the negative temperature dependence.

  7. Electron-exchange rates of polypyridine complexes: electron-transfer reactions involving the tris(polypyridine)nickel(II/III) couple in acidic aqueous media

    SciTech Connect

    Macartney, D.H.; Sutin, N.

    1983-01-01

    The kinetics of the reduction of NiL/sub 3//sup 3 +/ by NiL'/sub 3//sup 2 +/ complexes (where L and L' are substituted 2,2'-bipyridine or 1,10-phenanthroline derivatives) and by NiH/sub 2/A/sup 2 +/ (H/sub 2/A = 3,14-dimethyl-4,7,10,13-tetraazahexadeca-3,13-diene-2,15-dione dioxime), tris(5-nitro-1,10-phenanthroline)ruthenium(II), and Fe(H/sub 2/O)/sub 6//sup 2 +/ in acidic aqueous media have been studied by the stopped-flow technique. The kinetic data yield 1.5 x 10/sup 3/ M/sup -1/ s/sup -1/ for the NiL/sub 3//sup 2 +/-NiL/sub 3//sup 3 +/ self-exchange rate constant at 25/sup 0/C and 1.00 M ionic strength. The Fe(H/sub 2/O)/sup 62 +/ reduction of both Ni(4,4'-(CH/sub 3/)/sub 2/bpy)/sub 3//sup 3 +/ and Ni(bpy)/sub 3//sup 3 +/ is 10/sup 2/ times slower than predicted by the Marcus cross-relation, and reasons for this disagreement are discussed. The rate constant for the Ni(bpy)/sub 3//sup 2 +/-Ni(bpy)/sub 3//sup 3 +/ exchange is compared with other tris(2,2'-bipyridine) exchange rate constants, and the rate variations are discussed in terms of differences in the inner-shell reorganization barriers and electronic factors for the reactions. 39 references, 1 figure, 3 tables.

  8. Indoor transient SOA formation from ozone + α-pinene reactions: Impacts of air exchange and initial product concentrations, and comparison to limonene ozonolysis

    NASA Astrophysics Data System (ADS)

    Youssefi, Somayeh; Waring, Michael S.

    2015-07-01

    The ozonolysis of reactive organic gases (ROG), e.g. terpenes, generates secondary organic aerosol (SOA) indoors. The SOA formation strength of such reactions is parameterized by the aerosol mass fraction (AMF), a.k.a. SOA yield, which is the mass ratio of generated SOA to oxidized ROG. AMFs vary in magnitude both among and for individual ROGs. Here, we quantified dynamic SOA formation from the ozonolysis of α-pinene with 'transient AMFs,' which describe SOA formation due to pulse emission of a ROG in an indoor space with air exchange, as is common when consumer products are intermittently used in ventilated buildings. We performed 19 experiments at low, moderate, and high (0.30, 0.52, and 0.94 h-1, respectively) air exchange rates (AER) at varying concentrations of initial reactants. Transient AMFs as a function of peak SOA concentrations ranged from 0.071 to 0.25, and they tended to increase as the AER and product of the initial reactant concentrations increased. Compared to our similar research on limonene ozonolysis (Youssefi and Waring, 2014), for which formation strength was driven by secondary ozone reactions, the AER impact for α-pinene was opposite in direction and weaker, while the initial reactant product impact was in the same direction but stronger for α-pinene than for limonene. Linear fits of AMFs for α-pinene ozonolysis as a function of the AER and initial reactant concentrations are provided so that future indoor models can predict SOA formation strength.

  9. Silver Nanolabels-Assisted Ion-Exchange Reaction with CdTe Quantum Dots Mediated Exciton Trapping for Signal-On Photoelectrochemical Immunoassay of Mycotoxins.

    PubMed

    Lin, Youxiu; Zhou, Qian; Tang, Dianping; Niessner, Reinhard; Yang, Huanghao; Knopp, Dietmar

    2016-08-01

    Mycotoxins, highly toxic secondary metabolites produced by many invading species of filamentous fungi, contaminate different agricultural commodities under favorable temperature and humidity conditions. Herein, we successfully devised a novel signal-on photoelectrochemical immunosensing platform for the quantitative monitoring of mycotoxins (aflatoxin B1, AFB1, used as a model) in foodstuffs on the basis of silver nanolabels-assisted ion-exchange reaction with CdTe quantum dots (QDs) mediated hole-trapping. Initially, a competitive-type immunoreaction was carried out on a high-binding microplate by using silver nanoparticle (AgNP)-labeled AFB1-bovine serum albumin (AFB1-BSA) conjugates as the tags. Then, the carried AgNPs with AFB1-BSA were dissolved by acid to release numerous silver ions, which could induce ion-exchange reaction with the CdTe QDs immobilized on the electrode, thus resulting in formation of surface exciton trapping. Relative to pure CdTe QDs, the formed exciton trapping decreased the photocurrent of the modified electrode. In contrast, the detectable photocurrent increased with the increase of target AFB1 in a dynamic working range from 10 pg mL(-1) to 15 ng mL(-1) at a low limit of detection (LOD) of 3.0 pg mL(-1) under optimal conditions. In addition, the as-prepared photoelectrochemical immunosensing platform also displayed high specificity, good reproducibility, and acceptable method accuracy for detecting naturally contaminated/spiked blank peanut samples with consistent results obtained from the referenced enzyme-linked immunosorbent assay (ELISA) method. PMID:27348353

  10. Quasiclassical trajectory studies of 18O(3P) + NO2 isotope exchange and reaction to O2 + NO on D0 and D1 potentials

    NASA Astrophysics Data System (ADS)

    Fu, Bina; Zhang, Dong H.; Bowman, Joel M.

    2013-07-01

    We report quasiclassical trajectory calculations for the bimolecular reaction 18O(3P) + NO2 on the recent potential energy surfaces of the ground (D0) and first excited (D1) states of NO3 [B. Fu, J. M. Bowman, H. Xiao, S. Maeda, and K. Morokuma, J. Chem. Theory. Comput. 9, 893 (2013)], 10.1021/ct3009792. The branching ratio of isotope exchange versus O2 + NO formation, as well as the product angular distributions and energy and rovibrational state distributions are presented. The calculations are done at the collision energy of relevance to recent crossed beam experiments [K. A. Mar, A. L. Van Wyngarden, C.-W. Liang, Y. T. Lee, J. J. Lin, and K. A. Boering, J. Chem. Phys. 137, 044302 (2012)], 10.1063/1.4736567. Very good agreement is achieved between the current calculations and these experiments for the branching ratio and final translational energy and angular distributions of isotope exchange products 16O(3P) + NO2 and O2 + NO formation products. The reactant 18O atom results in 18O16O but not N18O for the O2 + NO formation product channel, consistent with the experiment. In addition, the detailed vibrational and rotational state information of diatomic molecules calculated currently for the 34O2 + NO formation channel on D0 and D1 states are in qualitative agreement with the previous experimental and theoretical results of the photodissociation of NO3 and are consistent with older thermal bimolecular kinetics measurements.

  11. Phosphorylation of adenosine in renal brush-border membrane vesicles by an exchange reaction catalysed by adenosine kinase.

    PubMed Central

    Sayós, J; Solsona, C; Mallol, J; Lluis, C; Franco, R

    1994-01-01

    Uptake of [3H]adenosine in brush-border membrane (BBM) vesicles from either rat or pig kidney leads to an accumulation of intravesicular [3H]AMP. The lack of significant levels of ATP and the presence of AMP in BBM indicated that a phosphotransfer between [3H]adenosine and AMP occurs. The phosphotransfer activity is inhibited by iodotubercidin, which suggests that it is performed by adenosine kinase acting in an ATP-independent manner. The existence of a similar phosphotransferase activity was demonstrated in membrane-free extracts from pig kidney. From the compounds tested it was shown that a variety of mononucleotides could act as phosphate donors. The results suggest that phosphotransfer reactions may be physiologically relevant in kidney. PMID:8110185

  12. Full-dimensional global potential energy surfaces describing abstraction and exchange for the H + H2S reaction.

    PubMed

    Lu, Dandan; Li, Jun

    2016-07-01

    For the H + H2S system, ∼34 000 data points are sampled over a large configuration space including both abstraction and exchange channels, and calculated at the level of explicitly correlated unrestricted coupled cluster method with singles, doubles, and perturbative triples excitations with the augmented correlation-consistent polarized triple zeta basis set (UCCSD(T)-F12a/aug-cc-pVTZ). The data set was fit using the newly proposed permutation invariant polynomial-neural network (PIP-NN) method with three different vectors as the input: two redundant sets of PIPs, one with the maximum order four (PES-I) and one with the maximum order three (PES-II), and nine non-redundant PIPs (PES-III). All these PESs show small fitting errors and essentially the same performance in representing the title system. Various kinetics and dynamical properties are calculated using the tunneling corrected transition state theory and quasi-classical trajectory, and compared with available experimental results. At a collision energy of 10 kcal/mol, both the H2 and SH products are found to be internally cold, with ∼20% of H2 at its first vibrational excited state, while SH is essentially a spectator. The angular distributions of the products are mainly in backward with considerable contributions from sideway direction. In addition, analytical partial derivatives of any PIP-NN PES with respect to the coordinates of atoms are derived by making use of the monomial symmetrization algorithm [Z. Xie and J. M. Bowman, J. Chem. Theory Comput. 6, 26-34 (2010)]. It can not only accelerate the evaluation of the derivatives, but also improve the energy convergence significantly. PMID:27394104

  13. Full-dimensional global potential energy surfaces describing abstraction and exchange for the H + H2S reaction

    NASA Astrophysics Data System (ADS)

    Lu, Dandan; Li, Jun

    2016-07-01

    For the H + H2S system, ˜34 000 data points are sampled over a large configuration space including both abstraction and exchange channels, and calculated at the level of explicitly correlated unrestricted coupled cluster method with singles, doubles, and perturbative triples excitations with the augmented correlation-consistent polarized triple zeta basis set (UCCSD(T)-F12a/aug-cc-pVTZ). The data set was fit using the newly proposed permutation invariant polynomial-neural network (PIP-NN) method with three different vectors as the input: two redundant sets of PIPs, one with the maximum order four (PES-I) and one with the maximum order three (PES-II), and nine non-redundant PIPs (PES-III). All these PESs show small fitting errors and essentially the same performance in representing the title system. Various kinetics and dynamical properties are calculated using the tunneling corrected transition state theory and quasi-classical trajectory, and compared with available experimental results. At a collision energy of 10 kcal/mol, both the H2 and SH products are found to be internally cold, with ˜20% of H2 at its first vibrational excited state, while SH is essentially a spectator. The angular distributions of the products are mainly in backward with considerable contributions from sideway direction. In addition, analytical partial derivatives of any PIP-NN PES with respect to the coordinates of atoms are derived by making use of the monomial symmetrization algorithm [Z. Xie and J. M. Bowman, J. Chem. Theory Comput. 6, 26-34 (2010)]. It can not only accelerate the evaluation of the derivatives, but also improve the energy convergence significantly.

  14. Development of a High-Speed Real-Time Polymerase Chain Reaction System Using a Circulating Water-Based Rapid Heat-Exchange

    NASA Astrophysics Data System (ADS)

    Terazono, Hideyuki; Takei, Hiroyuki; Hattori, Akihiro; Yasuda, Kenji

    2010-06-01

    Polymerase chain reaction (PCR) is a powerful technique to detect microorganisms, viruses, or cells by amplifying a single copy or a few copies of a fragment of a particular DNA sequence. To reduce acquisition time, it is necessary to decrease the temperature transition time between denaturation and extension. We have developed a simple rapid real-time microlitter-sample droplet PCR system accomplished by the rapid liquid-based heat-exchange of sample droplets by quick switching of two circulating hot waters of denaturation and extension, a microlitter-sized droplet and a thin-film aluminum chip. Using this system, rapid PCR amplification of a set of droplets lined up on an aluminum chip was conducted successfully as shown by the increase in fluorescence intensity, and was accomplished within 3.5 min in 40 cycles of 1 s denaturation and 3 s extension reaction, which is one magnitude faster than conventional fast PCR systems. This method allows the rapid detection of DNA fragments and has a possibility for measuring multiple samples simultaneously in a miniaturized microfluidic chip.

  15. A facile route to violet- to orange-emitting CdxZn1-xSe alloy nanocrystals via cation exchange reaction

    NASA Astrophysics Data System (ADS)

    Zhong, Xinhua; Feng, Yaoyu; Zhang, Yuliang; Gu, Zhenyu; Zou, Lei

    2007-09-01

    The most advanced CdSe-based binary semiconductor system does not work well for emission in the short wavelength spectral region from 420 to 500 nm, which is of special interest for the preparation of nanocrystal-based blue LEDs and white light generation. CdxZn1-xSe alloy nanocrystals are proven to be an attractive alternative as their emission color can be tuned from the UV spectral region (ZnSe) to the red region (CdSe) by changing the composition of the Zn/Cd ratio in the alloy. Herein we report a facile and 'green' alloying approach for the preparation of highly luminescent CdxZn1-xSe nanocrystals via cation exchange reaction of the pre-prepared ZnSe nanocrystals with Cd2+ at intermediate temperatures. Through this new synthetic strategy, high-quality alloy QDs with different desired emission wavelengths or colors (ranging from 370 to 600 nm) can be made reproducibly and precisely by varying the predetermined amounts of the reaction precursors.

  16. Metal-Carbon Hybrid Electrocatalysts Derived from Ion-Exchange Resin Containing Heavy Metals for Efficient Hydrogen Evolution Reaction.

    PubMed

    Zhou, Yucheng; Zhou, Weijia; Hou, Dongman; Li, Guoqiang; Wan, Jinquan; Feng, Chunhua; Tang, Zhenghua; Chen, Shaowei

    2016-05-01

    Transition metal-carbon hybrids have been proposed as efficient electrocatalysts for hydrogen evolution reaction (HER) in acidic media. Herein, effective HER electrocatalysts based on metal-carbon composites are prepared by controlled pyrolysis of resin containing a variety of heavy metals. For the first time, Cr2 O3 nanoparticles of 3-6 nm in diameter homogeneously dispersed in the resulting porous carbon framework (Cr-C hybrid) is synthesized as efficient HER electrocatalyst. Electrochemical measurements show that Cr-C hybrids display a high HER activity with an onset potential of -49 mV (vs reversible hydrogen electrode), a Tafel slope of 90 mV dec(-1) , a large catalytic current density of 10 mA cm(-2) at -123 mV, and the prominent electrochemical durability. X-ray photoelectron spectroscopic measurements confirm that electron transfer occurs from Cr2 O3 into carbon, which is consistent with the reported metal@carbon systems. The obtained correlation between metals and HER activities may be exploited as a rational guideline in the design and engineering of HER electrocatalysts. PMID:27061759

  17. Weathering reactions and hyporheic exchange controls on stream water chemistry in a glacial meltwater stream in the McMurdo Dry Valleys

    USGS Publications Warehouse

    Gooseff, M.N.; McKnight, Diane M.; Lyons, W.B.; Blum, A.E.

    2002-01-01

    In the McMurdo Dry Valleys, Antarctica, dilute glacial meltwater flows down well-established streambeds to closed basin lakes during the austral summer. During the 6-12 week flow season, a hyporheic zone develops in the saturated sediment adjacent to the streams. Longer Dry Valley streams have higher concentrations of major ions than shorter streams. The longitudinal increases in Si and K suggest that primary weathering contributes to the downstream solute increase. The hypothesis that weathering reactions in the hyporheic zone control stream chemistry was tested by modeling the downstream increase in solute concentration in von Guerard Stream in Taylor Valley. The average rates of solute supplied from these sources over the 5.2 km length of the stream were 6.1 ?? 10-9 mol Si L-1 m-1 and 3.7 ?? 10-9 mol K L-1 m-1, yielding annual dissolved Si loads of 0.02-1.30 tool Si m-2 of watershed land surface. Silicate minerals in streambed sediment were analyzed to determine the representative surface area of minerals in the hyporheic zone subject to primary weathering. Two strategies were evaluated to compute sediment surface area normalized weathering rates. The first applies a best linear fit to synoptic data in order to calculate a constant downstream solute concentration gradient, dC/dx (constant weathering rate contribution, CRC method); the second uses a transient storage model to simulate dC/dx, representing both hyporheic exchange and chemical weathering (hydrologic exchange, HE method). Geometric surface area normalized dissolution rates of the silicate minerals in the stream ranged from 0.6 ?? 10-12 mol Si m-2 s-1 to 4.5 ?? 10-12 mol Si m-2 s-1 and 0.4 ?? 10-12 mol K m-2 s-1 to 1.9 ?? 10-12 mol K m-2 s-1. These values are an order of magnitude lower than geometric surface area normalized weathering rates determined in laboratory studies and are an order of magnitude greater than geometric surface area normalized weathering rates determined in a warmer, wetter

  18. Weathering reactions and hyporheic exchange controls on stream water chemistry in a glacial meltwater stream in the McMurdo Dry Valleys

    NASA Astrophysics Data System (ADS)

    Gooseff, Michael N.; McKnight, Diane M.; Lyons, W. Berry; Blum, Alex E.

    2002-12-01

    In the McMurdo Dry Valleys, Antarctica, dilute glacial meltwater flows down well-established streambeds to closed basin lakes during the austral summer. During the 6-12 week flow season, a hyporheic zone develops in the saturated sediment adjacent to the streams. Longer Dry Valley streams have higher concentrations of major ions than shorter streams. The longitudinal increases in Si and K suggest that primary weathering contributes to the downstream solute increase. The hypothesis that weathering reactions in the hyporheic zone control stream chemistry was tested by modeling the downstream increase in solute concentration in von Guerard Stream in Taylor Valley. The average rates of solute supplied from these sources over the 5.2 km length of the stream were 6.1 × 10-9 mol Si L-1 m-1 and 3.7 × 10-9 mol K L-1 m-1, yielding annual dissolved Si loads of 0.02-1.30 mol Si m-2 of watershed land surface. Silicate minerals in streambed sediment were analyzed to determine the representative surface area of minerals in the hyporheic zone subject to primary weathering. Two strategies were evaluated to compute sediment surface area normalized weathering rates. The first applies a best linear fit to synoptic data in order to calculate a constant downstream solute concentration gradient, dC/dx (constant weathering rate contribution, CRC method); the second uses a transient storage model to simulate dC/dx, representing both hyporheic exchange and chemical weathering (hydrologic exchange, HE method). Geometric surface area normalized dissolution rates of the silicate minerals in the stream ranged from 0.6 × 10-12 mol Si m-2 s-1 to 4.5 × 10-12 mol Si m-2 s-1 and 0.4 × 10-12 mol K m-2 s-1 to 1.9 × 10-12 mol K m-2 s-1. These values are an order of magnitude lower than geometric surface area normalized weathering rates determined in laboratory studies and are an order of magnitude greater than geometric surface area normalized weathering rates determined in a warmer, wetter

  19. X-ray Lithography on Perovskite Nanocrystals Films: From Patterning with Anion-Exchange Reactions to Enhanced Stability in Air and Water

    PubMed Central

    2015-01-01

    Films of colloidal CsPbX3 (X = I, Br or Cl) nanocrystals, prepared by solution drop-casting or spin-coating on a silicon substrate, were exposed to a low flux of X-rays from an X-ray photoelectron spectrometer source, causing intermolecular C=C bonding of the organic ligands that coat the surface of the nanocrystals. This transformation of the ligand shell resulted in a greater stability of the film, which translated into the following features: (i) Insolubility of the exposed regions in organic solvents which caused instead complete dissolution of the unexposed regions. This enabled the fabrication of stable and strongly fluorescent patterns over millimeter scale areas. (ii) Inhibition of the irradiated regions toward halide anion exchange reactions, when the films were exposed either to halide anions in solution or to hydrohalic vapors. This feature was exploited to create patterned regions of different CsPbIxBryClz compositions, starting from a film with homogeneous CsPbX3 composition. (iii) Resistance of the films to degradation caused by exposure to air and moisture, which represents one of the major drawbacks for the integration of these materials in devices. (iv) Stability of the film in water and biological buffer, which can open interesting perspectives for applications of halide perovskite nanocrystals in aqueous environments. PMID:26617344

  20. Missing-Mass Spectroscopy of the 4-Neutron System by Exothermic Double-Charge Exchange Reaction 4He(8He,8Be)4n

    NASA Astrophysics Data System (ADS)

    Kisamori, Keiichi; Shimoura, Susumu; Miya, Hiroyuki; Assie, Marlene; Baba, Hidetada; Baba, Tatsuo; Beaumel, Didier; Dozono, Masanori; Fujii, Toshihiko; Fukuda, Naoki; Go, Shintaro; Hammache, Fariouz; Ideguchi, Eiji; Inabe, Naohiro; Itoh, Masatoshi; Kameda, Daisuke; Kawase, Shoichiro; Kawabata, Takahiro; Kobayashi, Motoki; Kondo, Yosuke; Kubo, Toshiyuki; Kubota, Yuki; Kurata-Nishimura, Mizuki; Lee, CheongSoo; Maeda, Yukie; Matsubara, Hiroaki; Michimasa, Shin'ichiro; Miki, Kenjiro; Nishi, Takahiro; Noji, Shumpei; Ota, Shinsuke; Sakaguchi, Satoshi; Sakai, Hideyuki; Sasamoto, Yoshiko; Sasano, Masaki; Sato, Hiromi; Shimizu, Yohei; Stolz, Andreas; Suzuki, Hiroshi; Takaki, Motonobu; Takeda, Hiroyuki; Takeuchi, Satoshi; Tamii, Atsushi; Tang, Leung; Tokieda, Hiroshi; Tsumura, Miho; Uesaka, Tomohiro; Yako, Kentaro; Yanagisawa, Yoshiyuki; Yokoyama, Rin

    A possible existence of the tetra-neutron system as a resonance state is still an open and fascinating question, while theoretical papers using ab-initio calculation suggests that the bound tetra-neutron does not exist. We have performed a missing-mass spectroscopy of the 4n system via the exothermic double-charge exchange reaction 4He(8He,8Be)4n. The experiment was carried out at the RIBF at RIKEN using the SHARAQ spectrometer. Since the secondary beam, 8He at 190 A MeV, has a large internal energy, it is possible to produce the 4n system with small momentum transfers of less than 20 MeV/c. In the present analysis, a new analytical framework to treat multi-particles under high beam rate condition (2 MHz) was developed for good statistics. At the SHARAQ spectrometer, 8Be can be identified by measuring the invariant mass of the coincident two alpha particles with a good signal-to-noise ratio. About several tens of candidate events are obtained above the 4n threshold.

  1. A review of the stability and durability of non-precious metal catalysts for the oxygen reduction reaction in proton exchange membrane fuel cells

    NASA Astrophysics Data System (ADS)

    Banham, Dustin; Ye, Siyu; Pei, Katie; Ozaki, Jun-ichi; Kishimoto, Takeaki; Imashiro, Yasuo

    2015-07-01

    A major hurdle to the widespread commercialization of proton exchange membrane fuel cells (PEMFCs) is the high loading of noble metal (Pt/Pt-alloy) catalyst at the cathode, which is necessary to facilitate the inherently sluggish oxygen reduction reaction (ORR). To eliminate the use of Pt/Pt-alloy catalysts at the cathode of PEMFCs and thus significantly reduce the cost, extensive research on non-precious metal catalysts (NPMCs) has been carried out over the past decade. Major advances in improving the ORR activity of NPMCs, particularly Fe- and Co-based NPMCs, have elevated these materials to a level at which they can start to be considered as potential alternatives to Pt/Pt-alloy catalysts. Unfortunately, the stability (performance loss following galvanostatic experiments) of these materials is currently unacceptably low and the durability (performance loss following voltage cycling) remains uncertain. The three primary mechanisms of instability are: (a) Leaching of the metal site, (b) Oxidative attack by H2O2, and (c) Protonation followed by possible anion adsorption of the active site. While (a) has largely been solved, further work is required to understand and prevent losses from (b) and/or (c). Thus, this review is focused on historical progress in (and possible future strategies for) improving the stability/durability of NPMCs.

  2. Competing Noncovalent Host-guest Interactions and H/D Exchange: Reactions of Benzyloxycarbonyl-Proline Glycine Dipeptide Variants with ND3

    NASA Astrophysics Data System (ADS)

    Miladi, Mahsan; Olaitan, Abayomi D.; Zekavat, Behrooz; Solouki, Touradj

    2015-11-01

    A combination of density functional theory calculations, hydrogen/deuterium exchange (HDX) reactions, ion mobility-mass spectrometry, and isotope labeling tandem mass spectrometry was used to study gas-phase "host-guest" type interactions of a benzyloxycarbonyl (Z)-capped proline (P) glycine (G) model dipeptide (i.e., Z-PG) and its various structural analogues with ND3. It is shown that in a solvent-free environment, structural differences between protonated and alkali metal ion (Na+, K+, or Cs+)-complexed species of Z-PG affect ND3 adduct formation. Specifically, [Z-PG + H]+ and [Z-PG-OCH3 + H]+ formed gas-phase ND3 adducts ([Z-PG (or Z-PG-OCH3) + H + ND3]+) but no ND3 adducts were observed for [Z-PG + alkali metal]+ or [Z-PG + H - CO2]+. Experimentally measured and theoretically calculated collision cross sections (CCSs) of protonated and alkali metal ion-complexed Z-PG species showed similar trends that agreed with the observed structural differences from molecular modeling results. Moreover, results from theoretical ND3 affinity calculations were consistent with experimental HDX observations, indicating a more stable ND3 adduct for [Z-PG + H]+ compared to [Z-PG + alkali metal]+ species. Molecular modeling and experimental MS results for [Z-PG + H]+ and [Z-PG + alkali metal]+ suggest that optimized cation-π and hydrogen bonding interactions of carbonyl groups in final products are important for ND3 adduct formation.

  3. Gram-level synthesis of core-shell structured catalysts for the oxygen reduction reaction in proton exchange membrane fuel cells

    NASA Astrophysics Data System (ADS)

    Luo, Mingchuan; Wei, Lingli; Wang, Fanghui; Han, Kefei; Zhu, Hong

    2014-12-01

    Over the past decade, Pt based core-shell structured alloys have been studied extensively as oxygen reduction reaction (ORR) catalysts for proton exchange membrane fuel cells (PEMFCs) because of their distinctive electrochemical performance and low Pt loading. In this paper, a facile route based on microwave-assisted polyol method and chemical dealloying process is proposed to synthesize carbon supported core-shell structured nanoparticles (NPs) in gram-level for ORR electrocatalysis in PEMFCs. The obtained samples are characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), inductively coupled plasma atomic emission spectroscopy (ICP-AES), and X-ray photoelectron spectroscopy (XPS). These physical characterization indicate that the final synthesized NPs are highly dispersed on the carbon support, and in a core-shell structure with CuPt alloy as the core and Pt as the shell. Electrochemical measurements, conducted by cyclic voltammetry (CV) and rotating disk electrode (RDE) tests, show the core-shell structured catalyst exhibit a 3× increase in mass activity and a 2× increase in specific activity over the commercial Pt/C catalyst, respectively. These results demonstrate that this route can be a reliable way to synthesize low-Pt catalyst in large-scale for PEMFCs.

  4. Real-time monitoring of in situ gas-phase H/D exchange reactions of cations by atmospheric pressure helium plasma ionization mass spectrometry (HePI-MS).

    PubMed

    Attygalle, Athula B; Gangam, Rekha; Pavlov, Julius

    2014-01-01

    An enclosed atmospheric-pressure helium-plasma ionization (HePI-MS) source avoids, or minimizes, undesired back-exchange reactions usually encountered during deuterium incorporation experiments under ambient-pressure open-source conditions. A simple adaptation of an ESI source provides an economical way of conducting gas phase hydrogen/deuterium (H/D) exchange reactions (HDX) in real time without the need for complicated hardware modifications. For example, the spectrum of [(2)H8]toluene recorded under exposed ambient conditions showed the base peak at m/z 96 due to fast leaching of ring hydrogens because of interactions with H2O vapor present in the open source. Such D/H exchanges are rapidly reversed if the deuterium-depleted [(2)H8]toluene is exposed to D2O vapor. In addition to the enumeration of labile protons, our procedure enables the identification of protonation sites in molecules unambiguously, by the number of H/D exchanges observed in real time. For example, molecules such as tetrahydrofuran and pyridine protonate at the heteroatom and consequently undergo only one H/D exchange, whereas ethylbenzene, which protonates at a ring position of the aromatic ring, undergoes six H/D exchanges. In addition, carbocations generated in situ by in-source fragmentation of precursor protonated species, such as benzyl alcohol, do not undergo any rapid H/D exchanges. Because radical cations, second-generation cations (ions formed by losing a small molecule from a precursor ion), or those formed by hydride abstraction do not undergo rapid H/D exchanges, our technique provides a way to distinguish these ions from protonated molecules. PMID:24325360

  5. Active microchannel heat exchanger

    DOEpatents

    Tonkovich, Anna Lee Y [Pasco, WA; Roberts, Gary L [West Richland, WA; Call, Charles J [Pasco, WA; Wegeng, Robert S [Richland, WA; Wang, Yong [Richland, WA

    2001-01-01

    The present invention is an active microchannel heat exchanger with an active heat source and with microchannel architecture. The microchannel heat exchanger has (a) an exothermic reaction chamber; (b) an exhaust chamber; and (c) a heat exchanger chamber in thermal contact with the exhaust chamber, wherein (d) heat from the exothermic reaction chamber is convected by an exothermic reaction exhaust through the exhaust chamber and by conduction through a containment wall to the working fluid in the heat exchanger chamber thereby raising a temperature of the working fluid. The invention is particularly useful as a liquid fuel vaporizer and/or a steam generator for fuel cell power systems, and as a heat source for sustaining endothermic chemical reactions and initiating exothermic reactions.

  6. Heterogeneous Electrocatalyst of Palladium-Cobalt-Phosphorus on Carbon Support for Oxygen Reduction Reaction in High Temperature Proton Exchange Membrane Fuel Cells.

    PubMed

    You, Dae Jong; Pak, Chanho; Jin, Seon-Ah; Lee, Kang Hee; Kwon, Kyungjung; Choi, Kyoung Hwan; Heo, Pil Won; Jang, Hongchul; Kim, Jun Young; Kim, Ji Man

    2016-05-01

    Palladium-cobalt-phosphorus (PdCoP) catalysts supported on carbon (Ketjen Black) were investigated as a cathode catalyst for oxygen reduction reaction (ORR) in high temperature proton exchange membrane fuel cells (HT-PEMFCs). The PdCoP catalyst was synthesized via a modified polyol process in teflon-sealed reactor by microwave-heating. From X-ray diffraction and transmission electron microscopic analysis, the PdCoP catalyst exhibits a face-centered cubic structure, similar to palladium (Pd), which is attributed to form a good solid solution of Co atoms and P atoms in the Pd lattice. The PdCoP nanoparticles with average diameter of 2.3 nm were uniformly distributed on the carbon support. The electrochemical surface area (ECSA) and ORR activity of PdP, PdCo and PdCoP catalysts were measured using a rotating disk electrode technique with cyclic voltammetry and the linear sweep method. The PdCoP catalysts showed the highest performances for ECSA and ORR, which might be attributed both to formation of small nanoparticle by phosphorus atom and to change in lattice constant of Pd by cobalt atom. Furthermore, The HT-PEMFCs single cell performance employing PdCoP catalyst exhibited an enhanced cell performance compared to a single cell using the PdP and PdCo catalysts. This result indicates the importance of electric and geometric control of Pd alloy nanoparticles that can improve the catalytic activity. This synergistic combination of Co and P with Pd could provide the direction of development of non-Pt catalyst for fuel cell system. PMID:27483757

  7. Competing noncovalent host-guest interactions and H/D exchange: reactions of benzyloxycarbonyl-proline glycine dipeptide variants with ND3.

    PubMed

    Miladi, Mahsan; Olaitan, Abayomi D; Zekavat, Behrooz; Solouki, Touradj

    2015-11-01

    A combination of density functional theory calculations, hydrogen/deuterium exchange (HDX) reactions, ion mobility-mass spectrometry, and isotope labeling tandem mass spectrometry was used to study gas-phase "host-guest" type interactions of a benzyloxycarbonyl (Z)-capped proline (P) glycine (G) model dipeptide (i.e., Z-PG) and its various structural analogues with ND3. It is shown that in a solvent-free environment, structural differences between protonated and alkali metal ion (Na(+), K(+), or Cs(+))-complexed species of Z-PG affect ND3 adduct formation. Specifically, [Z-PG + H](+) and [Z-PG-OCH3 + H](+) formed gas-phase ND3 adducts ([Z-PG (or Z-PG-OCH3) + H + ND3](+)) but no ND3 adducts were observed for [Z-PG + alkali metal](+) or [Z-PG + H - CO2](+). Experimentally measured and theoretically calculated collision cross sections (CCSs) of protonated and alkali metal ion-complexed Z-PG species showed similar trends that agreed with the observed structural differences from molecular modeling results. Moreover, results from theoretical ND3 affinity calculations were consistent with experimental HDX observations, indicating a more stable ND3 adduct for [Z-PG + H](+) compared to [Z-PG + alkali metal](+) species. Molecular modeling and experimental MS results for [Z-PG + H](+) and [Z-PG + alkali metal](+) suggest that optimized cation-π and hydrogen bonding interactions of carbonyl groups in final products are important for ND3 adduct formation. Graphical Abstract ᅟ. PMID:26289383

  8. The purified and reconstituted ornithine/citrulline carrier from rat liver mitochondria: electrical nature and coupling of the exchange reaction with H+ translocation.

    PubMed Central

    Indiveri, C; Tonazzi, A; Stipani, I; Palmieri, F

    1997-01-01

    The mechanism and the electrical nature of ornithine/citrulline exchange has been investigated in proteoliposomes reconstituted with the ornithine/citrulline carrier purified from rat liver mitochondria. The stoichiometry of the exchanging substrates was close to 1:1. The exchange was not affected by inducing electrogenic flux of K+ with valinomycin. In contrast, the pH gradient generated by the K+/H+ exchanger nigericin in the presence of an outwardly directed K+ gradient stimulated the ornithineout/citrullinein exchange, but not the ornithine/ornithine homoexchange. Experiments in which either the internal or the external pH was varied, while keeping constant the pH in the other compartment, indicated that maximal exchange rates are found at pH 6 in the compartment containing citrulline and at pH 8 in the compartment containing ornithine. Changes in fluorescence of the pH indicator pyranine, included inside the proteoliposomes, showed that the exchanges ornithineout/citrullinein and citrullineout/ornithinein are accompanied by translocation of H+ in the same direction as citrulline. It is concluded that the mitochondrial ornithine/citrulline carrier catalyses an electroneutral exchange of ornithine+ for citrulline plus an H+. A reasonable model is one in which ornithine binds to a deprotonated carrier and citrulline to a protonated carrier and both substrate-carrier complexes are neutral. The physiological implications of this transport process are discussed. PMID:9359400

  9. Microfluidic chemical reaction circuits

    DOEpatents

    Lee, Chung-cheng; Sui, Guodong; Elizarov, Arkadij; Kolb, Hartmuth C.; Huang, Jiang; Heath, James R.; Phelps, Michael E.; Quake, Stephen R.; Tseng, Hsian-rong; Wyatt, Paul; Daridon, Antoine

    2012-06-26

    New microfluidic devices, useful for carrying out chemical reactions, are provided. The devices are adapted for on-chip solvent exchange, chemical processes requiring multiple chemical reactions, and rapid concentration of reagents.

