Sample records for hydrogen-deuterium exchange reactions

  1. Isomeric Differentiation of Green Tea Catechins using Gas-Phase Hydrogen/Deuterium Exchange Reactions (United States)

    Niemeyer, Emily D.; Brodbelt, Jennifer S.


    Hydrogen/deuterium exchange reactions in a quadrupole ion trap mass spectrometer are used to differentiate galloylated catechin stereoisomers (catechin gallate and epicatechin gallate; gallocatechin gallate and epigallocatechin gallate) and the non-galloylated analogs (catechin and epicatechin, gallocatechin and epigallocatechin). Significant differences in the hydrogen/deuterium exchange behavior of the four pairs of deprotonated catechin stereoisomers are observed upon reaction with D2O. Interestingly, the non-galloylated catechins undergo H/D exchange to a much greater extent than the galloylated species, incorporating deuterium at both aromatic/allylic and active phenolic sites. Non-galloylated catechin isomers are virtually indistinguishable by their H/D exchange kinetics over a wide range of reaction times (0.05 to 10 s). Our experimental results are explained using high-level ab initio calculations to elucidate the subtle structural variations in the catechin stereoisomers that lead to their differing H/D exchange kinetics. PMID:17702600

  2. Analysis of conformational changes in rhodopsin by histidine hydrogen-deuterium exchange. (United States)

    Lodowski, David T; Miyagi, Masaru


    Hydrogen-deuterium exchange (HDX) is a technique that measures the exchange of protein hydrogens for deuteriums in a D2O-containing buffer, providing readout of the structural dynamics. Histidine hydrogen-deuterium exchange mass spectrometry (His-HDX-MS) is a variation of this technique that measures the slow HDX of imidazole C2 hydrogens of histidines. This measurement, when accompanied by pH titration, provides both pK as and half-lives (t 1/2) of the HDX reaction for individual histidine residues in proteins. The pK a and t 1/2 values indicate the electrostatic environment and the degree of side-chain solvent accessibility of the histidine residues, respectively. Herein we describe an experimental protocol to characterize rhodopsin by His-HDX-MS. This technique can be used to monitor different states of rhodopsin and might be useful for monitoring longtime scale events in other GPCRs.

  3. [Utilization of Hydrogen/Deuterium Exchange in Biopharmaceutical Industry]. (United States)

    Coufalová, D; Vojtěšek, B; Hernychova, L

    The development of biopharmaceutics is the fastest growing segment of the present pharmaceutical industry. The analysis of proteins therapeutics is a challenging task due to their large size and complexity of spatial structure. Any changes in the primary, secondary, tertiary or quaternary protein structure can have huge impact on their function, efficiency and toxicity. Mass spectrometry proved itself to be a powerful tool for analysis of primary protein structure (amino acid sequence) and thanks to the development of new techniques in last years it is able to analyse higher order protein structures. One of these new techniques is hydrogen/deuterium exchange (HDX). HDX is based on exchange of amid protons with deuterium from solution on the protein backbone chain. Protons on the surface of protein are exchanging with deuterium much faster than protons buried inside of protein. HDX results could provide information about spatial protein structure and also about protein-protein interactions and protein-ligand interactions. Furthermore, by analysing of deuterium exchange in different time points this method could give information about dynamic changes of protein structure and dynamics of proteins interactions. Because of possibilities of this method, HDX become attractive method for characterization of protein biopharmaceuticals. This review article is focused on the utilization of mass spectrometry in biopharmaceutical industry and mainly on HDX method and its applications.Key words: mass spectrometry - proteomics - protein conformation - drug discovery - drug industry - hydrogen/deuterium exchangeThe work was supported by the project MEYS - NPS I - LO1413.The authors declare they have no potential conflicts of interest concerning drugs, products, or services used in the study.The Editorial Board declares that the manuscript met the ICMJE recommendation for biomedical papers.Submitted: 23. 5. 2016Accepted: 10. 6. 2016.

  4. Electrochemical reduction of disulfide-containing proteins for hydrogen/deuterium exchange monitored by mass spectrometry

    DEFF Research Database (Denmark)

    Mysling, Simon; Salbo, Rune; Ploug, Michael


    requires a high concentration (>200 mM) of the chemical reducing agent Tris(2-carboxyethyl)phosphine (TCEP) as its reduction rate constant is decreased at low pH and temperature. Serious adverse effects on chromatographic and mass spectrometric performances have been reported when using high concentrations......Characterization of disulfide bond-containing proteins by hydrogen/deuterium exchange monitored by mass spectrometry (HDX-MS) requires reduction of the disulfide bonds under acidic and cold conditions, where the amide hydrogen exchange reaction is quenched (pH 2.5, 0 °C). The reduction typically...... some challenges in using electrochemical reduction in HDX-MS analyses and provide possible conditions to attenuate these limitations. For example, high salt concentrations hamper disulfide bond reduction, necessitating additional dilution of the sample with aqueous acidic solution at quench conditions....

  5. Dual Studies on a Hydrogen-Deuterium Exchange of Resorcinol and the Subsequent Kinetic Isotope Effect (United States)

    Giles, Richard; Kim, Iris; Chao, Weyjuin Eric; Moore, Jennifer; Jung, Kyung Woon


    An efficient laboratory experiment has been developed for undergraduate students to conduct hydrogen-deuterium (H-D) exchange of resorcinol by electrophilic aromatic substitution using D[subscript 2]O and a catalytic amount of H[subscript 2]SO[subscript 4]. The resulting labeled product is characterized by [superscript 1]H NMR. Students also…

  6. Combining size-exclusion chromatography with differential hydrogen-deuterium exchange to study protein conformational changes. (United States)

    Makarov, Alexey A; Helmy, Roy


    Methods for protein characterization are being actively developed based on the growing importance of protein therapies and applications. The goal of this study was to demonstrate the use of size-exclusion chromatography (SEC) in combination with differential hydrogen-deuterium exchange (HDX) to compare protein global conformational changes at different solution conditions. Using chaotropic mobile phase additive, differential HDX was used to detect a number of solvent accessible labile protons of protein on-column at pH and temperature conditions which provided unrestricted intrinsic H/D exchange (all-or-nothing approach). Varying SEC on-column conditions allowed for protein conformational changes to be observed. Temperature and pressure were independently studied with regards to their effect on the proteins' (insulin, cytochrome C, ubiquitin, and myoglobin) conformational changes in the solution. The obtained ΔHDX profiles revealed protein conformational changes in solution under varied conditions manifested as the difference in the number of protons exchanged to deuterons, or vice-versa. The approach described in this manuscript could prove useful for protein batch-to-batch comparisons, for optimization of chemical reactions with enzyme as catalyst or for protein chemical modification reactions. Copyright © 2016 Elsevier B.V. All rights reserved.

  7. Hydrogen/deuterium exchange mass spectrometry applied to IL-23 interaction characteristics: potential impact for therapeutics. (United States)

    Iacob, Roxana E; Krystek, Stanley R; Huang, Richard Y-C; Wei, Hui; Tao, Li; Lin, Zheng; Morin, Paul E; Doyle, Michael L; Tymiak, Adrienne A; Engen, John R; Chen, Guodong


    IL-23 is an important therapeutic target for the treatment of inflammatory diseases. Adnectins are targeted protein therapeutics that are derived from domain III of human fibronectin and have a similar protein scaffold to antibodies. Adnectin 2 was found to bind to IL-23 and compete with the IL-23/IL-23R interaction, posing a potential protein therapeutic. Hydrogen/deuterium exchange mass spectrometry and computational methods were applied to probe the binding interactions between IL-23 and Adnectin 2 and to determine the correlation between the two orthogonal methods. This review summarizes the current structural knowledge about IL-23 and focuses on the applicability of hydrogen/deuterium exchange mass spectrometry to investigate the higher order structure of proteins, which plays an important role in the discovery of new and improved biotherapeutics.

  8. Probing conformational changes in rhodopsin using hydrogen-deuterium exchange coupled to mass spectrometry. (United States)

    Orban, Tivadar; Tsybovsky, Yaroslav


    Hydrogen-deuterium exchange coupled to mass spectrometry is a powerful tool to evaluate changes in protein conformation between two or more states. Here, we describe a complete methodology that can be used to assess conformational changes in rhodopsin accompanying its transition from the inactive to activated state upon light exposure. This approach may be employed to investigate the structure and conformational changes of various membrane proteins.

  9. Activity-regulating structural changes and autoantibody epitopes in transglutaminase 2 assessed by hydrogen/deuterium exchange

    National Research Council Canada - National Science Library

    Rasmus Iversen; Simon Mysling; Kathrin Hnida; Thomas J. D. Jørgensen; Ludvig M. Sollid


    .... To understand the regulation of TG2 activity and the enzyme's role as an autoantigen in celiac disease, we have addressed structural properties of TG2 in solution by using hydrogen/deuterium exchange...

  10. Localized Hydration in Lyophilized Myoglobin by Hydrogen-Deuterium Exchange Mass Spectrometry. 1. Exchange Mapping (United States)

    Sophocleous, Andreas M.; Zhang, Jun; Topp, Elizabeth M.


    The local effects of hydration on myoglobin (Mb) in solid matrices containing mannitol or sucrose (1:1 w/w, protein:additive) were mapped using hydrogen-deuterium exchange with mass spectrometric analysis (HDX-MS) at 5°C and compared to solution controls. Solid powders were exposed to D2O(g) at controlled activity (aw) followed by reconstitution and analysis of the intact protein and peptides produced by pepsin digestion. HDX varied with matrix type, aw, and position along the protein backbone. HDX was less in sucrose matrices than in mannitol matrices at all aw while the difference in solution was negligible. Differences in HDX in the two matrices were detectable despite similarities in their bulk water content. The extent of exchange in solids is proposed as a measure of the hydration of exchangeable amide groups, as well as protein conformation and dynamics; pepsin digestion allows these effects to be mapped with peptide-level resolution. PMID:22352965

  11. Measuring the hydrogen/deuterium exchange of proteins at high spatial resolution by mass spectrometry

    DEFF Research Database (Denmark)

    Rand, Kasper Dyrberg; Zehl, Martin; Jørgensen, Thomas J D


    the sum of the exchange kinetics for the individual backbone amides. Local exchange kinetics is typically achieved by using pepsin digestion under quench conditions (i.e., under cold acidic conditions where the amide hydrogen exchange rate is slowed by many orders of magnitude). The ability to localize...... resolution of the lowest-energy structure of the native ensemble. There is a growing need for sensitive analytical tools to explore all of the significant molecular structures in the conformational landscape of proteins. Hydrogen/deuterium exchange monitored by mass spectrometry (HDX-MS) has recently emerged...... as a powerful method for characterizing protein conformational dynamics. The basis of this method is the fact that backbone amides in stable hydrogen-bonded structures (e.g., α-helices and β-sheets) are protected against exchange with the aqueous solvent. All protein structures are dynamic, however...

  12. Localized hydration in lyophilized myoglobin by hydrogen-deuterium exchange mass spectrometry. 2. Exchange kinetics. (United States)

    Sophocleous, Andreas M; Topp, Elizabeth M


    Solid-state hydrogen-deuterium exchange with mass spectrometric analysis (ssHDX) is a promising method for characterizing proteins in amorphous solids. Though analysis of HDX kinetics is informative and well-established in solution, application of these methods to solid samples is complicated by possible heterogeneities in the solid. The studies reported here provide a detailed analysis of the kinetics of hydration and ssHDX for equine myoglobin (Mb) in solid matrices containing sucrose or mannitol. Water sorption was rapid relative to ssHDX, indicating that ssHDX kinetics was not limited by bulk water transport. Deuterium uptake in solids was well-characterized by a biexponential model; values for regression parameters provided insight into differences between the two solid matrices. Analysis of the widths of peptide mass envelopes revealed that, in solution, an apparent EX2 mechanism prevails, consistent with native conformation of the protein. In contrast, in mannitol-containing samples, a smaller non-native subpopulation exchanges by an EX1-like mechanism. Together, the results indicate that the analysis of ssHDX kinetic data and of the widths of peptide mass envelopes is useful in screening solid formulations of protein drugs for the presence of non-native species that cannot be detected by amide I FTIR.

  13. Localized Hydration in Lyophilized Myoglobin by Hydrogen-Deuterium Exchange Mass Spectrometry. 2. Exchange Kinetics (United States)

    Sophocleous, Andreas M.; Topp, Elizabeth M.


    Solid-state hydrogen deuterium exchange with mass spectrometric analysis (ssHDX) is a promising method for characterizing proteins in amorphous solids. Though analysis of HDX kinetics is informative and well-established in solution, application of these methods to solid samples is complicated by possible heterogeneities in the solid. The studies reported here provide a detailed analysis of the kinetics of hydration and ssHDX for equine myoglobin (Mb) in solid matrices containing sucrose or mannitol. Water sorption was rapid relative to ssHDX, indicating that ssHDX kinetics was not limited by bulk water transport. Deuterium uptake in solids was well-characterized by a bi-exponential model; values for regression parameters provided insight into differences between the two solid matrices. Analysis of the widths of peptide mass envelopes revealed that in solution, an apparent EX2 mechanism prevails, consistent with native conformation of the protein. In contrast, in mannitol-containing samples, a smaller non-native subpopulation exchanges by an EX1-like mechanism. Together, the results indicate that the analysis of ssHDX kinetic data and the widths of peptide mass envelopes are useful in screening solid formulations of protein drugs for the presence of non-native species that cannot be detected by amide I FTIR. PMID:22352990

  14. Investigating the Interaction between the Neonatal Fc Receptor and Monoclonal Antibody Variants by Hydrogen/Deuterium Exchange Mass Spectrometry

    DEFF Research Database (Denmark)

    Jensen, Pernille Foged; Larraillet, Vincent; Schlothauer, Tilman


    in understanding and modulating the IgG-FcRn interaction to optimize antibody pharmacokinetics and ultimately improve efficacy and safety. Here we studied the interaction between a full-length human IgG1 and human FcRn via hydrogen/deuterium exchange mass spectrometry and targeted electron transfer dissociation......-type glycosylated IgG. Our results provide new molecular insight into the IgG-FcRn interaction and illustrate the capability of hydrogen/deuterium exchange mass spectrometry to advance structural proteomics by providing detailed information on the conformation and dynamics of large protein complexes in solution....

  15. The Area Between Exchange Curves as a Measure of Conformational Differences in Hydrogen-Deuterium Exchange Mass Spectrometry Studies (United States)

    Mazur, Sharlyn J.; Weber, Daniel P.


    Hydrogen-deuterium exchange mass spectrometry (HDX-MS) provides information about protein conformational mobility under native conditions. The area between exchange curves, A bec , a functional data analysis concept, was adapted to the interpretation of HDX-MS data and provides a useful measure of exchange curve dissimilarity for tests of significance. Importantly, for most globular proteins under native conditions, A bec values provide an estimate of the log ratio of exchange-competent fractions in the two states, and thus are related to differences in the free energy of microdomain unfolding.

  16. Structural changes of ultrasonicated bovine serum albumin revealed by hydrogen-deuterium exchange and mass spectrometry. (United States)

    Zhang, Qiuting; Tu, Zongcai; Wang, Hui; Huang, Xiaoqin; Sha, Xiaomei; Xiao, Hui


    The structural changes of bovine serum albumin (BSA) under high-intensity ultrasonication were investigated by fluorescence spectroscopy and mass spectrometry. Evidence for the ultrasonication-induced conformational changes of BSA was provided by the intensity changes and maximum-wavelength shift in fluorescence spectrometry. Matrix-assisted laser desorption-ionization time-of-flight mass spectroscopy (MALDI-TOF MS) revealed the increased intensity of the peak at the charge state +5 and a newly emerged peak at charge state +6, indicating that the protein became unfolded after ultrasonication. Prevalent unfolding of BSA after ultrasonication was revealed by hydrogen-deuterium exchange coupled with mass spectrometry (HDX-MS). Increased intensity and duration of ultrasonication further promoted the unfolding of the protein. The unfolding induced by ultrasonication goes through an intermediate state similar to that induced by a low concentration of denaturant.

  17. In-ESI source hydrogen/deuterium exchange of carbohydrate ions. (United States)

    Kostyukevich, Yury; Kononikhin, Alexey; Popov, Igor; Nikolaev, Eugene


    We present the investigation of hydrogen/deuterium (H/D) exchange of carbohydrates ions occurring in the electrospray ion source. The shape of the deuterium distribution was observed to be considerably dependent on the temperature of the ion transfer tube and the solvent used. If deuterated alcohol (EtOD or MeOD) or D2O/deuterated alcohol is used as an electrospray solvent, then for high temperatures (>350 °C), intensive back exchange is observed, resulting in ∼30% depth of the deuterium exchange. At low temperatures (deuterium exchange is ∼70%. In the intermediate temperature region (∼250 °C), the deuterium distribution is unusually wide for methanol and bimodal for ethanol. The addition of 1% formic acid results in low (∼30%) depth of the deuterium exchange for any temperature in the operating region. The bimodal distribution for the ethanol can be possibly explained by the presence of differently folded gas-phase ions of carbohydrates.

  18. Affinity capture of biotinylated proteins at acidic conditions to facilitate hydrogen/deuterium exchange mass spectrometry analysis of multimeric protein complexes

    DEFF Research Database (Denmark)

    Jensen, Pernille Foged; Jørgensen, Thomas J. D.; Koefoed, Klaus


    of biotinylated proteins even under the extreme conditions for hydrogen/deuterium exchange quenching i.e. pH 2.5 and 0 °C. This biotin-streptavidin capture strategy allows hydrogen/deuterium exchange to occur in proteins in solution and enables characterization of specific proteins in heteromultimeric protein...... receptor (EGFR). We present a workflow for biotinylation and characterization of recombinant antibodies and demonstrate affinity capture of biotinylated antibodies under hydrogen/deuterium exchange quench conditions by the biotin-streptavidin strategy....

  19. Probing protein interactions with hydrogen/deuterium exchange and mass spectrometry-A review

    Energy Technology Data Exchange (ETDEWEB)

    Percy, Andrew J. [Department of Chemistry, University of Calgary, Alberta (Canada); Rey, Martial; Burns, Kyle M. [Department of Biochemistry and Molecular Biology, University of Calgary, Alberta (Canada); Schriemer, David C., E-mail: [Department of Chemistry, University of Calgary, Alberta (Canada); Department of Biochemistry and Molecular Biology, University of Calgary, Alberta (Canada)


    Highlights: Black-Right-Pointing-Pointer Protein chemistry generates mass shifts useful for structure-function studies. Black-Right-Pointing-Pointer H/DX supports a powerful mass shift method for protein interaction analysis. Black-Right-Pointing-Pointer H/DX mass shifts are useful for determining binding data (K{sub d}, off-rates). Black-Right-Pointing-Pointer Improved H/DX-MS workflows can accommodate complex protein systems. - Abstract: Assessing the functional outcome of protein interactions in structural terms is a goal of structural biology, however most techniques have a limited capacity for making structure-function determinations with both high resolution and high throughput. Mass spectrometry can be applied as a reader of protein chemistries in order to fill this void, and enable methodologies whereby protein structure-function determinations may be made on a proteome-wide level. Protein hydrogen/deuterium exchange (H/DX) offers a chemical labeling strategy suitable for tracking changes in 'dynamic topography' and thus represents a powerful means of monitoring protein structure-function relationships. This review presents the exchange method in the context of interaction analysis. Applications involving interface detection, quantitation of binding, and conformational responses to ligation are discussed, and commentary on recent analytical developments is provided.

  20. Analysis of overlapped and noisy hydrogen/deuterium exchange mass spectra. (United States)

    Guttman, Miklos; Weis, David D; Engen, John R; Lee, Kelly K


    Noisy and overlapped mass spectrometry data hinder the sequence coverage that can be obtained from hydrogen deuterium exchange analysis, and places a limit on the complexity of the samples that can be studied by this technique. Advances in instrumentation have addressed these limits, but as the complexity of the biological samples under investigation increases, these problems are re-encountered. Here we describe the use of binomial distribution fitting with asymmetric linear squares regression for calculating the accurate deuterium content for mass envelopes of low signal or that contain significant overlap. The approach is demonstrated with a test data set of HIV Env gp140 wherein inclusion of the new analysis regime resulted in obtaining exchange data for 42 additional peptides, improving the sequence coverage by 11%. At the same time, the precision of deuterium uptake measurements was improved for nearly every peptide examined. The improved processing algorithms also provide an efficient method for deconvolution of bimodal mass envelopes and EX1 kinetic signatures. All these functions and visualization tools have been implemented in the new version of the freely available software, HX-Express v2.

  1. Microsecond pulsed hydrogen/deuterium exchange of electrosprayed ubiquitin ions stored in a linear ion trap. (United States)

    Rajabi, Khadijeh


    A pulse of D2O vapour on the order of microseconds is allowed to react with the +6 to +9 charge states of ubiquitin confined in a linear ion trap (LIT). Two envelopes of peaks are detected for the ions of ubiquitin, corresponding to the ions that exchange more quickly and more slowly. The deuterium uptake of the protonated sites on ubiquitin ions accounts for the ion population with the fast exchange. The hydrogen/deuterium exchange (HDX) kinetics of ubiquitin ions trapped in the LIT for 200 ms showed comparable structural transitions to those trapped for 300 ms. When ions are trapped for longer, i.e. up to 2000 ms, mainly the slow exchanging ion population is detected. In all experiments the +7 ions exchange the most, suggesting a short distance between the surface protonated sites and nearby charged sites, and concomitantly high accessibility of surface protonated sites towards D2O. The +6 ions are more compact than the +7 ions but have one fewer protonated site, therefore fewer surface availabilities for D2O attack. The data suggest that the +6 ions keep most of their solution-phase contacts intact while the hydrophobic core is slightly interrupted in the +7 ions, possibly due to the exposure of charged His68 that is normally buried in the hydrophobic pocket. The +8 and +9 ions have more protonated sites but are less compact than the +7 ions because of Coulombic repulsion, resulting in a larger distance between the protonated sites and the basic sites. The data indicate that the HDX mechanism of ions with the slower exchange corresponding to the second envelope of peaks is primarily governed via a relay mechanism. The results suggest that the pulsed HDX MS method is sampling a population of ubiquitin ions with a similar backbone fold to the solution.

  2. Probing Conformational Dynamics of Tau Protein by Hydrogen/Deuterium Exchange Mass Spectrometry (United States)

    Huang, Richard Y.-C.; Iacob, Roxana E.; Sankaranarayanan, Sethu; Yang, Ling; Ahlijanian, Michael; Tao, Li; Tymiak, Adrienne A.; Chen, Guodong


    Fibrillization of the microtubule-associated protein tau has been recognized as one of the signature pathologies of the nervous system in Alzheimer's disease, progressive supranuclear palsy, and other tauopathies. The conformational transition of tau in the fibrillization process, tau monomer to soluble aggregates to fibrils in particular, remains unclear. Here we report on the use of hydrogen/deuterium exchange mass spectrometry (HDX-MS) in combination with other biochemical approaches, including Thioflavin S fluorescence measurements, enzyme-linked immunosorbent assay (ELISA), and Western blotting to understand the heparin-induced tau's fibrillization. HDX-MS studies including anti-tau antibody epitope mapping experiments provided molecular level details of the full-length tau's conformational dynamics and its regional solvent accessibility upon soluble aggregates formation. The results demonstrate that R3 region in the full-length tau's microtubule binding repeat region (MTBR) is stabilized in the aggregation process, leaving both N and C terminal regions to be solvent exposed in the soluble aggregates and fibrils. The findings also illustrate the practical utility of orthogonal analytical methodologies for the characterization of protein higher order structure. [Figure not available: see fulltext.