  10. Kinetic isotope effect of the (16)O + (36)O2 and (18)O + (32)O2 isotope exchange reactions: Dominant role of reactive resonances revealed by an accurate time-dependent quantum wavepacket study.

    PubMed

    Sun, Zhigang; Yu, Dequan; Xie, Wenbo; Hou, Jiayi; Dawes, Richard; Guo, Hua

    2015-05-01

    The O + O2 isotope exchange reactions play an important role in determining the oxygen isotopic composition of a number of trace gases in the atmosphere, and their temperature dependence and kinetic isotope effects (KIEs) provide important constraints on our understanding of the origin and mechanism of these and other unusual oxygen KIEs important in the atmosphere. This work reports a quantum dynamics study of the title reactions on the newly constructed Dawes-Lolur-Li-Jiang-Guo (DLLJG) potential energy surface (PES). The thermal reaction rate coefficients of both the (18)O + (32)O2 and (16)O + (36)O2 reactions obtained using the DLLJG PES exhibit a clear negative temperature dependence, in sharp contrast with the positive temperature dependence obtained using the earlier modified Siebert-Schinke-Bittererova (mSSB) PES. In addition, the calculated KIE shows an improved agreement with the experiment. These results strongly support the absence of the "reef" structure in the entrance/exit channels of the DLLJG PES, which is present in the mSSB PES. The quantum dynamics results on both PESs attribute the marked KIE to strong near-threshold reactive resonances, presumably stemming from the mass differences and/or zero point energy difference between the diatomic reactant and product. The accurate characterization of the reactivity for these near-thermoneutral reactions immediately above the reaction threshold is important for correct characterization of the thermal reaction rate coefficients. PMID:25956105

  11. Kinetic isotope effect of the 16O + 36O2 and 18O + 32O2 isotope exchange reactions: Dominant role of reactive resonances revealed by an accurate time-dependent quantum wavepacket study

    NASA Astrophysics Data System (ADS)

    Sun, Zhigang; Yu, Dequan; Xie, Wenbo; Hou, Jiayi; Dawes, Richard; Guo, Hua

    2015-05-01

    The O + O2 isotope exchange reactions play an important role in determining the oxygen isotopic composition of a number of trace gases in the atmosphere, and their temperature dependence and kinetic isotope effects (KIEs) provide important constraints on our understanding of the origin and mechanism of these and other unusual oxygen KIEs important in the atmosphere. This work reports a quantum dynamics study of the title reactions on the newly constructed Dawes-Lolur-Li-Jiang-Guo (DLLJG) potential energy surface (PES). The thermal reaction rate coefficients of both the 18O + 32O2 and 16O + 36O2 reactions obtained using the DLLJG PES exhibit a clear negative temperature dependence, in sharp contrast with the positive temperature dependence obtained using the earlier modified Siebert-Schinke-Bittererova (mSSB) PES. In addition, the calculated KIE shows an improved agreement with the experiment. These results strongly support the absence of the "reef" structure in the entrance/exit channels of the DLLJG PES, which is present in the mSSB PES. The quantum dynamics results on both PESs attribute the marked KIE to strong near-threshold reactive resonances, presumably stemming from the mass differences and/or zero point energy difference between the diatomic reactant and product. The accurate characterization of the reactivity for these near-thermoneutral reactions immediately above the reaction threshold is important for correct characterization of the thermal reaction rate coefficients.

  12. Nuclear Reaction Data Centers

    SciTech Connect

    McLane, V.; Nordborg, C.; Lemmel, H.D.; Manokhin, V.N.

    1988-01-01

    The cooperating Nuclear Reaction Data Centers are involved in the compilation and exchange of nuclear reaction data for incident neutrons, charged particles and photons. Individual centers may also have services in other areas, e.g., evaluated data, nuclear structure and decay data, reactor physics, nuclear safety; some of this information may also be exchanged between interested centers. 20 refs., 1 tab.

  13. Investigation of hydrogen isotope exchange reaction rate in mixed gas (H{sub 2} and D{sub 2}) at pressure up to 200 MPa using Raman spectroscopy

    SciTech Connect

    Tikhonov, V.V.; Yukhimchuk, A.A.; Musyayev, R.K.; Gurkin, A.I.

    2015-03-15

    Raman spectroscopy is a relevant method for obtaining objective data on isotopic exchange rate in a gaseous mix of hydrogen isotopes, since it allows one to determine a gaseous mix composition in real time without sampling. We have developed a high-pressure fiber-optic probe to be used for obtaining protium Raman spectra under pressures up to 400 MPa and we have recorded spectral line broadening induced by molecule collisions starting from ∼ 40 MPa. Using this fiber-optic probe we have performed experiments to study isotopic exchange kinetics in a gaseous mix of hydrogen isotopes (protium-deuterium) at pressures up to 200 MPa. Preliminary results show that the dependence of the average isotopic exchange rate related to pressure take unexpected values at the very beginning of the time evolution. More work is required to understand this inconsistency.

  14. Calculation of the cross section for the d(e,e') reaction near the threshold with inclusion of meson exchange currents

    SciTech Connect

    Korchin, A.Y.; Shebeko, A.V.

    1984-01-01

    The dependence of the cross section near the deuteron electrodisintegration threshold on the choice of the model for the NN interaction and for the form factors entering into the meson exchange current operator is studied. The results of the calculations are compared with new experimental data in a broad momentum-transfer range.

  15. Nucleophilic reactions at a vinylic center. XVI. Investigation of the nucleophilic exchange of fluorine in. beta. -fluoroacrylonitriles by the MINDO/3 method

    SciTech Connect

    Shainyan, B.A.

    1986-01-10

    The potential energy surfaces of the reactions of F/sup -/ with cis- and trans-..beta..-fluoroacrylonitriles were calculated by the MINDO/3 method. It was shown that three reaction paths can be realized in the system, i.e., attack by the nucleophile at the ..beta..-carbon atom, the elimination of a proton from the ..cap alpha.. position, and the elimination of a proton from the ..beta.. position. All three reaction paths are exothermic in the gas phase, and the elimination of the proton from the ..cap alpha.. position is 70 kJ/mole more favorable than from the ..beta.. position. Allowance for the effect of the medium in terms of an unconcerted solvation model modes not lead to the appearance of an activation barrier, in contrast to the reactions of anions with ethylene.

  16. Oxidation of CO by N/sub 2/O between 1076 and 1228 K: determination of the rate constant of the exchange reaction

    SciTech Connect

    Loirat, H.; Caralp, F.; Destriau, M.; Lesclaux, R.

    1987-12-17

    New measurements of the rate constant of the direct reaction of CO with N/sub 2/O are reported with the principal purpose of removing some of the remaining discrepancies on its value. Experiments were performed at lower temperatures (1076-1228 K) and lower pressure (approx. 15 Torr) than those prevailing in most of previous works, by using a static reactor. It is shown that, under these experimental conditions, the reaction proceeds essentially according to the direct reaction CO + N/sub 2/O ..-->.. CO/sub 2/ + N/sub 2/ (1). The previously proposed wet mechanism is not significant under our experimental conditions. It has to be taken into account, however, to describe the observed production and consumption of molecular oxygen. The Arrhenius expression derived from these experiments is k/sub 1/ = 10/sup 14.4 +/- 0.3 exp(-(46 +- 2) kcal mol/sup -1/RT) cm/sup 3/ mol/sup -1/ s/sup -1/. A detailed analysis of the results shows that the uncertainties in side reactions do not greatly influence the value of k/sub 1/. A critical discussion of the data reported in the literature is presented. In spite of remaining uncertainties in the reaction mechanism, the present results, obtained in a low-temperature range, show that the low activation energy values of reaction 1, reported in several works performed at higher temperatures, are highly unlikely

  17. An Easy Student Synthesis of a Substituted 1,3-Dioxane by Use of an Ion-Exchange Resin as Catalyst: Clean Illustration of the Prins Reaction.

    ERIC Educational Resources Information Center

    Delmas, Michael; And Others

    1982-01-01

    Background information and experimental procedures are provided for a Prins reaction (condensation of an aldehyde with an alkene). The preparation of 4-(4-hydroxy, 3-methoxy-phenyl) 5-methyl, 1,3-dioxane realized from isoeugenol (natural plant product, commercially available) can be completed in a three-hour laboratory period. (Author/JN)

  18. Signatures of the chiral two-pion exchange electromagnetic currents in the {sup 2}H and {sup 3}He photodisintegration reactions

    SciTech Connect

    RozpePdzik, D.; Golak, J.; Skibinski, R.; Witala, H.; Koelling, S.; Epelbaum, E.; Krebs, H.

    2011-06-15

    The recently derived long-range two-pion exchange (TPE) contributions to the nuclear current operator that appear at next-to-leading order (NLO) of the chiral expansion are used to describe electromagnetic processes. We study their role in the photodisintegration of {sup 2}H and {sup 3}He and compare our predictions with the experimental data. The bound and scattering states are calculated using five different parametrizations of the chiral next-to-next-to-leading order (N{sup 2}LO) nucleon-nucleon (NN) potential, which allows us to estimate the theoretical uncertainty at a given order in the chiral expansion. For some observables the results are very close to the predictions based on the AV18 NN potential and the current operator (partly) consistent with this force. In most cases, the addition of long-range TPE currents improved the description of the experimental data.

  19. A transient exchange of the photosystem II reaction center protein D1:1 with D1:2 during low temperature stress of Synechococcus sp. PCC 7942 in the light lowers the redox potential of QB.

    PubMed

    Sane, P V; Ivanov, Alexander G; Sveshnikov, Dmitry; Huner, Norman P A; Oquist, Gunnar

    2002-09-01

    Upon exposure to low temperature under constant light conditions, the cyanobacterium Synechococcus sp. PCC 7942 exchanges the photosystem II reaction center D1 protein form 1 (D1:1) with D1 protein form 2 (D1:2). This exchange is only transient, and after acclimation to low temperature the cells revert back to D1:1, which is the preferred form in acclimated cells (Campbell, D., Zhou, G., Gustafsson, P., Oquist, G., and Clarke, A. K. (1995) EMBO J. 14, 5457-5466). In the present work we use thermoluminescence to study charge recombination events between the acceptor and donor sides of photosystem II in relation to D1 replacement. The data indicate that in cold-stressed cells exhibiting D1:2, the redox potential of Q(B) becomes lower approaching that of Q(A). This was confirmed by examining the Synechococcus sp. PCC 7942 inactivation mutants R2S2C3 and R2K1, which possess only D1:1 or D1:2, respectively. In contrast, the recombination of Q(A)(-) with the S(2) and S(3) states did not show any change in their redox characteristics upon the shift from D1:1 to D1:2. We suggest that the change in redox properties of Q(B) results in altered charge equilibrium in favor of Q(A). This would significantly increase the probability of Q(A)(-) and P680(+) recombination. The resulting non-radiative energy dissipation within the reaction center of PSII may serve as a highly effective protective mechanism against photodamage upon excessive excitation. The proposed reaction center quenching is an important protective mechanism because antenna and zeaxanthin cycle-dependent quenching are not present in cyanobacteria. We suggest that lowering the redox potential of Q(B) by exchanging D1:1 for D1:2 imparts the increased resistance to high excitation pressure induced by exposure to either low temperature or high light. PMID:12105211

  20. Stereodirectional Origin of anti-Arrhenius Kinetics for a Tetraatomic Hydrogen Exchange Reaction: Born-Oppenheimer Molecular Dynamics for OH + HBr.

    PubMed

    Coutinho, Nayara D; Aquilanti, Vincenzo; Silva, Valter H C; Camargo, Ademir J; Mundim, Kleber C; de Oliveira, Heibbe C B

    2016-07-14

    Among four-atom processes, the reaction OH + HBr → H2O + Br is one of the most studied experimentally: its kinetics has manifested an unusual anti-Arrhenius behavior, namely, a marked decrease of the rate constant as the temperature increases, which has intrigued theoreticians for a long time. Recently, salient features of the potential energy surface have been characterized and most kinetic aspects can be considered as satisfactorily reproduced by classical trajectory simulations. Motivation of the work reported in this paper is the investigation of the stereodirectional dynamics of this reaction as the prominent reason for the peculiar kinetics: we started in a previous Letter ( J. Phys. Chem. Lett. 2015 , 6 , 1553 - 1558 ) a first-principles Born-Oppenheimer "canonical" molecular dynamics approach. Trajectories are step-by-step generated on a potential energy surface quantum mechanically calculated on-the-fly and are thermostatically equilibrated to correspond to a specific temperature. Here, refinements of the method permitted a major increase of the number of trajectories and the consideration of four temperatures -50, +200, +350, and +500 K, for which the sampling of initial conditions allowed us to characterize the stereodynamical effect. The role is documented of the adjustment of the reactants' mutual orientation to encounter the entrance into the "cone of acceptance" for reactivity. The aperture angle of this cone is dictated by a range of directions of approach compatible with the formation of the specific HOH angle of the product water molecule; and consistently the adjustment is progressively less effective the higher the kinetic energy. Qualitatively, this emerging picture corroborates experiments on this reaction, involving collisions of aligned and oriented molecular beams, and covering a range of energies higher than the thermal ones. The extraction of thermal rate constants from this molecular dynamics approach is discussed and the systematic

  1. The inner-sphere reorganization energies for AH{sub 2} + AH{sub 2}{sup +(-)} (A = Al, Si, P, S) electron self-exchange reactions in electron-transfer processes from ab initio calculations

    SciTech Connect

    Yuxiang Bu; Zhaohua Cao; Zailun Yang

    1995-08-15

    This article presents an application of the accurate calculation scheme proposed recently for the inner-sphere reorganization energies of molecules of the type AH{sub 2} (A = Al, Si, P, and S). A reasonable extension has been made. The inner-sphere reorganization energies for the title thermal electron self-exchange reactions are calculated in terms of ab initio MO self-consistent field method (HFSCF) at different basis-set levels (6-31G**, 6-31 + G**, DZ, and DZP) and the involved parameters are also determined. These calculated results have been calibrated by comparing optimized molecular geometrical parameters and corresponding energy properties with the experimental findings or other theoretical values. An approximation, in which the contribution from the bond length-bond angle to the potential energy surface is neglected, is adopted in constructing the calculation formulas via the function model. Its adequacy is discussed. Agreement among different calculation schemes is analyzed. 32 refs., 2 tabs.

  2. Structure - property relationship of permutite-like amorphous silicates, Nax+2yM3+xSi1-xO2+y(M3+= Al, Mn, Fe, Y), for ion-exchange reactions.

    SciTech Connect

    Pless, Jason D.; Nenoff, Tina Maria; Maxwell, Robert S.; Phillips, Mark L. F.; Axness, Marlene

    2005-03-01

    A series of amorphous silicate materials with the general formula Na{sub x+2y}M{sub x}{sup 3+}Si{sub 1-x}O{sub 2+y}(M{sup 3+} = Al, Mn, Fe, Y) were studied. Samples were synthesized by a precipitation reaction at room temperature. The results indicate that the ion-exchange capacity (IEC) decreases as follows: Al > Fe > Mn > Y. Additionally, the IEC increases with increasing aluminum concentration. Structural studies show that the relative amount of octahedrally coordinated aluminum increases with increasing Al content, as does the total amount of AlO{sub 4} species increases. The data suggest that the IEC value of these amorphous aluminosilicates is dependent on the tetrahedrally coordinated aluminum. Regeneration of the Al-silicate with acetic acid does not decrease the IEC significantly.

  3. Platinum-cobalt catalysts for the oxygen reduction reaction in high temperature proton exchange membrane fuel cells - Long term behavior under ex-situ and in-situ conditions

    NASA Astrophysics Data System (ADS)

    Schenk, Alexander; Grimmer, Christoph; Perchthaler, Markus; Weinberger, Stephan; Pichler, Birgit; Heinzl, Christoph; Scheu, Christina; Mautner, Franz-Andreas; Bitschnau, Brigitte; Hacker, Viktor

    2014-11-01

    Platinum cobalt catalysts (Pt-Co) have attracted much interest as cathode catalysts for proton exchange membrane fuel cells (PEMFCs) due to their high activity toward oxygen reduction reaction (ORR). Many of the reported catalysts show outstanding performance in ex-situ experiments. However, the laborious synthesis protocols of these Pt-Co catalysts disable an efficient and economic production of membrane electrode assemblies (MEAs). We present an economic, flexible and continuous Pt-M/C catalyst preparation method as part of a large scale membrane electrode assembly manufacturing. In comparison, the as-prepared Pt-Co/C based high temperature (HT)-PEM MEA showed an equal performance to a commercially available HT-PEM MEA during 600 h of operation under constant load, although the commercial one had a significantly higher Pt loading at the cathode.

  4. Decay of {sup 6}Be populated in the {sup 6}Li({sup 3}He,{sup 3}H) charge-exchange reaction

    SciTech Connect

    Papka, P.; Nemulodi, F.; Bark, R. A.; Kheswa, N. Y.; Lawrie, E. A.; Lawrie, J. J.; Lieder, E. O.; Lieder, R. M.; Madiba, T. E.; Mullins, S. M.; Newman, R. T.; Shirinda, O.; Singo, T. D.; Alvarez-Rodriguez, R.; Fox, S. P.; Gal, J.; Kalinka, G.; Molnar, J.; Nyako, B. M.; Timar, J.

    2010-05-15

    A complete kinematic measurement of the {sup 6}Li({sup 3}He,{sup 3}H)alphapp reaction is performed at E{sub lab}=50 MeV, to investigate the cluster structure of {sup 6}Be. The energy and angular distributions of the breakup particles, emitted from the ground and first excited states of {sup 6}Be, are compared to three-body resonance and two-body sequential decay calculations. The results indicate a rather pure three-body configuration of the 2{sup +} state of {sup 6}Be but they are not conclusive regarding the decay mode of the 0{sup +} state. No branching ratio between sequential and three-body decay paths could be extracted. Excitations above the 2{sup +} state were populated at E{sub x}=1.67-23 MeV. Decay through {sup 5}Li-p and {sup 2}He-{sup 4}He channels is identified in the continuum of {sup 6}Be, and the reaction mechanism is discussed.

  5. Impact of liquid water on oxygen reaction in cathode catalyst layer of proton exchange membrane fuel cell: A simple and physically sound model

    NASA Astrophysics Data System (ADS)

    Zhang, Xiaoxian; Gao, Yuan

    2016-06-01

    When cells work at high current density, liquid water accumulates in their catalyst layer (CL) and the gaseous oxygen could dissolve into the water and the ionomer film simultaneously; their associated dissolved concentrations in equilibrium with the gaseous oxygen are also different. Based on a CL acquired using tomography, we present new methods in this paper to derive agglomerate models for partly saturated CL by viewing the movement and reaction of the dissolved oxygen in the two liquids (water and ionomer) and the agglomerate as two independent random processes. Oxygen dissolved in the water moves differently from oxygen dissolved in the ionomer, and to make the analysis tractable, we use an average distribution function to describe the average movement of all dissolved oxygen. A formula is proposed to describe this average distribution function, which, in combination with the exponential distribution assumed in the literature for oxygen reaction, leads to a simple yet physically sound agglomerate model. The model has three parameters which can be directly calculated from CL structure rather than by calibration. We explain how to calculate these parameters under different water contents for a given CL structure, and analyse the impact of liquid water on cell performance.

  6. Nanoparticle conversion chemistry: Kirkendall effect, galvanic exchange, and anion exchange

    NASA Astrophysics Data System (ADS)

    Anderson, Bryan D.; Tracy, Joseph B.

    2014-10-01

    Conversion chemistry is a rapidly maturing field, where chemical conversion of template nanoparticles (NPs) into new compositions is often accompanied by morphological changes, such as void formation. The principles and examples of three major classes of conversion chemical reactions are reviewed: the Kirkendall effect for metal NPs, galvanic exchange, and anion exchange, each of which can result in void formation in NPs. These reactions can be used to obtain complex structures that may not be attainable by other methods. During each kind of conversion chemical reaction, NPs undergo distinct chemical and morphological changes, and insights into the mechanisms of these reactions will allow for improved fine control and prediction of the structures of intermediates and products. Conversion of metal NPs into oxides, phosphides, sulphides, and selenides often occurs through the Kirkendall effect, where outward diffusion of metal atoms from the core is faster than inward diffusion of reactive species, resulting in void formation. In galvanic exchange reactions, metal NPs react with noble metal salts, where a redox reaction favours reduction and deposition of the noble metal (alloying) and oxidation and dissolution of the template metal (dealloying). In anion exchange reactions, addition of certain kinds of anions to solutions containing metal compound NPs drives anion exchange, which often results in significant morphological changes due to the large size of anions compared to cations. Conversion chemistry thus allows for the formation of NPs with complex compositions and structures, for which numerous applications are anticipated arising from their novel catalytic, electronic, optical, magnetic, and electrochemical properties.

  7. Cumulative reaction probabilities and transition state properties: A study of the H{sup +}+H{sub 2} and H{sup +}+D{sub 2} proton exchange reactions

    SciTech Connect

    Jambrina, P. G.; Aoiz, F. J.; Eyles, C. J.; Herrero, V. J.; Saez Rabanos, V.

    2009-05-14

    Cumulative reaction probabilities (CRPs) have been calculated by accurate (converged, close coupling) quantum mechanical (QM), quasiclassical trajectory (QCT), and statistical QCT (SQCT) methods for the H{sup +}+H{sub 2} and H{sup +}+D{sub 2} reactions at collision energies up to 1.2 eV and total angular momentum J=0-4. A marked resonance structure is found in the QM CRP, most especially for the H{sub 3}{sup +} system and J=0. When the CRPs are resolved in their ortho and para contributions, a clear steplike structure is found associated with the opening of internal states of reactants and products. The comparison of the QCT results with those of the other methods evinces the occurrence of two transition states, one at the entrance and one at the exit. At low J values, except for the quantal resonance structure and the lack of quantization in the product channel, the agreement between QM and QCT is very good. The SQCT model, that reflects the steplike structure associated with the opening of initial and final states accurately, clearly tends to overestimate the value of the CRP as the collision energy increases. This effect seems more marked for the H{sup +}+D{sub 2} isotopic variant. For sufficiently high J values, the growth of the centrifugal barrier leads to an increase in the threshold of the CRP. At these high J values the discrepancy between SQCT and QCT becomes larger and is magnified with growing collision energy. The total CRPs calculated with the QCT and SQCT methods allowed the determination of the rate constant for the H{sup +}+D{sub 2} reaction. It was found that the rate, in agreement with experiment, decreases with temperature as expected for an endothermic reaction. In the range of temperatures between 200 and 500 K the differences between SQCT and QCT rate results are relatively minor. Although exact QM calculations are formidable for an exact determination of the k(T), it can be reliably expected that their value will lie between those given by

  8. High performance fluorine doped (Sn,Ru)O2 oxygen evolution reaction electro-catalysts for proton exchange membrane based water electrolysis

    NASA Astrophysics Data System (ADS)

    Kadakia, Karan; Datta, Moni Kanchan; Velikokhatnyi, Oleg I.; Jampani, Prashanth; Park, Sung Kyoo; Chung, Sung Jae; Kumta, Prashant N.

    2014-01-01

    Identification of electro-catalysts containing non-noble metal or significantly reduced amounts of expensive noble metals (e.g. RuO2) is highly desirable. Development of such a catalyst with comparable electrochemical performance to the standard noble metal oxide for proton exchange membrane (PEM) based water electrolysis would constitute a pioneering breakthrough in hydrogen generation by water electrolysis. In line with these goals, by exploiting a two-pronged theoretical first principles and experimental approach herein we demonstrate that a nano-structured solid solution of SnO2:10 wt% F containing only 20 at.% RuO2 [e.g. (Sn0.80Ru0.20)O2:10F] displays a remarkably similar electrochemical activity and moreover, comparable or even much improved electrochemical stability and durability compared to pure the noble metal counterpart, RuO2. Density functional theory calculations have demonstrated direct dependence of the catalytic activity on the electronic structure peculiarities of the F-doped (Ru,Sn)O2 which corresponds well with the experimental results.

  9. Thiolate exchange in [TmR]ZnSR' complexes and relevance to the mechanisms of thiolate alkylation reactions involving zinc enzymes and proteins.

    PubMed

    Melnick, Jonathan G; Zhu, Guang; Buccella, Daniela; Parkin, Gerard

    2006-05-01

    The zinc and cadmium thiolate complexes [TmBut]MSCH2C(O)N(H)Ph (M = Zn, Cd) may be obtained via treatment of the respective methyl complex [TmBut]MMe with PhN(H)C(O)CH2SH. The molecular structure of [TmBut]ZnSCH2C(O)N(H)Ph has been determined by X-ray diffraction, thereby demonstrating the presence of an intramolecular N-H S hydrogen bond between the amide N-H group and thiolate sulfur atom. [TmBut]ZnSCH2C(O)N(H)Ph mimics the function of the Ada DNA repair protein by undergoing alkylation with MeI to give [TmBut]ZnI and MeSCH2C(O)N(H)Ph. A series of crossover experiments and 1H NMR magnetization transfer studies establish that thiolate exchange between [TmR]ZnSR' derivatives is facile in this system, an observation that supports the previous suggestion that the alkylation of [TmPh]ZnSCH2C(O)N(H)Ph by MeI may proceed via a sequence that involves dissociation of [PhN(H)C(O)CH2S]-. PMID:16516971

  10. Insight into the photoinduced ligand exchange reaction pathway of cis-[Rh2(μ-O2CCH3)2(CH3CN)6]2+ with a DNA model chelate.

    PubMed

    Chifotides, Helen T; Lutterman, Daniel A; Dunbar, Kim R; Turro, Claudia

    2011-12-01

    We previously showed that [Rh(2)(O(2)CCH(3))(2)(CH(3)CN)(6)](2+) binds to dsDNA only upon irradiation with visible light and that photolysis results in a 34-fold enhancement of its cytotoxicity toward Hs-27 human skin fibroblasts, making it potentially useful for photodynamic therapy (PDT). With the goal of gaining further insight on the photoinduced binding of DNA to the complex, we investigated by NMR spectroscopy the mechanism by which 2,2'-bipyridine (bpy), a model for biologically relevant bidentate nitrogen donor ligands, binds to [Rh(2)(O(2)CCH(3))(2)(CH(3)CN)(6)](2+) upon irradiation in D(2)O. The photochemical results are compared to the reactivity in the dark in D(2)O and CD(3)CN. The photolysis of [Rh(2)(O(2)CCH(3))(2)(CH(3)CN)(6)](2+) with equimolar bpy solutions in D(2)O with visible light affords [Rh(2)(O(2)CCH(3))(2)(eq/eq-bpy)(CH(3)CN)(2)(D(2)O(ax))(2)](2+) (eq/eq) with the reaction reaching completion in ~8 h. Only vestiges of eq/eq are observed at the same time in the dark, however, and the reaction is ~20 times slower. Conversely, the dark reaction of [Rh(2)(O(2)CCH(3))(2)(CH(3)CN)(6)](2+) with an equimolar amount of bpy in CD(3)CN affords [Rh(2)(O(2)CCH(3))(2)(η(1)-bpy(ax))(CH(3)CN)(5)](2+) (η(1)-bpy(ax)), which remains present even after 5 days of reaction. The photolysis results in D(2)O are consistent with the exchange of one equiv CH(3)CNeq for solvent, and the resulting species quickly reacting with bpy to generate eq/eq; the initial eq ligand dissociation is assisted by absorption of a photon, thus greatly enhancing the reaction rate. The photolytic reaction of [Rh(2)(O(2)CCH(3))(2)(CH(3)CN)(6)](2+):bpy in a 1:2 ratio in D(2)O affords the eq/eq and (eq/eq)(2) adducts. The observed differences in the reactivity in D(2)O vs CD(3)CN are explained by the relative ease of substitution of eq D(2)O vs CD(3)CN by the incoming bpy molecule. These results clearly highlight the importance of dissociation of an eq CH(3)CN molecule from the dirhodium

  11. Borate Exchanges of Lemna minor L. as Studied with the Help of the Enriched Stable Isotopes and of a (n,α) Nuclear Reaction 1

    PubMed Central

    Thellier, Michel; Duval, Yves; Demarty, Maurice

    1979-01-01

    Despite the lack of a convenient radioisotope of boron, it is possible to measure unidirectional fluxes of borate between cellular systems and their external medium. It was accomplished by using the two purified stable isotopes (10B and 11B), with 10B specifically detected by a (n,α) nuclear reaction. The method was applied to compartmental analysis of borate with intact plants of Lemna minor L. Four compartments were suggested. Three of them apparently correspond to the three classical ones: free space (including easily dissociable borate monoesters), cytoplasm, and vacuole. The fourth one was interpreted as corresponding to very stable borate diesters in the cell walls. The method allows the determination of the borate capacities of the various compartments and of the borate unidirectional fluxes between the different compartments, at borate flux equilibrium. Other physicochemical data (mono and diester mass action constants, turn over numbers) were evaluated. The results are consistent with what is known of pure substances. PMID:16660714

  12. Cyclometalated iridium complexes of bis(aryl) phosphine ligands: catalytic C-H/C-D exchanges and C-C coupling reactions.

    PubMed

    Campos, Jesús; Espada, María F; López-Serrano, Joaquín; Carmona, Ernesto

    2013-06-01

    This work details the synthesis and structural identification of a series of complexes of the (η(5)-C5Me5)Ir(III) unit coordinated to cyclometalated bis(aryl)phosphine ligands, PR'(Ar)2, for R' = Me and Ar = 2,4,6-Me3C6H2, 1b; 2,6-Me2-4-OMe-C6H2, 1c; 2,6-Me2-4-F-C6H2, 1d; R' = Et, Ar = 2,6-Me2C6H3, 1e. Both chloride- and hydride-containing compounds, 2b-2e and 3b-3e, respectively, are described. Reactions of chlorides 2 with NaBArF (BArF = B(3,5-C6H3(CF3)2)4) in the presence of CO form cationic carbonyl complexes, 4(+), with ν(CO) values in the narrow interval 2030-2040 cm(-1), indicating similar π-basicity of the Ir(III) center of these complexes. In the absence of CO, NaBArF forces κ(4)-P,C,C',C″ coordination of the metalated arm (studied for the selected complexes 5b, 5d, and 5e), a binding mode so far encountered only when the phosphine contains two benzylic groups. A base-catalyzed intramolecular, dehydrogenative, C-C coupling reaction converts the κ(4) species 5d and 5e into the corresponding hydrido phosphepine complexes 6d and 6e. Using CD3OD as the source of deuterium, the chlorides 2 undergo deuteration of their 11 benzylic positions whereas hydrides 3 experience only D incorporation into the Ir-H and Ir-CH2 sites. Mechanistic schemes that explain this diversity have come to light thanks to experimental and theoretical DFT studies that are also reported. PMID:23675910

  13. Mesoporous Pt-Co oxygen reduction reaction (ORR) catalysts for low temperature proton exchange membrane fuel cell synthesized by alternating sputtering

    NASA Astrophysics Data System (ADS)

    Sievers, Gustav; Mueller, Steffen; Quade, Antje; Steffen, Florian; Jakubith, Sven; Kruth, Angela; Brueser, Volker

    2014-12-01

    Mesoporous catalysts with enhanced oxygen reduction reaction (ORR) activity for PEM fuel cells are synthesized by alternating sputtering of Pt and Co onto gas diffusion layers with microporous layers. Co is acting as a template for synthesis of a porous Pt nanostructure. For such proposed Pt-Co catalysts the kinetic current in the ORR was found to be increased by a factor of up to 16 and the mass specific current in PEM single cells by a factor of up to 7. Co was found to be deposited at the grain boundary of the Pt layer and dissolves under acidic conditions resulting in a mesoporous Pt catalyst which is advantageous for gas diffusion catalysts. Microstructural and compositional parameters were optimised in order to obtain a high kinetic current and lower onset potential for the ORR. The most favourable Co layer thickness was determined to be 2 nm. The optimal Pt-Co catalyst can be synthesized by continuously varying the Pt layer thickness. The highest Pt mass activity was found at a layer thickness of 30.5 nm. Catalysts were characterised by SEM, EDX, electrochemical half cell and PEM single cell tests.

  14. The Third Dimension of a More O’Ferrall-Jencks Diagram for Hydrogen Atom Transfer in the Isoelectronic Hydrogen Exchange Reactions of (PhX)2H• with X = O, NH, and CH2

    PubMed Central

    Cembran, Alessandro; Provorse, Makenzie R.; Wang, Changwei

    2012-01-01

    A critical element in theoretical characterization of the mechanism of proton-coupled electron transfer (PCET) reactions, including hydrogen atom transfer (HAT), is the formulation of the electron and proton localized diabatic states, based on which a More O’Ferrall-Jencks diagram can be represented to determine the step-wise and concerted nature of the reaction. Although the More O’Ferrall-Jencks diabatic states have often been used empirically to develop theoretical models for PCET reactions, the potential energy surfaces for these states have never been determined directly based on first principles calculations using electronic structure theory. The difficulty is due to a lack of practical method to constrain electron and proton localized diabatic states in wave function or density functional theory calculations. Employing a multistate density functional theory (MSDFT), in which the electron and proton localized diabatic configurations are constructed through block-localization of Kohn-Sham orbitals, we show that distinction between concerted proton-electron transfer (CPET) and HAT, which are not distinguishable experimentally from phenomenological kinetic data, can be made by examining the third dimension of a More O’Ferrall-Jencks diagram that includes both the ground and excited state potential surfaces. In addition, we formulate a pair of effective two-state valence bond models to represent the CPET and HAT mechanisms. We found that the lower energy of the CPET and HAT effective diabatic states at the intersection point can be used as an energetic criterion to distinguish the two mechanisms. In the isoelectronic series of hydrogen exchange reaction in (PhX)2H•, where X = O, NH, and CH2, there is a continuous transition from a CPET mechanism for the phenoxy radical-phenol pair to a HAT process for benzyl radical and toluene, while the reaction between PhNH2 and PhNH• has a mechanism intermediate of CPET and HAT. The electronically nonadiabatic

  15. The Third Dimension of a More O'Ferrall-Jencks Diagram for Hydrogen Atom Transfer in the Isoelectronic Hydrogen Exchange Reactions of (PhX)(2)H(•) with X = O, NH, and CH(2).