  3. Understanding Curli Amyloid-Protein Aggregation by Hydrogen-Deuterium Exchange and Mass Spectrometry. (United States)

    Wang, Hanliu; Shu, Qin; Rempel, Don L; Frieden, Carl; Gross, Michael L


    Bacteria within Curli biofilms are protected from environmental pressures (e.g., disinfectants, antibiotics), and this is responsible for intractable infections. Understanding aggregation of the major protein component of Curli, CsgA, may uncover disease-associated amyloidogenesis mechanisms. Here, we report the application of pulsed hydrogen-deuterium exchange and mass spectrometry (HDX-MS) to study CsgA aggregation, thereby obtaining region-specific information. By following time-dependent peptide signal depletion, presumably a result of insoluble fibril formation, we acquired sigmoidal profiles that are specific for regions (region-specific) of the protein. These signal-depletion profiles not only provide an alternative aggregation measurement, but also give insight on soluble species in the aggregation. The HDX data present as bimodal isotopic distributions, one representing a highly disordered species whereas the other a well-structured one. Although the extents of deuterium uptake of the two species remain the same with time, the relative abundance of the lower mass, less-exchanged species increases in a region-specific manner. The same region-specific aggregation properties also pertain to different aggregation conditions. Although CsgA is an intrinsically disordered protein, within the fibril it is thought to consist of five imperfect β-strand repeating units (labeled R1-R5). We found that the exterior repeating units R1 and R5 have higher aggregation propensities than do the interior units R2, R3, and R4. We also employed TEM to obtain complementary information of the well-structured species. The results provide insight on aggregation and a new approach for further application of HDX-MS to unravel aggregation mechanisms of amyloid proteins.

  4. Subzero Celsius separations in three-zone temperature controlled hydrogen deuterium exchange mass spectrometry. (United States)

    Wales, Thomas E; Fadgen, Keith E; Eggertson, Michael J; Engen, John R


    Hydrogen deuterium exchange mass spectrometry (HDX MS) reports on the conformational landscape of proteins by monitoring the exchange between backbone amide hydrogen atoms and deuterium in the solvent. To maintain the label for analysis, quench conditions of low temperature and pH are required during the chromatography step performed after protease digestion but before mass spectrometry. Separation at 0°C is often chosen as this is the temperature where the most deuterium can be recovered without freezing of the typical water and acetonitrile mobile phases. Several recent reports of separations at subzero Celsius emphasize the promise for retaining more deuterium and using a much longer chromatographic gradient or direct infusion time. Here we present the construction and validation of a modified Waters nanoACQUITY HDX manager with a third temperature-controlled zone for peptide separations at subzero temperatures. A new Peltier-cooled door replaces the door of a traditional main cooling chamber and the separations and trapping column are routed through the door housing. To prevent freezing, 35% methanol is introduced post online digestion. No new pumps are required and online digestion is performed as in the past. Subzero separations, using conventional HPLC column geometry of 3μ m particles in a 1×50mm column, did not result in major changes to chromatographic efficiency when lowering the temperature from 0 to -20°C. There were significant increases in deuterium recovery for both model peptides and biologically relevant protein systems. Given the higher levels of deuterium recovery, expanded gradient programs can be used to allow for higher chromatographic peak capacity and therefore the analysis of larger and more complex proteins and systems. Copyright © 2017 Elsevier B.V. All rights reserved.

  5. Platform Dependencies in Bottom-up Hydrogen/Deuterium Exchange Mass Spectrometry* (United States)

    Burns, Kyle M.; Rey, Martial; Baker, Charles A. H.; Schriemer, David C.


    Hydrogen-deuterium exchange mass spectrometry is an important method for protein structure-function analysis. The bottom-up approach uses protein digestion to localize deuteration to higher resolution, and the essential measurement involves centroid mass determinations on a very large set of peptides. In the course of evaluating systems for various projects, we established two (HDX-MS) platforms that consisted of a FT-MS and a high-resolution QTOF mass spectrometer, each with matched front-end fluidic systems. Digests of proteins spanning a 20–110 kDa range were deuterated to equilibrium, and figures-of-merit for a typical bottom-up (HDX-MS) experiment were compared for each platform. The Orbitrap Velos identified 64% more peptides than the 5600 QTOF, with a 42% overlap between the two systems, independent of protein size. Precision in deuterium measurements using the Orbitrap marginally exceeded that of the QTOF, depending on the Orbitrap resolution setting. However, the unique nature of FT-MS data generates situations where deuteration measurements can be inaccurate, because of destructive interference arising from mismatches in elemental mass defects. This is shown through the analysis of the peptides common to both platforms, where deuteration values can be as low as 35% of the expected values, depending on FT-MS resolution, peptide length and charge state. These findings are supported by simulations of Orbitrap transients, and highlight that caution should be exercised in deriving centroid mass values from FT transients that do not support baseline separation of the full isotopic composition. PMID:23197788

  6. Structural Insights of Glucan Phosphatase Dynamics using Amide Hydrogen/Deuterium Exchange Mass Spectrometry (United States)

    Hsu, Simon; Kim, Youngjun; Li, Sheng; Durrant, Eric S.; Pace, Rachel M.; Woods, Virgil L.; Gentry, Matthew S.


    Laforin and Starch Excess 4 (SEX4) are founding members of a class of phosphatases that dephosphorylate phosphoglucans. Each protein contains a carbohydrate binding module (CBM) and a dual specificity phosphatase (DSP) domain. The gene encoding laforin is mutated in a fatal neurodegenerative disease called Lafora disease (LD). In the absence of laforin function, insoluble glucans accumulate that are hyperphosphorylated and exhibit sparse branching. It is hypothesized that these accumulations trigger the neurodegeneration and premature death of LD patients. We recently demonstrated that laforin removes phosphate from phosphoglucans and hypothesized that this function inhibits insoluble glucan accumulation. Loss of SEX4 function in plants yields a similar cellular phenotype; cells accumulate an excess amount of insoluble, hyperphosphorylated glucans. While multiple groups have shown that these phosphatases dephosphorylate phosphoglucans, there is no structure of a glucan phosphatase and little is known about the mechanism whereby they perform this action. We utilized hydrogen-deuterium exchange mass spectrometry (DXMS) and structural modeling to probe the conformational and structural dynamics of the glucan phosphatase SEX4. We found that the enzyme does not undergo a global conformational change upon glucan binding, but instead undergoes minimal rearrangement upon binding. The CBM undergoes increased protection from deuteration when bound to glucans, confirming its role in glucan binding. More interestingly, we identified structural components of the DSP that also undergo increased protection from deuteration upon glucan addition. To determine the position of these regions, we generated a homology model of the SEX4 DSP. The homology model shows that all of these regions are adjacent the DSP active site. Therefore, our results suggest that these regions of the DSP participate in presenting the phosphoglucan to the active site and provide the first structural analysis

  7. Hydrogen/Deuterium Exchange Mass Spectrometry for Probing Higher Order Structure of Protein Therapeutics: Methodology and Applications (United States)

    Wei, Hui; Mo, Jingjie; Tao, Li; Russell, Reb J.; Tymiak, Adrienne A.; Chen, Guodong; Iacob, Roxana E.; Engen, John R.


    The higher order structure of protein therapeutics can be interrogated with hydrogen/deuterium exchange mass spectrometry (HDX-MS). HDX-MS is now a widely used tool in the structural characterization of protein therapeutics. In this article, HDX-MS based workflows designed for both protein therapeutic discovery and development processes are presented, focusing on the specific applications of epitope mapping for protein/drug interactions and biopharmaceutical comparability studies. Future trends in the application of HDX-MS to protein therapeutics characterization are also described. PMID:23928097

  8. Hydrogen/deuterium exchange of cross-linkable α-amino acid derivatives in deuterated triflic acid. (United States)

    Wang, Lei; Murai, Yuta; Yoshida, Takuma; Okamoto, Masashi; Masuda, Katsuyoshi; Sakihama, Yasuko; Hashidoko, Yasuyuki; Hatanaka, Yasumaru; Hashimoto, Makoto


    In this paper we report here a hydrogen/deuterium exchange (H/D exchange) of cross-linkable α-amino acid derivatives with deuterated trifluoromethanesulfonic acid (TfOD). H/D exchange with TfOD was easily applied to o-catechol containing phenylalanine (DOPA) within an hour. A partial H/D exchange was observed for trifluoromethyldiazirinyl (TFMD) phenylalanine derivatives. N-Acetyl-protected natural aromatic α-amino acids (Tyr and Trp) were more effective in H/D exchange than unprotected ones. The N-acetylated TFMD phenylalanine derivative afforded slightly higher H/D exchange than unprotected derivatives. An effective post-deuteration method for cross-linkable α-amino acid derivatives will be useful for the analysis of biological functions of bioactive peptides and proteins by mass spectrometry.

  9. Screen-printed digital microfluidics combined with surface acoustic wave nebulization for hydrogen-deuterium exchange measurements. (United States)

    Monkkonen, Lucas; Edgar, J Scott; Winters, Daniel; Heron, Scott R; Mackay, C Logan; Masselon, Christophe D; Stokes, Adam A; Langridge-Smith, Patrick R R; Goodlett, David R


    An inexpensive digital microfluidic (DMF) chip was fabricated by screen-printing electrodes on a sheet of polyimide. This device was manually integrated with surface acoustic wave nebulization (SAWN) MS to conduct hydrogen/deuterium exchange (HDX) of peptides. The HDX experiment was performed by DMF mixing of one aqueous droplet of angiotensin II with a second containing various concentrations of D2O. Subsequently, the degree of HDX was measured immediately by SAWN-MS. As expected for a small peptide, the isotopically resolved mass spectrum for angiotensin revealed that maximum deuterium exchange was achieved using 50% D2O. Additionally, using SAWN-MS alone, the global HDX kinetics of ubiquitin were found to be similar to published NMR data and back exchange rates for the uncooled apparatus using high inlet capillary temperatures was less than 6%. Copyright © 2016. Published by Elsevier B.V.

  10. Characterizing the dynamics of alpha-synuclein oligomers using hydrogen/deuterium exchange monitored by mass spectrometry

    DEFF Research Database (Denmark)

    Mysling, Simon; Betzer, Cristine; Jensen, Poul H


    SN (residues 94-140) underwent isotopic exchange very rapidly, demonstrating a highly dynamic region in the oligomeric state. Three regions (residues 4-17, 39-54, and 70-89) were strongly protected against isotopic exchange in the oligomers, indicating the presence of a stable hydrogen-bonded or solvent...... hydrogen/deuterium exchange monitored by mass spectrometry (HDX-MS), we have analyzed the structural dynamics of soluble αSN oligomers. The analyzed oligomers were metastable, slowly dissociating to monomers over a period of 21 days, after excess monomer had been removed. The C-terminal region of α...... analyses performed on αSN fibrils and indicated a possible zipperlike maturation mechanism for αSN aggregates. We find the protected N-terminus (residues 4-17) to be of particular interest, as this region has previously been observed to be highly dynamic for both monomeric and fibrillar αSN. This region...

  11. Investigating the Interaction between the Neonatal Fc Receptor and Monoclonal Antibody Variants by Hydrogen/Deuterium Exchange Mass Spectrometry* (United States)

    Jensen, Pernille Foged; Larraillet, Vincent; Schlothauer, Tilman; Kettenberger, Hubert; Hilger, Maximiliane; Rand, Kasper D.


    The recycling of immunoglobulins by the neonatal Fc receptor (FcRn) is of crucial importance in the maintenance of antibody levels in plasma and is responsible for the long half-lives of endogenous and recombinant monoclonal antibodies. From a therapeutic point of view there is great interest in understanding and modulating the IgG–FcRn interaction to optimize antibody pharmacokinetics and ultimately improve efficacy and safety. Here we studied the interaction between a full-length human IgG1 and human FcRn via hydrogen/deuterium exchange mass spectrometry and targeted electron transfer dissociation to map sites perturbed by binding on both partners of the IgG–FcRn complex. Several regions in the antibody Fc region and the FcRn were protected from exchange upon complex formation, in good agreement with previous crystallographic studies of FcRn in complex with the Fc fragment. Interestingly, we found that several regions in the IgG Fab region also showed reduced deuterium uptake. Our findings indicate the presence of hitherto unknown FcRn interaction sites in the Fab region or a possible conformational link between the IgG Fc and Fab regions upon FcRn binding. Further, we investigated the role of IgG glycosylation in the conformational response of the IgG–FcRn interaction. Removal of antibody glycans increased the flexibility of the FcRn binding site in the Fc region. Consequently, FcRn binding did not induce a similar conformational stabilization of deglycosylated IgG as observed for the wild-type glycosylated IgG. Our results provide new molecular insight into the IgG–FcRn interaction and illustrate the capability of hydrogen/deuterium exchange mass spectrometry to advance structural proteomics by providing detailed information on the conformation and dynamics of large protein complexes in solution. PMID:25378534

  12. Investigating the interaction between the neonatal Fc receptor and monoclonal antibody variants by hydrogen/deuterium exchange mass spectrometry. (United States)

    Jensen, Pernille Foged; Larraillet, Vincent; Schlothauer, Tilman; Kettenberger, Hubert; Hilger, Maximiliane; Rand, Kasper D


    The recycling of immunoglobulins by the neonatal Fc receptor (FcRn) is of crucial importance in the maintenance of antibody levels in plasma and is responsible for the long half-lives of endogenous and recombinant monoclonal antibodies. From a therapeutic point of view there is great interest in understanding and modulating the IgG-FcRn interaction to optimize antibody pharmacokinetics and ultimately improve efficacy and safety. Here we studied the interaction between a full-length human IgG(1) and human FcRn via hydrogen/deuterium exchange mass spectrometry and targeted electron transfer dissociation to map sites perturbed by binding on both partners of the IgG-FcRn complex. Several regions in the antibody Fc region and the FcRn were protected from exchange upon complex formation, in good agreement with previous crystallographic studies of FcRn in complex with the Fc fragment. Interestingly, we found that several regions in the IgG Fab region also showed reduced deuterium uptake. Our findings indicate the presence of hitherto unknown FcRn interaction sites in the Fab region or a possible conformational link between the IgG Fc and Fab regions upon FcRn binding. Further, we investigated the role of IgG glycosylation in the conformational response of the IgG-FcRn interaction. Removal of antibody glycans increased the flexibility of the FcRn binding site in the Fc region. Consequently, FcRn binding did not induce a similar conformational stabilization of deglycosylated IgG as observed for the wild-type glycosylated IgG. Our results provide new molecular insight into the IgG-FcRn interaction and illustrate the capability of hydrogen/deuterium exchange mass spectrometry to advance structural proteomics by providing detailed information on the conformation and dynamics of large protein complexes in solution. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

  13. Activity-regulating structural changes and autoantibody epitopes in transglutaminase 2 assessed by hydrogen/deuterium exchange

    DEFF Research Database (Denmark)

    Iversen, Rasmus; Mysling, Simon; Hnida, Kathrin


    The multifunctional enzyme transglutaminase 2 (TG2) is the target of autoantibodies in the gluten-sensitive enteropathy celiac disease. In addition, the enzyme is responsible for deamidation of gluten peptides, which are subsequently targeted by T cells. To understand the regulation of TG2 activity...... and the enzyme's role as an autoantigen in celiac disease, we have addressed structural properties of TG2 in solution by using hydrogen/deuterium exchange monitored by mass spectrometry. We demonstrate that Ca(2+) binding, which is necessary for TG2 activity, induces structural changes in the catalytic core...... domain of the enzyme. Cysteine oxidation was found to abolish these changes, suggesting a mechanism whereby disulfide bond formation inactivates the enzyme. Further, by using TG2-specific human monoclonal antibodies generated from intestinal plasma cells of celiac disease patients, we observed...

  14. Characterizing rapid, activity-linked conformational transitions in proteins via sub-second hydrogen deuterium exchange mass spectrometry. (United States)

    Resetca, Diana; Wilson, Derek J


    This review outlines the application of time-resolved electrospray ionization mass spectrometry (TRESI-MS) and hydrogen-deuterium exchange (HDX) to study rapid, activity-linked conformational transitions in proteins. The method is implemented on a microfluidic chip which incorporates all sample-handling steps required for a 'bottom-up' HDX workflow: a capillary mixer for sub-second HDX labeling, a static mixer for HDX quenching, a microreactor for rapid protein digestion, and on-chip electrospray. By combining short HDX labeling pulses with rapid digestion, this approach provides a detailed characterization of the structural transitions that occur during protein folding, ligand binding, post-translational modification and catalytic turnover in enzymes. This broad spectrum of applications in areas largely inaccessible to conventional techniques means that microfluidics-enabled TRESI-MS/HDX is a unique and powerful approach for investigating the dynamic basis of protein function. © 2013 FEBS.

  15. Conformational Analysis of Proteins in Highly Concentrated Solutions by Dialysis-Coupled Hydrogen/Deuterium Exchange Mass Spectrometry

    DEFF Research Database (Denmark)

    Houde, Damian; Esmail Nazari, Zeinab; Bou-Assaf, George M


    When highly concentrated, an antibody solution can exhibit unusual behaviors, which can lead to unwanted properties, such as increased levels of protein aggregation and unusually high viscosity. Molecular modeling, along with many indirect biophysical measurements, has suggested that the cause...... for these phenomena can be due to short range electrostatic and/or hydrophobic protein-protein interactions. Hydrogen/deuterium exchange mass spectrometry (HDX-MS) is a useful tool for investigating protein conformation, dynamics, and interactions. However, "traditional" continuous dilution labeling HDX......-MS experiments have limited utility for the direct analysis of solutions with high concentrations of protein. Here, we present a dialysis-based HDX-MS (di-HDX-MS) method as an alternative HDX-MS labeling format, which takes advantage of passive dialysis rather than the classic dilution workflow. We applied...

  16. KRAS G12C Drug Development: Discrimination between Switch II Pocket Configurations Using Hydrogen/Deuterium-Exchange Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Lu, Jia; Harrison, Rane A.; Li, Lianbo; Zeng, Mei; Gondi, Sudershan; Scott, David; Gray, Nathanael S.; Engen, John R.; Westover, Kenneth D. (NEU); (DFCI); (UTSMC); (Harvard-Med)


    KRAS G12C, the most common RAS mutation found in non-small-cell lung cancer, has been the subject of multiple recent covalent small-molecule inhibitor campaigns including efforts directed at the guanine nucleotide pocket and separate work focused on an inducible pocket adjacent to the switch motifs. Multiple conformations of switch II have been observed, suggesting that switch II pocket (SIIP) binders may be capable of engaging a range of KRAS conformations. Here we report the use of hydrogen/deuterium-exchange mass spectrometry (HDX MS) to discriminate between conformations of switch II induced by two chemical classes of SIIP binders. We investigated the structural basis for differences in HDX MS using X-ray crystallography and discovered a new SIIP configuration in response to binding of a quinazoline chemotype. These results have implications for structure-guided drug design targeting the RAS SIIP.

  17. Sites involved in intra- and interdomain allostery associated with the activation of factor VIIa pinpointed by hydrogen-deuterium exchange and electron transfer dissociation mass spectrometry

    DEFF Research Database (Denmark)

    Song, Hongjian; Olsen, Ole H; Persson, Egon


    enhancement remain elusive. Here we have applied hydrogen/deuterium exchange mass spectrometry coupled to electron transfer dissociation to pinpoint individual residues in the heavy chain of FVIIa whose conformation and/or local interaction pattern changes when the enzyme transitions to the active form...

  18. Study of the conformational change of adsorbed proteins on biomaterial surfaces using hydrogen-deuterium exchange with mass spectroscopy. (United States)

    Kim, Jinku


    There is no doubt that protein adsorption plays a crucial role in determining biocompatibility of biomaterials. Despite the information of the identity and composition of blood plasma/serum proteins adsorbed on surfaces of biomaterials to understand which proteins are involved in blood/biomaterial interactions, it still does not provide information about the conformations and orientations of adsorbed protein, which are very important in determining biological responses to biomaterials. Therefore, our laboratory has developed an experimental technology to probe protein conformations on materials that is applicable to mixtures of proteins. Herein, the new application of hydrogen/deuterium (H/D) exchange combined with mass spectrometry was applied to determine conformational changes of adsorbed proteins at biomaterial surfaces. The results suggest that there may be a significant conformational change in adsorbed proteins at 'low' bulk concentrations that leads to a large change in the kinetics of H/D exchange as compared to 'high' bulk concentrations. This technique may eventually be useful for the study of the kinetics of protein conformational changes. Copyright © 2016 Elsevier B.V. All rights reserved.

  19. Effects of sucrose and benzyl alcohol on GCSF conformational dynamics revealed by hydrogen deuterium exchange mass spectrometry. (United States)

    Zhang, Jun; Banks, Douglas D; He, Feng; Treuheit, Michael J; Becker, Gerald W


    Protein stability, one of the major concerns for therapeutic protein development, can be optimized during process development by evaluating multiple formulation conditions. This can be a costly and lengthy procedure where different excipients and storage conditions are tested for their impact on protein stability. A better understanding of the effects of different formulation conditions at the molecular level will provide information on the local interactions within the protein leading to a more rational design of stable and efficacious formulations. In this study, we examined the roles of the excipients, sucrose and benzyl alcohol, on the conformational dynamics of recombinant human granulocyte colony stimulating factor using hydrogen/deuterium exchange coupled with mass spectrometry (HDX-MS). Under physiological pH and temperature, sucrose globally protects the whole molecule from deuterium uptake, whereas benzyl alcohol induces increased deuterium uptake of the regions within the α-helical bundle, with even larger extent. The HDX experiments described were incorporated a set of internal peptides (Zhang et al., 2012. Anal Chem 84:4942-4949) to monitor the differences in intrinsic exchange rates in different formulations. In addition, we discussed the feasibility of implementing HDX-MS with these peptide probes in protein formulation development. © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association.

  20. Characterization of Stress-Exposed Granulocyte Colony Stimulating Factor Using ELISA and Hydrogen/Deuterium Exchange Mass Spectrometry (United States)

    Tsuchida, Daisuke; Yamazaki, Katsuyoshi; Akashi, Satoko


    Information on the higher-order structure is important in the development of biopharmaceutical drugs. Recently, hydrogen/deuterium exchange coupled with mass spectrometry (HDX-MS) has been widely used as a tool to evaluate protein conformation, and unique automated systems for HDX-MS are now commercially available. To investigate the potential of this technique for the prediction of the activity of biopharmaceuticals, granulocyte colony stimulating factor (G-CSF), which had been subjected to three different stress types, was analyzed using HDX-MS and through comparison with receptor-binding activity. It was found that HDX-MS, in combination with ion mobility separation, was able to identify conformational changes in G-CSF induced by stress, and a good correlation with the receptor-binding activity was demonstrated, which cannot be completely determined by conventional peptide mapping alone. The direct evaluation of biological activity using bioassay is absolutely imperative in biopharmaceutical development, but HDX-MS can provide the alternative information in a short time on the extent and location of the structural damage caused by stresses. Furthermore, the present study suggests the possibility of this system being a versatile evaluation method for the preservation stability of biopharmaceuticals.

  1. Ion Mobility Spectrometry-Mass Spectrometry Coupled with Gas-Phase Hydrogen/Deuterium Exchange for Metabolomics Analyses (United States)

    Maleki, Hossein; Karanji, Ahmad K.; Majuta, Sandra; Maurer, Megan M.; Valentine, Stephen J.


    Ion mobility spectrometry-mass spectrometry (IMS-MS) in combination with gas-phase hydrogen/deuterium exchange (HDX) and collision-induced dissociation (CID) is evaluated as an analytical method for small-molecule standard and mixture characterization. Experiments show that compound ions exhibit unique HDX reactivities that can be used to distinguish different species. Additionally, it is shown that gas-phase HDX kinetics can be exploited to provide even further distinguishing capabilities by using different partial pressures of reagent gas. The relative HDX reactivity of a wide variety of molecules is discussed in light of the various molecular structures. Additionally, hydrogen accessibility scoring (HAS) and HDX kinetics modeling of candidate (in silico) ion structures is utilized to estimate the relative ion conformer populations giving rise to specific HDX behavior. These data interpretation methods are discussed with a focus on developing predictive tools for HDX behavior. Finally, an example is provided in which ion mobility information is supplemented with HDX reactivity data to aid identification efforts of compounds in a metabolite extract. [Figure not available: see fulltext.