    PubMed

    Cembran, Alessandro; Provorse, Makenzie R; Wang, Changwei; Wu, Wei; Gao, Jiali

    2012-11-13

    A critical element in theoretical characterization of the mechanism of proton-coupled electron transfer (PCET) reactions, including hydrogen atom transfer (HAT), is the formulation of the electron and proton localized diabatic states, based on which a More O'Ferrall-Jencks diagram can be represented to determine the step-wise and concerted nature of the reaction. Although the More O'Ferrall-Jencks diabatic states have often been used empirically to develop theoretical models for PCET reactions, the potential energy surfaces for these states have never been determined directly based on first principles calculations using electronic structure theory. The difficulty is due to a lack of practical method to constrain electron and proton localized diabatic states in wave function or density functional theory calculations. Employing a multistate density functional theory (MSDFT), in which the electron and proton localized diabatic configurations are constructed through block-localization of Kohn-Sham orbitals, we show that distinction between concerted proton-electron transfer (CPET) and HAT, which are not distinguishable experimentally from phenomenological kinetic data, can be made by examining the third dimension of a More O'Ferrall-Jencks diagram that includes both the ground and excited state potential surfaces. In addition, we formulate a pair of effective two-state valence bond models to represent the CPET and HAT mechanisms. We found that the lower energy of the CPET and HAT effective diabatic states at the intersection point can be used as an energetic criterion to distinguish the two mechanisms. In the isoelectronic series of hydrogen exchange reaction in (PhX)(2)H(•), where X = O, NH, and CH(2), there is a continuous transition from a CPET mechanism for the phenoxy radical-phenol pair to a HAT process for benzyl radical and toluene, while the reaction between PhNH(2) and PhNH(•) has a mechanism intermediate of CPET and HAT. The electronically nonadiabatic

  16. NEUTRONIC REACTION SYSTEM

    DOEpatents

    Wigner, E.P.

    1963-09-01

    A nuclear reactor system is described for breeding fissionable material, including a heat-exchange tank, a high- and a low-pressure chamber therein, heat- exchange tubes connecting these chambers, a solution of U/sup 233/ in heavy water in a reaction container within the tank, a slurry of thorium dioxide in heavy water in a second container surrounding the first container, an inlet conduit including a pump connecting the low pressure chamber to the reaction container, an outlet conduit connecting the high pressure chamber to the reaction container, and means of removing gaseous fission products released in both chambers. (AEC)

  17. Electron paramagnetic resonance investigation of photosynthetic reaction centers from Rhodobacter sphaeroides R-26 in which Fe2+ was replaced by Cu2+. Determination of hyperfine interactions and exchange and dipole-dipole interactions between Cu2+ and QA-.

    PubMed Central

    Calvo, R; Passeggi, M C; Isaacson, R A; Okamura, M Y; Feher, G

    1990-01-01

    We report electron paramagnetic resonance (EPR) experiments in frozen solutions of unreduced and reduced photosynthetic reaction centers (RCs) from Rhodobacter sphaeroides R-26 in which Fe2+ has been chemically replaced by the isotope 65Cu2+. Samples in which the primary quinone acceptor QA is unreduced (Cu2+QA:RCs) give a powder EPR spectrum typical for Cu2+ having axial symmetry, corresponding to a d(x2 - y2) ground state orbital, with g values g parallel = 2.314 +/- 0.001 and g perpendicular = 2.060 +/- 0.003. The spectrum shows a hyperfine structure for the nuclear spin of copper (65I = 3/2) with A parallel = (-167 +/- 1) x 10(-4) cm-1 and /A perpendicular/ = (16 +/- 2) x 10(-4) cm-1, and hyperfine couplings with three nitrogen ligands. This has been verified in samples containing the naturally occurring 14N isotope (l = 1), and in samples where the nitrogen ligands to copper were replaced by the isotope 15N (l = 1/2). We introduce a model for the electronic structure at the position of the metal ion which reflects the recently determined three-dimensional structure of the RCs of Rb. sphaeroides (Allen, J. P., G. Feher, T. O. Yeates, H. Komiya, and D. C. Rees. 1987. Proc. Natl. Acad. Sci. USA. 84:5730: Allen, J. P., G. Feher, T. O. Yeates, H. Komiya, and D. C. Rees. 1988. Proc. Natl. Acad. Sci. USA, 85:8487) as well as our EPR results. In this model the copper ion is octahedrally coordinated to three nitrogens from histidine residues and to one carboxylate oxygen from a glutamic acid, forming a distorted square in the plane of the d(x2 = y2) ground state orbital. It is also bound to a nitrogen of another histidine and to the other carboxylate oxygen of the same glutamic acid residue, in a direction approximately normal to this plane. The EPR spectrum changes drastically when the quinone acceptor QA is chemically reduced (Cu2+QA-:RCs); the change is due to the exchange and dipole-dipole interactions between the Cu2+ and QA- spins. A model spin Hamiltonian

  18. Test procedure for cation exchange chromatography

    SciTech Connect

    Cooper, T.D.

    1994-08-24

    The purpose of this test plan is to demonstrate the synthesis of inorganic antimonate ion exchangers and compare their performance against the standard organic cation exchangers. Of particular interest is the degradation rate of both inorganic and organic cation exchangers. This degradation rate will be tracked by determining the ion exchange capacity and thermal stability as a function of time, radiation dose, and chemical reaction.

  19. The Dynamics of Multilateral Exchange

    NASA Astrophysics Data System (ADS)

    Hausken, Kjell; Moxnes, John F.

    The article formulates a dynamic mathematical model where arbitrarily many players produce, consume, exchange, loan, and deposit arbitrarily many goods over time to maximize utility. Consuming goods constitutes a benefit, and producing, exporting, and loaning away goods constitute a cost. Utilities are benefits minus costs, which depend on the exchange ratios and bargaining functions. Three-way exchange occurs when one player acquires, through exchange, one good from another player with the sole purpose of using this good to exchange against the desired good from a third player. Such a triple handshake is not merely a set of double handshakes since the player assigns no interest to the first good in his benefit function. Cognitive and organization costs increase dramatically for higher order exchanges. An exchange theory accounting for media of exchange follows from simple generalization of two-way exchange. The examples of r-way exchange are the triangle trade between Africa, the USA, and England in the 17th and 18th centuries, the hypothetical hypercycle involving RNAs as players and enzymes as goods, and reaction-diffusion processes. The emergence of exchange, and the role of trading agents are discussed. We simulate an example where two-way exchange gives zero production and zero utility, while three-way exchange causes considerable production and positive utility. Maximum utility for each player is reached when exchanges of the same order as the number of players in society are allowed. The article merges micro theory and macro theory within the social, natural, and physical sciences.

  20. Structure and Properties of Precursor/Successor Complex and Transition State of the FeCl(2+)/Fe(2+) Electron Self-Exchange Reaction via the Inner-Sphere Pathway.

    PubMed

    Rotzinger, François P

    2015-11-01

    The electron self-exchange reaction FeCl(OH2)5(2+) + Fe(OH2)6(2+) → Fe(OH2)6(2+) + FeCl(OH2)5(2+), proceeding via the inner-sphere pathway, was investigated with quantum chemical methods. Geometry and vibrational frequencies of the precursor/successor complex, (H2O)5Fe(III)ClFe(II)(OH2)5(4+)/(H2O)5Fe(II)ClFe(III)(OH2)5(4+) (P/S), and the transition state, (H2O)5FeClFe(OH2)5(4+⧧) (TS), were computed with the LC-BOP functional and CPCM hydration. Bent and linear structures were computed for the TS and P/S. The electronic coupling matrix element (Hab) and the electronic energies were calculated with multistate extended general multiconfiguration quasi-degenerate second-order perturbation theory (XGMC-QDPT2) and spin-orbit configuration interaction (SO-CI). Since the Fe···Fe distance changes considerably along the electron transfer step, the transformation P → TS → S, equations based on the hypothesis of a fixed donor-acceptor distance cannot be applied. Hence, the rate constant for the electron transfer step (ket) was calculated as described previously (Rotzinger, F. P. Inorg. Chem. 2014, 53, 9923). ket is very fast, ∼9.4 × 10(8)-6.6 × 10(9) s(-1) at 0 °C. The experimental rate constant of the title reaction (k) is much slower and controlled by the formation of the precursor complex. The substitution of a water ligand by FeCl(OH2)5(2+) at Fe(OH2)6(2+) is rate-determining. PMID:26479082

  1. HEAT EXCHANGER

    DOEpatents

    Fox, T.H. III; Richey, T. Jr.; Winders, G.R.

    1962-10-23

    A heat exchanger is designed for use in the transfer of heat between a radioactive fiuid and a non-radioactive fiuid. The exchanger employs a removable section containing the non-hazardous fluid extending into the section designed to contain the radioactive fluid. The removable section is provided with a construction to cancel out thermal stresses. The stationary section is pressurized to prevent leakage of the radioactive fiuid and to maintain a safe, desirable level for this fiuid. (AEC)

  2. Science exchanges

    NASA Astrophysics Data System (ADS)

    Richman, Barbara T.

    Dwindling scientific and technical exchange between the United States and the Soviet Union and prospects for enhancing such exchanges were discussed at an August 2 hearing by the Foreign Affairs Committee of the U.S. House of Representatives. The committee also heard overviews on the United States' approach to international exchange of science and technology. The hearing was the first in a series on current and future international science and technology programs.Four of eight science and technology agreements with the USSR that have expired in the last 15 months, including one on space, have not been renewed. The remaining four agreements have been extended into 1987 and 1988. Two others, including one on oceanography, are scheduled to run out in 1984.

  3. Heat exchanger

    SciTech Connect

    Drury, C.R.

    1988-02-02

    A heat exchanger having primary and secondary conduits in heat-exchanging relationship is described comprising: at least one serpentine tube having parallel sections connected by reverse bends, the serpentine tube constituting one of the conduits; a group of open-ended tubes disposed adjacent to the parallel sections, the open-ended tubes constituting the other of the conduits, and forming a continuous mass of contacting tubes extending between and surrounding the serpentine tube sections; and means securing the mass of tubes together to form a predetermined cross-section of the entirety of the mass of open-ended tubes and tube sections.

  4. Heat exchanger

    DOEpatents

    Daman, Ernest L.; McCallister, Robert A.

    1979-01-01

    A heat exchanger is provided having first and second fluid chambers for passing primary and secondary fluids. The chambers are spaced apart and have heat pipes extending from inside one chamber to inside the other chamber. A third chamber is provided for passing a purge fluid, and the heat pipe portion between the first and second chambers lies within the third chamber.

  5. Extension of a Kinetic-Theory Approach for Computing Chemical-Reaction Rates to Reactions with Charged Particles

    NASA Technical Reports Server (NTRS)

    Liechty, Derek S.; Lewis, Mark J.

    2010-01-01

    Recently introduced molecular-level chemistry models that predict equilibrium and nonequilibrium reaction rates using only kinetic theory and fundamental molecular properties (i.e., no macroscopic reaction rate information) are extended to include reactions involving charged particles and electronic energy levels. The proposed extensions include ionization reactions, exothermic associative ionization reactions, endothermic and exothermic charge exchange reactions, and other exchange reactions involving ionized species. The extensions are shown to agree favorably with the measured Arrhenius rates for near-equilibrium conditions.

  6. Composite ion exchange materials

    SciTech Connect

    Amarasinghe, S.; Zook, L.; Leddy, J.

    1994-12-31

    Composite ion exchange materials can be formed by sorbing ion exchange polymers on inert, high surface area substrates. In general, the flux of ions and molecules through these composites, as measured electrochemically, increases as the ratio of the surface area of the substrate increases relative to the volume of the ion exchanger. This suggests that fields and gradients established at the interface between the ion exchanger and substrate are important in determining the transport characteristics of the composites. Here, the authors will focus on composites formed with a cation exchange polymer, Nafion, and two different types of microbeads: polystyrene microspheres and polystyrene coated magnetic microbeads. For the polystyrene microbeads, scanning electron micrographs suggest the beads cluster in a self-similar manner, independent of the bead diameter. Flux of Ru(NH3)63+ through the composites was studied as a function of bead fraction, bead radii, and fixed surface area with mixed bead sizes. Flux was well modeled by surface diffusion along a fractal interface. Magnetic composites were formed with columns of magnetic microbeads normal to the electrode surface. Flux of Ru(NH3)63+ through these composites increased exponentially with bead fraction. For electrolyses, the difference in the molar magnetic susceptibility of the products and reactants, Dcm, tends to be non-zero. For seven redox reactions, the ratio of the flux through the magnetic composites to the flux through a Nafion film increases monotonically with {vert_bar}Dcm{vert_bar}, with enhancements as large as thirty-fold. For reversible species, the electrolysis potential through the magnetic composites is 35 mV positive of that for the Nafion films.

  7. Kinetic isotope effect of the {sup 16}O + {sup 36}O{sub 2} and {sup 18}O + {sup 32}O{sub 2} isotope exchange reactions: Dominant role of reactive resonances revealed by an accurate time-dependent quantum wavepacket study

    SciTech Connect

    Sun, Zhigang Yu, Dequan; Xie, Wenbo; Hou, Jiayi; Dawes, Richard; Guo, Hua

    2015-05-07

    The O + O{sub 2} isotope exchange reactions play an important role in determining the oxygen isotopic composition of a number of trace gases in the atmosphere, and their temperature dependence and kinetic isotope effects (KIEs) provide important constraints on our understanding of the origin and mechanism of these and other unusual oxygen KIEs important in the atmosphere. This work reports a quantum dynamics study of the title reactions on the newly constructed Dawes-Lolur-Li-Jiang-Guo (DLLJG) potential energy surface (PES). The thermal reaction rate coefficients of both the {sup 18}O + {sup 32}O{sub 2} and {sup 16}O + {sup 36}O{sub 2} reactions obtained using the DLLJG PES exhibit a clear negative temperature dependence, in sharp contrast with the positive temperature dependence obtained using the earlier modified Siebert-Schinke-Bittererova (mSSB) PES. In addition, the calculated KIE shows an improved agreement with the experiment. These results strongly support the absence of the “reef” structure in the entrance/exit channels of the DLLJG PES, which is present in the mSSB PES. The quantum dynamics results on both PESs attribute the marked KIE to strong near-threshold reactive resonances, presumably stemming from the mass differences and/or zero point energy difference between the diatomic reactant and product. The accurate characterization of the reactivity for these near-thermoneutral reactions immediately above the reaction threshold is important for correct characterization of the thermal reaction rate coefficients.

  8. The ring-opening and H/D exchange reactions of (C{sub 5}H{sub 4}Me){sub 2}Zr(H) (THF){sup +}. Evidence for hydrogenolysis of Zr-Cp bonds

    SciTech Connect

    Guo, Zhao-yu; Bradley, P.K.; Jordan, R.F.

    1992-07-01

    The cationic hydride Cp{prime}{sub 2}Zr(H)(THF){sup +} (5; Cp{prime} = C{sub 5}H{sub 4}Me) reacts slowly in THF solution via THF ring opening to yield Cp{prime}{sub 2}Zr(O{sup n}Bu)(THF){sup +} (7). Hydride 5 undergoes rapid H/D exchange with D{sub 2} at the Zr-H site, and slow H/D exchange at the {beta} Cp{prime}-H sites. No H/D exchange at the {alpha} Cp{prime}-H or Cp{prime}-CH{sub 3} sites is detected. It is proposed that H/D exchange at the Zr-H site proceeds by a conventional {sigma}-bond methathesis process and that exchange at the {beta} Cp{prime}-H site involves an intermediate (Cp{prime})(methylcyclopentadiene)Zr species formed by D{sub 2} addition across a Zr-Cp{prime} bond. Exchange of H{sup -} and {sup n}BuO{sup -} ligands between Cp{prime}{sub 2}Zr centers also leads indirectly to H/D exchange at the {beta} Cp{prime}-H sites of 7. 20 refs.

  9. Heat exchanger

    DOEpatents

    Brackenbury, Phillip J.

    1986-04-01

    A heat exchanger comparising a shell attached at its open end to one side of a tube sheet and a detachable head connected to the other side of said tube sheet. The head is divided into a first and second chamber in fluid communication with a nozzle inlet and nozzle outlet, respectively, formed in said tube sheet. A tube bundle is mounted within said shell and is provided with inlets and outlets formed in said tube sheet in communication with said first and second chambers, respectively.

  10. Segmented heat exchanger

    DOEpatents

    Baldwin, Darryl Dean; Willi, Martin Leo; Fiveland, Scott Byron; Timmons, Kristine Ann

    2010-12-14

    A segmented heat exchanger system for transferring heat energy from an exhaust fluid to a working fluid. The heat exchanger system may include a first heat exchanger for receiving incoming working fluid and the exhaust fluid. The working fluid and exhaust fluid may travel through at least a portion of the first heat exchanger in a parallel flow configuration. In addition, the heat exchanger system may include a second heat exchanger for receiving working fluid from the first heat exchanger and exhaust fluid from a third heat exchanger. The working fluid and exhaust fluid may travel through at least a portion of the second heat exchanger in a counter flow configuration. Furthermore, the heat exchanger system may include a third heat exchanger for receiving working fluid from the second heat exchanger and exhaust fluid from the first heat exchanger. The working fluid and exhaust fluid may travel through at least a portion of the third heat exchanger in a parallel flow configuration.

  11. Reactor for exothermic reactions

    DOEpatents

    Smith, L.A. Jr.; Hearn, D.; Jones, E.M. Jr.

    1993-03-02

    A liquid phase process is described for oligomerization of C[sub 4] and C[sub 5] isoolefins or the etherification thereof with C[sub 1] to C[sub 6] alcohols wherein the reactants are contacted in a reactor with a fixed bed acid cation exchange resin catalyst at an LHSV of 5 to 20, pressure of 0 to 400 psig and temperature of 120 to 300 F. Wherein the improvement is the operation of the reactor at a pressure to maintain the reaction mixture at its boiling point whereby at least a portion but less than all of the reaction mixture is vaporized. By operating at the boiling point and allowing a portion of the reaction mixture to vaporize, the exothermic heat of reaction is dissipated by the formation of more boil up and the temperature in the reactor is controlled.

  12. Reactor for exothermic reactions

    DOEpatents

    Smith, Jr., Lawrence A.; Hearn, Dennis; Jones, Jr., Edward M.

    1993-01-01

    A liquid phase process for oligomerization of C.sub.4 and C.sub.5 isoolefins or the etherification thereof with C.sub.1 to C.sub.6 alcohols wherein the reactants are contacted in a reactor with a fixed bed acid cation exchange resin catalyst at an LHSV of 5 to 20, pressure of 0 to 400 psig and temperature of 120.degree. to 300.degree. F. Wherein the improvement is the operation of the reactor at a pressure to maintain the reaction mixture at its boiling point whereby at least a portion but less than all of the reaction mixture is vaporized. By operating at the boiling point and allowing a portion of the reaction mixture to vaporize, the exothermic heat of reaction is dissipated by the formation of more boil up and the temperature in the reactor is controlled.

  13. Educator Exchange Resource Guide.

    ERIC Educational Resources Information Center

    Garza, Cris; Rodriguez, Victor

    This resource guide was developed for teachers and administrators interested in participating in intercultural and international exchange programs or starting an exchange program. An analysis of an exchange program's critical elements discusses exchange activities; orientation sessions; duration of exchange; criteria for participation; travel,…

  14. Pion exchange at high energies

    SciTech Connect

    Jones, L.M.

    1980-07-01

    The state of Regge pion exchange calculations for high-energy reactions is reviewed. Experimental evidence is summarized to show that (i) the pion trajectory has a slope similar to that of other trajectories; (ii) the pion exchange contribution can dominate contributions of higher trajectories up to quite a large energy; (iii) many two-body cross sections with large pion contributions can be fit only by models which allow for kinematical conspiracy at t=0. The theory of kinematic conspiracy is reviewed for two-body amplitudes, and calculations of the conspiring pion--Pomeron cut discussed. The author then summarizes recent work on pion exchange in Reggeized Deck models for multiparticle final states, with emphasis on the predictions of various models (with and without resonances) for phases of the partial wave amplitudes.

  15. Corrosive resistant heat exchanger

    DOEpatents

    Richlen, Scott L.

    1989-01-01

    A corrosive and errosive resistant heat exchanger which recovers heat from a contaminated heat stream. The heat exchanger utilizes a boundary layer of innocuous gas, which is continuously replenished, to protect the heat exchanger surface from the hot contaminated gas. The innocuous gas is conveyed through ducts or perforations in the heat exchanger wall. Heat from the heat stream is transferred by radiation to the heat exchanger wall. Heat is removed from the outer heat exchanger wall by a heat recovery medium.

  16. Charge exchange in the Io torus and exosphere

    NASA Technical Reports Server (NTRS)

    Johnson, R. E.; Strobel, D. F.

    1982-01-01

    Charge-exchange cross sections and their velocity dependence have been estimated for the most important reactions in the Io torus and exosphere. The methods used for calculating the cross sections are given and discussed in some detail. For symmetric-resonant single and double charge exchange, the cross sections are slowly varying functions of velocity. For inelastic charge-exchange collisions, the transition probabilities into a given final state can depend critically on velocity. Models are described which can be used to estimate both the most rapid charge-exchange processes and those states which play an important role. Calculated cross sections are used to obtain reaction rates as a function of radial position, demonstrating the importance of charge exchange in the inner torus. Charge-exchange reactions of torus ions with molecular species in Io's exosphere may yield a net supply of neutrals and plasma to the torus.

  17. Woven heat exchanger

    DOEpatents

    Piscitella, Roger R.

    1987-05-05

    In a woven ceramic heat exchanger using the basic tube-in-shell design, each heat exchanger consisting of tube sheets and tube, is woven separately. Individual heat exchangers are assembled in cross-flow configuration. Each heat exchanger is woven from high temperature ceramic fiber, the warp is continuous from tube to tube sheet providing a smooth transition and unitized construction.

  18. Woven heat exchanger

    DOEpatents

    Piscitella, R.R.

    1984-07-16

    This invention relates to a heat exchanger for waste heat recovery from high temperature industrial exhaust streams. In a woven ceramic heat exchanger using the basic tube-in-shell design, each heat exchanger consisting of tube sheets and tube, is woven separately. Individual heat exchangers are assembled in cross-flow configuration. Each heat exchanger is woven from high temperature ceramic fiber, the warp is continuous from tube to tube sheet providing a smooth transition and unitized construction.

  19. Formaldehyde reactions in dark clouds

    NASA Technical Reports Server (NTRS)

    Sen, A. D.; Anicich, V. G.; Federman, S. R.

    1992-01-01

    The low-pressure reactions of formaldehyde (H2CO) with D(+), D2(+), D3(+), and He(+) are studied by the ion-cyclotron resonance technique. These reactions are potential loss processes for formaldehyde in cores of dark interstellar clouds. The deuterated reactants represent direct analogs for protons. Rate coefficients and branching ratios of product channels have been measured. Charge transfer is observed to be the dominant reaction of H2CO with D(+), D2(+), and He(+) ions. Only the D3(+) reaction exhibits a proton-transfer channel. All reactions proceed at rate coefficients near the collision limit. Proton-deuteron exchange reactions are found to be inefficient processes in the formaldehyde system.

  20. Concerted hydrogen atom exchange between three HF molecules

    NASA Technical Reports Server (NTRS)

    Komornicki, Andrew; Dixon, David A.; Taylor, Peter R.

    1992-01-01

    The termolecular reaction involving concerted hydrogen-atom exchange between three HF molecules was investigated with particular attention given to the effects of correlation at the various stationary points along the reaction. Using large segmented Gaussian basis sets to locate the (HF)3 stationary points at the SCF level, the geometries of the stable hydrogen-bonded trimer, which is of C(3h) symmetry, were located, together with the transition state for hydrogen exchange, which is of D(3h) symmetry. Then, using a large atomic natural orbital basis and correlating all valence electrons, the energetics of the exchange reaction were evaluated at the correlated level.

  1. Real-time Monitoring of Intermediates Reveals the Reaction Pathway in the Thiol-Disulfide Exchange between Disulfide Bond Formation Protein A (DsbA) and B (DsbB) on a Membrane-immobilized Quartz Crystal Microbalance (QCM) System*

    PubMed Central

    Yazawa, Kenjiro; Furusawa, Hiroyuki; Okahata, Yoshio

    2013-01-01

    Disulfide bond formation protein B (DsbBS-S,S-S) is an inner membrane protein in Escherichia coli that has two disulfide bonds (S-S, S-S) that play a role in oxidization of a pair of cysteine residues (SH, SH) in disulfide bond formation protein A (DsbASH,SH). The oxidized DsbAS-S, with one disulfide bond (S-S), can oxidize proteins with SH groups for maturation of a folding preprotein. Here, we have described the transient kinetics of the oxidation reaction between DsbASH,SH and DsbBS-S,S-S. We immobilized DsbBS-S,S-S embedded in lipid bilayers on the surface of a 27-MHz quartz crystal microbalance (QCM) device to detect both formation and degradation of the reaction intermediate (DsbA-DsbB), formed via intermolecular disulfide bonds, as a mass change in real time. The obtained kinetic parameters (intermediate formation, reverse, and oxidation rate constants (kf, kr, and kcat, respectively) indicated that the two pairs of cysteine residues in DsbBS-S,S-S were more important for the stability of the DsbA-DsbB intermediate than ubiquinone, an electron acceptor for DsbBS-S,S-S. Our data suggested that the reaction pathway of almost all DsbASH,SH oxidation processes would proceed through this stable intermediate, avoiding the requirement for ubiquinone. PMID:24145032

  2. Real-time monitoring of intermediates reveals the reaction pathway in the thiol-disulfide exchange between disulfide bond formation protein A (DsbA) and B (DsbB) on a membrane-immobilized quartz crystal microbalance (QCM) system.

    PubMed

    Yazawa, Kenjiro; Furusawa, Hiroyuki; Okahata, Yoshio

    2013-12-13

    Disulfide bond formation protein B (DsbBS-S,S-S) is an inner membrane protein in Escherichia coli that has two disulfide bonds (S-S, S-S) that play a role in oxidization of a pair of cysteine residues (SH, SH) in disulfide bond formation protein A (DsbASH,SH). The oxidized DsbAS-S, with one disulfide bond (S-S), can oxidize proteins with SH groups for maturation of a folding preprotein. Here, we have described the transient kinetics of the oxidation reaction between DsbASH,SH and DsbBS-S,S-S. We immobilized DsbBS-S,S-S embedded in lipid bilayers on the surface of a 27-MHz quartz crystal microbalance (QCM) device to detect both formation and degradation of the reaction intermediate (DsbA-DsbB), formed via intermolecular disulfide bonds, as a mass change in real time. The obtained kinetic parameters (intermediate formation, reverse, and oxidation rate constants (kf, kr, and kcat, respectively) indicated that the two pairs of cysteine residues in DsbBS-S,S-S were more important for the stability of the DsbA-DsbB intermediate than ubiquinone, an electron acceptor for DsbBS-S,S-S. Our data suggested that the reaction pathway of almost all DsbASH,SH oxidation processes would proceed through this stable intermediate, avoiding the requirement for ubiquinone. PMID:24145032

  3. Tilting mode in nuclear reactions

    SciTech Connect

    Dossing, T.; Randrup, J.

    1986-02-01

    The relation between tilting relaxation and the reaction plane dynamics is discussed, providing an intuitive understanding of the expression for the cross section close to the beam direction, which has recently been derived. Second, the tilting relaxation time and the related wriggling relaxation time are discussed, based upon nucleon exchange transport (window friction). Finally, recent experimental information on the tilting mode relaxation is discussed, and the dynamics of the tilting mode is discussed qualitatively for the three different types of nuclear reactions considered, compound nucleus fission, quasifission, and damped nuclear reactions. 9 refs., 3 figs.

  4. Nuclear reactions at intermediate energies

    NASA Astrophysics Data System (ADS)

    Shyam, Radhey

    2016-05-01

    In the domain of Nuclear reactions at intermediate energies, the QCD coupling constant αs is large enough (~ 0.3 - 0.5) to render the perturbative calculational techniques inapplicable. In this regime the quarks are confined into colorless hadrons and it is expected that effective field theories of hadron interactions via exchange of hadrons, provide useful tools to describe such reactions. In this contribution we discuss the application of one such theory, the effective Lagrangian model, in describing the hadronic reactions at intermediate energies whose measurements are the focus of a vast international experimental program.

  5. Indiana Health Information Exchange

    Cancer.gov

    The Indiana Health Information Exchange is comprised of various Indiana health care institutions, established to help improve patient safety and is recognized as a best practice for health information exchange.

  6. Charge exchange system

    DOEpatents

    Anderson, Oscar A.

    1978-01-01

    An improved charge exchange system for substantially reducing pumping requirements of excess gas in a controlled thermonuclear reactor high energy neutral beam injector. The charge exchange system utilizes a jet-type blanket which acts simultaneously as the charge exchange medium and as a shield for reflecting excess gas.

  7. Syntheses, structural variants and characterization of AInM‧S4 (A=alkali metals, Tl; M‧ = Ge, Sn) compounds; facile ion-exchange reactions of layered NaInSnS4 and KInSnS4 compounds

    NASA Astrophysics Data System (ADS)

    Yohannan, Jinu P.; Vidyasagar, Kanamaluru

    2016-06-01

    Ten AInM‧S4 (A=alkali metals, Tl; M‧= Ge, Sn) compounds with diverse structure types have been synthesized and characterized by single crystal and powder X-ray diffraction and a variety of spectroscopic methods. They are wide band gap semiconductors. KInGeS4(1-β), RbInGeS4(2), CsInGeS4(3-β), TlInGeS4(4-β), RbInSnS4(8-β) and CsInSnS4(9) compounds with three-dimensional BaGa2S4 structure and CsInGeS4(3-α) and TlInGeS4(4-α) compounds with a layered TlInSiS4 structure have tetrahedral [InM‧S4]- frameworks. On the other hand, LiInSnS4(5) with spinel structure and NaInSnS4(6), KInSnS4(7), RbInSnS4(8-α) and TlInSnS4(10) compounds with layered structure have octahedral [InM‧S4]- frameworks. NaInSnS4(6) and KInSnS4(7) compounds undergo facile topotactic ion-exchange, at room temperature, with various mono-, di- and tri-valent cations in aqueous medium to give rise to metastable layered phases.

  8. Bifunctional anion-exchange resins with improved selectivity and exchange kinetics

    DOEpatents

    Alexandratos, Spiro D.; Brown, Gilbert M.; Bonnesen, Peter V.; Moyer, Bruce A.

    2000-01-01

    Disclosed herein are a class of anion exchange resins containing two different exchange sites with improved selectivity and sorptive capability for chemical species in solution, such as heptavalent technetium (as pertechnetate anion, TcO.sub.4.sup.-). The resins are prepared by first reacting haloalkylated crosslinked copolymer beads with a large tertiary amine in a solvent in which the resin beads can swell, followed by reaction with a second, smaller, tertiary amine to more fully complete the functionalization of the resin. The resins have enhanced selectivity, capacity, and exchange kinetics.

  9. Lipid exchange between membranes.

    PubMed Central

    Jähnig, F

    1984-01-01

    The exchange of lipid molecules between vesicle bilayers in water and a monolayer forming at the water surface was investigated theoretically within the framework of thermodynamics. The total number of exchanged molecules was found to depend on the bilayer curvature as expressed by the vesicle radius and on the boundary condition for exchange, i.e., whether during exchange the radius or the packing density of the vesicles remains constant. The boundary condition is determined by the rate of flip-flop within the bilayer relative to the rate of exchange between bi- and monolayer. If flip-flop is fast, exchange is independent of the vesicle radius; if flip-flop is slow, exchange increases with the vesicle radius. Available experimental results agree with the detailed form of this dependence. When the theory was extended to exchange between two bilayers of different curvature, the direction of exchange was also determined by the curvatures and the boundary conditions for exchange. Due to the dependence of the boundary conditions on flip-flop and, consequently, on membrane fluidity, exchange between membranes may partially be regulated by membrane fluidity. PMID:6518251

  10. Reaction product imaging

    SciTech Connect

    Chandler, D.W.

    1993-12-01

    Over the past few years the author has investigated the photochemistry of small molecules using the photofragment imaging technique. Bond energies, spectroscopy of radicals, dissociation dynamics and branching ratios are examples of information obtained by this technique. Along with extending the technique to the study of bimolecular reactions, efforts to make the technique as quantitative as possible have been the focus of the research effort. To this end, the author has measured the bond energy of the C-H bond in acetylene, branching ratios in the dissociation of HI, the energetics of CH{sub 3}Br, CD{sub 3}Br, C{sub 2}H{sub 5}Br and C{sub 2}H{sub 5}OBr dissociation, and the alignment of the CD{sub 3} fragment from CD{sub 3}I photolysis. In an effort to extend the technique to bimolecular reactions the author has studied the reaction of H with HI and the isotopic exchange reaction between H and D{sub 2}.

  11. Ion Exchange Formation via Sulfonated Bicomponent Nonwovens

    NASA Astrophysics Data System (ADS)

    Stoughton, Hannah L.

    For many years ion exchange resins were used to: remove heavy metals from water, recover materials from wastewater, and eliminate harmful gases from the air. While use of these resin beads dominates the ion exchange industry, the beads have limitations that should be considered when decisions are made to employ them. For instance, officials must balance the inherent zero sum surface area and porosity of the materials. This series of studies investigates the use of bicomponent nonwovens as a base substrate for producing high surface area ion exchange materials for the removal of heavy metal ions. Functionalized materials were produced in a two-step process: (1) PET/PE spunbond bicomponent fibers were fractured completely, producing the high surface area nonwoven to be used as the base ion exchange material, and (2) the conditions for functionalizing the PET fibers of the nonwoven webs were investigated where an epoxy containing monomer was grafted to the surface followed by sulfonation of the monomer. The functionalization reactions of the PET fibers were monitored based on: weight gain, FTIR, TOF-SIMS, and SEM. Ion exchange properties were evaluated using titration and copper ion removal capacity from test solutions. The relationship between web structure and removal efficiency of the metal ions was defined through a comparison of the bicomponent and homocomponent nonwovens for copper ion removal efficiency. The investigation revealed that utilizing the high surface area, fractured bicomponent nonwoven ion exchange materials with capacities comparable to commercially available ion exchange resins could be produced.

  12. Drug Reactions

    MedlinePlus

    Most of the time, medicines make our lives better. They reduce aches and pains, fight infections, and control problems such as high blood pressure or diabetes. But medicines can also cause unwanted reactions. One problem is ...