  2. Ion Mobility Spectrometry-Hydrogen Deuterium Exchange Mass Spectrometry of Anions: Part 2. Assessing Charge Site Location and Isotope Scrambling. (United States)

    Khakinejad, Mahdiar; Kondalaji, Samaneh Ghassabi; Donohoe, Gregory C; Valentine, Stephen J


    Ion mobility spectrometry (IMS) coupled with gas-phase hydrogen deuterium exchange (HDX)-mass spectrometry (MS) and molecular dynamic simulations (MDS) has been used for structural investigation of anions produced by electrospraying a sample containing a synthetic peptide having the sequence KKDDDDDIIKIIK. In these experiments the potential of the analytical method for locating charge sites on ions as well as for utilizing collision-induced dissociation (CID) to reveal the degree of deuterium uptake within specific amino acid residues has been assessed. For diffuse (i.e., more elongated) [M - 2H](2-) ions, decreased deuterium content along with MDS data suggest that the D4 and D6 residues are charge sites, whereas for the more diffuse [M - 3H](3-) ions, the data suggest that the D4, D7, and the C-terminus are deprotonated. Fragmentation of mobility-selected, diffuse [M - 2H](2-) ions to determine deuterium uptake at individual amino acid residues reveals a degree of deuterium retention at incorporation sites. Although the diffuse [M - 3H](3-) ions may show more HD scrambling, it is not possible to clearly distinguish HD scrambling from the expected deuterium uptake based on a hydrogen accessibility model. The capability of the IMS-HDX-MS/MS approach to provide relevant details about ion structure is discussed. Additionally, the ability to extend the approach for locating protonation sites on positively-charged ions is presented.

  3. Ion Mobility Spectrometry-Hydrogen Deuterium Exchange Mass Spectrometry of Anions: Part 3. Estimating Surface Area Exposure by Deuterium Uptake. (United States)

    Khakinejad, Mahdiar; Kondalaji, Samaneh Ghassabi; Donohoe, Gregory C; Valentine, Stephen J


    Gas-phase hydrogen deuterium exchange (HDX), collision cross section (CCS) measurement, and molecular dynamics simulation (MDS) techniques were utilized to develop and compare three methods for estimating the relative surface area exposure of separate peptide chains within bovine insulin ions. Electrosprayed [M - 3H](3-) and [M - 5H](5-) insulin ions produced a single conformer type with respective collision cross sections of 528 ± 5 Å(2) and 808 ± 2 Å(2). [M - 4H](4-) ions were comprised of more compact (Ω = 676 ± 3 Å(2)) and diffuse (i.e., more elongated, Ω = 779 ± 3 Å(2)) ion conformer types. Ions were subjected to HDX in the drift tube using D2O as the reagent gas. Collision-induced dissociation was used to fragment mobility-selected, isotopically labeled [M - 4H](4-) and [M - 5H](5-) ions into the protein subchains. Deuterium uptake levels of each chain can be explained by limited inter-chain isotopic scrambling upon collisional activation. Using nominal ion structures from MDS and a hydrogen accessibility model, the deuterium uptake for each chain was correlated to its exposed surface area. In separate experiments, the per-residue deuterium content for the protonated and deprotonated ions of the synthetic peptide KKDDDDDIIKIIK were compared. The differences in deuterium content indicated the regional HDX accessibility for cations versus anions. Using ions of similar conformational type, this comparison highlights the complementary nature of HDX data obtained from positive- and negative-ion analysis.

  4. Applications of hydrogen deuterium exchange (HDX for the characterization of conformational dynamics in light-activated photoreceptors

    Directory of Open Access Journals (Sweden)

    Robert eLindner


    Full Text Available Rational design of optogenetic tools is inherently linked to the understanding of photoreceptor function. Structural analysis of elements involved in signal integration in individual sensor domains provides an initial idea of their mode of operation, but understanding how local structural rearrangements eventually affect signal transmission to output domains requires inclusion of the effector regions in the characterization. However, the dynamic nature of these assemblies renders their structural analysis challenging and therefore a combination of high- and low-resolution techniques is required to appreciate functional aspects of photoreceptors.This review focuses on the potential of Hydrogen-Deuterium exchange coupled to mass spectrometry (HDX-MS for complementing the structural characterization of photoreceptors. In this respect, the ability of HDX-MS to provide information on the conformational dynamics and the possibility to address multiple functionally relevant states in solution render this methodology ideally suitable. We highlight recent examples demonstrating the potential of HDX-MS and discuss how these results can help to improve existing optogenetic systems or guide the design of novel optogenetic tools.

  5. QUDeX-MS: hydrogen/deuterium exchange calculation for mass spectra with resolved isotopic fine structure. (United States)

    Salisbury, Joseph P; Liu, Qian; Agar, Jeffrey N


    Hydrogen/deuterium exchange (HDX) coupled to mass spectrometry permits analysis of structure, dynamics, and molecular interactions of proteins. HDX mass spectrometry is confounded by deuterium exchange-associated peaks overlapping with peaks of heavy, natural abundance isotopes, such as carbon-13. Recent studies demonstrated that high-performance mass spectrometers could resolve isotopic fine structure and eliminate this peak overlap, allowing direct detection and quantification of deuterium incorporation. Here, we present a graphical tool that allows for a rapid and automated estimation of deuterium incorporation from a spectrum with isotopic fine structure. Given a peptide sequence (or elemental formula) and charge state, the mass-to-charge ratios of deuterium-associated peaks of the specified ion is determined. Intensities of peaks in an experimental mass spectrum within bins corresponding to these values are used to determine the distribution of deuterium incorporated. A theoretical spectrum can then be calculated based on the estimated distribution of deuterium exchange to confirm interpretation of the spectrum. Deuterium incorporation can also be detected for ion signals without a priori specification of an elemental formula, permitting detection of exchange in complex samples of unidentified material such as natural organic matter. A tool is also incorporated into QUDeX-MS to help in assigning ion signals from peptides arising from enzymatic digestion of proteins. MATLAB-deployable and standalone versions are available for academic use at and . Isotopic fine structure HDX-MS offers the potential to increase sequence coverage of proteins being analyzed through mass accuracy and deconvolution of overlapping ion signals. As previously demonstrated, however, the data analysis workflow for HDX-MS data with resolved isotopic fine structure is distinct. QUDeX-MS we hope will aid in the adoption of isotopic fine structure HDX

  6. Patterns of structural dynamics in RACK1 protein retained throughout evolution: a hydrogen-deuterium exchange study of three orthologs. (United States)

    Tarnowski, Krzysztof; Fituch, Kinga; Szczepanowski, Roman H; Dadlez, Michal; Kaus-Drobek, Magdalena


    RACK1 is a member of the WD repeat family of proteins and is involved in multiple fundamental cellular processes. An intriguing feature of RACK1 is its ability to interact with at least 80 different protein partners. Thus, the structural features enabling such interactomic flexibility are of great interest. Several previous studies of the crystal structures of RACK1 orthologs described its detailed architecture and confirmed predictions that RACK1 adopts a seven-bladed β-propeller fold. However, this did not explain its ability to bind to multiple partners. We performed hydrogen-deuterium (H-D) exchange mass spectrometry on three orthologs of RACK1 (human, yeast, and plant) to obtain insights into the dynamic properties of RACK1 in solution. All three variants retained similar patterns of deuterium uptake, with some pronounced differences that can be attributed to RACK1's divergent biological functions. In all cases, the most rigid structural elements were confined to B-C turns and, to some extent, strands B and C, while the remaining regions retained much flexibility. We also compared the average rate constants for H-D exchange in different regions of RACK1 and found that amide protons in some regions exchanged at least 1000-fold faster than in others. We conclude that its evolutionarily retained structural architecture might have allowed RACK1 to accommodate multiple molecular partners. This was exemplified by our additional analysis of yeast RACK1 dimer, which showed stabilization, as well as destabilization, of several interface regions upon dimer formation. © 2014 The Protein Society.

  7. Effective Application of Bicelles for Conformational Analysis of G Protein-Coupled Receptors by Hydrogen/Deuterium Exchange Mass Spectrometry (United States)

    Duc, Nguyen Minh; Du, Yang; Thorsen, Thor S.; Lee, Su Youn; Zhang, Cheng; Kato, Hideaki; Kobilka, Brian K.; Chung, Ka Young


    G protein-coupled receptors (GPCRs) have important roles in physiology and pathology, and 40% of drugs currently on the market target GPCRs for the treatment of various diseases. Because of their therapeutic importance, the structural mechanism of GPCR signaling is of great interest in the field of drug discovery. Hydrogen/deuterium exchange mass spectrometry (HDX-MS) is a useful tool for analyzing ligand binding sites, the protein-protein interaction interface, and conformational changes of proteins. However, its application to GPCRs has been limited for various reasons, including the hydrophobic nature of GPCRs and the use of detergents in their preparation. In the present study, we tested the application of bicelles as a means of solubilizing GPCRs for HDX-MS studies. GPCRs (e.g., β2-adrenergic receptor [β2AR], μ-opioid receptor, and protease-activated receptor 1) solubilized in bicelles produced better sequence coverage (greater than 90%) than GPCRs solubilized in n-dodecyl-β-D-maltopyranoside (DDM), suggesting that bicelles are a more effective method of solubilization for HDX-MS studies. The HDX-MS profile of β2AR in bicelles showed that transmembrane domains (TMs) undergo lower deuterium uptake than intracellular or extracellular regions, which is consistent with the fact that the TMs are highly ordered and embedded in bicelles. The overall HDX-MS profiles of β2AR solubilized in bicelles and in DDM were similar except for intracellular loop 3. Interestingly, we detected EX1 kinetics, an important phenomenon in protein dynamics, at the C-terminus of TM6 in β2AR. In conclusion, we suggest the application of bicelles as a useful method for solubilizing GPCRs for conformational analysis by HDX-MS.

  8. Differential isotopic enrichment to facilitate characterization of asymmetric multimeric proteins using hydrogen/deuterium exchange mass spectrometry. (United States)

    Goswami, Devrishi; Tuske, Steve; Pascal, Bruce D; Bauman, Joseph D; Patel, Disha; Arnold, Eddy; Griffin, Patrick R


    Hydrogen/deuterium exchange (HDX) coupled to mass spectrometry has emerged as a powerful tool for analyzing the conformational dynamics of protein-ligand and protein-protein interactions. Recent advances in instrumentation and methodology have expanded the utility of HDX for the analysis of large and complex proteins; however, asymmetric dimers with shared amino acid sequence present a unique challenge for HDX because assignment of peptides with identical sequence to their subunit of origin remains ambiguous. Here we report the use of differential isotopic labeling to facilitate HDX analysis of multimers using HIV-1 reverse transcriptase (RT) as a model. RT is an asymmetric heterodimer of 51 kDa (p51) and 66 kDa (p66) subunits. The first 440 residues of p51 and p66 are identical. In this study differentially labeled RT was reconstituted from isotopically enriched ((15)N-labeled) p51 and unlabeled p66. To enable detection of (15)N-deuterated RT peptides, the software HDX Workbench was modified to follow a 100% (15)N model. Our results demonstrated that (15)N enrichment of p51 did not affect its conformational dynamics compared to unlabeled p51, but (15)N-labeled p51 did show different conformational dynamics than p66 in the RT heterodimer. Differential HDX-MS of isotopically labeled RT in the presence of the non-nucleoside reverse transcriptase inhibitor (NNRTI) efavirenz (EFV) showed subunit-specific perturbation in the rate of HDX consistent with previously published results and the RT-EFV cocrystal structure.

  9. Polar Aprotic Modifiers for Chromatographic Separation and Back-Exchange Reduction for Protein Hydrogen/Deuterium Exchange Monitored by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (United States)

    Valeja, Santosh G.; Emmett, Mark R.; Marshall, Alan G.


    Hydrogen/deuterium exchange monitored by mass spectrometry is an important non-perturbing tool to study protein structure and protein–protein interactions. However, water in the reversed-phase liquid chromatography mobile phase leads to back-exchange of D for H during chromatographic separation of proteolytic peptides following H/D exchange, resulting in incorrect identification of fast-exchanging hydrogens as unexchanged hydrogens. Previously, fast high-performance liquid chromatography (HPLC) and supercritical fluid chromatography have been shown to decrease back-exchange. Here, we show that replacement of up to 40% of the water in the LC mobile phase by the modifiers, dimethylformamide (DMF) and N-methylpyrrolidone (NMP) (i.e., polar organic modifiers that lack rapid exchanging hydrogens), significantly reduces back-exchange. On-line LC micro-ESI FT-ICR MS resolves overlapped proteolytic peptide isotopic distributions, allowing for quantitative determination of the extent of back-exchange. The DMF modified solvent composition also improves chromatographic separation while reducing back-exchange relative to conventional solvent. PMID:22298288

  10. Difference in fibril core stability between two tau four-repeat domain proteins: a hydrogen-deuterium exchange coupled to mass spectrometry study. (United States)

    Ramachandran, Gayathri; Udgaonkar, Jayant B


    One of the signatures of Alzheimer's disease and tauopathies is fibrillization of the microtubule-associated protein tau. The purpose of this study was to compare the high-resolution structure of fibrils formed by two different tau four-repeat domain constructs, tau4RD and tauK18, using hydrogen-deuterium exchange coupled to mass spectrometry as a tool. While the two fibrils are found to be constructed on similar structural principles, the tauK18 fibril has a slightly more stable core. This difference in fibril core stability appears to be reflective of the mechanistic differences in the aggregation pathways of the two proteins.

  11. Predicting Protein Aggregation during Storage in Lyophilized Solids Using Solid State Amide Hydrogen/Deuterium Exchange with Mass Spectrometric Analysis (ssHDX-MS)


    Moorthy, Balakrishnan S.; Schultz, Steven G.; Kim, Sherry G.; Topp, Elizabeth M.


    Solid state amide hydrogen/deuterium exchange with mass spectrometric analysis (ssHDX-MS) was used to assess the conformation of myoglobin (Mb) in lyophilized formulations, and the results correlated with the extent of aggregation during storage. Mb was colyophilized with sucrose (1:1 or 1:8 w/w), mannitol (1:1 w/w), or NaCl (1:1 w/w) or in the absence of excipients. Immediately after lyophilization, samples of each formulation were analyzed by ssHDX-MS and Fourier transform infrared spectros...

  12. Hydrogen/Deuterium Exchange Mass Spectrometry Reveals Specific Changes in the Local Flexibility of Plasminogen Activator Inhibitor 1 upon Binding to the Somatomedin B Domain of Vitronectin

    DEFF Research Database (Denmark)

    Trelle, Morten Beck; Hirschberg, Daniel; Jansson, Anna


    The native fold of plasminogen activator inhibitor 1 (PAI-1) represents an active metastable conformation that spontaneously converts to an inactive latent form. Binding of the somatomedin B domain (SMB) of the endogenous cofactor vitronectin to PAI-1 delays the transition to the latent state...... and increases the thermal stability of the protein dramatically. We have used hydrogen/deuterium exchange mass spectrometry to assess the inherent structural flexibility of PAI-1 and to monitor the changes induced by SMB binding. Our data show that the PAI-1 core consisting of β-sheet B is rather protected...

  13. Dissecting the Binding Mode of Low Affinity Phage Display Peptide Ligands to Protein Targets by Hydrogen/Deuterium Exchange Coupled to Mass Spectrometry

    DEFF Research Database (Denmark)

    Leurs, Ulrike; Lohse, Brian; Ming, Shonoi A


    of hydrogen/deuterium exchange mass spectrometry (HDX-MS) to characterize interactions of low affinity peptides with their cognate protein targets. The HDX-MS workflow was optimized to accurately detect low-affinity peptide-protein interactions by use of ion mobility, electron transfer dissociation, non......Phage display (PD) is frequently used to discover peptides capable of binding to biological protein targets. The structural characterization of peptide-protein complexes is often challenging due to their low binding affinities and high structural flexibility. Here, we investigate the use...

  14. Probing the Conformational and Functional Consequences of Disulfide Bond Engineering in Growth Hormone by Hydrogen-Deuterium Exchange Mass Spectrometry Coupled to Electron Transfer Dissociation

    DEFF Research Database (Denmark)

    Seger, Signe T; Breinholt, Jens; Faber, Johan H


    Human growth hormone (hGH), and its receptor interaction, is essential for cell growth. To stabilize a flexible loop between helices 3 and 4, while retaining affinity for the hGH receptor, we have engineered a new hGH variant (Q84C/Y143C). Here, we employ hydrogen-deuterium exchange mass...... spectrometry (HDX-MS) to map the impact of the new disulfide bond on the conformational dynamics of this new hGH variant. Compared to wild type hGH, the variant exhibits reduced loop dynamics, indicating a stabilizing effect of the introduced disulfide bond. Furthermore, the disulfide bond exhibits longer...

  15. Using Hydrogen/Deuterium Exchange Mass Spectrometry to Define the Specific Interactions of the Phospholipase A2 Superfamily with Lipid Substrates, Inhibitors, and Membranes* (United States)

    Cao, Jian; Burke, John E.; Dennis, Edward A.


    The phospholipase A2 (PLA2) superfamily consists of 16 groups and many subgroups and constitutes a diverse set of enzymes that have a common catalytic activity due to convergent evolution. However, different PLA2 types have unique three-dimensional structures and catalytic residues as well as specific tissue localization and distinct biological functions. Understanding how the different PLA2 enzymes associate with phospholipid membranes, specific phospholipid substrate molecules, and inhibitors on a molecular basis has advanced in recent years due to the introduction of hydrogen/deuterium exchange mass spectrometry. Its theory, practical considerations, and application to understanding PLA2/membrane interactions are addressed. PMID:23209293

  16. Hydrogen-deuterium substitution in solid ethanol by surface reactions at low temperatures (United States)

    Oba, Yasuhiro; Osaka, Kazuya; Chigai, Takeshi; Kouchi, Akira; Watanabe, Naoki


    Ethanol (CH3CH2OH) is one of the most abundant complex organic molecules in star-forming regions. Despite its detection in the gas phase only, ethanol is believed to be formed by low-temperature grain-surface reactions. Methanol, the simplest alcohol, has been a target for observational, experimental, and theoretical studies in view of its deuterium enrichment in the interstellar medium; however, the deuterium chemistry of ethanol has not yet been an area of focus. Recently, deuterated dimethyl ether, a structural isomer of ethanol, was found in star-forming regions, indicating that deuterated ethanol can also be present in those environments. In this study, we performed laboratory experiments on the deuterium fractionation of solid ethanol at low temperatures through a reaction with deuterium (D) atoms at 10 K. Hydrogen (H)-D substitution, which increases the deuteration level, was found to occur on the ethyl group but not on the hydroxyl group. In addition, when deuterated ethanol (e.g. CD3CD2OD) solid was exposed to H atoms at 10 K, D-H substitution that reduced the deuteration level occurred on the ethyl group. Based on the results, it is likely that deuterated ethanol is present even under H-atom-dominant conditions in the interstellar medium.

  17. Approach to characterization of the higher order structure of disulfide-containing proteins using hydrogen/deuterium exchange and top-down mass spectrometry. (United States)

    Wang, Guanbo; Kaltashov, Igor A


    Top-down hydrogen/deuterium exchange (HDX) with mass spectrometric (MS) detection has recently matured to become a potent biophysical tool capable of providing valuable information on higher order structure and conformational dynamics of proteins at an unprecedented level of structural detail. However, the scope of the proteins amenable to the analysis by top-down HDX MS still remains limited, with the protein size and the presence of disulfide bonds being the two most important limiting factors. While the limitations imposed by the physical size of the proteins gradually become more relaxed as the sensitivity, resolution and dynamic range of modern MS instrumentation continue to improve at an ever accelerating pace, the presence of the disulfide linkages remains a much less forgiving limitation even for the proteins of relatively modest size. To circumvent this problem, we introduce an online chemical reduction step following completion and quenching of the HDX reactions and prior to the top-down MS measurements of deuterium occupancy of individual backbone amides. Application of the new methodology to the top-down HDX MS characterization of a small (99 residue long) disulfide-containing protein β2-microglobulin allowed the backbone amide protection to be probed with nearly a single-residue resolution across the entire sequence. The high-resolution backbone protection pattern deduced from the top-down HDX MS measurements carried out under native conditions is in excellent agreement with the crystal structure of the protein and high-resolution NMR data, suggesting that introduction of the chemical reduction step to the top-down routine does not trigger hydrogen scrambling either during the electrospray ionization process or in the gas phase prior to the protein ion dissociation.

  18. Dissecting the effect of RNA aptamer binding on the dynamics of plasminogen activator inhibitor 1 using hydrogen/deuterium exchange mass spectrometry

    DEFF Research Database (Denmark)

    Trelle, Morten B; Dupont, Daniel Miotto; Madsen, Jeppe Buur


    RNA aptamers, selected from large synthetic libraries, are attracting increasing interest as protein ligands, with potential uses as prototype pharmaceuticals, conformational probes, and reagents for specific quantification of protein levels in biological samples. Very little is known, however......, about their effects on protein conformation and dynamics. We have employed hydrogen/deuterium exchange (HDX) mass spectrometry to study the effect of RNA aptamers on the structural flexibility of the serpin plasminogen activator inhibitor-1 (PAI-1). The aptamers have characteristic effects...... of the aptamers to PAI-1 is associated with substantial and widespread protection against deuterium uptake in PAI-1. The aptamers induce protection against exchange with the solvent both in the protein-aptamer interface as well as in other specific areas. Interestingly, the aptamers induce substantial protection...

  19. A membrane cell for on-line hydrogen/deuterium exchange to study protein folding and protein-protein interactions by mass spectrometry. (United States)

    Astorga-Wells, Juan; Landreh, Michael; Johansson, Jan; Bergman, Tomas; Jörnvall, Hans


    A membrane cell for hydrogen and deuterium exchange on-line with mass spectrometry has been developed to monitor protein-protein interactions and protein conformations. It consists of two channels separated by a semipermeable membrane, where one channel carries the protein sample and the other deuterium oxide. The membrane allows transfer of deuterium oxide into the sample flow. The labeling time is controlled via the flow rate in the sample channel. This cell was validated against three models commonly used in hydrogen-deuterium exchange mass spectrometry: monitoring of folded and unfolded states in a protein, mapping the protein secondary structure at the peptide level, and detection of protein and antibody interactions. The system avoids the conventionally used sample dilution and handling, allowing for potential automation.

  20. A Membrane Cell for On-line Hydrogen/Deuterium Exchange to Study Protein Folding and Protein-Protein Interactions by Mass Spectrometry* (United States)

    Astorga-Wells, Juan; Landreh, Michael; Johansson, Jan; Bergman, Tomas; Jörnvall, Hans


    A membrane cell for hydrogen and deuterium exchange on-line with mass spectrometry has been developed to monitor protein-protein interactions and protein conformations. It consists of two channels separated by a semipermeable membrane, where one channel carries the protein sample and the other deuterium oxide. The membrane allows transfer of deuterium oxide into the sample flow. The labeling time is controlled via the flow rate in the sample channel. This cell was validated against three models commonly used in hydrogen-deuterium exchange mass spectrometry: monitoring of folded and unfolded states in a protein, mapping the protein secondary structure at the peptide level, and detection of protein and antibody interactions. The system avoids the conventionally used sample dilution and handling, allowing for potential automation. PMID:21610101

  1. Hydrogen/deuterium exchange, a unique and effective method for MS fragmentation behavior elucidation of ginkgolides and its application to systematic research in Ginkgo biloba. (United States)

    Niu, Xingliang; Luo, Jun; Xu, Deran; Zou, Hongyan; Kong, Lingyi


    Ginkgolides, the main active constituents of Ginkgo biloba, possess significant selectively inhibition on platelet-activating factor and pancreatic lipase and attract wide attention in pharmacological research area. In our study, an effective hydrogen/deuterium (H/D) exchange method was developed by exchanging the α-Hs of lactone groups in ginkgolides with Ds, which was very useful for the elucidation of the fragmentation patterns of ginkgolides in Quadrupole Time-of-flight Mass Spectrometry (Q-TOF-MS), especially in accurately distinguishing the type and position of substituent in framework of ginkgolides. Then, a systematic research strategy for qualitative and quantitative analysis of ginkgolides, based on H/D exchange, tandem solid-phase extraction and LC-Q-TOF-MS, was developed, which was successfully applied in each medicinal part of G. biloba, which indicated that ginkgolide B was the most abundant ginkgolide in the seeds of G. biloba (60.6μg/g). This research was the successful application of H/D exchange in natural products, and proved that H/D exchange is a potential method for analysis research of complex TCMs active constituents. Copyright © 2016 Elsevier B.V. All rights reserved.