  13. Preparation of Pt-Co nanoparticles by galvanostatic pulse electrochemical codeposition on in situ electrochemical reduced graphene nanoplates based carbon paper electrode for oxygen reduction reaction in proton exchange membrane fuel cell

    NASA Astrophysics Data System (ADS)

    Yaldagard, Maryam; Seghatoleslami, Naser; Jahanshahi, Mohsen

    2014-10-01

    Nanocomposite films of Pt-Co nanoparticles deposited on graphene nanoplate based gas diffusion layer electrode are fabricated via an electrochemical route involving a series of electrochemical process. Pt-Co nanoparticles of 11.37 nm in average size are prepared by galvanostatic codeposition in 0.5 M NaCl at PH of 2.5 at 300 mA cm-2 on the surface of in situ reduced graphene nanoplates on carbon paper. The topographical features, structure, morphology and composition of the prepared film samples are characterized by Atomic Force microscopy, Raman Spectroscopy, FTIR analysis, X-ray Diffraction, FESEM and EDS. At the same time, the catalytic activities of prepared electrodes for the oxygen reduction reaction are evaluated through cyclic voltammetry, linear sweep voltammetry and chronoamperometry and electrochemical impedance spectroscopy measurements. Raman spectroscopy measurements confirmed the graphitic structure of the produced graphene nanoplates. The nanoparticles in the film were observed to be uniform spherical objects and well distributed. Catalytic properties of Pt-Co/GNP/GDL electrode were compared with Pt/C/GDL using half cell polarization measurements based on both mass activity and specific activity. The as prepared Pt-Co/GNP/GDL electrode exhibits high catalytic activity for the ORR, which may be attributed to structural changes caused by alloying and the high specific surface area of graphene nanoplates catalyst support. The mass activity peak current is found to be as high as 728.25 mA mgPt-1.

  14. Feasibility of Production of Moly-99 via 1-neutron Exchange Reaction 98 Mo +100 Mo -->299Mo in Strong-Focusing Auto Collider (``EXYDER'') of natural Molybdenum nuclei based on T and He-3 production data from d +d weak focusing Auto-Collider MIGMA IV

    NASA Astrophysics Data System (ADS)

    Hester, Tim; Maglich, Bogdan; Calsec Collaboration

    2015-10-01

    Copious T and 3He production from D(d, p) T and D(d, n) 3He reactions in 725 KeV colliding beams was observed in weak-focusing Self-Collider1-4 radius 15 cm, in B = 3.12 T, stabilized5 non-linearly by electron cloud oscillations with confinement time ~ 23 s. BARC's simulations7 predict that by switching to Strong Focusing Self Collider proposed by Blewett6, 10 deuterons 0.75 MeV each, will generate 1 3He + 1T +1p + 1n at a total input energy cost of 10.72 MeV. Economic value of T and 3He is 65 and 120 MeV/atom respectively. While energy balance is negative, we project economic gain 205 MeV/10.72 MeV ~ 20 i.e. 3He production/sale will fund cost of T. Assuming the luminosity achieved in MIGMA IV, we replace D beam injection with a high energy beam of 14 times ionized natural Mo ions and look for the 1-neutron reactions of the type 98Mo+100Mo -->299Mo, where 99Mo14+ will be EM channeled into a mass spectrometer and collected at one loci/ radius, while all other masses/radii rejected. Physics and engineering parameters required to produce at least 1 g of 99Mo per day, at an electricity cost of 100K, will be presented. 2- and 3-neutron exchange reactions will be considered, too.

  15. Nonsurvivable momentum exchange system

    NASA Technical Reports Server (NTRS)

    Roder, Russell (Inventor); Ahronovich, Eliezer (Inventor); Davis, III, Milton C. (Inventor)

    2007-01-01

    A demiseable momentum exchange system includes a base and a flywheel rotatably supported on the base. The flywheel includes a web portion defining a plurality of web openings and a rim portion. The momentum exchange system further includes a motor for driving the flywheel and a cover for engaging the base to substantially enclose the flywheel. The system may also include components having a melting temperature below 1500 degrees Celsius. The momentum exchange system is configured to demise on reentry.

  16. Text Exchange System

    NASA Technical Reports Server (NTRS)

    Snyder, W. V.; Hanson, R. J.

    1986-01-01

    Text Exchange System (TES) exchanges and maintains organized textual information including source code, documentation, data, and listings. System consists of two computer programs and definition of format for information storage. Comprehensive program used to create, read, and maintain TES files. TES developed to meet three goals: First, easy and efficient exchange of programs and other textual data between similar and dissimilar computer systems via magnetic tape. Second, provide transportable management system for textual information. Third, provide common user interface, over wide variety of computing systems, for all activities associated with text exchange.

  17. Method for conducting exothermic reactions

    DOEpatents

    Smith, L. Jr.; Hearn, D.; Jones, E.M. Jr.

    1993-01-05

    A liquid phase process for oligomerization of C[sub 4] and C[sub 5] isoolefins or the etherification thereof with C[sub 1] to C[sub 6] alcohols wherein the reactants are contacted in a reactor with a fixed bed acid cation exchange resin catalyst at an LHSV of 5 to 20, pressure of 0 to 400 psig and temperature of 120 to 300 F. wherein the improvement is the operation of the reactor at a pressure to maintain the reaction mixture at its boiling point whereby at least a portion but less than all of the reaction mixture is vaporized. By operating at the boiling point and allowing a portion of the reaction mixture to vaporize, the exothermic heat of reaction is dissipated by the formation of more boil up and the temperature in the reactor is controlled.

  18. Method for conducting exothermic reactions

    DOEpatents

    Smith, Jr., Lawrence; Hearn, Dennis; Jones, Jr., Edward M.

    1993-01-01

    A liquid phase process for oligomerization of C.sub.4 and C.sub.5 isoolefins or the etherification thereof with C.sub.1 to C.sub.6 alcohols wherein the reactants are contacted in a reactor with a fixed bed acid cation exchange resin catalyst at an LHSV of 5 to 20, pressure of 0 to 400 psig and temperature of 120.degree. to 300.degree. F. wherein the improvement is the operation of the reactor at a pressure to maintain the reaction mixture at its boiling point whereby at least a portion but less than all of the reaction mixture is vaporized. By operating at the boiling point and allowing a portion of the reaction mixture to vaporize, the exothermic heat of reaction is dissipated by the formation of more boil up and the temperature in the reactor is controlled.

  19. Electrical and magnetic properties of ion-exchangeable layered ruthenates

    SciTech Connect

    Sugimoto, Wataru . E-mail: wsugi@shinshu-u.ac.jp; Omoto, Masashi; Yokoshima, Katsunori; Murakami, Yasushi; Takasu, Yoshio

    2004-12-01

    An ion-exchangeable ruthenate with a layered structure, K{sub 0.2}RuO{sub 2.1}, was prepared by solid-state reactions. The interlayer cation was exchanged with H{sup +}, C{sub 2}H{sub 5}NH{sub 3}{sup +}, and ((C{sub 4}H{sub 9}){sub 4}N{sup +}) through proton-exchange, ion-exchange, and guest-exchange reactions. The electrical and magnetic properties of the products were characterized by DC resistivity and susceptibility measurements. Layered K{sub 0.2}RuO{sub 2.1} exhibited metallic conduction between 300 and 13K. The products exhibited similar magnetic behavior despite the differences in the type of interlayer cation, suggesting that the ruthenate sheet in the protonated form and the intercalation compounds possesses metallic nature.

  20. Chemical Reactions in DSMC

    SciTech Connect

    Bird, G. A.

    2011-05-20

    DSMC simulations of chemically reacting gas flows have generally employed procedures that convert the macroscopic chemical rate equations to reaction cross-sections at the microscopic level. They therefore depend on the availability of experimental data that has been fitted to equations of the Arrhenius form. This paper presents a physical model for dissociation and recombination reactions and a phenomenological model for exchange and chain reactions. These are based on the vibrational states of the colliding molecules and do not require any experimentally-based data. The simplicity of the models allows the corresponding rate equations to be written down and, while these are not required for the implementation of the models, they facilitate their validation. The model is applied to a typical hypersonic atmospheric entry problem and the results are compared with the corresponding results from the traditional method. It is also used to investigate both spontaneous and forced ignition as well as the structure of a deflagration wave in an oxygen-hydrogen mixture.

  1. Chemical Reactions in DSMC

    NASA Astrophysics Data System (ADS)

    Bird, G. A.

    2011-05-01

    DSMC simulations of chemically reacting gas flows have generally employed procedures that convert the macroscopic chemical rate equations to reaction cross-sections at the microscopic level. They therefore depend on the availability of experimental data that has been fitted to equations of the Arrhenius form. This paper presents a physical model for dissociation and recombination reactions and a phenomenological model for exchange and chain reactions. These are based on the vibrational states of the colliding molecules and do not require any experimentally-based data. The simplicity of the models allows the corresponding rate equations to be written down and, while these are not required for the implementation of the models, they facilitate their validation. The model is applied to a typical hypersonic atmospheric entry problem and the results are compared with the corresponding results from the traditional method. It is also used to investigate both spontaneous and forced ignition as well as the structure of a deflagration wave in an oxygen-hydrogen mixture.

  2. Drug Reactions

    MedlinePlus

    ... using any of these products. Some types of food may also cause adverse drug reactions. For example, grapefruit and grapefruit juice, as well as alcohol and caffeine, may affect how drugs work. Every time your doctor ... interactions with any foods or beverages. What about medicines I've used ...

  3. ZEOLITE PERFORMANCE AS AN ANION EXCHANGER FOR ARSENIC SEQUESTRATION IN WATER

    EPA Science Inventory

    Zeolites are well known for their use in ion exchange and acid catalysis reactions. The use of zeolites in anion or ligand exchange reactions is less studied. The NH4+ form of zeolite Y (NY6, Faujasite) has been tested in this work to evaluate its performance for arsenic removal...

  4. Closed cycle ion exchange method for regenerating acids, bases and salts

    DOEpatents

    Dreyfuss, Robert M.

    1976-01-01

    A method for conducting a chemical reaction in acidic, basic, or neutral solution as required and then regenerating the acid, base, or salt by means of ion exchange in a closed cycle reaction sequence which comprises contacting the spent acid, base, or salt with an ion exchanger, preferably a synthetic organic ion-exchange resin, so selected that the counter ions thereof are ions also produced as a by-product in the closed reaction cycle, and then regenerating the spent ion exchanger by contact with the by-product counter ions. The method is particularly applicable to closed cycle processes for the thermochemical production of hydrogen.

  5. Neopentane and solid acids: direct hydron exchange before cracking.

    PubMed

    Walspurger, Stéphane; Sun, Yinyong; Souna Sido, Abdelkarim Sani; Sommer, Jean

    2006-09-21

    The hydrogen/deuterium exchange reaction of 2,2-dimethylpropane (neopentane) over D(2)O-exchanged zeolites (MOR, FAU, BEA, MFI) using a batch recirculation reactor was studied by means of gas chromatography coupled with mass spectrometer. In the temperature range 473-573 K, H/D exchange proceeds without side reaction such as cracking at short contact times. Indeed the C-H bond has appeared favorably involved in the activation of neopentane compared to the less accessible C-C bond. The transition state allowing hydron exchange is most likely a carbonium species (pentacoordinated carbon) as in the case of the H/D exchange between methane and solid acid. The activation energies of the H/D exchange between neopentane and zeolites are the same for all zeolites indicating a common carbonium ion type transition state. On the basis of previous results in the case of the exchange between methane and liquid superacids, the deuterium exchange rates in neopentane were tentatively related to the acidity of the solids. However the order of activity MOR > MFI > BEA > FAU seems to be related to the size of the pores, which may suggest the involvement of a confinement effect in the zeolites cavities. Moreover we found that H/D exchange takes also place between neopentane and deuterated sulfated zirconia (SZ) emphasizing its strong acidity. PMID:16970460

  6. Higher Education Exchange, 2008

    ERIC Educational Resources Information Center

    Brown, David W., Ed.; Witte, Deborah, Ed.

    2008-01-01

    "Higher Education Exchange" publishes case studies, analyses, news, and ideas about efforts within higher education to develop more democratic societies. Contributors to this issue of the "Higher Education Exchange" examine whether institutions of higher learning are doing anything to increase the capacity of citizens to shape their future.…

  7. Higher Education Exchange, 2010

    ERIC Educational Resources Information Center

    Brown, David W., Ed.; Witte, Deborah, Ed.

    2010-01-01

    "Higher Education Exchange" publishes case studies, analyses, news, and ideas about efforts within higher education to develop more democratic societies. Contributors to this issue of the "Higher Education Exchange" examine whether institutions of higher learning are doing anything to increase the capacity of citizens to shape their future.…

  8. Direct fired heat exchanger

    DOEpatents

    Reimann, Robert C.; Root, Richard A.

    1986-01-01

    A gas-to-liquid heat exchanger system which transfers heat from a gas, generally the combustion gas of a direct-fired generator of an absorption machine, to a liquid, generally an absorbent solution. The heat exchanger system is in a counterflow fluid arrangement which creates a more efficient heat transfer.

  9. Handicapping Social Exchange Theory.

    ERIC Educational Resources Information Center

    Mishler, Barbara

    The economic theory of social exchange has some serious shortcomings when applied to minorities--especially the disabled. First, it assumes dyads comprise the basic unit where exchange occurs and that rewards and costs must occur at that level. Second, the model standardizes the experience of white, Western European and American males. The model…

  10. Building Relationships through Exchange

    ERIC Educational Resources Information Center

    Primavera, Angi; Hall, Ellen

    2011-01-01

    From the moment of birth, children form and develop relationships with others in their world based on exchange. Children recognize that engaging in such encounters offers them the opportunity to enter into a relationship with another individual and to nurture that relationship through the exchange of messages and gifts, items and ideas. At Boulder…

  11. Higher Education Exchange, 2011

    ERIC Educational Resources Information Center

    Brown, David W., Ed.; Witte, Deborah, Ed.

    2011-01-01

    "Higher Education Exchange" publishes case studies, analyses, news, and ideas about efforts within higher education to develop more democratic societies. Contributors to this issue of the "Higher Education Exchange" examine whether institutions of higher learning are doing anything to increase the capacity of citizens to shape their future.…

  12. Optimization of Heat Exchangers

    SciTech Connect

    Ivan Catton

    2010-10-01

    The objective of this research is to develop tools to design and optimize heat exchangers (HE) and compact heat exchangers (CHE) for intermediate loop heat transport systems found in the very high temperature reator (VHTR) and other Generation IV designs by addressing heat transfer surface augmentation and conjugate modeling. To optimize heat exchanger, a fast running model must be created that will allow for multiple designs to be compared quickly. To model a heat exchanger, volume averaging theory, VAT, is used. VAT allows for the conservation of mass, momentum and energy to be solved for point by point in a 3 dimensional computer model of a heat exchanger. The end product of this project is a computer code that can predict an optimal configuration for a heat exchanger given only a few constraints (input fluids, size, cost, etc.). As VAT computer code can be used to model characteristics )pumping power, temperatures, and cost) of heat exchangers more quickly than traditional CFD or experiment, optimization of every geometric parameter simultaneously can be made. Using design of experiment, DOE and genetric algorithms, GE, to optimize the results of the computer code will improve heat exchanger disign.

  13. Higher Education Exchange, 2012

    ERIC Educational Resources Information Center

    Brown, David W., Ed.; Witte, Deborah, Ed.

    2012-01-01

    "Higher Education Exchange" publishes case studies, analyses, news, and ideas about efforts within higher education to develop more democratic societies. Contributors to this issue of the "Higher Education Exchange" examine whether institutions of higher learning are doing anything to increase the capacity of citizens to shape their future.…

  14. Higher Education Exchange, 2007

    ERIC Educational Resources Information Center

    Brown, David W., Ed.; Witte, Deborah, Ed.

    2007-01-01

    "Higher Education Exchange" publishes case studies, analyses, news, and ideas about efforts within higher education to develop more democratic societies. Contributors to this issue of the "Higher Education Exchange" discuss the concept of growing public scholars; each contribution incorporates a student component. Articles include: (1) "Foreword"…

  15. Money and Exchange.

    ERIC Educational Resources Information Center

    Walstad, William B.; And Others

    1982-01-01

    This teaching guide begins with an explanation of the role of money in the economy, focusing on its circulation or exchange. The use of money as a unit of account, a store of value, and a medium of exchange are explained. Three brief teaching units are included. The grade K-2 unit, "Money Counts," provides games and activities which develop the…

  16. Controlled optical properties of water-soluble CdTe nanocrystals via anion exchange.

    PubMed

    Li, Jing; Jia, Jianguang; Lin, Yuan; Zhou, Xiaowen

    2016-02-01

    We report a study on anion exchange reaction of CdTe nanocrystals with S(2-) in aqueous solution under ambient condition. We found that the optical properties of CdTe nanocrystals can be well tuned by controlling the reaction conditions, in which the reaction temperature is crucially important. At low reaction temperature, the product nanocrystals showed blue-shifts in both absorption and PL spectra, while the photoluminescence quantum yield (PLQY) was significantly enhanced. When anion exchanges were carried out at higher reaction temperature, on the other hand, obvious red shifts in absorption and PL spectra accompanied by a fast increase followed by gradual decrease in PLQY were observed. On variation of S(2-) concentration, it was found that the overall kinetics of Te(2-) for S(2-) exchanges depends also on [S(2-)] when anion exchanges were performed at higher temperature. A possible mechanism for anion exchanges in CdTe NCs was proposed. PMID:26520812

  17. Systematics of pion double charge exchange

    SciTech Connect

    Gilman, R.A.

    1985-10-01

    Differential cross sections have been measured for pion-induced double-charge-exchange (DCX) reactions leading to double-isobaric-analog states (DIAS) and low-lying nonanalog states in the residual nuclei. A description of the experimental details and data analysis is presented. The experimentally observed systematics of reactions leading to DIAS, to nonanalog ground states, and to low-lying 2 states are described. Lowest-order optical-model calculations of DIAS DCX are compared to the data. Efforts to understand the anomalies by invoking additional reaction-mechanism amplitudes and a higher-order optical potential are described. Calculations of nonanalog DCX reactions leading to J/sup / = 0 states were performed within a distorted-wave impulse-approximation framework. The sensitivities of these calculations to input parameters are discussed. 58 refs., 41 figs., 16 tabs.

  18. Process for operating equilibrium controlled reactions

    DOEpatents

    Nataraj, Shankar; Carvill, Brian Thomas; Hufton, Jeffrey Raymond; Mayorga, Steven Gerard; Gaffney, Thomas Richard; Brzozowski, Jeffrey Richard

    2001-01-01

    A cyclic process for operating an equilibrium controlled reaction in a plurality of reactors containing an admixture of an adsorbent and a reaction catalyst suitable for performing the desired reaction which is operated in a predetermined timed sequence wherein the heating and cooling requirements in a moving reaction mass transfer zone within each reactor are provided by indirect heat exchange with a fluid capable of phase change at temperatures maintained in each reactor during sorpreaction, depressurization, purging and pressurization steps during each process cycle.

  19. Anion exchange membrane

    DOEpatents

    Verkade, John G; Wadhwa, Kuldeep; Kong, Xueqian; Schmidt-Rohr, Klaus

    2013-05-07

    An anion exchange membrane and fuel cell incorporating the anion exchange membrane are detailed in which proazaphosphatrane and azaphosphatrane cations are covalently bonded to a sulfonated fluoropolymer support along with anionic counterions. A positive charge is dispersed in the aforementioned cations which are buried in the support to reduce the cation-anion interactions and increase the mobility of hydroxide ions, for example, across the membrane. The anion exchange membrane has the ability to operate at high temperatures and in highly alkaline environments with high conductivity and low resistance.

  20. Wound tube heat exchanger

    DOEpatents

    Ecker, Amir L.

    1983-01-01

    What is disclosed is a wound tube heat exchanger in which a plurality of tubes having flattened areas are held contiguous adjacent flattened areas of tubes by a plurality of windings to give a double walled heat exchanger. The plurality of windings serve as a plurality of effective force vectors holding the conduits contiguous heat conducting walls of another conduit and result in highly efficient heat transfer. The resulting heat exchange bundle is economical and can be coiled into the desired shape. Also disclosed are specific embodiments such as the one in which the tubes are expanded against their windings after being coiled to insure highly efficient heat transfer.

  1. Heat and mass exchanger

    SciTech Connect

    Lowenstein, Andrew; Sibilia, Marc J.; Miller, Jeffrey A.; Tonon, Thomas

    2011-06-28

    A mass and heat exchanger includes at least one first substrate with a surface for supporting a continuous flow of a liquid thereon that either absorbs, desorbs, evaporates or condenses one or more gaseous species from or to a surrounding gas; and at least one second substrate operatively associated with the first substrate. The second substrate includes a surface for supporting the continuous flow of the liquid thereon and is adapted to carry a heat exchange fluid therethrough, wherein heat transfer occurs between the liquid and the heat exchange fluid.

  2. Heat and mass exchanger

    SciTech Connect

    Lowenstein, Andrew; Sibilia, Marc J.; Miller, Jeffrey A.; Tonon, Thomas

    2007-09-18

    A mass and heat exchanger includes at least one first substrate with a surface for supporting a continuous flow of a liquid thereon that either absorbs, desorbs, evaporates or condenses one or more gaseous species from or to a surrounding gas; and at least one second substrate operatively associated with the first substrate. The second substrate includes a surface for supporting the continuous flow of the liquid thereon and is adapted to carry a heat exchange fluid therethrough, wherein heat transfer occurs between the liquid and the heat exchange fluid.

  3. Microtube strip heat exchanger

    SciTech Connect

    Doty, F.D.

    1991-10-16

    This progress report is for the September--October 1991 quarter. We have demonstrated feasibility of higher specific conductance by a factor of five than any other work in high-temperature gas-to-gas exchangers. These laminar-flow, microtube exchangers exhibit extremely low pressure drop compared to alternative compact designs under similar conditions because of their much shorter flow length and larger total flow area for lower flow velocities. The design appears to be amenable to mass production techniques, but considerable process development remains. The reduction in materials usage and the improved heat exchanger performance promise to be of enormous significance in advanced engine designs and in cryogenics.

  4. Outdoor heat exchanger section

    SciTech Connect

    Kessler, A.F.; Smiley, W.A. III; Wendt, M.E.

    1988-02-09

    An outdoor section for an air conditioning system is described comprising: a compressor; a heat exchanger; a cabinet having an upper cabinet section, a lower cabinet section and a louvered lower section top cover, the heat exchanger and the compressor being housed in the lower cabinet section and the upper cabinet section having a solid top which overlies the louvers in the lower section top cover; and a fan disposed in the lower cabinet section to draw air through the sides of the lower cabinet section and through the heat exchanger housed therein, the fan discharging air, after having been drawn through the heat exchanger, upward through the louvers in the lower cabinet section top cover and into the interior of the upper cabinet section.

  5. Exchange transfusion - series (image)

    MedlinePlus

    ... her back, usually under a radiant warmer. The umbilical vein is catheterized with a fluid-filled catheter. ... plasma is injected. After the exchange transfusion, an umbilical catheter may be left in place in case ...

  6. Anion exchange polymer electrolytes

    SciTech Connect

    Kim, Yu Seung; Kim, Dae Sik

    2015-06-02

    Anion exchange polymer electrolytes that include guanidinium functionalized polymers may be used as membranes and binders for electrocatalysts in preparation of anodes for electrochemical cells such as solid alkaline fuel cells.

  7. Data exchange in metrology.

    PubMed

    Badger, P

    1996-01-01

    The adoption of the directives 71/316/EEC on measuring instruments and 90/384/EEC on non-automatic weighing instruments has resulted in a considerable quantity of certificates to be exchanged between the Central Metrological Authorities and the Local Metrological Authorities, in the member states. This requirement to exchange data, prompted the setting up of the WELMEC working group, to explore how computerisation could help the member states perform their tasks. PMID:10172832

  8. Microtube Strip Heat Exchanger

    SciTech Connect

    Doty, F.D.

    1990-12-27

    Doty Scientific (DSI) believes their Microtube-Strip Heat Exchanger will contribute significantly to (a) the closed Brayton cycles being pursued at MIT, NASA, and elsewhere; (b) reverse Brayton cycle cryocoolers, currently being investigated by NASA for space missions, being applied to MRI superconducting magnets; and (c) high-efficiency cryogenic gas separation schemes for CO{sub 2} removal from exhaust stacks. The goal of this current study is to show the potential for substantial progress in high-effectiveness, low-cost, gas-to-gas heat exchangers for diverse applications at temperatures from below 100 K to above 1000 K. To date, the highest effectiveness measured is about 98%, and relative pressure drops below 0.1% with a specific conductance of about 45 W/kgK are reported. During the pre-award period DSI built and tested a 3-module heat exchanger bank using 103-tube microtube strip (MTS) modules. To add to their analytical capabilities, DSI has acquired computational fluid dynamics (CFD) software. This report describes the pre-award work and the status of the ten tasks of the current project, which are: analyze flow distribution and thermal stresses within individual modules; design a heat exchanger bank of ten modules with 400 microtube per module; obtain production quality tubestrip die and AISI 304 tubestrips; obtain production quality microtubing; construct revised MTS heat exchanger; construct dies and fixtures for prototype heat exchanger; construct 100 MTS modules; assemble 8-10 prototype MTS heat exchangers; test prototype MTS heat exchanger; and verify test through independent means. 7 refs., 9 figs. 1 tab. (CK)

  9. Thiol-Disulfide Exchange Reactions in the Mammalian Extracellular Environment.

    PubMed

    Yi, Michael C; Khosla, Chaitan

    2016-06-01

    Disulfide bonds represent versatile posttranslational modifications whose roles encompass the structure, catalysis, and regulation of protein function. Due to the oxidizing nature of the extracellular environment, disulfide bonds found in secreted proteins were once believed to be inert. This notion has been challenged by the discovery of redox-sensitive disulfides that, once cleaved, can lead to changes in protein activity. These functional disulfides are twisted into unique configurations, leading to high strain and potential energy. In some cases, cleavage of these disulfides can lead to a gain of function in protein activity. Thus, these motifs can be referred to as switches. We describe the couples that control redox in the extracellular environment, examine several examples of proteins with switchable disulfides, and discuss the potential applications of disulfides in molecular biology. PMID:27023663

  10. A degradable polydopamine coating based on disulfide-exchange reaction.

    PubMed

    Hong, Daewha; Lee, Hojae; Kim, Beom Jin; Park, Taegyun; Choi, Ji Yu; Park, Matthew; Lee, Juno; Cho, Hyeoncheol; Hong, Seok-Pyo; Yang, Sung Ho; Jung, Sun Ho; Ko, Sung-Bo; Choi, Insung S

    2015-12-21

    Although the programmed degradation of biocompatible films finds applications in various fields including biomedical and bionanotechnological areas, coating methods have generally been limited to be substrate-specific, not applicable to any kinds of substrates. In this paper, we report a dopamine derivative, which allows for both universal coating of various substrates and stimuli-responsive film degradation, inspired by mussel-adhesive proteins. Two dopamine moieties are linked together by the disulfide bond, the cleavage of which enables the programmed film degradation. Mechanistic analysis of the degradable films indicates that the initial cleavage of the disulfide linkage causes rapid uptake of water molecules, hydrating the films, which leads to rapid degradation. Our substrate-independent coating of degradable films provides an advanced tool for drug delivery systems, tissue engineering, and anti-fouling strategies. PMID:26572596

  11. A degradable polydopamine coating based on disulfide-exchange reaction

    NASA Astrophysics Data System (ADS)

    Hong, Daewha; Lee, Hojae; Kim, Beom Jin; Park, Taegyun; Choi, Ji Yu; Park, Matthew; Lee, Juno; Cho, Hyeoncheol; Hong, Seok-Pyo; Yang, Sung Ho; Jung, Sun Ho; Ko, Sung-Bo; Choi, Insung S.

    2015-11-01

    Although the programmed degradation of biocompatible films finds applications in various fields including biomedical and bionanotechnological areas, coating methods have generally been limited to be substrate-specific, not applicable to any kinds of substrates. In this paper, we report a dopamine derivative, which allows for both universal coating of various substrates and stimuli-responsive film degradation, inspired by mussel-adhesive proteins. Two dopamine moieties are linked together by the disulfide bond, the cleavage of which enables the programmed film degradation. Mechanistic analysis of the degradable films indicates that the initial cleavage of the disulfide linkage causes rapid uptake of water molecules, hydrating the films, which leads to rapid degradation. Our substrate-independent coating of degradable films provides an advanced tool for drug delivery systems, tissue engineering, and anti-fouling strategies.Although the programmed degradation of biocompatible films finds applications in various fields including biomedical and bionanotechnological areas, coating methods have generally been limited to be substrate-specific, not applicable to any kinds of substrates. In this paper, we report a dopamine derivative, which allows for both universal coating of various substrates and stimuli-responsive film degradation, inspired by mussel-adhesive proteins. Two dopamine moieties are linked together by the disulfide bond, the cleavage of which enables the programmed film degradation. Mechanistic analysis of the degradable films indicates that the initial cleavage of the disulfide linkage causes rapid uptake of water molecules, hydrating the films, which leads to rapid degradation. Our substrate-independent coating of degradable films provides an advanced tool for drug delivery systems, tissue engineering, and anti-fouling strategies. Electronic supplementary information (ESI) available: Synthesis, characterization, and other additional details. See DOI: 10.1039/c5nr06460k

  12. Cryptographic Combinatorial Securities Exchanges

    NASA Astrophysics Data System (ADS)

    Thorpe, Christopher; Parkes, David C.

    We present a useful new mechanism that facilitates the atomic exchange of many large baskets of securities in a combinatorial exchange. Cryptography prevents information about the securities in the baskets from being exploited, enhancing trust. Our exchange offers institutions who wish to trade large positions a new alternative to existing methods of block trading: they can reduce transaction costs by taking advantage of other institutions’ available liquidity, while third party liquidity providers guarantee execution—preserving their desired portfolio composition at all times. In our exchange, institutions submit encrypted orders which are crossed, leaving a “remainder”. The exchange proves facts about the portfolio risk of this remainder to third party liquidity providers without revealing the securities in the remainder, the knowledge of which could also be exploited. The third parties learn either (depending on the setting) the portfolio risk parameters of the remainder itself, or how their own portfolio risk would change if they were to incorporate the remainder into a portfolio they submit. In one setting, these third parties submit bids on the commission, and the winner supplies necessary liquidity for the entire exchange to clear. This guaranteed clearing, coupled with external price discovery from the primary markets for the securities, sidesteps difficult combinatorial optimization problems. This latter method of proving how taking on the remainder would change risk parameters of one’s own portfolio, without revealing the remainder’s contents or its own risk parameters, is a useful protocol of independent interest.

  13. Radial flow heat exchanger

    DOEpatents

    Valenzuela, Javier

    2001-01-01

    A radial flow heat exchanger (20) having a plurality of first passages (24) for transporting a first fluid (25) and a plurality of second passages (26) for transporting a second fluid (27). The first and second passages are arranged in stacked, alternating relationship, are separated from one another by relatively thin plates (30) and (32), and surround a central axis (22). The thickness of the first and second passages are selected so that the first and second fluids, respectively, are transported with laminar flow through the passages. To enhance thermal energy transfer between first and second passages, the latter are arranged so each first passage is in thermal communication with an associated second passage along substantially its entire length, and vice versa with respect to the second passages. The heat exchangers may be stacked to achieve a modular heat exchange assembly (300). Certain heat exchangers in the assembly may be designed slightly differently than other heat exchangers to address changes in fluid properties during transport through the heat exchanger, so as to enhance overall thermal effectiveness of the assembly.

  14. Vacuum powered heat exchanger

    SciTech Connect

    Ruffolo, R.F.

    1986-06-24

    In an internal combustion engine including an oil lubrication system, a liquid cooling system, and an improved air intake system is described. The improved air intake system comprises: a housing including a first opening in one end, which opening is open to the atmosphere and a second opening comprising an air outlet opening in the other end open to the air intake manifold of the engine, a heat exchanger positioned in the first opening. The heat exchanger consists of a series of coils positioned in the flow path of the atmospheric air as it enters the housing, the heat exchanger being fluidly connected to either the engine lubrication system or the cooling system to provide a warm heat source for the incoming air to the housing, acceleration means positioned in the housing downstream of the heat exchanger, the acceleration means comprising a honeycomb structure positioned across the air intake flow path. The honey-comb structure includes a multitude of honey combed mini-venturi cells through which the heated air flows in an accelerated mode, a removable air filter positioned between the heat exchanger and the acceleration means and a single opening provided in the housing through which the air filter can be passed and removed, and additional openings in the housing positioned downstream of the heat exchanger and upstream of the air filter, the additional openings including removable flaps for opening and closing the openings to control the temperature of the air flowing through the housing.

  15. Protein dynamics viewed by hydrogen exchange

    PubMed Central

    Skinner, John J; Lim, Woon K; Bédard, Sabrina; Black, Ben E; Englander, S Walter

    2012-01-01

    To examine the relationship between protein structural dynamics and measurable hydrogen exchange (HX) data, the detailed exchange behavior of most of the backbone amide hydrogens of Staphylococcal nuclease was compared with that of their neighbors, with their structural environment, and with other information. Results show that H-bonded hydrogens are protected from exchange, with HX rate effectively zero, even when they are directly adjacent to solvent. The transition to exchange competence requires a dynamic structural excursion that removes H-bond protection and allows exposure to solvent HX catalyst. The detailed data often make clear the nature of the dynamic excursion required. These range from whole molecule unfolding, through smaller cooperative unfolding reactions of secondary structural elements, and down to local fluctuations that involve as little as a single peptide group or side chain or water molecule. The particular motion that dominates the exchange of any hydrogen is the one that allows the fastest HX rate. The motion and the rate it produces are determined by surrounding structure and not by nearness to solvent or the strength of the protecting H-bond itself or its acceptor type (main chain, side chain, structurally bound water). Many of these motions occur over time scales that are appropriate for biochemical function. PMID:22544544

  16. Protein dynamics viewed by hydrogen exchange.

    PubMed

    Skinner, John J; Lim, Woon K; Bédard, Sabrina; Black, Ben E; Englander, S Walter

    2012-07-01

    To examine the relationship between protein structural dynamics and measurable hydrogen exchange (HX) data, the detailed exchange behavior of most of the backbone amide hydrogens of Staphylococcal nuclease was compared with that of their neighbors, with their structural environment, and with other information. Results show that H-bonded hydrogens are protected from exchange, with HX rate effectively zero, even when they are directly adjacent to solvent. The transition to exchange competence requires a dynamic structural excursion that removes H-bond protection and allows exposure to solvent HX catalyst. The detailed data often make clear the nature of the dynamic excursion required. These range from whole molecule unfolding, through smaller cooperative unfolding reactions of secondary structural elements, and down to local fluctuations that involve as little as a single peptide group or side chain or water molecule. The particular motion that dominates the exchange of any hydrogen is the one that allows the fastest HX rate. The motion and the rate it produces are determined by surrounding structure and not by nearness to solvent or the strength of the protecting H-bond itself or its acceptor type (main chain, side chain, structurally bound water). Many of these motions occur over time scales that are appropriate for biochemical function. PMID:22544544

  17. Proton channels and exchangers in cancer.

    PubMed

    Spugnini, Enrico Pierluigi; Sonveaux, Pierre; Stock, Christian; Perez-Sayans, Mario; De Milito, Angelo; Avnet, Sofia; Garcìa, Abel Garcìa; Harguindey, Salvador; Fais, Stefano

    2015-10-01

    Although cancer is characterized by an intratumoral genetic heterogeneity, a totally deranged pH control is a common feature of most cancer histotypes. Major determinants of aberrant pH gradient in cancer are proton exchangers and transporters, including V-ATPase, Na+/H+ exchanger (NHE), monocarboxylate transporters (MCTs) and carbonic anhydrases (CAs). Thanks to the activity of these proton transporters and exchangers, cancer becomes isolated and/or protected not only from the body reaction against the growing tumor, but also from the vast majority of drugs that when protonated into the acidic tumor microenvironment do not enter into cancer cells. Proton transporters and exchangers represent a key feature tumor cells use to survive in the very hostile microenvironmental conditions that they create and maintain. Detoxifying mechanisms may thus represent both a key survival option and a selection outcome for cells that behave as unicellular microorganisms rather than belonging to an organ, compartment or body. It is, in fact, typical of malignant tumors that, after a clinically measurable yet transient initial response to a therapy, resistant tumor clones emerge and proliferate, thus bursting a more malignant behavior and rapid tumor progression. This review critically presents the background of a novel and efficient approach that aims to fight cancer through blocking or inhibiting well characterized proton exchangers and transporters active in human cancer cells. This article is part of a Special Issue entitled: Membrane channels and transporters in cancers. PMID:25449995

  18. Computing in mammalian cells with nucleic acid strand exchange

    NASA Astrophysics Data System (ADS)

    Groves, Benjamin; Chen, Yuan-Jyue; Zurla, Chiara; Pochekailov, Sergii; Kirschman, Jonathan L.; Santangelo, Philip J.; Seelig, Georg

    2016-03-01

    DNA strand displacement has been widely used for the design of molecular circuits, motors, and sensors in cell-free settings. Recently, it has been shown that this technology can also operate in biological environments, but capabilities remain limited. Here, we look to adapt strand displacement and exchange reactions to mammalian cells and report DNA circuitry that can directly interact with a native mRNA. We began by optimizing the cellular performance of fluorescent reporters based on four-way strand exchange reactions and identified robust design principles by systematically varying the molecular structure, chemistry and delivery method. Next, we developed and tested AND and OR logic gates based on four-way strand exchange, demonstrating the feasibility of multi-input logic. Finally, we established that functional siRNA could be activated through strand exchange, and used native mRNA as programmable scaffolds for co-localizing gates and visualizing their operation with subcellular resolution.

  19. Computing in mammalian cells with nucleic acid strand exchange

    PubMed Central

    Pochekailov, Sergii; Kirschman, Jonathan L.; Santangelo, Philip J.; Seelig, Georg

    2015-01-01

    DNA strand displacement has been widely used for the design of molecular circuits, motors, and sensors in cell-free settings. Recently, it has been shown that this technology can also operate in biological environments, but capabilities remain limited. Here, we look to adapt strand displacement and exchange reactions to mammalian cells and report DNA circuitry that can directly interact with a native mRNA. We began by optimizing the cellular performance of fluorescent reporters based on four-way strand exchange reactions and identified robust design principles by systematically varying the molecular structure, chemistry and delivery method. Next, we developed and tested AND and OR logic gates based on four-way strand exchange, demonstrating the feasibility of multi-input logic. Finally, we established that functional siRNA could be activated through strand exchange, and used native mRNA as programmable scaffolds for co-localizing gates and visualizing their operation with subcellular resolution. PMID:26689378

  20. Computing in mammalian cells with nucleic acid strand exchange.

    PubMed

    Groves, Benjamin; Chen, Yuan-Jyue; Zurla, Chiara; Pochekailov, Sergii; Kirschman, Jonathan L; Santangelo, Philip J; Seelig, Georg

    2016-03-01

    DNA strand displacement has been widely used for the design of molecular circuits, motors, and sensors in cell-free settings. Recently, it has been shown that this technology can also operate in biological environments, but capabilities remain limited. Here, we look to adapt strand displacement and exchange reactions to mammalian cells and report DNA circuitry that can directly interact with a native mRNA. We began by optimizing the cellular performance of fluorescent reporters based on four-way strand exchange reactions and identified robust design principles by systematically varying the molecular structure, chemistry and delivery method. Next, we developed and tested AND and OR logic gates based on four-way strand exchange, demonstrating the feasibility of multi-input logic. Finally, we established that functional siRNA could be activated through strand exchange, and used native mRNA as programmable scaffolds for co-localizing gates and visualizing their operation with subcellular resolution. PMID:26689378

  1. FASTGAS: Fast Gas Sampling for palladium exchange tests

    SciTech Connect

    Malinowski, M.E.; Stewart, K.D.; VerBerkmoes, A.A.

    1991-06-01

    A mass spectrometric technique for measuring the composition of gas flows in rapid H/D exchange reactions in palladium compacts has been developed. This method, called FASTGAS (Fast Gas Sampling)'' has been used at atmospheric pressures and above with a time response of better than 100 ms. The current implementation of the FASTGAS technique is described in detail and examples of its application to palladium hydride exchange tests are given. 12 refs., 10 figs.

  2. Heat exchanger restart evaluation

    SciTech Connect

    Morrison, J.M.; Hirst, C.W.; Lentz, T.F.

    1992-02-28

    On December 24, 1991, the K-Reactor was in the shutdown mode with full AC process water flow and full cooling water flow. Safety rod testing was being performed as part of the power ascension testing program. The results of cooling water samples indicated tritium concentrations higher than allowable. Further sampling and testing confirmed a Process Water System to Cooling Water System leak in heat exchanger 4A (HX 4A). The heat exchanger was isolated and the plant shutdown. Heat exchanger 4kA was removed from the plant and moved to C-Area prior to performing examinations and diagnostic testing. This included locating and identifying the leaking tube or tubes, eddy current examination of the leaking tube and a number of adjacent tubes, visually inspecting the leaking tube from both the inside as well as the area surrounding the failure mechanism. In addition ten other tubes that either exhibited eddy current indications or would represent a baseline condition were removed from heat exchanger 4A for metallurgical examination. Additional analysis and review of heat exchanger leakage history was performed to determine if there are any patterns which can be used for predictive purposes. Compensatory actions have been taken to improve the sensitivity and response time to any future events of this type. The results of these actions are summarized herein.

  3. Heat exchanger restart evaluation

    SciTech Connect

    Morrison, J.M.; Hirst, C.W.; Lentz, T.F.

    1992-03-18

    On December 24, 1991, the K-Reactor was in the shutdown mode with full AC process water flow and full cooling water flow. Safety rod testing was being performed as part of the power ascension testing program. The results of cooling water samples indicated tritium concentrations higher than allowable. Further sampling and testing confirmed a Process Water System to Cooling Water System leak in heat exchanger 4A (HX 4A). The heat exchanger was isolated and the plant shutdown. Heat exchanger 4A was removed from the plant and moved to C-Area prior to performing examinations and diagnostic testing. This included locating and identifying the leaking tube or tubes, eddy current examination of the leaking tube and a number of adjacent tubes, visually inspecting the leaking tube from both the inside as well as the area surrounding the identified tube. The leaking tube was removed and examined metallurgically to determine the failure mechanism. In addition ten other tubes that either exhibited eddy current indications or would represent a baseline condition were removed from heat exchanger 4A for metallurgical examination. Additional analysis and review of heat exchanger leakage history was performed to determine if there are any patterns which can be used for predictive purposes. Compensatory actions have been taken to improve the sensitivity and response time to any future events of this type. The results of these actions are summary herein.

  4. Heat exchanger restart evaluation

    SciTech Connect

    Morrison, J.M.; Hirst, C.W.; Lentz, T.F.

    1992-03-18

    On December 24, 1991, the K-Reactor was in the shutdown mode with full AC process water flow and full cooling water flow. Safety rod testing was being performed as part of the power ascension testing program. The results of cooling water samples indicated tritium concentrations higher than allowable. Further sampling and testing confirmed a Process Water System to Cooling Water System leak in heat exchanger 4A (HX 4A). The heat exchanger was isolated and the plant shutdown. Heat exchanger 4A was removed from the plant and moved to C-Area prior to performing examinations and diagnostic testing. This included locating and identifying the leaking tube or tubes, eddy current examination of the leaking tube and a number of adjacent tubes, visually inspecting the leaking tube from both the inside as well as the area surrounding the identified tube. The leaking tube was removed and examined metallurgically to determine the failure mechanism. In addition ten other tubes that either exhibited eddy current indications or would represent a baseline condition were removed from heat exchanger 4A for metallurgical examination. Additional analysis and review of heat exchanger leakage history was performed to determine if there are any patterns which can be used for predictive purposes. Compensatory actions have been taken to improve the sensitivity and response time to any future events of this type. The results of these actions are summarized.

  5. Downhole heat exchangers

    SciTech Connect

    Culver, G.; Lund, J.W.

    1999-09-01

    The downhole heat exchanger (DHE) eliminates the problem of disposal of geothermal fluid, since only heat is taken from the well. The exchanger consists of a system of pipes or tubes suspended in the well through which clean secondary water is pumped or allowed to circulate by natural convection. These systems offer substantial economic savings over surface heat exchangers where a single-well system is adequate (typically less than 0.8 MWt, with well depths up to about 500 ft) and may be economical under certain conditions at well depths to 1500 ft. Several designs have proven successful; but, the most popular are a simple hairpin loop or multiple loops of iron pipe (similar to the tubes in a U-tube and shell exchanger) extending to near the well bottom. An experimental design consisting of multiple small tubes with headers at each end suspended just below the water surface appears to offer economic and heating capacity advantages. The paper describes design and construction details and New Zealand`s experience with downhole heat exchangers.

  6. Equilibrious Strand Exchange Promoted by DNA Conformational Switching

    NASA Astrophysics Data System (ADS)

    Wu, Zhiguo; Xie, Xiao; Li, Puzhen; Zhao, Jiayi; Huang, Lili; Zhou, Xiang

    2013-01-01

    Most of DNA strand exchange reactions in vitro are based on toehold strategy which is generally nonequilibrium, and intracellular strand exchange mediated by proteins shows little sequence specificity. Herein, a new strand exchange promoted by equilibrious DNA conformational switching is verified. Duplexes containing c-myc sequence which is potentially converted into G-quadruplex are designed in this strategy. The dynamic equilibrium between duplex and G4-DNA is response to the specific exchange of homologous single-stranded DNA (ssDNA). The SER is enzyme free and sequence specific. No ATP is needed and the displaced ssDNAs are identical to the homologous ssDNAs. The SER products and exchange kenetics are analyzed by PAGE and the RecA mediated SER is performed as the contrast. This SER is a new feature of G4-DNAs and a novel strategy to utilize the dynamic equilibrium of DNA conformations.

  7. Equilibrious Strand Exchange Promoted by DNA Conformational Switching

    PubMed Central

    Wu, Zhiguo; Xie, Xiao; Li, Puzhen; Zhao, Jiayi; Huang, Lili; Zhou, Xiang

    2013-01-01

    Most of DNA strand exchange reactions in vitro are based on toehold strategy which is generally nonequilibrium, and intracellular strand exchange mediated by proteins shows little sequence specificity. Herein, a new strand exchange promoted by equilibrious DNA conformational switching is verified. Duplexes containing c-myc sequence which is potentially converted into G-quadruplex are designed in this strategy. The dynamic equilibrium between duplex and G4-DNA is response to the specific exchange of homologous single-stranded DNA (ssDNA). The SER is enzyme free and sequence specific. No ATP is needed and the displaced ssDNAs are identical to the homologous ssDNAs. The SER products and exchange kenetics are analyzed by PAGE and the RecA mediated SER is performed as the contrast. This SER is a new feature of G4-DNAs and a novel strategy to utilize the dynamic equilibrium of DNA conformations. PMID:23350029

  8. Equilibrious strand exchange promoted by DNA conformational switching.

    PubMed

    Wu, Zhiguo; Xie, Xiao; Li, Puzhen; Zhao, Jiayi; Huang, Lili; Zhou, Xiang

    2013-01-01

    Most of DNA strand exchange reactions in vitro are based on toehold strategy which is generally nonequilibrium, and intracellular strand exchange mediated by proteins shows little sequence specificity. Herein, a new strand exchange promoted by equilibrious DNA conformational switching is verified. Duplexes containing c-myc sequence which is potentially converted into G-quadruplex are designed in this strategy. The dynamic equilibrium between duplex and G4-DNA is response to the specific exchange of homologous single-stranded DNA (ssDNA). The SER is enzyme free and sequence specific. No ATP is needed and the displaced ssDNAs are identical to the homologous ssDNAs. The SER products and exchange kenetics are analyzed by PAGE and the RecA mediated SER is performed as the contrast. This SER is a new feature of G4-DNAs and a novel strategy to utilize the dynamic equilibrium of DNA conformations. PMID:23350029

  9. Modular heat exchanger

    DOEpatents

    Culver, Donald W.

    1978-01-01

    A heat exchanger for use in nuclear reactors includes a heat exchange tube bundle formed from similar modules each having a hexagonal shroud containing a large number of thermally conductive tubes which are connected with inlet and outlet headers at opposite ends of each module, the respective headers being adapted for interconnection with suitable inlet and outlet manifold means. In order to adapt the heat exchanger for operation in a high temperature and high pressure environment and to provide access to all tube ports at opposite ends of the tube bundle, a spherical tube sheet is arranged in sealed relation across the chamber with an elongated duct extending outwardly therefrom to provide manifold means for interconnection with the opposite end of the tube bundle.

  10. Ion exchange phenomena

    SciTech Connect

    Bourg, I.C.; Sposito, G.

    2011-05-01

    Ion exchange phenomena involve the population of readily exchangeable ions, the subset of adsorbed solutes that balance the intrinsic surface charge and can be readily replaced by major background electrolyte ions (Sposito, 2008). These phenomena have occupied a central place in soil chemistry research since Way (1850) first showed that potassium uptake by soils resulted in the release of an equal quantity of moles of charge of calcium and magnesium. Ion exchange phenomena are now routinely modeled in studies of soil formation (White et al., 2005), soil reclamation (Kopittke et al., 2006), soil fertilitization (Agbenin and Yakubu, 2006), colloidal dispersion/flocculation (Charlet and Tournassat, 2005), the mechanics of argillaceous media (Gajo and Loret, 2007), aquitard pore water chemistry (Tournassat et al., 2008), and groundwater (Timms and Hendry, 2007; McNab et al., 2009) and contaminant hydrology (Chatterjee et al., 2008; van Oploo et al., 2008; Serrano et al., 2009).

  11. On exchangeable multinomial distributions

    PubMed Central

    George, E. Olusegun; Cheon, Kyeongmi; Yuan, Yilian; Szabo, Aniko

    2016-01-01

    We derive an expression for the joint distribution of exchangeable multinomial random variables, which generalizes the multinomial distribution based on independent trials while retaining some of its important properties. Unlike de Finneti's representation theorem for a binary sequence, the exchangeable multinomial distribution derived here does not require that the finite set of random variables under consideration be a subset of an infinite sequence. Using expressions for higher moments and correlations, we show that the covariance matrix for exchangeable multinomial data has a different form from that usually assumed in the literature, and we analyse data from developmental toxicology studies. The proposed analyses have been implemented in R and are available on CRAN in the CorrBin package.

  12. Microgravity condensing heat exchanger

    NASA Technical Reports Server (NTRS)

    Thomas, Christopher M. (Inventor); Ma, Yonghui (Inventor); North, Andrew (Inventor); Weislogel, Mark M. (Inventor)

    2011-01-01

    A heat exchanger having a plurality of heat exchanging aluminum fins with hydrophilic condensing surfaces which are stacked and clamped between two cold plates. The cold plates are aligned radially along a plane extending through the axis of a cylindrical duct and hold the stacked and clamped portions of the heat exchanging fins along the axis of the cylindrical duct. The fins extend outwardly from the clamped portions along approximately radial planes. The spacing between fins is symmetric about the cold plates, and are somewhat more closely spaced as the angle they make with the cold plates approaches 90.degree.. Passageways extend through the fins between vertex spaces which provide capillary storage and communicate with passageways formed in the stacked and clamped portions of the fins, which communicate with water drains connected to a pump externally to the duct. Water with no entrained air is drawn from the capillary spaces.

  13. Water exchange dynamics around H3O+ and OH- ions

    NASA Astrophysics Data System (ADS)

    Roy, Santanu; Dang, Liem X.

    2015-05-01

    In this letter, we report the first computer simulation of the dynamics of water exchanging between the first and second solvation shells of H3O+. Employing different rate theories for chemical reactions such as the transition state theory, the Grote-Hynes theory, the reactive flux method, and the Impey-Madden-McDonald method, we calculate the solvent exchange rates from molecular dynamics simulations that account for explicit polarization effects. In addition, we also study water exchanges around OH- and find that the corresponding time scale is much smaller than that for H3O+.

  14. Heat exchanger for fuel cell power plant reformer

    DOEpatents

    Misage, Robert; Scheffler, Glenn W.; Setzer, Herbert J.; Margiott, Paul R.; Parenti, Jr., Edmund K.

    1988-01-01

    A heat exchanger uses the heat from processed fuel gas from a reformer for a fuel cell to superheat steam, to preheat raw fuel prior to entering the reformer and to heat a water-steam coolant mixture from the fuel cells. The processed fuel gas temperature is thus lowered to a level useful in the fuel cell reaction. The four temperature adjustments are accomplished in a single heat exchanger with only three heat transfer cores. The heat exchanger is preheated by circulating coolant and purge steam from the power section during startup of the latter.

  15. Energy absorber for sodium-heated heat exchanger

    DOEpatents

    Essebaggers, J.

    1975-12-01

    A heat exchanger is described in which water-carrying tubes are heated by liquid sodium and in which the results of accidental contact between the water and the sodium caused by failure of one or more of the water tubes is minimized. An energy absorbing chamber contains a compressible gas and is connected to the body of flowing sodium by a channel so that, in the event of a sodium-water reaction, products of the reaction will partially fill the energy absorbing chamber to attenuate the rise in pressure within the heat exchanger.

  16. Determination of the cation-exchange capacity of muscovite mica

    SciTech Connect

    Osman, M.A.; Suter, U.W.

    2000-04-01

    High cation-exchange capacity (CEC) muscovite mica with a homoionic surface was prepared by replacing the Li{sup +} surface ions of partially delaminated Li-mica with K{sup +}. The CEC of this K-mica was determined by exchanging its surface cations with Cs{sup +}, NH{sub 4}{sup +}, methylene blue (MB{sup +}), and copper triethylenetetramine [Cu(trien){sup 2+}]. The kinetics of these exchange reactions were studied and showed large differences depending on their relative affinities to mica. The NH{sub 4}{sup +}/K{sup +} exchange was slow, while the Cs{sup +} and Cu(trien){sup 2+}/K{sup +} exchange was fast. The MB{sup +}/K{sup +} exchange was quite slow and was not completed even after 99 h. Insufficient reaction time is one of the main reasons for the contradictory results reported in the literature for the CEC of aluminosilicates obtained by different methods. The CEC of mica can be photometrically measured by exchanging its surface cations with Cu(trien){sup 2+}.

  17. Heat exchanger panel

    NASA Technical Reports Server (NTRS)

    Warburton, Robert E. (Inventor); Cuva, William J. (Inventor)

    2005-01-01

    The present invention relates to a heat exchanger panel which has broad utility in high temperature environments. The heat exchanger panel has a first panel, a second panel, and at least one fluid containment device positioned intermediate the first and second panels. At least one of the first panel and the second panel have at least one feature on an interior surface to accommodate the at least one fluid containment device. In a preferred embodiment, each of the first and second panels is formed from a high conductivity, high temperature composite material. Also, in a preferred embodiment, the first and second panels are joined together by one or more composite fasteners.

  18. Microscale Regenerative Heat Exchanger

    NASA Technical Reports Server (NTRS)

    Moran, Matthew E.; Stelter, Stephan; Stelter, Manfred

    2006-01-01

    The device described herein is designed primarily for use as a regenerative heat exchanger in a miniature Stirling engine or Stirling-cycle heat pump. A regenerative heat exchanger (sometimes called, simply, a "regenerator" in the Stirling-engine art) is basically a thermal capacitor: Its role in the Stirling cycle is to alternately accept heat from, then deliver heat to, an oscillating flow of a working fluid between compression and expansion volumes, without introducing an excessive pressure drop. These volumes are at different temperatures, and conduction of heat between these volumes is undesirable because it reduces the energy-conversion efficiency of the Stirling cycle.

  19. Alert Exchange Process Protocol

    NASA Technical Reports Server (NTRS)

    Groen, Frank

    2015-01-01

    The National Aeronautics and Space Administration of the United States of America (NASA), and the European Space Agency (ESA), and the Japanese Aerospace Exploration Agency (JAXA), acknowledging that NASA, ESA and JAXA have a mutual interest in exchanging Alerts and Alert Status Lists to enhance the information base for each system participant while fortifying the general level of cooperation between the policy agreement subscribers, and each Party will exchange Alert listings on regular basis and detailed Alert information on a need to know basis to the extent permitted by law.

  20. Gas exchange measurements in natural systems

    SciTech Connect

    Broecker, W.S.; Peng, T.H.

    1983-01-01

    Direct knowledge of the rates of gas exchange in lakes and the ocean is based almost entirely on measurements of the isotopes /sup 14/C, /sup 222/Rn and /sup 3/He. The distribution of natural radiocarbon has yielded the average rate of CO/sub 2/ exchange for the ocean and for several closed basin lakes. That of bomb produced radiocarbon has been used in the same systems. The /sup 222/Rn to /sup 226/Ra ratio in open ocean surface water has been used to give local short term gas exchange rates. The radon method generally cannot be used in lakes, rivers, estuaries or shelf areas because of the input of radon from sediments. A few attempts have been made to use the excess /sup 3/He produced by decay of bomb produced tritium in lakes to give gas transfer rates. The uncertainty in the molecular diffusivity of helium and in the diffusivity dependence of the rate of gas transfer holds back the application of this method. A few attempts have been made to enrich the surface waters of small lakes with /sup 226/Ra and /sup 3/H in order to allow the use of the /sup 222/Rn and /sup 3/He methods. While these studies give broadly concordant results, many questions remain unanswered. The wind velocity dependence of gas exchange rate has yet to be established in field studies. The dependence of gas exchange rate on molecular diffusivity also remains in limbo. Finally, the degree of enhancement of CO/sub 2/ exchange through chemical reactions has been only partially explored. 49 references, 2 figures, 2 tables.

  1. Securities and Exchange Commission Semiannual Regulatory Agenda

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-04-26

    ... [Securities and Exchange Commission Semiannual Regulatory Agenda ] Part XXIII Securities and Exchange Commission Semiannual Regulatory Agenda ] SECURITIES AND EXCHANGE COMMISSION (SEC) SECURITIES AND EXCHANGE COMMISSION 17 CFR Ch. II Regulatory Flexibility Agenda AGENCY: Securities and Exchange Commission. ACTION: Semiannual regulatory...

  2. Ceramic Spheres From Cation Exchange Beads

    NASA Technical Reports Server (NTRS)

    Dynys, F. W.

    2003-01-01

    Porous ZrO2 and hollow TiO2 spheres were synthesized from a strong acid cation exchange resin. Spherical cation exchange beads, polystyrene based polymer, were used as a morphological-directing template. Aqueous ion exchange reaction was used to chemically bind (ZrO)(2+) ions to the polystyrene structure. The pyrolysis of the polystyrene at 600 C produces porous ZrO2 spheres with a surface area of 24 sq m/g with a mean sphere size of 42 microns. Hollow TiO2 spheres were synthesized by using the beads as a micro-reactor. A direct surface reaction - between titanium isopropoxide and the resin beads forms a hydrous TiO2 shell around the polystyrene core. The pyrolysis of the polystyrene core at 600 C produces hollow anatase spheres with a surface area of 42 sq m/g with a mean sphere size of 38 microns. The formation of ceramic spheres was studied by XRD, SEM and B.E.T. nitrogen adsorption measurements.

  3. Deuterium Exchange in the Systems of H2O+/H2O and H3O+/H2O

    NASA Technical Reports Server (NTRS)

    Anicich, V. G.; Sen, A. D.

    1995-01-01

    Using tandem mass spectrometry various water ion interactions were observed. These reactions consisted of a series of charge transfer, proton transfer, and isotopic exchange steps. The experimental data sets consist of variations of ion abundances over a neutral pressure range. An expected sequence of isotopic exchange reactions is given along with differential equation solutions & reaction rate data.

  4. Currency Exchange Rates.

    ERIC Educational Resources Information Center

    Siler, Carl R.

    This curriculum unit of the Muncie (Indiana) Southside High School is to simulate the dynamics of foreign currency exchange rates from the perspectives of: (1) a major U.S. corporation, ABB Power T & D Company, Inc., of Muncie, Indiana, a manufacturer of large power transformers for the domestic and foreign markets; and (2) individual consumers…

  5. Estimate exchanger vibration

    SciTech Connect

    Nieh, C.D.; Zengyan, H.

    1986-04-01

    Based on the classical beam theory, a simple method for calculating the natural frequency of unequally spanned tubes is presented. The method is suitable for various boundary conditions. Accuracy of the calculations is sufficient for practical applications. This method will help designers and operators estimate the vibration of tubular exchangers. In general, there are three reasons why a tube vibrates in cross flow: vortex shedding, fluid elasticity and turbulent buffeting. No matter which is the cause, the basic reason is that the frequency of exciting force is approximately the same as or equal to the natural frequency of the tube. To prevent the heat exchanger from vibrating, it is necessary to select correctly the shell-side fluid velocity so that the frequency of exciting force is different from the natural frequency of the tube, or to vary the natural frequency of the heat exchanger tube. So precisely determining the natural frequency of the heat exchanger, especially its foundational frequency under various supporting conditions, is of significance.

  6. Research Exchange, 2002.

    ERIC Educational Resources Information Center

    Research Exchange, 2002

    2002-01-01

    These three issues of the "Research Exchange" focus on how better to conduct disability research and disseminate research results. The first issue examines the topic of human subject/human research participant protection, with a focus on research funded through the National Institute on Disability and Rehabilitation Research (NIDRR). It provides…

  7. Higher Education Exchange 2006

    ERIC Educational Resources Information Center

    Brown, David W., Ed.; Witte, Deborah, Ed.

    2006-01-01

    Contributors to this issue of the Higher Education Exchange debate the issues around knowledge production, discuss the acquisition of deliberative skills for democracy, and examine how higher education prepares, or does not prepare, students for citizenship roles. Articles include: (1) "Foreword" (Deborah Witte); (2) "Knowledge, Judgment and…

  8. Technology Performance Exchange

    SciTech Connect

    2015-09-01

    To address the need for accessible, high-quality data, the Department of Energy has developed the Technology Performance Exchange (TPEx). TPEx enables technology suppliers, third-party testing laboratories, and other entities to share product performance data. These data are automatically transformed into a format that technology evaluators can easily use in their energy modeling assessments to inform procurement decisions.

  9. Heat exchange enhancement structure

    SciTech Connect

    Cornelison, R.C.; Kreith, F.

    1980-12-02

    A passive heat exchange enhancement structure which operates by free convection includes a flat mounting portion having a plurality of integral fins bent outwardly from one side edge thereof. The mounting portion is securable around a stovepipe, to a flat surface or the like for transferring heat from the pipe through the fins to the surrounding air by rotation-enhanced free convection.

  10. Higher Education Exchange, 2014

    ERIC Educational Resources Information Center

    Brown, David W., Ed.; Witte, Deborah, Ed.

    2014-01-01

    Research shows that not only does higher education not see the public; when the public, in turn, looks at higher education, it sees mostly malaise, inefficiencies, expense, and unfulfilled promises. Yet, the contributors to this issue of the "Higher Education Exchange" tell of bright spots in higher education where experiments in working…

  11. Nature's Heat Exchangers.

    ERIC Educational Resources Information Center

    Barnes, George

    1991-01-01

    Discusses the heat-transfer systems of different animals. Systems include heat conduction into the ground, heat transferred by convection, heat exchange in lizards, fish and polar animals, the carotid rete system, electromagnetic radiation from animals and people, and plant and animal fiber optics. (MDH)

  12. Chimney heat exchanger

    SciTech Connect

    Whiteley, I.C.

    1981-09-01

    A heat exchanger for installation on the top of a chimney of a building includes a housing having a lower end receiving the top of the chimney and an upper end with openings permitting the escape of effluent from the chimney and a heat exchanger assembly disposed in the housing including a central chamber and a spirally arranged duct network defining an effluent spiral path between the top of the chimney and the central chamber and a fresh air spiral path between an inlet disposed at the lower end of the housing and the central chamber, the effluent and fresh air spiral paths being in heat exchange relationship such that air passing through the fresh air spiral path is heated by hot effluent gases passing upward through the chimney and the effluent spiral path for use in heating the building. A pollution trap can be disposed in the central chamber of the heat exchanger assembly for removing pollutants from the effluent, the pollution trap including a rotating cage carrying pumice stones for absorbing pollutants from the effluent with the surface of the pumice gradually ground off to reveal fresh stone as the cage rotates.

  13. Visiting Scholar Exchange Reports.

    ERIC Educational Resources Information Center

    Rubin, Kyna, Ed.

    1986-01-01

    Provides reports of four United States scholars who visited China as part of the Visiting Scholar Exchange Program. The titles of the reports are (1) "China Journey: A Political Scientist's Look at Yan'an," (2) "The Social Consequences of Land Reclamation in Chinese Coastal Ecosystems," (3) "Anthropology Lectures in South China," and (4) "The Use…

  14. Higher Education Exchange

    ERIC Educational Resources Information Center

    Brown, David W., Ed.; Witte, Deborah, Ed.

    2009-01-01

    This volume begins with an essay by Noelle McAfee, a contributor who is familiar to readers of Higher Education Exchange (HEX). She reiterates Mathews' argument regarding the disconnect between higher education's sense of engagement and the public's sense of engagement, and suggests a way around the epistemological conundrum of "knowledge produced…

  15. Higher Education Exchange, 2009

    ERIC Educational Resources Information Center

    Brown, David W., Ed.; Witte, Deborah, Ed.

    2009-01-01

    This volume begins with an essay by Noelle McAfee, a contributor who is familiar to readers of Higher Education Exchange (HEX). She reiterates Kettering's president David Mathews' argument regarding the disconnect between higher education's sense of engagement and the public's sense of engagement, and suggests a way around the epistemological…

  16. Protein hydrogen exchange: testing current models.

    PubMed

    Skinner, John J; Lim, Woon K; Bédard, Sabrina; Black, Ben E; Englander, S Walter

    2012-07-01

    To investigate the determinants of protein hydrogen exchange (HX), HX rates of most of the backbone amide hydrogens of Staphylococcal nuclease were measured by NMR methods. A modified analysis was used to improve accuracy for the faster hydrogens. HX rates of both near surface and well buried hydrogens are spread over more than 7 orders of magnitude. These results were compared with previous hypotheses for HX rate determination. Contrary to a common assumption, proximity to the surface of the native protein does not usually produce fast exchange. The slow HX rates for unprotected surface hydrogens are not well explained by local electrostatic field. The ability of buried hydrogens to exchange is not explained by a solvent penetration mechanism. The exchange rates of structurally protected hydrogens are not well predicted by algorithms that depend only on local interactions or only on transient unfolding reactions. These observations identify some of the present difficulties of HX rate prediction and suggest the need for returning to a detailed hydrogen by hydrogen analysis to examine the bases of structure-rate relationships, as described in the companion paper (Skinner et al., Protein Sci 2012;21:996-1005). PMID:22544567

  17. Counterflow Regolith Heat Exchanger

    NASA Technical Reports Server (NTRS)

    Zubrin, Robert; Jonscher, Peter

    2013-01-01

    A problem exists in reducing the total heating power required to extract oxygen from lunar regolith. All such processes require heating a great deal of soil, and the heat energy is wasted if it cannot be recycled from processed material back into new material. The counterflow regolith heat exchanger (CoRHE) is a device that transfers heat from hot regolith to cold regolith. The CoRHE is essentially a tube-in-tube heat exchanger with internal and external augers attached to the inner rotating tube to move the regolith. Hot regolith in the outer tube is moved in one direction by a right-hand - ed auger, and the cool regolith in the inner tube is moved in the opposite direction by a left-handed auger attached to the inside of the rotating tube. In this counterflow arrangement, a large fraction of the heat from the expended regolith is transferred to the new regolith. The spent regolith leaves the heat exchanger close to the temperature of the cold new regolith, and the new regolith is pre-heated close to the initial temperature of the spent regolith. Using the CoRHE can reduce the heating requirement of a lunar ISRU system by 80%, reducing the total power consumption by a factor of two. The unique feature of this system is that it allows for counterflow heat exchange to occur between solids, instead of liquids or gases, as is commonly done. In addition, in variants of this concept, the hydrogen reduction can be made to occur within the counterflow heat exchanger itself, enabling a simplified lunar ISRU (in situ resource utilization) system with excellent energy economy and continuous nonbatch mode operation.

  18. Electron self-exchange in hemoglobins revealed by deutero-hemin substitution.

    PubMed

    Athwal, Navjot Singh; Alagurajan, Jagannathan; Sturms, Ryan; Fulton, D Bruce; Andreotti, Amy H; Hargrove, Mark S

    2015-09-01

    Hemoglobins (phytoglobins) from rice plants (nsHb1) and from the cyanobacterium Synechocystis (PCC 6803) (SynHb) can reduce hydroxylamine with two electrons to form ammonium. The reaction requires intermolecular electron transfer between protein molecules, and rapid electron self-exchange might play a role in distinguishing these hemoglobins from others with slower reaction rates, such as myoglobin. A relatively rapid electron self-exchange rate constant has been measured for SynHb by NMR, but the rate constant for myoglobin is equivocal and a value for nsHb1 has not yet been measured. Here we report electron self-exchange rate constants for nsHb1 and Mb as a test of their role in hydroxylamine reduction. These proteins are not suitable for analysis by NMR ZZ exchange, so a method was developed that uses cross-reactions between each hemoglobin and its deutero-hemin substituted counterpart. The resulting electron transfer is between identical proteins with low driving forces and thus closely approximates true electron self-exchange. The reactions can be monitored spectrally due to the distinct spectra of the prosthetic groups, and from this electron self-exchange rate constants of 880 (SynHb), 2900 (nsHb1), and 0.05M(-1) s(-1) (Mb) have been measured for each hemoglobin. Calculations of cross-reactions using these values accurately predict hydroxylamine reduction rates for each protein, suggesting that electron self-exchange plays an important role in the reaction. PMID:26141377

  19. A corrosive resistant heat exchanger

    DOEpatents

    Richlen, S.L.

    1987-08-10

    A corrosive and erosive resistant heat exchanger which recovers heat from a contaminated heat stream. The heat exchanger utilizes a boundary layer of innocuous gas, which is continuously replenished, to protect the heat exchanger surface from the hot contaminated gas. The innocuous gas is pumped through ducts or perforations in the heat exchanger wall. Heat from the heat stream is transferred by radiation to the heat exchanger wall. Heat is removed from the outer heat exchanger wall by a heat recovery medium. 3 figs., 3 tabs.