  2. Automated Data Reduction for Hydrogen/Deuterium Exchange Experiments, Enabled by High-Resolution Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (United States)

    Kazazic, Sasa; Zhang, Hui-Min; Schaub, Tanner M.; Emmett, Mark R.; Hendrickson, Christopher L.; Blakney, Gregory T.; Marshall, Alan G.


    Mass analysis of proteolytic fragment peptides following hydrogen/deuterium exchange offers a general measure of solvent accessibility/hydrogen bonding (and thus conformation) of solution-phase proteins and their complexes. The primary problem in such mass analyses is reliable and rapid assignment of mass spectral peaks to the correct charge state and degree of deuteration of each fragment peptide, in the presence of substantial overlap between isotopic distributions of target peptides, autolysis products, and other interferant species. Here, we show that at sufficiently high mass resolving power (m/Δm50% ≥ 100,000), it becomes possible to resolve enough of those overlaps so that automated data reduction becomes possible, based on the actual elemental composition of each peptide without the need to deconvolve isotopic distributions. We demonstrate automated, rapid, reliable assignment of peptide masses from H/D exchange experiments, based on electrospray ionization FT-ICR mass spectra from H/D exchange of solution-phase myoglobin. Combined with previously demonstrated automated data acquisition for such experiments, the present data reduction algorithm enhances automation (and thus expands generality and applicability) for high-resolution mass spectrometry- based analysis of H/D exchange of solution-phase proteins. PMID:20116280

  3. Observation of hydrogen-deuterium exchange of ubiquitin by direct analysis of electrospray capillary-skimmer dissociation with Fourier transform ion cyclotron resonance mass spectrometry. (United States)

    Akashi, S; Naito, Y; Takio, K


    The structure of ubiquitin, a small cytoplasmic protein with an extended beta-sheet and an alpha-helix surrounding a hydrophobic core, has been characterized by hydrogen-deuterium (H/D) exchange labeling in conjunction with successive analysis by capillary-skimmer dissociation with electrospray ionization-Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR MS). The deuterium content of each fragment ion was investigated at different times, and the results indicate that the deuterium incorporation rate into the backbone amides of ubiquitin varied depending on the environment of the amide hydrogens. Amide hydrogens of the N-terminal beta-strand showed quite slow exchange while those of the 35-39 loop were exchanged within a short exposure time to deuterium oxide. It was also possible to evaluate the difference in hydrogen-bond stability. The present data are consistent with the structural features obtained by X-Ray and NMR analyses. Although some of the labeling information might be lost by the scrambling of amide protons during capillary-skimmer dissociation, the results demonstrate that the present method provides useful higher-order structural information for proteins.

  4. Determination of Equine Cytochrome c Backbone Amide Hydrogen/Deuterium Exchange Rates by Mass Spectrometry Using a Wider Time Window and Isotope Envelope (United States)

    Hamuro, Yoshitomo


    A new strategy to analyze amide hydrogen/deuterium exchange mass spectrometry (HDX-MS) data is proposed, utilizing a wider time window and isotope envelope analysis of each peptide. While most current scientific reports present HDX-MS data as a set of time-dependent deuteration levels of peptides, the ideal HDX-MS data presentation is a complete set of backbone amide hydrogen exchange rates. The ideal data set can provide single amide resolution, coverage of all exchange events, and the open/close ratio of each amide hydrogen in EX2 mechanism. Toward this goal, a typical HDX-MS protocol was modified in two aspects: measurement of a wider time window in HDX-MS experiments and deconvolution of isotope envelope of each peptide. Measurement of a wider time window enabled the observation of deuterium incorporation of most backbone amide hydrogens. Analysis of the isotope envelope instead of centroid value provides the deuterium distribution instead of the sum of deuteration levels in each peptide. A one-step, global-fitting algorithm optimized exchange rate and deuterium retention during the analysis of each amide hydrogen by fitting the deuterated isotope envelopes at all time points of all peptides in a region. Application of this strategy to cytochrome c yielded 97 out of 100 amide hydrogen exchange rates. A set of exchange rates determined by this approach is more appropriate for a patent or regulatory filing of a biopharmaceutical than a set of peptide deuteration levels obtained by a typical protocol. A wider time window of this method also eliminates false negatives in protein-ligand binding site identification.

  5. Mechanism and kinetics of tyrosinase inhibition by glycolic acid: a study using conventional spectroscopy methods and hydrogen/deuterium exchange coupling with mass spectrometry. (United States)

    Ma, Da; Tu, Zong-Cai; Wang, Hui; Zhang, Lu; He, Na; McClements, David Julian


    Tyrosinase is an enzyme that promotes enzymatic browning of fruits and vegetables, thereby reducing product quality. A variety of analytical tools were used to characterize the interactions between tyrosinase and a natural tyrosinase inhibitor (glycolic acid). Hydrogen/deuterium exchange coupling with mass spectrometry (HDX-MS) was used to elucidate the interaction mechanism between glycolic acid and tyrosinase. UV-visible, fluorescence and circular dichroism spectroscopy analysis indicated that glycolic acid inhibited tyrosinase activity in a mixed-type manner with an IC50 of 83 ± 14 μM. The results of these techniques suggested that glycolic acid bound to tyrosinase through hydrophobic attraction, and this interaction led to a pronounced conformational change of the enzyme molecules. HDX-MS analysis showed that the activity of tyrosinase was primarily inhibited by a structural perturbation of its active site (His 263). This study provides a comprehensive understanding of the interaction between glycolic acid and tyrosinase, which could lead to new approaches to control tyrosinase activity in foods and other products.

  6. Design and Validation of In-Source Atmospheric Pressure Photoionization Hydrogen/Deuterium Exchange Mass Spectrometry with Continuous Feeding of D2O (United States)

    Acter, Thamina; Lee, Seulgidaun; Cho, Eunji; Jung, Maeng-Joon; Kim, Sunghwan


    In this study, continuous in-source hydrogen/deuterium exchange (HDX) atmospheric pressure photoionization (APPI) mass spectrometry (MS) with continuous feeding of D2O was developed and validated. D2O was continuously fed using a capillary line placed on the center of a metal plate positioned between the UV lamp and nebulizer. The proposed system overcomes the limitations of previously reported APPI HDX-MS approaches where deuterated solvents were premixed with sample solutions before ionization. This is particularly important for APPI because solvent composition can greatly influence ionization efficiency as well as the solubility of analytes. The experimental parameters for APPI HDX-MS with continuous feeding of D2O were optimized, and the optimized conditions were applied for the analysis of nitrogen-, oxygen-, and sulfur-containing compounds. The developed method was also applied for the analysis of the polar fraction of a petroleum sample. Thus, the data presented in this study clearly show that the proposed HDX approach can serve as an effective analytical tool for the structural analysis of complex mixtures. [Figure not available: see fulltext.

  7. Different conformational dynamics of PDZ1 and PDZ2 in full-length EBP50 analyzed by hydrogen/deuterium exchange mass spectrometry. (United States)

    Park, Ji Young; Duc, Nguyen Minh; Kim, Dong Kyun; Lee, Su Youn; Li, Sheng; Seo, Min-Duk; Woods, Virgil L; Chung, Ka Young


    Ezrin-radixin-moesin-binding protein 50 (EBP50) is a scaffolding protein expressed in polarized epithelial cells in various organs, including the liver, kidney, and small intestine, in which it regulates the trafficking and targeting cellular proteins. EBP50 contains two postsynaptic density-95/disk-large/ZO-1 homology (PDZ) domains (e.g., PDZ1 and PDZ2) and an ezrin/radixin/moesin-binding (EB) domain. PDZ domains are one of the major scaffolding domains regulating protein-protein interactions with critical biological roles in cell polarity, migration, proliferation, recognition, and cell-cell interaction. PDZ1 and PDZ2 in EBP50 have different ligand selectivity, although several high-resolution structural studies of isolated PDZ1 and PDZ2 showed similar structures. We studied the conformations of full-length EBP50 and isolated PDZ1 and PDZ2 using hydrogen/deuterium exchange mass spectrometry (HDX-MS). The deuterium uptake profiles of isolated PDZ1 and PDZ2 were similar to those of full-length EBP50. Interestingly, PDZ1 was more dynamic than PDZ2, and these PDZ domains underwent different conformational changes upon ligand binding. These results might explain the differences in ligand-selectivity between PDZ1 and PDZ2.

  8. Hydrogen/Deuterium Exchange Reveals Distinct Agonist/Partial Agonist Receptor Dynamics within the intact Vitamin D Receptor/Retinoid X Receptor Heterodimer (United States)

    Zhang, Jun; Chalmers, Michael J.; Stayrook, Keith R.; Burris, Lorri L.; Garcia-Ordonez, Ruben D.; Pascal, Bruce D.; Burris, Thomas P.; Dodge, Jeffery A.; Griffin, Patrick R.


    Summary Regulation of nuclear receptor (NR) activity is driven by alterations in the conformational dynamics of the receptor upon ligand binding. Previously we demonstrated that hydrogen/deuterium exchange (HDX) can be applied to determine novel mechanism of action of PPARγ ligands and in predicting tissue specificity of selective estrogen receptor modulators. Here we applied HDX to probe the conformational dynamics of the ligand binding domain (LBD) of the vitamin D receptor (VDR) upon binding its natural ligand 1α,25-dihydroxyvitamin D3 (1,25D3), and two analogs, alfacalcidol and ED-71. Comparison of HDX profiles from ligands in complex with the LBD with full-length receptor bound to its cognate receptor retinoid X receptor (RXR) revealed unique receptor dynamics that could not be inferred from static crystal structures. These results demonstrate that ligands modulate the dynamics of the heterodimer interface as well as providing insight into the role of AF-2 dynamics in the action of VDR partial agonists. PMID:20947021

  9. In vivo metabolic investigation of moxifloxacin using liquid chromatography/electrospray ionization tandem mass spectrometry in combination with online hydrogen/deuterium exchange experiments. (United States)

    Raju, B; Ramesh, M; Borkar, Roshan M; Srinivas, R; Padiya, Raju; Banerjee, Sanjay K


    Tuberculosis is a leading cause of death from an infectious disease and moxifloxacin is an effective drug as compared to other fluoroquinolones. To date only two metabolites of the drug are known. Therefore, the present study on characterization of hitherto unknown in vivo metabolites of moxifloxacin using liquid chromatography/electrospray ionization tandem mass spectrometry (LC/ESI-MS/MS) is undertaken. In vivo metabolites of moxifloxacin have been identified and characterized by using LC/ESI-MS/MS in combination with an online hydrogen/deuterium (H/D) exchange technique. To identify in vivo metabolites, blood, urine and faeces samples were collected after oral administration of moxifloxacin to Sprague-Dawley rats. The samples were prepared using an optimized sample preparation approach involving protein precipitation, liquid-liquid extraction followed by solid-phase extraction and LC/MS/MS analysis. A total of nine phase I and ten phase II metabolites of moxifloxacin have been identified in urine samples including N-sulphated, glucuronide and hydroxylated metabolites which are also observed in plasma samples. In faeces samples, only the N-sulphated metabolite is observed. The structures of metabolites have been elucidated based on fragmentation patterns, accurate mass measurements and online H/D exchange LC/MS/MS experiments. Online H/D exchange experiments are used to support the identification and structural characterization of drug metabolites. A total of 19 in vivo metabolites of moxifloxacin have been characterized using LC/ESI-MS/MS in combination with accurate mass measurements and online H/D exchange experiments. The main phase I metabolites of moxifloxacin are hydroxylated, decarbonylated, desmethylated and desmethylhydroxylated metabolites which undergo subsequent phase II glucuronidation pathways. Copyright © 2012 John Wiley & Sons, Ltd.