  20. Anion exchange in Zn-Al layered double hydroxides: In situ X-ray diffraction study

    NASA Astrophysics Data System (ADS)

    Salak, Andrei N.; Tedim, João; Kuznetsova, Alena I.; Zheludkevich, Mikhail L.; Ferreira, Mário G. S.

    2010-07-01

    Anion exchange capacity is a key factor for the application of Zn-Al layered double hydroxides (LDHs) as nano-containers in active corrosion protection. In this work, the nitrate-pyrovanadate anion exchange/re-exchange processes in these LDHs were investigated in situ. We demonstrate that the exchange reactions lead to a decrease of the average crystallite size of LDHs as a result of mechanical fragmentation of the crystallites rather than dissolution/recrystallization. The fragmentation occurs due to fast anion exchange in the initial stage, and can be controlled by changing the ratio of the available substituent anions to the replacement anions and application of a mechanical activation.

  1. Is the simplest chemical reaction really so simple?

    PubMed Central

    Jankunas, Justin; Sneha, Mahima; Zare, Richard N.; Bouakline, Foudhil; Althorpe, Stuart C.; Herráez-Aguilar, Diego; Aoiz, F. Javier

    2014-01-01

    Modern computational methods have become so powerful for predicting the outcome for the H + H2 → H2 + H bimolecular exchange reaction that it might seem further experiments are not needed. Nevertheless, experiments have led the way to cause theorists to look more deeply into this simplest of all chemical reactions. The findings are less simple. PMID:24367084

  2. Heterogeneous catalytic isotopic exchange of benzylic compounds in solution

    SciTech Connect

    Azran, J; Shimoni, M.; Buchman, O. )

    1994-08-01

    Isotopic exchange reactions of bibenzyl and benzylic derivatives with deuterium (D[sub 2]) and tritium (T[sub 2]) gas, catalyzed by Pd/C, have been performed in solution. Catalyst pre-washed with the reacting gas showed improved H/D or H/T exchange. In aprotic solvents such as dioxane, ethyl acetate, and cyclohexane, 3.1 to 3.5 D atoms were exchanged under standard conditions in 1 h, while in benzene 1 D atom was exchanged. D atoms adsorbed on the catalyst surface were rapidly replaced by H from methanol, diluting the D[sub 2] gas phase. Compounds containing O or N atoms enhanced the rate of exchange, while S atoms inhibited the catalyst activity. The H/D exchange obeyed pseudo-first order kinetics when D[sub 2] gas was used in large excess. When T[sub 2] gas replaced D[sub 2], a substantial decrease in rate of exchange was observed, due to the slower dissociative chemisorption of T[sub 2] on the catalyst surface. The results indicated that this exchange process occurred through two simultaneous mechanisms. The breaking of the C-H bond appeared to be the rate-determining step. 22 refs., 1 fig., 5 tabs.

  3. Oxygen-exchange Pathways in Aluminum Polyoxocations

    SciTech Connect

    Rustad, James R.; Loring, J. S.; Casey, William H.

    2004-07-15

    Using molecular dynamics simulations and electronic structure methods, we postulate a mechanism to explain the complicated reactivity trends that are observed for oxygen isotope exchange reactions between sites in aluminum polyoxocations of the E-Keggin type and bulk solution. Experimentally, the molecules have four nonequivalent oxygens that differ considerably in reactivity both within a molecule, and between molecules in the series: Al13, GaAl12, and GeAl12 [MO4Al12(OH)24(H2O)12 n*(aq); with M=Al(III) for Al13, n=7; M=Ga(III) for GaAl12, n=7; M=Ge(IV) for GeAl12, n=8]. We find that a partly dissociated, metastable intermediate molecule of expanded volume is necessary for exchange of both sets of u2-OH and that the steady-state concentration of this intermediate reflects the bond strengths between the central metal and the u4-O. Thus the central metal exerts extraordinary control over reactions at hydroxyl bridges, although these are three bonds away. This mechanism not only explains the reactivity trends for oxygen isotope exchange in u2-OH and u-OH2 sites in the E-Keggin aluminum molecules, but also explains the observation that the reactivities of minerals tend to reflect the presence of highly coordinated oxygens, such as the u4-O in boehmite, a-, and y-Al2O3 and their Fe(III) analogs. The partial dissociation of these highly coordinated oxygens, coupled with simultaneous activation and displacement of neighboring metal centers, may be a fundamental process by which metals atoms undergo ligand exchanges at mineral surfaces.

  4. Phosphonic acid based exchange resins

    DOEpatents

    Horwitz, E. Philip; Alexandratos, Spiro D.; Gatrone, Ralph C.; Chiarizia, Ronato

    1995-01-01

    An ion exchange resin for extracting metal ions from a liquid waste stream. An ion exchange resin is prepared by copolymerizing a vinylidene diphosphonic acid with styrene, acrylonitrile and divinylbenzene.

  5. Phosphonic acid based exchange resins

    DOEpatents

    Horwitz, E.P.; Alexandratos, S.D.; Gatrone, R.C.; Chiarizia, R.

    1995-09-12

    An ion exchange resin is described for extracting metal ions from a liquid waste stream. An ion exchange resin is prepared by copolymerizing a vinylidene diphosphonic acid with styrene, acrylonitrile and divinylbenzene. 10 figs.

  6. Lipid Exchange by Ultracentrifugation.

    PubMed

    Drachmann, Nikolaj Düring; Olesen, Claus

    2016-01-01

    Lipids play an important role in maintaining P-type ATPase structure and function, and often they are crucial for ATPase activity. When the P-type ATPases are in the membrane, they are surrounded by a mix of different lipid species with varying aliphatic chain lengths and saturation, and the complex interplay between the lipids and the P-type ATPases are still not well understood. We here describe a robust method to exchange the majority of the lipids surrounding the ATPase after solubilisation and/or purification with a target lipid of interest. The method is based on an ultracentrifugation step, where the protein sample is spun through a dense buffer containing large excess of the target lipid, which results in an approximately 80-85 % lipid exchange. The method is a very gently technique that maintains protein folding during the process, hence allowing further characterization of the protein in the presence of a target lipid of interest. PMID:26695050

  7. Heat exchanger tube mounts

    DOEpatents

    Wolowodiuk, W.; Anelli, J.; Dawson, B.E.

    1974-01-01

    A heat exchanger in which tubes are secured to a tube sheet by internal bore welding is described. The tubes may be moved into place in preparation for welding with comparatively little trouble. A number of segmented tube support plates are provided which allow a considerable portion of each of the tubes to be moved laterally after the end thereof has been positioned in preparation for internal bore welding to the tube sheet. (auth)

  8. Thermoelectric heat exchange element

    DOEpatents

    Callas, James J.; Taher, Mahmoud A.

    2007-08-14

    A thermoelectric heat exchange module includes a first substrate including a heat receptive side and a heat donative side and a series of undulatory pleats. The module may also include a thermoelectric material layer having a ZT value of 1.0 or more disposed on at least one of the heat receptive side and the heat donative side, and an electrical contact may be in electrical communication with the thermoelectric material layer.

  9. Heat exchange apparatus

    DOEpatents

    Degtiarenko, Pavel V.

    2003-08-12

    A heat exchange apparatus comprising a coolant conduit or heat sink having attached to its surface a first radial array of spaced-apart parallel plate fins or needles and a second radial array of spaced-apart parallel plate fins or needles thermally coupled to a body to be cooled and meshed with, but not contacting the first radial array of spaced-apart parallel plate fins or needles.

  10. Soviets seek scientific exchange

    NASA Astrophysics Data System (ADS)

    GEOS-A, associated with the Soviet Union's Institute of Earth Physics, is seeking to promote exchange between Soviet and Western geophysicists. GEOS-A is a nonprofit, private organization formed by specialists from the U.S.S.R. Academy of Scientists.GEOS-A aims to promote the transfer of academic research results to industry and education. It also seeks to stimulate international scientific exchange and to support independent nongovernmental programs and expertise in geophysics and ecology. The organization would like to cooperate with Western universities in exchanging students and young scientists and in building scientific relationships between the two countries. This would include inviting students and young specialists for collaborative scientific research, consultations, language practice, and graduate study in any institute of the U.S.S.R. Academy of Sciences. Participants would live in rented private apartments in downtown Moscow for approximately one week to several months. All living expenses would be covered at a rate higher than the academy's standard one (unfortunately travel to and from the Soviet Union cannot be covered).

  11. The exchangeability of shape

    PubMed Central

    2010-01-01

    Background Landmark based geometric morphometrics (GM) allows the quantitative comparison of organismal shapes. When applied to systematics, it is able to score shape changes which often are undetectable by traditional morphological studies and even by classical morphometric approaches. It has thus become a fast and low cost candidate to identify cryptic species. Due to inherent mathematical properties, shape variables derived from one set of coordinates cannot be compared with shape variables derived from another set. Raw coordinates which produce these shape variables could be used for data exchange, however they contain measurement error. The latter may represent a significant obstacle when the objective is to distinguish very similar species. Results We show here that a single user derived dataset produces much less classification error than a multiple one. The question then becomes how to circumvent the lack of exchangeability of shape variables while preserving a single user dataset. A solution to this question could lead to the creation of a relatively fast and inexpensive systematic tool adapted for the recognition of cryptic species. Conclusions To preserve both exchangeability of shape and a single user derived dataset, our suggestion is to create a free access bank of reference images from which one can produce raw coordinates and use them for comparison with external specimens. Thus, we propose an alternative geometric descriptive system that separates 2-D data gathering and analyzes. PMID:20964872

  12. Calculations of ion-molecule deuterium fractionation reactions involving HD

    NASA Technical Reports Server (NTRS)

    Maluendes, Sergio A.; Mclean, A. D.; Herbst, Eric

    1992-01-01

    Gas-phase chemical models of deuterium fractionation in dense interstellar clouds utilize a small number of exothermic reactions to achieve fractionation. Although HD is a major repository of deuterium, it appears not to exchange deuterium with many molecular ions. Useful semiquantitative reasons have been given for the unusual lack of reactivity of exothermic ion-HD deuterium exchange systems, but quantum chemical studies are needed to understand these ideas in more detail and to determine if the lack of reactivity pertains at very low temperatures not studied in the laboratory, or whether tunneling can drive the reactions. Accordingly, the potential energy surfaces of three representative ion-molecule exchange reactions involving protonated ions and HD have been investigated with ab initio quantum chemical techniques. Our results generally confirm the semiquantitative picture as to which reactions are likely to occur and show that tunneling at low temperatures is unlikely to alter this picture.

  13. ION-EXCHANGE PROCESSES AND MECHANISMS IN GLASSES

    EPA Science Inventory

    Recent performance assessment calculations of a disposal system at Hanford, Washington for low activity waste glass show that a Na ion-exchange reaction can effectively increase the radionuclide release rate by over a factor of 1000 and so is a major factor that currently limits ...

  14. AGRICULTURAL EXCHANGE RATE DATA SHEET

    EPA Science Inventory

    The ERS data set contains annual and monthly data for exchange rates important to U.S. agriculture. It includes both nominal and real exchange rates for 80 countries (plus the European Union) as well as real trade-weighted exchange rate indexes for many commodities and aggregatio...

  15. Thrombotic thrombocytopenic purpura treated with plasma exchange or exchange transfusions.

    PubMed Central

    Shepard, K. V.; Fishleder, A.; Lucas, F. V.; Goormastic, M.; Bukowski, R. M.

    1991-01-01

    Of 40 patients with thrombotic thrombocytopenic purpura, 17 were treated with plasma exchange, 15 with exchange transfusions, and 6 with both types of therapy. One patient died before being treated and another patient was seen but not treated. Plasma exchange was performed daily for a mean of seven exchanges per patient. The replacement fluid during plasma exchange was fresh frozen plasma in all cases. The complete response rates for each type of treatment were as follows: 88% for plasma exchange (15 patients), 47% for exchange transfusions (7 patients), and 67% for exchange transfusions and plasma exchange (4 patients). Clinical and laboratory factors were examined for any statistically significant association with therapy response. Treatment with plasma exchange was statistically the initial factor most strongly associated with prognosis. Paresis, paresthesias, seizures, mental status change, and coma showed no association with response to treatment. Some of the laboratory factors that did not show significant association with treatment response were the initial creatinine, hemoglobin, platelet count, lactate dehydrogenase, and total bilirubin. This study supports the hypothesis that plasma exchange has significantly improved the prognosis of patients with thrombotic thrombocytopenic purpura. These patients should be treated aggressively regardless of the severity of their symptoms. PMID:1877181

  16. Sorption of iron(III) from chromate solution by the aminocarboxylic ion exchanger ANKB-2

    SciTech Connect

    Stoyanova, O.F.; Izmailova, D.R.; Kurolap, N.S.; Uglyanskaya, V.A.

    1986-12-20

    The possibility of iron(III) sorption by the amphoteric ion exchanger ANKB-2 from chromate solution and its superiority over the cation exchanger KU-23 (10/60) have been demonstrated. By means of IR spectroscopy it has been shown that iron(III) sorption from chromate solution by ANKB-2 proceeds via both ionic and coordination reactions. The proportion of these kinds of reaction does not depend on the Cr(VI) content of the initial solution.

  17. Lightweight Long Life Heat Exchanger

    NASA Technical Reports Server (NTRS)

    Moore, E. K.

    1976-01-01

    A shuttle orbiter flight configuration aluminum heat exchanger was designed, fabricated, and tested. The heat exchanger utilized aluminum clad titanium composite parting sheets for protection against parting sheet pin hole corrosion. The heat exchanger, which is fully interchangeable with the shuttle condensing heat exchanger, includes slurpers (a means for removing condensed water from the downstream face of the heat exchanger), and both the core air passes and slurpers were hydrophilic coated to enhance wettability. The test program included performance tests which demonstrated the adequacy of the design and confirmed the predicted weight savings.

  18. Emittance and Phase Space Exchange

    SciTech Connect

    Xiang, Dao; Chao, Alex; /SLAC

    2011-08-19

    Alternative chicane-type beam lines are proposed for exact emittance exchange between horizontal phase space (x; x{prime}) and longitudinal phase space (z; {delta}). Methods to achieve exact phase space exchanges, i.e. mapping x to z, x{prime} to {delta}, z to x and {delta} to x{prime} are suggested. Methods to mitigate the thick-lens effect of the transverse cavity on emittance exchange are discussed. Some applications of the phase space exchanger and the feasibility of an emittance exchange experiment with the proposed chicane-type beam line at SLAC are discussed.

  19. Kinetic theory of oxygen isotopic exchange between minerals and water

    USGS Publications Warehouse

    Criss, R.E.; Gregory, R.T.; Taylor, H.P., Jr.

    1987-01-01

    Kinetic and mass conservation equations are used to describe oxygen isotopic exchange between minerals and water in "closed" and open hydrothermal systems. In cases where n coexisting mineral phases having different reaction rates are present, the exchange process is described by a system of n + 1 simultaneous differential equations consisting of n pseudo first-order rate equations and a conservation of mass equation. The simultaneous solutions to these equations generate curved exchange trajectories on ??-?? plots. Families of such trajectories generated under conditions allowing for different fluid mole fractions, different fluid isotopic compositions, or different fluid flow rates are connected by positive-sloped isochronous lines. These isochrons reproduce the effects observed in hydrothermally exchanged mineral pairs including 1) steep positive slopes, 2) common reversals in the measured fractionation factors (??), and 3) measured fractionations that are highly variable over short distances where no thermal gradient can be geologically demonstrated. ?? 1987.

  20. Origins of Linear Partitioning in Binary Solutions: the Exchange Coefficient

    NASA Astrophysics Data System (ADS)

    Morse, S. A.

    2006-05-01

    Linear partitioning occurs when, as often in petrologic systems and perhaps always in azeotropes, a straight- line relationship occurs when the partition coefficient D = X1S/X1L is plotted against the solid composition X2S and runs from an intercept value KD at pure (2) to 1.0 at pure (1). The equation is then D = KD*X2S + X1S (Morse 1997, JGeol 105:471; 2000 GCA, 64:2309). The notation KD was taken from its long-standing familiarity in binary solutions (Roeder & Emslie 1970, CMP 29:275) and described as the exchange coefficient (Beattie et al. 1993 GCA 57:1605). But the binary loop is not in itself an exchange equilibrium; it is a transfer equilibrium marching to a different drummer, and that causes a problem (Kretz 2005, CanMin 43:1349). In at least three ways, the binary loop qualifies as an exchange reaction and justifies calling the intercept KD. To the experimentalist this issue never arises. In a perfect liquidus experiment, an infinitesimal mass of liquid is indeed transferred to the crystal. A second bulk composition is then made, and at the new liquidus a second mass transfer occurs. The ensemble of all such perfect partitioning experiments in sufficient number then completely delineates the binary loop without any continuous transfer at changing T having taken place. The partitionings are therefore truly independent of the path. Moreover, each equilibrium pair defines a common tangent in G-X space whose intercept at pure (2) unarguably gives the value of the common chemical potential, a partial Gibbs energy. But where is the exchange reaction? The real experimentalist makes no perfect experiments, and neither does nature. In reality, the barrier to nucleation (particularly formidable in the case of plagioclase) dictates that the crystals nucleate only at some supercooling. They therefore have some composition between the initial solidus and the liquid lying at the bulk composition (BC). Over time the two phases may drift apart by diffusion, the crystal

  1. Exam Question Exchange.

    ERIC Educational Resources Information Center

    Alexander, John J., Ed.

    1978-01-01

    Two exam questions are presented. One suitable for advanced undergraduate or beginning graduate courses in organic chemistry, is on equivalent expressions for the description of several pericyclic reactions. The second, for general chemistry students, asks for an estimation of the rate of decay of a million-year-old Uranium-238 sample. (BB)

  2. Exchange lists: revised 1986.

    PubMed

    Franz, M J; Barr, P; Holler, H; Powers, M A; Wheeler, M L; Wylie-Rosett, J

    1987-01-01

    A committee composed of members of The American Dietetic Association and the American Diabetes Association has revised Exchange List for Meal Planning. Changes were made, as deemed necessary, on the basis of nutritional recommendations for persons with diabetes as understood in 1986. Major changes include rewriting the text to make it more useful in the education of persons with diabetes; changing the order of the exchange lists to emphasize a high-carbohydrate, high-fiber diet, as well as to better reflect the order of foods in menu planning; adding symbols to foods high in fiber and sodium; changing nutritive values for the starch/bread and fruit lists; adding lists of combination foods, free foods, and foods recommended only for occasional use; developing a data base; and initiating a plan for field testing and evaluation. The committee also developed a simplified meal planning tool, Healthy Food Choices, to be used for initial or "survival" level education. In poster format, foods are grouped by calories into six food groups. Approximate portion sizes of commonly used foods are listed. Blank lines are provided for the nutrition counselor to write in a suggested menu or meal plan for the client. Because the booklet does not use the word "diabetes" specifically, it is appropriate as a general teaching tool. PMID:3794130

  3. Heat exchanger-accumulator

    DOEpatents

    Ecker, Amir L.

    1980-01-01

    What is disclosed is a heat exchanger-accumulator for vaporizing a refrigerant or the like, characterized by an upright pressure vessel having a top, bottom and side walls; an inlet conduit eccentrically and sealingly penetrating through the top; a tubular overflow chamber disposed within the vessel and sealingly connected with the bottom so as to define an annular outer volumetric chamber for receiving refrigerant; a heat transfer coil disposed in the outer volumetric chamber for vaporizing the liquid refrigerant that accumulates there; the heat transfer coil defining a passageway for circulating an externally supplied heat exchange fluid; transferring heat efficiently from the fluid; and freely allowing vaporized refrigerant to escape upwardly from the liquid refrigerant; and a refrigerant discharge conduit penetrating sealingly through the top and traversing substantially the length of the pressurized vessel downwardly and upwardly such that its inlet is near the top of the pressurized vessel so as to provide a means for transporting refrigerant vapor from the vessel. The refrigerant discharge conduit has metering orifices, or passageways, penetrating laterally through its walls near the bottom, communicating respectively interiorly and exteriorly of the overflow chamber for controllably carrying small amounts of liquid refrigerant and oil to the effluent stream of refrigerant gas.

  4. Catalytic gasification: Isotopic labeling and transient reaction

    SciTech Connect

    Saber, J.M.; Falconer, J.L.; Brown, L.F.

    1985-01-01

    Temperature-programmed reaction was used with labeled isotopes (/sup 13/C and /sup 18/O) to study interactions between carbon black and potassium carbonate in pure He and 10% CO/sub 2//90% He atmospheres. Catalytic gasification precursor complexes were observed. Carbon and oxygen-bearing carbon surface groups interacted with the carbonate above 500 K to form surface complexes. Between 500 K and 950 K, and in the presence of gaseous carbon dioxide, the complexes promoted carbon and oxygen exchange between the gas-phase CO/sub 2/ and the surface. Oxygen exchanged between the surface complexes; but carbon did not exchange between the carbonate and the carbon black. As the temperature rose, the complexes decomposed to produce carbon dioxide, and catalytic gasification then began. Elemental potassium formed, and the active catalyst appears to alternate between potassium metal and a potassium-oxygen-carbon complex.

  5. Asymmetric petasis reactions catalyzed by chiral biphenols.

    PubMed

    Lou, Sha; Schaus, Scott E

    2008-06-01

    Chiral biphenols catalyze the enantioselective Petasis reaction of alkenyl boronates, secondary amines, and ethyl glyoxylate. The reaction requires the use of 15 mol % of (S)-VAPOL as the catalyst, alkenyl boronates as nucleophiles, ethyl glyoxylate as the aldehyde component, and 3 A molecular sieves as an additive. The chiral alpha-amino ester products are obtained in good yields (71-92%) and high enantiomeric ratios (89:11-98:2). Mechanistic investigations indicate single ligand exchange of acyclic boronate with VAPOL and tetracoordinate boronate intermediates. PMID:18459782

  6. Charged-current neutrino-208Pb reactions

    NASA Astrophysics Data System (ADS)

    Volpe, C.; Auerbach, N.; Colò, G.; van Giai, N.

    2002-04-01

    We present theoretical results on the non-flux-averaged 208Pb(νe,e-)208Bi and 208Pb(νμ,μ-)208Bi reaction cross sections, obtained within the charge-exchange random-phase-approximation. A detailed knowledge of these cross sections is important in different contexts. In particular, it is necessary to assess the possibility of using lead as a detector in future experiments on supernova neutrinos, such as OMNIS and LAND, and eventually detect neutrino oscillation signals by exploiting the spectroscopic properties of 208Bi. We discuss the present status on the theoretical predictions of the reaction cross sections.

  7. The reaction of ornithine aminotransferase with ornithine.

    PubMed Central

    Williams, J A; Bridge, G; Fowler, L J; John, R A

    1982-01-01

    Rat liver ornithine aminotransferase is found to exchange the pro-S hydrogen on the delta-carbon atom of ornithine exclusively, thus showing that the mammalian enzyme transfers the delta-amino group and not the alpha-amino group as has been demonstrated with the plant enzyme [Mestichelli, Gupta & Spenser (1979) J. Biol. Chem. 254, 640-647]. The enzyme also transfers the alpha-amino group of glutamate and the kinetics of the half reactions between the enzyme and both amino acids are compared. Rate and dissociation constants for both reactions are determined. PMID:6282258

  8. Kinetics of tritium removal from heavy water by exchange with deuterochloroform

    SciTech Connect

    Hsiao, P.

    1983-03-14

    A technique was developed to determine the rate and equilibrium constants for the base-catalyzed exchange of tritium from ehavy water to deuterochloroform. An activation energy and entropy were also calculated. These quantities are comparable with those reported in the literature for a similar reaction involving the exchange of deuterium from deuterochloroform to water. It was found that the exchange reaction occurred predominately between the dissolved reactants in the D/sub 2/O and CDCl/sub 3/ phases. The rate constant is a strong direct function of temperature while the equilibrium constant is a weak inverse function.

  9. Selective Facet Reactivity During Cation Exchange in Cadmium Sulfide Nanorods

    SciTech Connect

    Sadtler, Bryce; Demchenko, Denis; Zheng, Haimei; Hughes, Steven; Merkle, Maxwell; Dahmen, Ulrich; Wang, Lin-Wang; Alivisatos, A. Paul

    2008-12-18

    The partial transformation of ionic nanocrystals through cation exchange has been used to synthesize nanocrystal heterostructures. We demonstrate that the selectivity for cation exchange to take place at different facets of the nanocrystal plays an important role in determining the resulting morphology of the binary heterostructure. In the case of copper I (Cu+) cation exchange in cadmium sulfide (CdS) nanorods, the reaction starts preferentially at the ends of the nanorods such that copper sulfide (Cu2S) grows inwards from either end. The resulting morphology is very different from the striped pattern obtained in our previous studies of silver I (Ag+) exchange in CdS nanorods where non-selective nucleation of silver sulfide (Ag2S) occurs. From interface formation energies calculated for several models of epitaxialconnections between CdS and Cu2S or Ag2S, we infer the relative stability of each interface during the nucleation and growth of Cu2S or Ag2S within the CdS nanorods. The epitaxial connections of Cu2S to the end facets of CdS nanorods minimize the formation energy, making these interfaces stable throughout the exchange reaction. However, as the two end facets of wurtzite CdS nanorods are crystallographically nonequivalent, asymmetric heterostructures can be produced.

  10. Concerted hydrogen atom exchange between three HF molecules

    NASA Technical Reports Server (NTRS)

    Komornicki, Andrew; Dixon, David A.; Taylor, Peter R.

    1992-01-01

    We have investigated the termolecular reaction involving concerted hydrogen exchange between three HF molecules, with particular emphasis on the effects of correlation at the various stationary points along the reaction. Using an extended basis, we have located the geometries of the stable hydrogen-bonded trimer, which is of C(sub 3h) symmetry, and the transition state for hydrogen exchange, which is of D(sub 3h) symmetry. The energies of the exchange reation were then evaluated at the correlated level, using a large atomic natural orbital basis and correlating all valence electrons. Several correlation treatments were used, namely, configration interaction with single and double excitations, coupled-pair functional, and coupled-cluster methods. We are thus able to measure the effect of accounting for size-extensivity. Zero-point corrections to the correlated level energetics were determined using analytic second derivative techniques at the SCF level. Our best calculations, which include the effects of connected triple excitations in the coupled-cluster procedure, indicate that the trimer is bound by 9 +/- 1 kcal/mol relative to three separate monomers, in excellent agreement with previous estimates. The barrier to concerted hydrogen exchange is 15 kcal/mol above the trimer, or only 4.7 kcal/mol above three separated monomers. Thus the barrier to hydrogen exchange between HF molecules via this termolecular process is very low.

  11. Ion exchange technology assessment report

    SciTech Connect

    Duhn, E.F.

    1992-01-01

    In the execution of its charter, the SRS Ion Exchange Technology Assessment Team has determined that ion exchange (IX) technology has evolved to the point where it should now be considered as a viable alternative to the SRS reference ITP/LW/PH process. The ion exchange media available today offer the ability to design ion exchange processing systems tailored to the unique physical and chemical properties of SRS soluble HLW's. The technical assessment of IX technology and its applicability to the processing of SRS soluble HLW has demonstrated that IX is unquestionably a viable technology. A task team was chartered to evaluate the technology of ion exchange and its potential for replacing the present In-Tank Precipitation and proposed Late Wash processes to remove Cs, Sr, and Pu from soluble salt solutions at the Savannah River Site. This report documents the ion exchange technology assessment and conclusions of the task team.

  12. Ion exchange technology assessment report

    SciTech Connect

    Duhn, E.F.

    1992-12-31

    In the execution of its charter, the SRS Ion Exchange Technology Assessment Team has determined that ion exchange (IX) technology has evolved to the point where it should now be considered as a viable alternative to the SRS reference ITP/LW/PH process. The ion exchange media available today offer the ability to design ion exchange processing systems tailored to the unique physical and chemical properties of SRS soluble HLW`s. The technical assessment of IX technology and its applicability to the processing of SRS soluble HLW has demonstrated that IX is unquestionably a viable technology. A task team was chartered to evaluate the technology of ion exchange and its potential for replacing the present In-Tank Precipitation and proposed Late Wash processes to remove Cs, Sr, and Pu from soluble salt solutions at the Savannah River Site. This report documents the ion exchange technology assessment and conclusions of the task team.

  13. The Glyoxal Clock Reaction

    ERIC Educational Resources Information Center

    Ealy, Julie B.; Negron, Alexandra Rodriguez; Stephens, Jessica; Stauffer, Rebecca; Furrow, Stanley D.

    2007-01-01

    Research on the glyoxal clock reaction has led to adaptation of the clock reaction to a general chemistry experiment. This particular reaction is just one of many that used formaldehyde in the past. The kinetics of the glyoxal clock makes the reaction suitable as a general chemistry lab using a Calculator Based Laboratory (CBL) or a LabPro. The…

  14. Biological Ion Exchanger Resins

    PubMed Central

    Damadian, Raymond; Goldsmith, Michael; Zaner, K. S.

    1971-01-01

    Biological selectivity is shown to vary with medium osmotic strength and temperature. Selectivity reversals occur at 4°C and at an external osmolality of 0.800 indicating that intracellular hydration and endosolvent (intracellular water) structure are important determinants in selectivity. Magnetic resonance measurements of line width by steady-state nuclear magnetic resonance (NMR) indicate a difference in the intracellular water signal of 16 Hz between the K form and Na form of Escherichia coli, providing additional evidence that changes in the ionic composition of cells are accompanied by changes in endosolvent structure. The changes were found to be consistent with the thermodynamic and magnetic resonance properties of aqueous electrolyte solutions. Calculation of the dependence of ion-pairing forces on medium dielectric reinforces the role of endosolvent structure in determining ion exchange selectivity. PMID:4943653

  15. Cross-Shelf Exchange.

    PubMed

    Brink, K H

    2016-01-01

    Cross-shelf exchange dominates the pathways and rates by which nutrients, biota, and materials on the continental shelf are delivered and removed. This follows because cross-shelf gradients of most properties are usually far greater than those in the alongshore direction. The resulting transports are limited by Earth's rotation, which inhibits flow from crossing isobaths. Thus, cross-shelf flows are generally weak compared with alongshore flows, and this leads to interesting observational issues. Cross-shelf flows are enabled by turbulent mixing processes, nonlinear processes (such as momentum advection), and time dependence. Thus, there is a wide range of possible effects that can allow these critical transports, and different natural settings are often governed by different combinations of processes. This review discusses examples of representative transport mechanisms and explores possible observational and theoretical paths to future progress. PMID:26747520

  16. Monogroove liquid heat exchanger

    NASA Technical Reports Server (NTRS)

    Brown, Richard F. (Inventor); Edelstein, Fred (Inventor)

    1990-01-01

    A liquid supply control is disclosed for a heat transfer system which transports heat by liquid-vapor phase change of a working fluid. An assembly (10) of monogroove heat pipe legs (15) can be operated automatically as either heat acquisition devices or heat discharge sources. The liquid channels (27) of the heat pipe legs (15) are connected to a reservoir (35) which is filled and drained by respective filling and draining valves (30, 32). Information from liquid level sensors (50, 51) on the reservoir (35) is combined (60) with temperature information (55) from the liquid heat exchanger (12) and temperature information (56) from the assembly vapor conduit (42) to regulate filling and draining of the reservoir (35), so that the reservoir (35) in turn serves the liquid supply/drain needs of the heat pipe legs (15), on demand, by passive capillary action (20, 28).

  17. Hybrid Heat Exchangers

    NASA Technical Reports Server (NTRS)

    Tu, Jianping Gene; Shih, Wei

    2010-01-01

    A hybrid light-weight heat exchanger concept has been developed that uses high-conductivity carbon-carbon (C-C) composites as the heat-transfer fins and uses conventional high-temperature metals, such as Inconel, nickel, and titanium as the parting sheets to meet leakage and structural requirements. In order to maximize thermal conductivity, the majority of carbon fiber is aligned in the fin direction resulting in 300 W/m.K or higher conductivity in the fin directions. As a result of this fiber orientation, the coefficient of thermal expansion (CTE) of the C-C composite in both non-fiber directions matches well with the CTE of various high-temperature metal alloys. This allows the joining of fins and parting sheets by using high-temperature braze alloys.

  18. South Atlantic interbasin exchange

    NASA Technical Reports Server (NTRS)

    Rintoul, Stephen Rich

    1991-01-01

    The exchange of mass and heat between the South Atlantic and the neighboring ocean basins was estimated using hydrographic data and inverse methods, in order to gain information on the links between the deep-water formation processes occurring within the Atlantic and the global thermohaline circulation. Results demonstrate that the global thermohaline cell associated with the formation and export of North Atlantic deep water (NADW) is closed primarily by a 'cold water path' in which deep water leaving the Atlantic ultimately returns as intermediate water entering the basin through Drake Passage. This conclusion conflicts with the suggestion by Gordon (1986) that the global thermohaline circulation associated with the formation of NADW is closed primarily by a 'warm water path', in which the export of NADW is compensated by an inflow of warm Indian Ocean thermocline water south of Africa.

  19. Heat exchanger bypass test report

    SciTech Connect

    De Vries, M.L.

    1995-01-26

    This test report documents the results that were obtained while conducting the test procedure which bypassed the heat exchangers in the HC-21C sludge stabilization process. The test was performed on November 15, 1994 using WHC-SD-CP-TC-031, ``Heat Exchanger Bypass Test Procedure.`` The primary objective of the test procedure was to determine if the heat exchangers were contributing to condensation of moisture in the off-gas line. This condensation was observed in the rotameters. Also, a secondary objective was to determine if temperatures at the rotameters would be too high and damage them or make them inaccurate without the heat exchangers in place.

  20. Ion-exchange hollow fibers

    NASA Technical Reports Server (NTRS)

    Rembaum, A.; Yen, S. P. S.; Klein, E. (Inventor)

    1976-01-01

    An ion-exchange hollow fiber is prepared by introducing into the wall of the fiber polymerizable liquid monomers, and polymerizing the monomers therein to form solid, insoluble, crosslinked, ion-exchange resin particles which embed in the wall of the fiber. Excess particles blocking the central passage or bore of the fiber are removed by forcing liquid through the fiber. The fibers have high ion-exchange capacity, a practical wall permeability and good mechanical strength even with very thin wall dimensions. Experimental investigation of bundles of ion-exchange hollow fibers attached to a header assembly have shown the fiber to be very efficient in removing counterions from solution.

  1. Ion-exchange hollow fibers

    NASA Technical Reports Server (NTRS)

    Rembaum, Alan (Inventor); Yen, Shiao-Ping S. (Inventor); Klein, Elias (Inventor)

    1980-01-01

    An ion-exchange hollow fiber is prepared by introducing into the wall of the fiber polymerizable liquid monomers, and polymerizing the monomers therein to form solid, insoluble, cross-linked, ion-exchange resin particles which embed in the wall of the fiber. Excess particles blocking the central passage or bore of the fiber are removed by forcing liquid through the fiber. The fibers have high ion-exchange capacity, a practical wall permeability and good mechanical strength even with very thin wall dimensions. Experimental investigation of bundles of ion-exchange hollow fibers attached to a header assembly have shown the fiber to be very efficient in removing counterions from solution.

  2. Ion-exchange hollow fibers

    NASA Technical Reports Server (NTRS)

    Rembaum, Alan (Inventor); Yen, Shiao-Ping S. (Inventor); Klein, Elias (Inventor)

    1977-01-01

    An ion-exchange hollow fiber is prepared by introducing into the wall of the fiber polymerizable liquid monomers, and polymerizing the monomers therein to form solid, insoluble, cross-linked, ion-exchange resin particles which embed in the wall of the fiber. Excess particles blocking the central passage or bore of the fiber are removed by forcing liquid through the fiber. The fibers have high ion-exchange capacity, a practical wall permeability and good mechanical strength even with very thin wall dimensions. Experimental investigation of bundles of ion-exchange hollow fibers attached to a header assembly have shown the fiber to be very efficient in removing counterions from solution.

  3. Gas Exchange of Algae

    PubMed Central

    Ammann, Elizabeth C. B.; Lynch, Victoria H.

    1966-01-01

    Changes in the oxygen partial pressure of air over the range of 8 to 258 mm of Hg did not adversely affect the photosynthetic capacity of Chlorella pyrenoidosa. Gas exchange and growth measurements remained constant for 3-week periods and were similar to air controls (oxygen pressure of 160 mm of Hg). Oxygen partial pressures of 532 and 745 mm of Hg had an adverse effect on algal metabolism. Carbon dioxide consumption was 24% lower in the gas mixture containing oxygen at a pressure 532 mm of Hg than in the air control, and the growth rate was slightly reduced. Oxygen at a partial pressure of 745 mm of Hg decreased the photosynthetic rate 39% and the growth rate 37% over the corresponding rates in air. The lowered metabolic rates remained constant during 14 days of measurements, and the effect was reversible after this time. Substitution of helium or argon for the nitrogen in air had no effect on oxygen production, carbon dioxide consumption, or growth rate for 3-week periods. All measurements were made at a total pressure of 760 mm of Hg, and all gas mixtures were enriched with 2% carbon dioxide. Thus, the physiological functioning and reliability of a photosynthetic gas exchanger should not be adversely affected by: (i) oxygen partial pressures ranging from 8 to 258 mm of Hg; (ii) the use of pure oxygen at reduced total pressure (155 to 258 mm of Hg) unless pressure per se affects photosynthesis, or (iii) the inclusion of helium or argon in the gas environment (up to a partial pressure of 595 mm of Hg). PMID:5927028

  4. Practice Gaps: Drug Reactions.

    PubMed

    Wolverton, Stephen E

    2016-07-01

    The term "drug reactions" is relevant to dermatology in three categories of reactions: cutaneous drug reactions without systemic features, cutaneous drug reactions with systemic features, and systemic drugs prescribed by the dermatologist with systematic adverse effects. This article uses examples from each of these categories to illustrate several important principles central to drug reaction diagnosis and management. The information presented will help clinicians attain the highest possible level of certainty before making clinical decisions. PMID:27363888

  5. Preparation of an Ester-Containing Grignard Reagent by Halogen-Metal Exchange

    ERIC Educational Resources Information Center

    Snider, Barry B.

    2015-01-01

    In this experiment, students carry out a halogen-metal exchange reaction of methyl 2-iodobenzoate with isopropylmagnesium chloride in THF at 0°C to afford 2-carbomethoxyphenylmagnesium chloride, which is treated with "p"-methoxybenzaldehyde to give a lactone (phthalide) product. This reaction introduces students to the modern method of…

  6. Heat partition in damped reactions

    SciTech Connect

    Chattopadhyay, S.; Pal, D. )

    1990-12-01

    The effect of driving force on the division of excitation energy between the asymmetric colliding partners in deep inelastic heavy-ion collisions is studied in the nucleon-exchange model. For this purpose an event-by-event analysis using Monte Carlo simulation technique is performed. It is seen that the fraction of the total excitation energy carried by the projectile-like fragment is sensitive to the mass drift. The model is also applied to analyze the correlation between fragment mass and excitation energy for a given total energy loss and significant correlation is found. The reactions induced by {sup 56}Fe at 9 MeV/nucleon and {sup 74}Ge at 8.5 MeV/nucleon on {sup 165}Ho are considered in our analysis and the calculated correlations are in good agreement with the results obtained from the kinematic coincidence experiments.

  7. StarBright Learning Exchange

    ERIC Educational Resources Information Center

    Kalinowski, Michael

    2007-01-01

    This article features StarBright Learning Exchange, a program that provides a cross-cultural exchange between Australian and South African early childhood educators. The program was originated when its president, Carol Allen, and her colleague, Karen Williams, decided that they could no longer sit by and watch the unfolding social catastrophe that…

  8. Educators Exchange: A Program Evaluation.

    ERIC Educational Resources Information Center

    Armstrong, William B.

    The Educators Exchange Program (EEP) was established under a training and educational exchange agreement reached by California's San Diego Community College District (SDCCD) and the republic of Mexico. In the program, the District provided a 4-week technological training program to faculty at Centros de Capacitacion Tecnologica Industrial…

  9. Technology Performance Exchange (Fact Sheet)

    SciTech Connect

    Not Available

    2012-10-01

    This fact sheet, 'The Technology Performance Exchange' will be presented at the ET Summit, held at the Pasadena Convention Center on October 15-17, 2012. The Technology Performance Exchange will be a centralized, Web-based portal for finding and sharing energy performance data for commercial building technologies.

  10. Exchange Rates and Old People.

    ERIC Educational Resources Information Center

    Dowd, James J.

    1980-01-01

    Extends earlier work on aging as a process of exchange by focusing on the issue of exchange rates and how they are negotiated. Access to power resources declines with age, placing the old person in the position of negotiating from weakness. (Author)

  11. Organ donation as gift exchange.

    PubMed

    Vernale, C; Packard, S A

    1990-01-01

    Organ donation, considered by sociologists as a type of gift exchange, involves moral, social, psychological, religious and legal issues. This gift exchange paradigm can be used as a framework to understand donor and recipient issues, cadaveric organ donation and the importance of the role of nurses during organ procurement. PMID:2292445

  12. Professional Exchange: Mapping the Future.

    ERIC Educational Resources Information Center

    Dingman, Robert L.

    1993-01-01

    New associate editor of Professional Exchange section of "Journal of Mental Health Counseling" discusses importance of section. Lists potential topics suggested in 1989, then adds several other topics to the list. Concludes with guidelines for submission to Professional Exchange section. (NB)

  13. EXCHANGE. Volume 9-92

    SciTech Connect

    Boltz, J.C.

    1992-09-01

    EXCHANGE is published monthly by the Idaho National Engineering Laboratory (INEL), a multidisciplinary facility operated for the US Department of Energy (DOE). The purpose of EXCHANGE is to inform computer users about about recent changes and innovations in both the mainframe and personal computer environments and how these changes can affect work being performed at DOE facilities.

  14. Heat exchanger performance monitoring guidelines

    SciTech Connect

    Stambaugh, N. ); Closser, W. Jr. ); Mollerus, F.J. )

    1991-12-01

    Fouling can occur in many heat exchanger applications in a way that impedes heat transfer and fluid flow and reduces the heat transfer or performance capability of the heat exchanger. Fouling may be significant for heat exchanger surfaces and flow paths in contact with plant service water. This report presents guidelines for performance monitoring of heat exchangers subject to fouling. Guidelines include selection of heat exchangers to monitor based on system function, safety function and system configuration. Five monitoring methods are discussed: the heat transfer, temperature monitoring, temperature effectiveness, delta P and periodic maintenance methods. Guidelines are included for selecting the appropriate monitoring methods and for implementing the selected methods. The report also includes a bibliography, example calculations, and technical notes applicable to the heat transfer method.

  15. High Temperature Heat Exchanger Project

    SciTech Connect

    Anthony E. Hechanova, Ph.D.

    2008-09-30

    The UNLV Research Foundation assembled a research consortium for high temperature heat exchanger design and materials compatibility and performance comprised of university and private industry partners under the auspices of the US DOE-NE Nuclear Hydrogen Initiative in October 2003. The objectives of the consortium were to conduct investigations of candidate materials for high temperature heat exchanger componets in hydrogen production processes and design and perform prototypical testing of heat exchangers. The initial research of the consortium focused on the intermediate heat exchanger (located between the nuclear reactor and hydrogen production plan) and the components for the hydrogen iodine decomposition process and sulfuric acid decomposition process. These heat exchanger components were deemed the most challenging from a materials performance and compatibility perspective

  16. In situ NRA study of hydrogen isotope exchange in self-ion damaged tungsten exposed to neutral atoms

    NASA Astrophysics Data System (ADS)

    Markelj, S.; Založnik, A.; Schwarz-Selinger, T.; Ogorodnikova, O. V.; Vavpetič, P.; Pelicon, P.; Čadež, I.

    2016-02-01

    Isotope exchange was studied in-situ by Nuclear Reaction Analysis in the bulk of self-ion damaged tungsten at 600 K. Both variations of isotope exchange of H by D and of D by H were measured. The deuterium isothermal desorption was also studied and evaluated in order to be able to resolve the self-desorption from the isotope exchange at 600 K. The isotope exchange was also studied on the surface by Elastic Recoil Detection Analysis at 480 K and 380 K. The exchange mechanism was effective both on the surface and in the bulk of damaged tungsten. A simple model was introduced to describe the exchange efficiency on the surface and in the bulk obtaining the exchange cross sections on the surface and in bulk. In both cases an isotope effect was observed, where the exchange of H atoms by D atoms was more efficient than for the reverse sequence.

  17. Fault-Tolerant Heat Exchanger

    NASA Technical Reports Server (NTRS)

    Izenson, Michael G.; Crowley, Christopher J.

    2005-01-01

    A compact, lightweight heat exchanger has been designed to be fault-tolerant in the sense that a single-point leak would not cause mixing of heat-transfer fluids. This particular heat exchanger is intended to be part of the temperature-regulation system for habitable modules of the International Space Station and to function with water and ammonia as the heat-transfer fluids. The basic fault-tolerant design is adaptable to other heat-transfer fluids and heat exchangers for applications in which mixing of heat-transfer fluids would pose toxic, explosive, or other hazards: Examples could include fuel/air heat exchangers for thermal management on aircraft, process heat exchangers in the cryogenic industry, and heat exchangers used in chemical processing. The reason this heat exchanger can tolerate a single-point leak is that the heat-transfer fluids are everywhere separated by a vented volume and at least two seals. The combination of fault tolerance, compactness, and light weight is implemented in a unique heat-exchanger core configuration: Each fluid passage is entirely surrounded by a vented region bridged by solid structures through which heat is conducted between the fluids. Precise, proprietary fabrication techniques make it possible to manufacture the vented regions and heat-conducting structures with very small dimensions to obtain a very large coefficient of heat transfer between the two fluids. A large heat-transfer coefficient favors compact design by making it possible to use a relatively small core for a given heat-transfer rate. Calculations and experiments have shown that in most respects, the fault-tolerant heat exchanger can be expected to equal or exceed the performance of the non-fault-tolerant heat exchanger that it is intended to supplant (see table). The only significant disadvantages are a slight weight penalty and a small decrease in the mass-specific heat transfer.

  18. Modular heat exchanger

    DOEpatents

    Giardina, A.R.

    1981-03-03

    A shell and tube heat exchanger is described having a plurality of individually removable tube bundle modules. A lattice of structural steel forming rectangular openings therein is placed at each end of a cylindrical shell. Longitudinal structural members are placed in the shell between corners of the rectangular openings situated on opposite ends of the shell. Intermediate support members interconnect the longitudinal supports so as to increase the longitudinal supports rigidity. Rectangular parallelepiped tube bundle modules occupy the space defined by the longitudinal supports and end supports and each include a rectangular tube sheet situated on each end of a plurality of tubes extending there through, a plurality of rectangular tube supports located between the tube sheets, and a tube bundle module stiffening structure disposed about the bundle's periphery and being attached to the tube sheets and tube supports. The corners of each tube bundle module have longitudinal framework members which are mateable with and supported by the longitudinal support members. Intermediate support members constitute several lattices, each of which is situated in a plane between the end support members. The intermediate support members constituting the several lattices extend horizontally and vertically between longitudinal supports of adjacent tube module voids. An alternative embodiment for intermediate support members constitute a series of structural plates situated at the corners of the module voids and having recesses therein for receiving the respective longitudinal support members adjacent thereto, protrusions separating the recesses, and a plurality of struts situated between protrusions of adjacent structural plates. 12 figs.

  19. Modular heat exchanger

    DOEpatents

    Giardina, Angelo R. [Marple Township, Delaware County, PA

    1981-03-03

    A shell and tube heat exchanger having a plurality of individually removable tube bundle modules. A lattice of structural steel forming rectangular openings therein is placed at each end of a cylindrical shell. Longitudinal structural members are placed in the shell between corners of the rectangular openings situated on opposite ends of the shell. Intermediate support members interconnect the longitudinal supports so as to increase the longitudinal supports rigidity. Rectangular parallelpiped tube bundle moldules occupy the space defined by the longitudinal supports and end supports and each include a rectangular tube sheet situated on each end of a plurality of tubes extending therethrough, a plurality of rectangular tube supports located between the tube sheets, and a tube bundle module stiffening structure disposed about the bundle's periphery and being attached to the tube sheets and tube supports. The corners of each tube bundle module have longitudinal framework members which are mateable with and supported by the longitudinal support members. Intermediate support members constitute several lattice, each of which is situate d in a plane between the end support members. The intermediate support members constituting the several lattice extend horizontally and vertically between longitudinal supports of adjacent tube module voids. An alternative embodiment for intermediate support members constitute a series of structural plates situated at the corners of the module voids and having recesses therein for receiving the respective longitudinal support members adjacent thereto, protrusions separating the recesses, and a plurality of struts situated between protrusions of adjacent structural plates.

  20. Energy-Exchange Project

    SciTech Connect

    Not Available

    1982-04-01

    The purpose of the study was to determine what energy savings can be achieved by coordinating the resources and requirements of two facilities, the 26th Ward Water Pollution Control Plant (WPCP) and a housing development named Starrett City with its own total energy system. It was determined that three energy exchange options were economically and technically feasible. These include: the transfer of digester gas produced at the 26th Ward to the boilers at the Starrett City's total energy plant (TEP); the transfer of hot water heated at the TEP to the 26th Ward for space and process heating; and the transfer of coal effluent waste water from the 26th Ward to the condenser cooling systems at the TEP. Technical information is presented to support the findings. The report addresses those tasks of the statement of work dedicated to data acquisition, analysis, and energy conservation strategies internal to the Starrett City TEP and the community it supplies as well as to the 26th Ward WPCP. (MCW)

  1. Electrically switched ion exchange

    SciTech Connect

    Lilga, M.A.; Schwartz, D.T.; Genders, D.

    1997-10-01

    A variety of waste types containing radioactive {sup 137}Cs are found throughout the DOE complex. These waste types include water in reactor cooling basins, radioactive high-level waste (HLW) in underground storage tanks, and groundwater. Safety and regulatory requirements and economics require the removal of radiocesium before these wastes can be permanently disposed of. Electrically Switched Ion Exchange (ESIX) is an approach for radioactive cesium separation that combines IX and electrochemistry to provide a selective, reversible, and economic separation method that also produces little or no secondary waste. In the ESIX process, an electroactive IX film is deposited electrochemically onto a high-surface area electrode, and ion uptake and elution are controlled directly by modulating the potential of the film. For cesium, the electroactive films under investigation are ferrocyanides, which are well known to have high selectivities for cesium in concentrated sodium solutions. When a cathode potential is applied to the film, Fe{sup +3} is reduced to the Fe{sup +2} state, and a cation must be intercalated into the film to maintain charge neutrality (i.e., Cs{sup +} is loaded). Conversely, if an anodic potential is applied, a cation must be released from the film (i.e., Cs{sup +} is unloaded). Therefore, to load the film with cesium, the film is simply reduced; to unload cesium, the film is oxidized.

  2. Cumulative Significance of Hyporheic Exchange and Biogeochemical Processing in River Networks

    NASA Astrophysics Data System (ADS)

    Harvey, J. W.; Gomez-Velez, J. D.

    2014-12-01

    Biogeochemical reactions in rivers that decrease excessive loads of nutrients, metals, organic compounds, etc. are enhanced by hydrologic interactions with microbially and geochemically active sediments of the hyporheic zone. The significance of reactions in individual hyporheic flow paths has been shown to be controlled by the contact time between river water and sediment and the intrinsic reaction rate in the sediment. However, little is known about how the cumulative effects of hyporheic processing in large river basins. We used the river network model NEXSS (Gomez-Velez and Harvey, submitted) to simulate hyporheic exchange through synthetic river networks based on the best available models of network topology, hydraulic geometry and scaling of geomorphic features, grain size, hydraulic conductivity, and intrinsic reaction rates of nutrients and metals in river sediment. The dimensionless reaction significance factor, RSF (Harvey et al., 2013) was used to quantify the cumulative removal fraction of a reactive solute by hyporheic processing. SF scales reaction progress in a single pass through the hyporheic zone with the proportion of stream discharge passing through the hyporheic zone for a specified distance. Reaction progress is optimal where the intrinsic reaction timescale in sediment matches the residence time of hyporheic flow and is less efficient in longer residence time hyporheic flow as a result of the decreasing proportion of river flow that is processed by longer residence time hyporheic flow paths. In contrast, higher fluxes through short residence time hyporheic flow paths may be inefficient because of the repeated surface-subsurface exchanges required to complete the reaction. Using NEXSS we found that reaction efficiency may be high in both small streams and large rivers, although for different reasons. In small streams reaction progress generally is dominated by faster pathways of vertical exchange beneath submerged bedforms. Slower exchange

  3. 76 FR 28358 - Retail Foreign Exchange Transactions

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-05-17

    ... Off-Exchange Retail Foreign Exchange Transactions and Intermediaries, 75 FR 55409 (Sept. 10, 2010... Act. Regulation of Off-Exchange Retail Foreign Exchange Transactions and Intermediaries, 75 FR 3281 (Jan. 20, 2010) (Proposed CFTC Retail Forex Rule). \\13\\ See Retail Foreign Exchange Transactions, 76...

  4. Continuous detonation reaction engine

    NASA Technical Reports Server (NTRS)

    Lange, O. H.; Stein, R. J.; Tubbs, H. E.

    1968-01-01

    Reaction engine operates on the principles of a controlled condensed detonation rather than on the principles of gas expansion. The detonation results in reaction products that are expelled at a much higher velocity.

  5. Allergic reactions (image)

    MedlinePlus

    Allergic reaction is a sensitivity to a specific substance, called an allergen, that is contacted through the skin, inhaled into the lungs, swallowed or injected. The body's reaction to an allergen can be mild, such as ...

  6. Allergic reactions (image)

    MedlinePlus

    Allergic reaction can be provoked by skin contact with poison plants, chemicals and animal scratches, as well as by ... dust, nuts and shellfish, may also cause allergic reaction. Medications such as penicillin and other antibiotics are ...

  7. Microscale Thermite Reactions.

    ERIC Educational Resources Information Center

    Arnaiz, Francisco J.; Aguado, Rafael; Arnaiz, Susana

    1998-01-01

    Describes the adaptation of thermite (aluminum with metal oxides) reactions from whole-class demonstrations to student-run micro-reactions. Lists detailed directions and possible variations of the experiment. (WRM)

  8. Multidimensional Electronic Spectroscopy of Photochemical Reactions.

    PubMed

    Nuernberger, Patrick; Ruetzel, Stefan; Brixner, Tobias

    2015-09-21

    Coherent multidimensional electronic spectroscopy can be employed to unravel various channels in molecular chemical reactions. This approach is thus not limited to analysis of energy transfer or charge transfer (i.e. processes from photophysics), but can also be employed in situations where the investigated system undergoes permanent structural changes (i.e. in photochemistry). Photochemical model reactions are discussed by using the example of merocyanine/spiropyran-based molecular switches, which show a rich variety of reaction channels, in particular ring opening and ring closing, cis-trans isomerization, coherent vibrational wave-packet motion, radical ion formation, and population relaxation. Using pump-probe, pump-repump-probe, coherent two-dimensional and three-dimensional, triggered-exchange 2D, and quantum-control spectroscopy, we gain intuitive pictures on which product emerges from which reactant and which reactive molecular modes are associated. PMID:26382095

  9. 75 FR 34186 - Self-Regulatory Organizations; BATS Exchange, Inc.; EDGA Exchange, Inc.; EDGX Exchange, Inc...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-06-16

    ...; New York Stock Exchange LLC; NYSE Amex LLC; NYSE Arca, Inc.; The NASDAQ Stock Market LLC; Chicago.... (``NYSEArca''), The NASDAQ Stock Market LLC (``NASDAQ''), National Stock Exchange, Inc. (``NSX'') and Chicago... proposed rules may exacerbate market volatility rather than reduce it due to the interplay of stock...

  10. Reaction coordinates for electron transfer reactions

    SciTech Connect

    Rasaiah, Jayendran C.; Zhu Jianjun

    2008-12-07

    The polarization fluctuation and energy gap formulations of the reaction coordinate for outer sphere electron transfer are linearly related to the constant energy constraint Lagrangian multiplier m in Marcus' theory of electron transfer. The quadratic dependence of the free energies of the reactant and product intermediates on m and m+1, respectively, leads to similar dependence of the free energies on the reaction coordinates and to the same dependence of the activation energy on the reorganization energy and the standard reaction free energy. Within the approximations of a continuum model of the solvent and linear response of the longitudinal polarization to the electric field in Marcus' theory, both formulations of the reaction coordinate are expected to lead to the same results.

  11. Catalytic diastereoselective petasis reactions.

    PubMed

    Muncipinto, Giovanni; Moquist, Philip N; Schreiber, Stuart L; Schaus, Scott E

    2011-08-22

    Multicomponent Petasis reactions: the first diastereoselective Petasis reaction catalyzed by chiral biphenols that enables the synthesis of syn and anti β-amino alcohols in pure form has been developed. The reaction exploits a multicomponent approach that involves boronates, α-hydroxy aldehydes, and amines. PMID:21751322

  12. Reaction efficiency effects on binary chemical reactions

    NASA Astrophysics Data System (ADS)

    Lazaridis, Filippos; Savara, Aditya; Argyrakis, Panos

    2014-09-01

    We study the effect of the variation of reaction efficiency in binary reactions. We use the well-known A + B → 0 model, which has been extensively studied in the past. We perform simulations on this model where we vary the efficiency of reaction, i.e., when two particles meet they do not instantly react, as has been assumed in previous studies, but they react with a probability γ, where γ is in the range 0 < γ < 1. Our results show that at small γ values the system is reaction limited, but as γ increases it crosses over to a diffusion limited behavior. At early times, for small γ values, the particle density falls slower than for larger γ values. This fall-off goes over a crossover point, around the value of γ = 0.50 for high initial densities. Under a variety of conditions simulated, we find that the crossover point was dependent on the initial concentration but not on the lattice size. For intermediate and long times simulations, all γ values (in the depleted reciprocal density versus time plot) converge to the same behavior. These theoretical results are useful in models of epidemic reactions and epidemic spreading, where a contagion from one neighbor to the next is not always successful but proceeds with a certain probability, an analogous effect with the reaction probability examined in the current work.

  13. Heat exchange assembly

    DOEpatents

    Lowenstein, Andrew; Sibilia, Marc; Miller, Jeffrey; Tonon, Thomas S.

    2004-06-08

    A heat exchange assembly comprises a plurality of plates disposed in a spaced-apart arrangement, each of the plurality of plates includes a plurality of passages extending internally from a first end to a second end for directing flow of a heat transfer fluid in a first plane, a plurality of first end-piece members equaling the number of plates and a plurality of second end-piece members also equaling the number of plates, each of the first and second end-piece members including a recessed region adapted to fluidly connect and couple with the first and second ends of the plate, respectively, and further adapted to be affixed to respective adjacent first and second end-piece members in a stacked formation, and each of the first and second end-piece members further including at least one cavity for enabling entry of the heat transfer fluid into the plate, exit of the heat transfer fluid from the plate, or 180.degree. turning of the fluid within the plate to create a serpentine-like fluid flow path between points of entry and exit of the fluid, and at least two fluid conduits extending through the stacked plurality of first and second end-piece members for providing first fluid connections between the parallel fluid entry points of adjacent plates and a fluid supply inlet, and second fluid connections between the parallel fluid exit points of adjacent plates and a fluid discharge outlet so that the heat transfer fluid travels in parallel paths through each respective plate.

  14. Hear Exchange Assembly

    DOEpatents

    Lowenstein, Andrew; Sibilia, Marc; Miller, Jeffrey; Tonon, Thomas S.

    2003-05-27

    A heat exchange assembly comprises a plurality of plates disposed in a spaced-apart arrangement, each of the plurality of plates includes a plurality of passages extending internally from a first end to a second end for directing flow of a heat transfer fluid in a first plane, a plurality of first end-piece members equaling the number of plates and a plurality of second end-piece members also equaling the number of plates, each of the first and second end-piece members including a recessed region adapted to fluidly connect and couple with the first and second ends of the plate, respectively, and further adapted to be affixed to respective adjacent first and second end-piece members in a stacked formation, and each of the first and second end-piece members further including at least one cavity for enabling entry of the heat transfer fluid into the plate, exit of the heat transfer fluid from the plate, or 180.degree. turning of the fluid within the plate to create a serpentine-like fluid flow path between points of entry and exit of the fluid, and at least two fluid conduits extending through the stacked plurality of first and second end-piece members for providing first fluid connections between the parallel fluid entry points of adjacent plates and a fluid supply inlet, and second fluid connections between the parallel fluid exit points of adjacent plates and a fluid discharge outlet so that the heat transfer fluid travels in parallel paths through each respective plate.

  15. Effect of polyamine reagents on exchange capacity in ion exchangers

    NASA Astrophysics Data System (ADS)

    Petrova, T. I.; Dyachenko, F. V.; Bogatyreva, Yu. V.; Borodastov, A. K.; Ershova, I. S.

    2016-05-01

    Effect of compounds involved in complex reagents is described using Helamin 906H reagent as an example. The working exchange capacity of KU-2-8chs cation exchanger in hydrogen form and Amberlite IRA 900Cl anion exchanger in OH form remained almost unchanged when they were used repeatedly to purify water that contained Helamin 906H reagent; in addition, this capacity was the same upon filtration of water that did not contain this reagent. Leakage of total organic carbon was observed earlier than that of calcium ions upon filtration of the solution through the cation exchanger layer. The test results obtained in industrial conditions indicated that using H-OH filters to purify turbine condensate enables the decrease of the concentration of organic and other impurities therein.

  16. Plasma exchange in endocrine ophthalmopathy.

    PubMed

    Berlin, G; Hjelm, H; Liedén, G; Tegler, L

    1990-01-01

    We studied the effects of intensive plasma exchange on endocrine ophthalmopathy in 12 patients with Graves' disease and one with Hashimoto's thyroiditis. All patients were euthyroid at the time of plasma exchange. All but five had concomitant treatment with azathioprine. Each patient had a treatment period consisting of six plasma exchanges performed in 2-3 weeks; two patients were treated in two periods. Each time a mean of 2.4 liters plasma was exchanged. There was a prompt reduction in the concentration of circulating immune complexes and/or thyrotropin receptor antibodies following plasma exchange. Six of the 13 patients improved their proptosis; their median duration of eye symptoms before treatment was less than 8 months. In patients suffering from eye symptoms for more than 1 year improvement was rare. Overall the Hertel values were 24.1 +/- 4.4 (SD) before and 22.8 +/- 3.4 after plasma exchange for the left eyes (P = 0.07) and 23.8 +/- 4.0 before and 23.0 +/- 3.8 after for the right eyes (P = 0.09). Nine patients altogether improved their ophthalmopathy index and periorbital oedema. In patients with disabling endocrine ophthalmopathy plasma exchange may sometimes be of value to induce a relief of the ophthalmopathy; when it is used it should be instituted before fibrotic changes occur. We suggest that concomitant immunosuppressive drugs should be given to prevent rebound phenomenon induced by plasma exchange. To establish the role of plasma exchange in the treatment of endocrine ophthalmopathy controlled studies should be performed. PMID:2228998

  17. Custom, contract, and kidney exchange.

    PubMed

    Healy, Kieran; Krawiec, Kimberly D

    2012-01-01

    In this Essay, we examine a case in which the organizational and logistical demands of a novel form of organ exchange (the nonsimultaneous, extended, altruistic donor (NEAD) chain) do not map cleanly onto standard cultural schemas for either market or gift exchange, resulting in sociological ambiguity and legal uncertainty. In some ways, a NEAD chain resembles a form of generalized exchange, an ancient and widespread instance of the norm of reciprocity that can be thought of simply as the obligation to “pay it forward” rather than the obligation to reciprocate directly with the original giver. At the same time, a NEAD chain resembles a string of promises and commitments to deliver something in exchange for some valuable consideration--that is, a series of contracts. Neither of these salient "social imaginaries" of exchange--gift giving or formal contract--perfectly meets the practical demands of the NEAD system. As a result, neither contract nor generalized exchange drives the practice of NEAD chains. Rather, the majority of actual exchanges still resemble a simpler form of exchange: direct, simultaneous exchange between parties with no time delay or opportunity to back out. If NEAD chains are to reach their full promise for large-scale, nonsimultaneous organ transfer, legal uncertainties and sociological ambiguities must be finessed, both in the practices of the coordinating agencies and in the minds of NEAD-chain participants. This might happen either through the further elaboration of gift-like language and practices, or through a creative use of the cultural form and motivational vocabulary, but not necessarily the legal and institutional machinery, of contract. PMID:23461002

  18. Structural and theoretical basis for ligand exchange on thiolate monolayer protected gold nanoclusters.

    PubMed

    Heinecke, Christine L; Ni, Thomas W; Malola, Sami; Mäkinen, Ville; Wong, O Andrea; Häkkinen, Hannu; Ackerson, Christopher J

    2012-08-15

    Ligand exchange reactions are widely used for imparting new functionality on or integrating nanoparticles into devices. Thiolate-for-thiolate ligand exchange in monolayer protected gold nanoclusters has been used for over a decade; however, a firm structural basis of this reaction has been lacking. Herein, we present the first single-crystal X-ray structure of a partially exchanged Au(102)(p-MBA)(40)(p-BBT)(4) (p-MBA = para-mercaptobenzoic acid, p-BBT = para-bromobenzene thiol) with p-BBT as the incoming ligand. The crystal structure shows that 2 of the 22 symmetry-unique p-MBA ligand sites are partially exchanged to p-BBT under the initial fast kinetics in a 5 min timescale exchange reaction. Each of these ligand-binding sites is bonded to a different solvent-exposed Au atom, suggesting an associative mechanism for the initial ligand exchange. Density functional theory calculations modeling both thiol and thiolate incoming ligands postulate a mechanistic pathway for thiol-based ligand exchange. The discrete modification of a small set of ligand binding sites suggests Au(102)(p-MBA)(44) as a powerful platform for surface chemical engineering. PMID:22816317

  19. Coupled acoustic-gravity field for dynamic evaluation of ion exchange with a single resin bead.

    PubMed

    Kanazaki, Takahiro; Hirawa, Shungo; Harada, Makoto; Okada, Tetsuo

    2010-06-01

    A coupled acoustic-gravity field is efficient for entrapping a particle at the position determined by its acoustic properties rather than its size. This field has been applied to the dynamic observation of ion-exchange reactions occurring in a single resin bead. The replacement of counterions in an ion-exchange resin induces changes in its acoustic properties, such as density and compressibility. Therefore, we can visually trace the advancement of an ion-exchange reaction as a time change in the levitation position of a resin bead entrapped in the field. Cation-exchange reactions occurring in resin beads with diameters of 40-120 microm are typically completed within 100-200 s. Ion-exchange equilibrium or kinetics is often evaluated with off-line chemical analyses, which require a batch amount of ion exchangers. Measurements with a single resin particle allow us to evaluate ion-exchange dynamics and kinetics of ions including those that are difficult to measure by usual off-line analyses. The diffusion properties of ions in resins have been successfully evaluated from the time change in the levitation positions of resin beads. PMID:20462180

  20. Hydrogen atom scrambling in ion-molecule reactions of methane and ethylene.

    NASA Technical Reports Server (NTRS)

    Huntress, W. T., Jr.

    1972-01-01

    The extent of hydrogen atom exchange in the reaction, CH3(+) + CH4 yields C2H5(+) + H2, is determined by examining the product distribution for the reactions CH3(+) + CD4 and CD3(+) + CH4 as a function of relative kinetic energy from thermal energies to 10 eV. It is found that the reaction of CH4(+) with the parent neutral proceeds both via proton transfer and hydrogen abstraction accompanied by approximately 10% hydrogen atom exchange during the reaction.

  1. Insoluble polyelectrolyte and ion-exchange hollow fiber impregnated therewith

    NASA Technical Reports Server (NTRS)

    Rembaum, A. (Inventor)

    1977-01-01

    The number of quaternary sites and ion exchange capacity of a polyquaternary, cross linked, insoluble copolymer of a vinyl pyridine and a dihalo organic compound is increased by about 15-35% by reaction of the polymer with an amine followed by quaternization, if required. The polymer forms spontaneously in the presence of a substrate such as within the pores of a hollow fiber. The improved resin impregnated fiber may be utilized to remove ions from waste or process steams.

  2. Meson-baryon interaction in the meson exchange picture

    SciTech Connect

    Doering, M.

    2011-10-24

    Elastic {pi}N scattering and the reaction {pi}{sup +}p{yields}K{sup +}{Sigma}{sup +} are described simultaneously in a unitary coupled-channels approach which respects analyticity. SU(3) flavor symmetry is used to relate the t- and u- channel exchanges that drive the meson-baryon interaction in the different channels. Angular distributions, polarizations, and spin-rotation parameters are compared with available experimental data. The pole structure of the amplitudes is extracted from the analytic continuation.

  3. Charge exchange molecular ion source

    DOEpatents

    Vella, Michael C.

    2003-06-03

    Ions, particularly molecular ions with multiple dopant nucleons per ion, are produced by charge exchange. An ion source contains a minimum of two regions separated by a physical barrier and utilizes charge exchange to enhance production of a desired ion species. The essential elements are a plasma chamber for production of ions of a first species, a physical separator, and a charge transfer chamber where ions of the first species from the plasma chamber undergo charge exchange or transfer with the reactant atom or molecules to produce ions of a second species. Molecular ions may be produced which are useful for ion implantation.

  4. Heat exchanger with ceramic elements

    DOEpatents

    Corey, John A.

    1986-01-01

    An annular heat exchanger assembly includes a plurality of low thermal growth ceramic heat exchange members with inlet and exit flow ports on distinct faces. A mounting member locates each ceramic member in a near-annular array and seals the flow ports on the distinct faces into the separate flow paths of the heat exchanger. The mounting member adjusts for the temperature gradient in the assembly and the different coefficients of thermal expansion of the members of the assembly during all operating temperatures.

  5. Heat exchanger for electrothermal devices

    NASA Technical Reports Server (NTRS)

    Zavesky, Ralph J. (Inventor); Sovey, James S. (Inventor); Mirtich, Michael J. (Inventor); Marinos, Charalampus (Inventor); Penko, Paul F. (Inventor)

    1986-01-01

    An improved electrothermal device is disclosed. An electrothermal thruster utilizes a generally cylindrical heat exchanger chamber to convert electricity to heat which raises the propellant temperature. A textured, high emissivity heat element radiatively transfers heat to the inner wall of this chamber that is ion beam morphologically controlled for high absorptivity. This, in turn, raises the temperature of a porous heat exchanger material in an annular chamber surrounding the cylindrical chamber. Propellant gas flows through the annular chamber and is heated by the heat exchanger material.

  6. Corrosion protected reversing heat exchanger

    SciTech Connect

    Zawierucha, R.

    1984-09-25

    A reversing heat exchanger of the plate and fin type having multiple aluminum parting sheets in a stacked arrangement with corrugated fins separating the sheets to form multiple flow paths, means for closing the ends of the sheets, an input manifold arrangement of headers for the warm end of of the exchanger and an output manifold arrangement for the cold end of the exchanger with the input air feed stream header and the waste gas exhaust header having an alloy of zinc and aluminum coated on the inside surface for providing corrosion protection to the stack.

  7. Heat exchanger using graphite foam

    SciTech Connect

    Campagna, Michael Joseph; Callas, James John

    2012-09-25

    A heat exchanger is disclosed. The heat exchanger may have an inlet configured to receive a first fluid and an outlet configured to discharge the first fluid. The heat exchanger may further have at least one passageway configured to conduct the first fluid from the inlet to the outlet. The at least one passageway may be composed of a graphite foam and a layer of graphite material on the exterior of the graphite foam. The layer of graphite material may form at least a partial barrier between the first fluid and a second fluid external to the at least one passageway.

  8. Structural Insight into the Ion-Exchange Mechanism of the Sodium/Calcium Exchanger

    SciTech Connect

    Liao, Jun; Li, Hua; Zeng, Weizhong; Sauer, David B.; Belmares, Ricardo; Jiang, Youxing

    2012-06-19

    Sodium/calcium (Na{sup +}/Ca{sup 2+}) exchangers (NCX) are membrane transporters that play an essential role in maintaining the homeostasis of cytosolic Ca{sup 2+} for cell signaling. We demonstrated the Na{sup +}/Ca{sup 2+}-exchange function of an NCX from Methanococcus jannaschii (NCX{_}Mj) and report its 1.9 angstrom crystal structure in an outward-facing conformation. Containing 10 transmembrane helices, the two halves of NCX{_}Mj share a similar structure with opposite orientation. Four ion-binding sites cluster at the center of the protein: one specific for Ca{sup 2+} and three that likely bind Na{sup +}. Two passageways allow for Na{sup +} and Ca{sup 2+} access to the central ion-binding sites from the extracellular side. Based on the symmetry of NCX{_}Mj and its ability to catalyze bidirectional ion-exchange reactions, we propose a structure model for the inward-facing NCX{_}Mj.

  9. Nonlocal exchange correlation in screened-exchange densityfunctional methods

    SciTech Connect

    Lee, Byounghak; Wang, Lin-Wang; Spataru, Catalin D.; Louie,Steven G.

    2007-04-22

    We present a systematic study on the exchange-correlationeffects in screened-exchange local density functional method. Toinvestigate the effects of the screened-exchange potential in the bandgap correction, we have compared the exchange-correlation potential termin the sX-LDA formalism with the self-energy term in the GWapproximation. It is found that the band gap correction of the sX-LDAmethod primarily comes from the downshift of valence band states,resulting from the enhancement of bonding and the increase of ionizationenergy. The band gap correction in the GW method, on the contrary, comesin large part from the increase of theconduction band energies. We alsostudied the effects of the screened-exchange potential in the totalenergy by investigating the exchange-correlation hole in comparison withquantum Monte Carlo calculations. When the Thomas-Fermi screening isused, the sX-LDA method overestimates (underestimates) theexchange-correlation hole in short (long) range. From theexchange-correlation energy analysis we found that the LDA method yieldsbetter absolute total energy than sX-LDA method.

  10. Marriage exchanges, seed exchanges, and the dynamics of manioc diversity

    PubMed Central

    Delêtre, Marc; McKey, Doyle B.; Hodkinson, Trevor R.

    2011-01-01

    The conservation of crop genetic resources requires understanding the different variables—cultural, social, and economic—that impinge on crop diversity. In small-scale farming systems, seed exchanges represent a key mechanism in the dynamics of crop genetic diversity, and analyzing the rules that structure social networks of seed exchange between farmer communities can help decipher patterns of crop genetic diversity. Using a combination of ethnobotanical and molecular genetic approaches, we investigated the relationships between regional patterns of manioc genetic diversity in Gabon and local networks of seed exchange. Spatially explicit Bayesian clustering methods showed that geographical discontinuities of manioc genetic diversity mirror major ethnolinguistic boundaries, with a southern matrilineal domain characterized by high levels of varietal diversity and a northern patrilineal domain characterized by low varietal diversity. Borrowing concepts from anthropology—kinship, bridewealth, and filiation—we analyzed the relationships between marriage exchanges and seed exchange networks in patrilineal and matrilineal societies. We demonstrate that, by defining marriage prohibitions, kinship systems structure social networks of exchange between farmer communities and influence the movement of seeds in metapopulations, shaping crop diversity at local and regional levels. PMID:22042843

  11. 75 FR 51138 - Self-Regulatory Organizations; BATS Exchange, Inc.; Chicago Board Options Exchange, Incorporated...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-08-18

    ... Exchange Act Release Nos. 62251 (June 10, 2010), 75 FR 34183 (June 16, 2010); 62252 (June 10, 2010), 75 FR...; BATS Exchange, Inc.; Chicago Board Options Exchange, Incorporated; Chicago Stock Exchange, Inc.; EDGA... Securities Exchange LLC; NASDAQ OMX BX, Inc.; The NASDAQ Stock Market LLC; National Stock Exchange, Inc.;...

  12. 22 CFR Appendix B to Part 62 - Exchange Visitor Program Services, Exchange-Visitor Program Application

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 22 Foreign Relations 1 2010-04-01 2010-04-01 false Exchange Visitor Program Services, Exchange-Visitor Program Application B Appendix B to Part 62 Foreign Relations DEPARTMENT OF STATE PUBLIC DIPLOMACY AND EXCHANGES EXCHANGE VISITOR PROGRAM Pt. 62, App. B Appendix B to Part 62—Exchange Visitor Program Services, Exchange-Visitor...

  13. Deuteration of pentacene in benzoic acid: Monitoring the reaction kinetics via low-temperature optical spectroscopy

    SciTech Connect

    Corval, A.; Casalegno, R.; Astilean, S.; Trommsdorff, H.P.

    1992-06-25

    In the deuteration of pentacene in benzoic acid, this reaction is monitored via low-temperature optical spectroscopy to observe the proton-deuterium rate of exchange between the solvent and solute molecules. Of the 14 pentacene protons, 6 have an exchange rate 2 orders of magnitude greater than the remaining 8. 20 refs., 3 figs.

  14. Anion exchange polymer electrolytes

    DOEpatents

    Kim, Yu Seung; Kim, Dae Sik; Lee, Kwan-Soo

    2013-07-23

    Solid anion exchange polymer electrolytes and compositions comprising chemical compounds comprising a polymeric core, a spacer A, and a guanidine base, wherein said chemical compound is uniformly dispersed in a suitable solvent and has the structure: ##STR00001## wherein: i) A is a spacer having the structure O, S, SO.sub.2, --NH--, --N(CH.sub.2).sub.n, wherein n=1-10, --(CH.sub.2).sub.n--CH.sub.3--, wherein n=1-10, SO.sub.2-Ph, CO-Ph, ##STR00002## wherein R.sub.5, R.sub.6, R.sub.7 and R.sub.8 each are independently --H, --NH.sub.2, F, Cl, Br, CN, or a C.sub.1-C.sub.6 alkyl group, or any combination of thereof; ii) R.sub.9, R.sub.10, R.sub.11, R.sub.12, or R.sub.13 each independently are --H, --CH.sub.3, --NH.sub.2, --NO, --CH.sub.nCH.sub.3 where n=1-6, HC.dbd.O--, NH.sub.2C.dbd.O--, --CH.sub.nCOOH where n=1-6, --(CH.sub.2).sub.n--C(NH.sub.2)--COOH where n=1-6, --CH--(COOH)--CH.sub.2--COOH, --CH.sub.2--CH(O--CH.sub.2CH.sub.3).sub.2, --(C.dbd.S)--NH.sub.2, --(C.dbd.NH)--N--(CH.sub.2).sub.nCH.sub.3, where n=0-6, --NH--(C.dbd.S)--SH, --CH.sub.2--(C.dbd.O)--O--C(CH.sub.3).sub.3, --O--(CH.sub.2).sub.n--CH--(NH.sub.2)--COOH, where n=1-6, --(CH.sub.2).sub.n--CH.dbd.CH wherein n=1-6, --(CH.sub.2).sub.n--CH--CN wherein n=1-6, an aromatic group such as a phenyl, benzyl, phenoxy, methylbenzyl, nitrogen-substituted benzyl or phenyl groups, a halide, or halide-substituted methyl groups; and iii) wherein the composition is suitable for use in a membrane electrode assembly.

  15. Surface Exchange and Bulk Diffusivity of LSCF as SOFC Cathode: Electrical Conductivity Relaxation and Isotope Exchange Characterizations

    SciTech Connect

    Li, Yihong; Gerdes, Kirk; Horita, Teruhisa; Liu, Xingbo

    2013-05-05

    The oxygen diffusion coefficient (D) and surface exchange coefficient (k) of a typical SOFC cathode material, La{sub 0.6}Sr{sub 0.4}Co{sub 0.2}Fe{sub 0.8}O{sub 3-δ} (LSCF) were characterized by both electrical conductivity relaxation (ECR) and oxygen isotope exchange (IE) methods. Conductivity relaxation experiments were conducted at 800°C for small step changes in partial pressure of oxygen (P{sub O{sub 2}} ), both decreasing and increasing, from 0.02 atm to 0.20 atm. The results revealed P{sub O{sub 2}} dependent hysteresis with the reduction process requiring more equilibration time than oxidation. Analysis of the experimental data indicated that the surface exchange coefficient is a function of the final oxygen partial pressure in an isothermal system. In addition, both forward and backward oxygen reduction reaction constants, which are vital for the fundamental understanding of SOFC cathode reaction mechanisms, are investigated based on the relationship between surface exchange coefficient and P{sub O{sub 2}} . The direct comparisons between the results from both ECR and IE were presented and the possible experimental errors in both methods were discussed.

  16. State-to-state reaction dynamics: A selective review

    NASA Astrophysics Data System (ADS)

    Teslja, Alexey; Valentini, James J.

    2006-10-01

    A selective review of state-to-state reaction dynamics experiments is presented. The review focuses on three classes of reactions that exemplify the rich history and illustrate the current state of the art in such work. These three reactions are (1) the hydrogen exchange reaction, H +H2→H2+H and its isotopomers; (2) the H +RH→H2+R reactions, where RH is an alkane, beginning with H +CH4→H2+CH3 and extending to much larger alkanes; and (3) the Cl +RH→HCl+R reactions, principally Cl +CH4→HCl+CH3. We describe the experiments, discuss their results, present comparisons with theory, and introduce heuristic models.

  17. Pu Anion Exchange Process Intensification

    SciTech Connect

    Taylor-Pashow, K.

    2015-10-08

    This project seeks to improve the efficiency of the plutonium anion-exchange process for purifying Pu through the development of alternate ion-exchange media. The objective of the project in FY15 was to develop and test a porous foam monolith material that could serve as a replacement for the current anion-exchange resin, Reillex® HPQ, used at the Savannah River Site (SRS) for purifying Pu. The new material provides advantages in efficiency over the current resin by the elimination of diffusive mass transport through large granular resin beads. By replacing the large resin beads with a porous foam there is much more efficient contact between the Pu solution and the anion-exchange sites present on the material. Several samples of a polystyrene based foam grafted with poly(4-vinylpyridine) were prepared and the Pu sorption was tested in batch contact tests.

  18. Phase Change Material Heat Exchangers

    NASA Video Gallery

    NASA’s Game Changing Development is taking on a technologydevelopment and demonstration effort to design, build, and test the next generation of Phase Change Material Heat Exchangers (PCM HXs) on ...

  19. Heat pipe array heat exchanger

    DOEpatents

    Reimann, Robert C.

    1987-08-25

    A heat pipe arrangement for exchanging heat between two different temperature fluids. The heat pipe arrangement is in a ounterflow relationship to increase the efficiency of the coupling of the heat from a heat source to a heat sink.

  20. Deuterium isotopic exchangeability of resin and amber at low thermal stress under hydrous conditions

    NASA Astrophysics Data System (ADS)

    Gonzalez, G.; Tappert, R.; Wolfe, A. P.; Muehlenbachs, K.

    2012-04-01

    Hydrous deuterium-exchange experiments have shown that a significant fraction of the original D/H composition of bulk kerogens, bitumens and expelled oils may participate in isotopic exchange reactions during burial diagenesis. However, it is unknown to what extent plant-derived secondary metabolites, namely resins and their fossil counterpart amber, exchange hydrogen isotopes following their biosynthesis. This situation hinders the application of resin D/H measurements in paleoenvironmental reconstruction. Here, we assess explicitly hydrogen exchange in resins and ambers using a series of immersion experiments in deuterated (D-enriched) waters over a period of several months at several temperatures. We are especially interested in assessing whether significant H-isotopic exchange occurs between resins and meteoric waters during early thermal maturation and polymerization. At 90°C, equivalent to ~3km of burial in most diagenetic regimes, modern conifer and angiosperm resins have an average post-metabolic H exchange of 4.6%, compared to only 1.1% for mature, polymerized ambers. At 55°C the degree of exchange is considerably lower: 1.9% for resins and 0.6% for ambers. These results indicate that most D/H isotopic exchange occurs prior to polymerization reactions, thereby confirming that D/H measurements from amber constitute a potentially sensitive proxy for environmental change.

  1. Expert System For Heat Exchanger

    NASA Technical Reports Server (NTRS)

    Bagby, D. Gordon; Cormier, Reginald A.

    1991-01-01

    Diagnosis simplified for non-engineers. Developmental expert-system computer program assists operator in controlling, monitoring operation, diagnosing malfunctions, and ordering repairs of heat-exchanger system dissipating heat generated by 20-kW radio transmitter. System includes not only heat exchanger but also pumps, fans, sensors, valves, reservoir, and associated plumbing. Program conceived to assist operator while avoiding cost of keeping engineer in full-time attendance. Similar programs developed for heating, ventilating, and air-conditioning systems.

  2. Vitrification of ion exchange resins

    DOEpatents

    Cicero-Herman, Connie A.; Workman, Rhonda Jackson

    2001-01-01

    The present invention relates to vitrification of ion exchange resins that have become loaded with hazardous or radioactive wastes, in a way that produces a homogenous and durable waste form and reduces the disposal volume of the resin. The methods of the present invention involve directly adding borosilicate glass formers and an oxidizer to the ion exchange resin and heating the mixture at sufficient temperature to produce homogeneous glass.

  3. Ion exchange - Simulation and experiment

    NASA Technical Reports Server (NTRS)

    Herrmann, Cal C.; Finn, John E.

    1991-01-01

    A FORTRAN program for simulating multicomponent adsorption by ion-exchange resins was adapted for use as both an ASPEN-callable module and as a free-standing simulator of the ion-exchange bed. Four polystyrene-divinylbenzene sulfonic acid resins have been characterized for three principal ions. It is concluded that a chelating resin appears appropriate as a heavy-metal trap. The same ASPEN-callable module is used to model this resin when Wilson parameters can be obtained.

  4. Discontinuous gas exchange in insects.

    PubMed

    Quinlan, Michael C; Gibbs, Allen G

    2006-11-01

    Insect respiratory physiology has been studied for many years, and interest in this area of insect biology has become revitalized recently for a number of reasons. Technical advances have greatly improved the precision, accuracy and ease with which gas exchange can be measured in insects. This has made it possible to go beyond classic models such as lepidopteran pupae and examine a far greater diversity of species. One striking result of recent work is the realization that insect gas exchange patterns are much more diverse than formerly recognized. Current work has also benefited from the inclusion of comparative methods that rigorously incorporate phylogenetic, ecological and life history information. We discuss these advances in the context of the classic respiratory pattern of insects, discontinuous gas exchange. This mode of gas exchange was exhaustively described in moth pupae in the 1950s and 1960s. Early workers concluded that discontinuous gas exchange was an adaptation to reduce respiratory water loss. This idea is no longer universally accepted, and several competing hypotheses have been proposed. We discuss the genesis of these alternative hypotheses, and we identify some of the predictions that might be used to test them. We are pleased to report that what was once a mature discipline, in which the broad parameters and adaptive significance of discontinuous gas exchange were thought to be well understood, is now a thriving and vigorous field of research. PMID:16870512

  5. Hartree potential dependent exchange functional.

    PubMed

    Constantin, Lucian A; Fabiano, Eduardo; Della Sala, Fabio

    2016-08-28

    We introduce a novel non-local ingredient for the construction of exchange density functionals: the reduced Hartree parameter, which is invariant under the uniform scaling of the density and represents the exact exchange enhancement factor for one- and two-electron systems. The reduced Hartree parameter is used together with the conventional meta-generalized gradient approximation (meta-GGA) semilocal ingredients (i.e., the electron density, its gradient, and the kinetic energy density) to construct a new generation exchange functional, termed u-meta-GGA. This u-meta-GGA functional is exact for the exchange of any one- and two-electron systems, is size-consistent and non-empirical, satisfies the uniform density scaling relation, and recovers the modified gradient expansion derived from the semiclassical atom theory. For atoms, ions, jellium spheres, and molecules, it shows a good accuracy, being often better than meta-GGA exchange functionals. Our construction validates the use of the reduced Hartree ingredient in exchange-correlation functional development, opening the way to an additional rung in the Jacob's ladder classification of non-empirical density functionals. PMID:27586907

  6. The many faces of ion-exchange resins

    SciTech Connect

    McNutty, J.T.

    1997-06-01

    Ion-exchange resins have been used commercially for over 60 years. Softening and demineralization of water for boiler feed and process use were then, and continue to be, the most familiar and widespread applications of ion-exchange resins throughout the chemical process industries (CPI). Several types of membrane-based technologies, such as electrodialysis, reverse osmosis and, more recently, electrodeionization are recognized as alternative methods for water treatment. Yet, modern versions of ion-exchange resins remain a major player in water treatment. In addition, these versatile materials can be found performing a wide range of tasks in both aqueous and nonaqueous environments. Some of these diverse applications include: acid or base catalysis; manufacture of high-purity solvents and reagent chemicals; separation of by-products of fermentation processes; deacidification of organic solvents; high-purity water production for semiconductor manufacture; recovery of valuable waste from dilute process effluents; controlled release of pharmaceutical products; and chromatography, both on the analytical and the industrial scale. The key to understanding the potential of ion-exchange resins is to look beyond their exchange and adsorptive characteristics, and to see their fundamental nature. In other words, it`s necessary to first consider them as spherical, particulate reactive polymers that perform chemical reactions.

  7. Base-catalyzed deuterium exchange of 6,6-dimethylfulvene

    SciTech Connect

    Hine, J.; Knight, D.B.

    1980-03-14

    The kinetics of the deuterium exchange of 6,6-dimethylfulvene have been studied in the presence of sodium methoxide-methanol-d and potassium tert-butoxide-tert-butyl alcohol-d. The rate of disappearance of undeuterated starting material was followed by mass spectral measurements. The rate of introduction of deuterium into the methyl groups and into the ring was followed by H NMR. The rates of methyl exchange and ring exchange were of the same order of magnitude. The reaction of tert-butyl alcohol-d was speeded by addition of cryptate (4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo(8.8.8)hexacosane). The occurrence of methyl exchange establishes a deprotonation mechanism (Scheme I) in both solvents. The greater rate in tert-butyl alcohol-d than in methanol-d is evidence that an addition-elimination mechanism for ring exchange is not important in tert-butyl alcohol-d solution, but its importance in methanol-d cannot be proven or disproven. 3 figures, 3 tables.

  8. Simultaneous Disulfide and Boronic Acid Ester Exchange in Dynamic Combinatorial Libraries

    PubMed Central

    Diemer, Sanna L.; Kristensen, Morten; Rasmussen, Brian; Beeren, Sophie R.; Pittelkow, Michael

    2015-01-01

    Dynamic combinatorial chemistry has emerged as a promising tool for the discovery of complex receptors in supramolecular chemistry. At the heart of dynamic combinatorial chemistry are the reversible reactions that enable the exchange of building blocks between library members in dynamic combinatorial libraries (DCLs) ensuring thermodynamic control over the system. If more than one reversible reaction operates in a single dynamic combinatorial library, the complexity of the system increases dramatically, and so does its possible applications. One can imagine two reversible reactions that operate simultaneously or two reversible reactions that operate independently. Both these scenarios have advantages and disadvantages. In this contribution, we show how disulfide exchange and boronic ester transesterification can function simultaneous in dynamic combinatorial libraries under appropriate conditions. We describe the detailed studies necessary to establish suitable reaction conditions and highlight the analytical techniques appropriate to study this type of system. PMID:26378519

  9. Investigation of the gas-phase hydrogen/deuterium exchange behavior of aromatic dicarboxylic acids in a quadrupole ion trap

    NASA Astrophysics Data System (ADS)

    Chipuk, Joseph E.; Brodbelt, Jennifer S.

    2007-11-01

    Gas-phase hydrogen/deuterium (H/D) exchange reactions of four deprotonated aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid and 2,6-naphthalic acid) with D2O were performed in a quadrupole ion trap mass spectrometer. Experimental results showed significant differences in the rate and extent of exchange when the relative position of the carboxylic acid groups varied. Spontaneous and near complete exchange of one aromatic hydrogen atom occurred when the carboxylic acid groups were in the meta-position, whereas no additional exchange was observed for either the ortho- or para-isomers or for the structurally similar naphthalic acid. Computational investigations support the participation of several possible exchange mechanisms with the contribution of each relying heavily on the relative orientation of the acid moieties. A relay mechanism that bridges the deprotonation site and the labile hydrogen site appears to be responsible for the H/D exchange of not only the labile hydrogen atom of isophthalic acid, but also for the formation of a stable carbanion and corresponding subsequent exchange of one aromatic hydrogen atom. The impact of hydrogen bonding on the relay mechanism is demonstrated by the reaction of phthalic acid as the extent and rate of reaction are greatly retarded by the favorable interaction of the two carboxylic acid groups. Finally, a flip-flop mechanism is likely responsible for the exchange of both terephthalic acid and 2,6-naphthalic acid where the reactive sites are too remote for exchange via relay.

  10. Vapor-phase catalytic oxidesulfurization (ODS) of organosulfur compounds over supported metal oxide catalysts

    NASA Astrophysics Data System (ADS)

    Choi, Sukwon

    Sulfur in transportation fuels remains a leading source of SOx emissions from vehicle engines and is a major source of air pollution. The very low levels of sulfur globally mandated for transportation fuels in the near future cannot be achieved by current practices of hydrodesulfurization (HDS) for sulfur removal, which operate under severe conditions (high T, P) and use valuable H2. Novel vapor-phase catalytic oxidesulfurization (ODS) processes of selectively oxidizing various organosulfur compounds (carbonyl sulfide, carbon disulfide, methanethiol, dimethyl sulfide (DMS), dimethyl disulfide (DMDS), thiophene, 2,5-dimenthylthiophene) typically found in various industrial streams (e.g., petroleum refining, pulp and paper) into valuable chemical intermediates (H 2CO, CO, H2, maleic anhydride and concentrated SO2) has been extensively studied. This research has primarily focused on establishing the fundamental kinetics and mechanisms of these selective oxidation reactions over well-defined supported metal oxide catalysts. The selective oxidation reactions of COS + O2 → CO + SO2; 2CS2 + 5O2 → 2CO + 4SO2; CH3SH + 2O 2 → H2CO + SO2 + H2O; C4 H4S + 3O2 → C4H2O 3 + H2O + SO2; were studied. Raman spectroscopy revealed that the supported metal oxide phases were 100% dispersed on the oxide substrate. All the catalysts were highly active and selective for the oxidesulfurization of carbonyl sulfide, carbon disulfide, methanethiol, and thiophene between 290--330°C, 230--270°C, 350--400°C, and 250--400°C, respectively and did not deactivate. The TOFs (turnover frequency, normalized activity per active catalytic site) for all ODS reactions over supported vanadia catalysts, only containing molecularly dispersed surface vanadia species, varied within one order of magnitude and revealed the V-O-Support bridging bond was involved in the critical rate-determining kinetic steps. The surface reaction mechanism for each reaction was revealed by in situ IR (infrared) and

  11. Anaphylactic reactions to cinoxacin.

    PubMed Central

    Stricker, B. H.; Slagboom, G.; Demaeseneer, R.; Slootmaekers, V.; Thijs, I.; Olsson, S.

    1988-01-01

    During 1981 to mid-1988 three cases of anaphylactic shock after treatment with the quinolone derivative cinoxacin were reviewed by the Netherlands Centre for Monitoring of Adverse Reactions to Drugs and 17 cases of an anaphylactic type of reaction notified to the World Health Organisation Collaborating Centre for International Drug Monitoring. In five out of six patients for whom data were available the reaction began shortly after taking a single capsule of a second or next course of treatment. Cinoxacin is related to nalidixic acid, and one patient previously treated with that agent subsequently had an anaphylactoid reaction to cinoxacin and later developed a skin reaction to nalidixic acid. There were no deaths, and patients treated as an emergency with plasma expanders or with adrenaline and corticosteroids generally recovered promptly and uneventfully. In view of the potentially fatal consequences of anaphylactic reactions to cinoxacin and other quinolones doctors should take care when prescribing these drugs. PMID:3147004

  12. Reactions to radiocontrast media.

    PubMed

    Hong, Sandra J; Wong, Johnson T; Bloch, Kurt J

    2002-01-01

    Adverse reactions to radiocontrast media (RCM) occur unexpectedly and may be life-threatening. This article describes an anaphylactoid reaction (AR) in one patient. The term AR refers to a syndrome clinically similar to anaphylaxis, but these reactions are independent of immunoglobulin E antibody-mediated mast cell or basophil degranulation. This article briefly reviews the literature regarding RCMs and types of reactions to RCM. The risk factors for AR to RCM infusions will be discussed along with current concepts of the pathogenesis of RCM-induced ARs. This article also describes the therapeutic management of patients who have had a previous adverse reaction to RCM and provides an approach to patients who have breakthrough reactions despite adequate premedication, but require additional radiographic studies. PMID:12476546

  13. Noncanonical Reactions of Flavoenzymes

    PubMed Central

    Sobrado, Pablo

    2012-01-01

    Enzymes containing flavin cofactors are predominantly involved in redox reactions in numerous cellular processes where the protein environment modulates the chemical reactivity of the flavin to either transfer one or two electrons. Some flavoenzymes catalyze reactions with no net redox change. In these reactions, the protein environment modulates the reactivity of the flavin to perform novel chemistries. Recent mechanistic and structural data supporting novel flavin functionalities in reactions catalyzed by chorismate synthase, type II isopentenyl diphosphate isomerase, UDP-galactopyranose mutase, and alkyl-dihydroxyacetonephosphate synthase are presented in this review. In these enzymes, the flavin plays either a direct role in acid/base reactions or as a nucleophile or electrophile. In addition, the flavin cofactor is proposed to function as a “molecular scaffold” in the formation of UDP-galactofuranose and alkyl-dihydroxyacetonephosphate by forming a covalent adduct with reaction intermediates. PMID:23203060

  14. Mechanisms in Knockout Reactions

    NASA Astrophysics Data System (ADS)

    Bazin, D.; Charity, R. J.; de Souza, R. T.; Famiano, M. A.; Gade, A.; Henzl, V.; Henzlova, D.; Hudan, S.; Lee, J.; Lukyanov, S.; Lynch, W. G.; McDaniel, S.; Mocko, M.; Obertelli, A.; Rogers, A. M.; Sobotka, L. G.; Terry, J. R.; Tostevin, J. A.; Tsang, M. B.; Wallace, M. S.

    2009-06-01

    We report the first detailed study of the relative importance of the stripping and diffraction mechanisms involved in nucleon knockout reactions, by the use of a coincidence measurement of the residue and fast proton following one-proton knockout reactions. The measurements used the S800 spectrograph in combination with the HiRA detector array at the NSCL. Results for the reactions Be9(C9,B8+X)Y and Be9(B8,Be7+X)Y are presented and compared with theoretical predictions for the two reaction mechanisms calculated using the eikonal model. The data show a clear distinction between the stripping and diffraction mechanisms and the measured relative proportions are very well reproduced by the reaction theory. This agreement adds support to the results of knockout reaction analyses and their applications to the spectroscopy of rare isotopes.

  15. Geochemical Reaction Mechanism Discovery from Molecular Simulation

    DOE PAGESBeta

    Stack, Andrew G.; Kent, Paul R. C.

    2014-11-10

    Methods to explore reactions using computer simulation are becoming increasingly quantitative, versatile, and robust. In this review, a rationale for how molecular simulation can help build better geochemical kinetics models is first given. We summarize some common methods that geochemists use to simulate reaction mechanisms, specifically classical molecular dynamics and quantum chemical methods and discuss their strengths and weaknesses. Useful tools such as umbrella sampling and metadynamics that enable one to explore reactions are discussed. Several case studies wherein geochemists have used these tools to understand reaction mechanisms are presented, including water exchange and sorption on aqueous species and mineralmore » surfaces, surface charging, crystal growth and dissolution, and electron transfer. The impact that molecular simulation has had on our understanding of geochemical reactivity are highlighted in each case. In the future, it is anticipated that molecular simulation of geochemical reaction mechanisms will become more commonplace as a tool to validate and interpret experimental data, and provide a check on the plausibility of geochemical kinetic models.« less

  16. Geochemical Reaction Mechanism Discovery from Molecular Simulation

    SciTech Connect

    Stack, Andrew G.; Kent, Paul R. C.

    2014-11-10

    Methods to explore reactions using computer simulation are becoming increasingly quantitative, versatile, and robust. In this review, a rationale for how molecular simulation can help build better geochemical kinetics models is first given. We summarize some common methods that geochemists use to simulate reaction mechanisms, specifically classical molecular dynamics and quantum chemical methods and discuss their strengths and weaknesses. Useful tools such as umbrella sampling and metadynamics that enable one to explore reactions are discussed. Several case studies wherein geochemists have used these tools to understand reaction mechanisms are presented, including water exchange and sorption on aqueous species and mineral surfaces, surface charging, crystal growth and dissolution, and electron transfer. The impact that molecular simulation has had on our understanding of geochemical reactivity are highlighted in each case. In the future, it is anticipated that molecular simulation of geochemical reaction mechanisms will become more commonplace as a tool to validate and interpret experimental data, and provide a check on the plausibility of geochemical kinetic models.

  17. Effects of diatomic reagent alignment on the A + BC reaction

    NASA Technical Reports Server (NTRS)

    Pattengill, M. D.; Zare, R. N.; Jaffe, R. L.

    1987-01-01

    A computational study is reported on the A + BC - AB + C bimolecular exchange reaction in which BC is aligned with respect to the approach direction of atom A so that the initial rotational angular momentum vector of BC is either parallel (or equivalently antiparallel) or perpendicular to the initial velocity vector of A. The calculations employ a modification of the extended LEPS potential, which permits straightforward generation of noncollinear minimum energy reaction paths. The calculations clearly demonstrate that diatomic reagent alignment can markedly affect the nature of reaction product early partitioning; they also demonstrate that diatomic reagent alignment affects reactive cross sections.

  18. Exploiting the reversibility of natural product glycosyltransferase-catalyzed reactions.

    PubMed

    Zhang, Changsheng; Griffith, Byron R; Fu, Qiang; Albermann, Christoph; Fu, Xun; Lee, In-Kyoung; Li, Lingjun; Thorson, Jon S

    2006-09-01

    Glycosyltransferases (GTs), an essential class of ubiquitous enzymes, are generally perceived as unidirectional catalysts. In contrast, we report that four glycosyltransferases from two distinct natural product biosynthetic pathways-calicheamicin and vancomycin-readily catalyze reversible reactions, allowing sugars and aglycons to be exchanged with ease. As proof of the broader applicability of these new reactions, more than 70 differentially glycosylated calicheamicin and vancomycin variants are reported. This study suggests the reversibility of GT-catalyzed reactions may be general and useful for generating exotic nucleotide sugars, establishing in vitro GT activity in complex systems, and enhancing natural product diversity. PMID:16946071

  19. Sleeve reaction chamber system

    SciTech Connect

    Northrup, M. Allen; Beeman, Barton V.; Benett, William J.; Hadley, Dean R.; Landre, Phoebe; Lehew, Stacy L.; Krulevitch, Peter A.

    2009-08-25

    A chemical reaction chamber system that combines devices such as doped polysilicon for heating, bulk silicon for convective cooling, and thermoelectric (TE) coolers to augment the heating and cooling rates of the reaction chamber or chambers. In addition the system includes non-silicon-based reaction chambers such as any high thermal conductivity material used in combination with a thermoelectric cooling mechanism (i.e., Peltier device). The heat contained in the thermally conductive part of the system can be used/reused to heat the device, thereby conserving energy and expediting the heating/cooling rates. The system combines a micromachined silicon reaction chamber, for example, with an additional module/device for augmented heating/cooling using the Peltier effect. This additional module is particularly useful in extreme environments (very hot or extremely cold) where augmented heating/cooling would be useful to speed up the thermal cycling rates. The chemical reaction chamber system has various applications for synthesis or processing of organic, inorganic, or biochemical reactions, including the polymerase chain reaction (PCR) and/or other DNA reactions, such as the ligase chain reaction.

  20. Metal-mullite reactions

    SciTech Connect

    Loehman, R.E.; Tomsia, A.P.

    1993-11-01

    Mullite was reacted with pure Al and with Ti or Zr dissolved in Ag-Cu eutectic alloys at 1100 C in Ar. Analysis of the Ti and Zr-containing specimens showed reaction zones with compositions of Ti{sub 50}Cu{sub 3O}O{sub 20} and ZrO{sub 2}, respectively. The Al-mullite specimen showed much more extensive penetration into the ceramic and a more diffuse reaction zone than the other two systems. Al{sub 2}O{sub 3} and Si were the main reaction products for Al-mullite reaction.