  10. Semi-automated screen for global protein conformational changes in solution by ion mobility spectrometry-massspectrometry combined with size-exclusion chromatography and differential hydrogen-deuterium exchange. (United States)

    Pierson, Nicholas A; Makarov, Alexey A; Strulson, Christopher A; Mao, Yun; Mao, Bing


    Development of methodologies for studying protein higher-order structure in solution helps to establish a better understanding of the intrinsic link between protein conformational structure and biological function and activity. The goal of this study was to demonstrate a simultaneous screening approach for global protein conformational changes in solution through the combination of ion mobility spectrometry-mass spectrometry (IMS-MS) with differential hydrogen-deuterium exchange (ΔHDX) on the size-exclusion chromatography (SEC) platform in a single on-line workflow. A semi-automated experimental setup based on the use of SEC on-column conditions allowed for tracking of protein conformational changes in solution as a function of acetonitrile concentration. In this setup, the SEC protein elution data was complemented by the ΔHDX profile which showed global protein conformational changes as a difference in the number of deuterons exchanged to protons. The ΔHDX data, in turn, was complemented by the changes in the drift time by IMS-MS. All three orthogonal techniques were applied for studying global higher-order structure of the proteins ubiquitin, cytochrome c and myoglobin, in solution simultaneously. The described approach allows for the use of a crude sample (or mixture of proteins) and could be suitable for rapid comparison of protein batch-to-batch higher-order structure or for optimizing conditions for enzymatic reactions. Copyright © 2017 Elsevier B.V. All rights reserved.

  11. Evidence for site-specific intra-ionic hydrogen/deuterium exchange in the low-energy collision-induced dissociation product ion spectra of protonated small molecules generated by electrospray ionisation. (United States)

    Holman, Stephen W; Wright, Patricia; Wells, Neil J; Langley, G John


    The experimental investigation of site-specific intra-ionic hydrogen/deuterium (H/D) exchange in the low-energy collision-induced dissociation (CID) product ion spectra of protonated small molecules generated by electrospray ionisation (ESI) is presented. The observation of intra-ionic H/D exchange in such ions under low-energy CID conditions has hitherto been rarely reported. The data suggest that the intra-ionic H/D exchange takes place in a site-specific manner between the ionising deuteron, localised at either a tertiary amine or a tertiary amine-N-oxide, and a gamma-hydrogen relative to the nitrogen atom. Nuclear magnetic resonance (NMR) spectroscopy measurements showed that no H/D exchange takes place in solution, indicating that the reaction occurs in the gas phase. The compounds analysed in this study suggested that electron-withdrawing groups bonded to the carbon atom bearing the gamma-hydrogen can preclude exchange. The effect of the electron-withdrawing group appears dependent upon its electronegativity, with lower chi value groups still allowing exchange to take place. However, the limited dataset available in this study prevented robust conclusions being drawn regarding the effect of the electron-withdrawing group. The observation of site-specific intra-ionic H/D exchange has application in the area of structural elucidation, where it could be used to introduce an isotopic label into the carbon skeleton of a molecule containing specific structural features. This could increase the throughput, and minimise the cost, of such studies due to the obviation of the need to produce a deuterium-labelled analogue by synthetic means. Copyright 2010 John Wiley & Sons, Ltd.

  12. Predicting protein aggregation during storage in lyophilized solids using solid state amide hydrogen/deuterium exchange with mass spectrometric analysis (ssHDX-MS). (United States)

    Moorthy, Balakrishnan S; Schultz, Steven G; Kim, Sherry G; Topp, Elizabeth M


    Solid state amide hydrogen/deuterium exchange with mass spectrometric analysis (ssHDX-MS) was used to assess the conformation of myoglobin (Mb) in lyophilized formulations, and the results correlated with the extent of aggregation during storage. Mb was colyophilized with sucrose (1:1 or 1:8 w/w), mannitol (1:1 w/w), or NaCl (1:1 w/w) or in the absence of excipients. Immediately after lyophilization, samples of each formulation were analyzed by ssHDX-MS and Fourier transform infrared spectroscopy (FTIR) to assess Mb conformation, and by dynamic light scattering (DLS) and size exclusion chromatography (SEC) to determine the extent of aggregation. The remaining samples were then placed on stability at 25 °C and 60% RH or 40 °C and 75% RH for up to 1 year, withdrawn at intervals, and analyzed for aggregate content by SEC and DLS. In ssHDX-MS of samples immediately after lyophilization (t = 0), Mb was less deuterated in solids containing sucrose (1:1 and 1:8 w/w) than in those containing mannitol (1:1 w/w), NaCl (1:1 w/w), or Mb alone. Deuterium uptake kinetics and peptide mass envelopes also indicated greater Mb structural perturbation in mannitol, NaCl, or Mb-alone samples at t = 0. The extent of deuterium incorporation and kinetic parameters related to rapidly and slowly exchanging amide pools (Nfast, Nslow), measured at t = 0, were highly correlated with the extent of aggregation on storage as measured by SEC. In contrast, the extent of aggregation was weakly correlated with FTIR band intensity and peak position measured at t = 0. The results support the use of ssHDX-MS as a formulation screening tool in developing lyophilized protein drug products.

  13. A Hydrogen-Deuterium Exchange Study on Nickel-based Binary-Ternary Amorphous and Crystalline Membranes (United States)

    Adibhatla, Anasuya

    Hydrogen is a major role player in current global sustainable energy scenario. Research around the world is carried out to harness hydrogen from all possible sources. One of these sources is water gas shift reaction after the coal gasification process. Sustainable infrastructure can be viable in countries like USA and Australia, making this process viable. Various methods are used to harness this hydrogen from the water gas. One of these methods is the use of inorganic membranes based on Pd, Ag, Ni, Zr and other transition metals. Pd addition to the membranes makes the membranes more expensive for commercial use. Various bulk properties like hydrogen permeation and absorption are studied on Pd and Pd-based alloys. Alternate alloys based on Ni, V, Ta etc are being studied to substitute the use of Pd making this technology more cost efficient. A current balance in research in this area is fund to exist by coating the non-precious metal membranes with Pd to improve the surface interaction with hydrogen. The nature of membranes used for hydrogen separation is important aspect for the overall performance. Crystalline materials provide better bulk properties, however, are not durable under high temperature and hydrogen pressure. In this research, non-Pd coated Ni-based amorphous membranes were made by melt spin technique, which have been studied for their surface properties. Gas phase H2-D2 exchange reaction has been carried out on the membrane surface. This provides a measure of catalytic activity of the above mentioned membranes. More studies included the crystallographic phase change determination, bulk hydrogen solubility measurements, surface conduction measurements and surface morphological studies. During this research, it has been observed that crystalline materials provide more surface activity for hydrogen than their amorphous counterparts. Ni64Zr36 alloy has been shown to exhibit similar kinetic rates as metallic Ni. Also, microkinetic analysis was performed

  14. Rapid Conformational Analysis of Protein Drugs in Formulation by Hydrogen/Deuterium Exchange Mass Spectrometry (HDX-MS)

    DEFF Research Database (Denmark)

    Esmail Nazari, Zeinab; van de Weert, Marco; Bou-Assaf, George


    pharmaceutically relevant formulation conditions. Of significant practical utility, the methodology allows global HDX-MS analyses to be performed without refrigeration or external cooling of the setup. In Mode 1, we used DMSO-containing solvents for SPE, allowing the HDX-MS analysis to be performed at acceptable...... back exchange levels (cooling any components of the setup. In mode 2, SPE and chromatography were performed using fast isocratic elution at 0 °C resulting in a back exchange of 10-30%. Real-world applicability was demonstrated by HDX-MS analyses of interferon-β-1a...

  15. Structural Dynamics of the GW182 Silencing Domain Including its RNA Recognition motif (RRM) Revealed by Hydrogen-Deuterium Exchange Mass Spectrometry (United States)

    Cieplak-Rotowska, Maja K.; Tarnowski, Krzysztof; Rubin, Marcin; Fabian, Marc R.; Sonenberg, Nahum; Dadlez, Michal; Niedzwiecka, Anna


    The human GW182 protein plays an essential role in micro(mi)RNA-dependent gene silencing. miRNA silencing is mediated, in part, by a GW182 C-terminal region called the silencing domain, which interacts with the poly(A) binding protein and the CCR4-NOT deadenylase complex to repress protein synthesis. Structural studies of this GW182 fragment are challenging due to its predicted intrinsically disordered character, except for its RRM domain. However, detailed insights into the properties of proteins containing disordered regions can be provided by hydrogen-deuterium exchange mass spectrometry (HDX/MS). In this work, we applied HDX/MS to define the structural state of the GW182 silencing domain. HDX/MS analysis revealed that this domain is clearly divided into a natively unstructured part, including the CCR4-NOT interacting motif 1, and a distinct RRM domain. The GW182 RRM has a very dynamic structure, since water molecules can penetrate the whole domain in 2 h. The finding of this high structural dynamics sheds new light on the RRM structure. Though this domain is one of the most frequently occurring canonical protein domains in eukaryotes, these results are - to our knowledge - the first HDX/MS characteristics of an RRM. The HDX/MS studies show also that the α2 helix of the RRM can display EX1 behavior after a freezing-thawing cycle. This means that the RRM structure is sensitive to environmental conditions and can change its conformation, which suggests that the state of the RRM containing proteins should be checked by HDX/MS in regard of the conformational uniformity. [Figure not available: see fulltext.

  16. Epitope mapping of inhibitory antibodies targeting the C2 domain of coagulation factor VIII by hydrogen-deuterium exchange mass spectrometry (United States)

    Sevy, Alexander M.; Healey, John F.; Deng, Wei; Spiegel, P. Clint; Meeks, Shannon L.; Li, Renhao


    Summary Background The development of anti-factor VIII (fVIII) antibodies (inhibitors) is a significant complication in the management of patients with hemophilia A, leading to significant increases in morbidity and treatment cost. Using a panel of anti-fVIII monoclonal antibodies (MAbs) to different epitopes on fVIII, we recently have shown that epitope specificity, inhibitor kinetics, and time to maximum inhibition are more important than inhibitor titer in predicting response to fVIII and the combination of fVIII and recombinant factor VIIa. In particular, a subset of high-titer inhibitors responded to high dose fVIII, which would not be predicted based on their inhibitor titer alone. Thus the ability to quickly map the epitope spectrum of patient plasma using a clinically feasible assay may fundamentally change how clinicians approach the treatment of high-titer inhibitor patients. Objectives To map the epitopes of anti-fVIII MAbs, of which 3 are classical inhibitors and one non-classical, using hydrogen-deuterium exchange coupled with liquid chromatography-mass spectrometry (HDX-MS). Methods Binding epitopes of 4 MAbs targeting fVIII C2 domain were mapped using HDX-MS. Results The epitopes determined by HDX-MS are consistent with those obtained earlier through structural characterization and antibody competition assays. In addition classical and non-classical inhibitor epitopes could be distinguished using a limited subset of C2-derived peptic fragments. Conclusion Our results demonstrate the effectiveness and robustness of the HDX-MS method for epitope mapping and suggest a potential role of rapid mapping of fVIII inhibitor epitopes in facilitating individualized treatment of inhibitor patients. PMID:24152306

  17. Hydrogen/Deuterium Exchange Mass Spectrometry and Site-Directed Disulfide Cross-Linking Suggest an Important Dynamic Interface between the Two Lysostaphin Domains (United States)

    Lu, Hai-Rong; Gu, Mei-Gang; Huang, Qiang; Huang, Jin-Jiang; Lu, Wan-Ying; Lu, Hong


    Lysostaphin is a peptidoglycan hydrolase secreted by Staphylococcus simulans. It can specifically lyse Staphylococcus aureus and is being tested as a novel antibacterial agent. The protein contains an N-terminal catalytic domain and a C-terminal cell wall targeting domain. Although the two domains from homologous enzymes were structurally determined, the structural organization of lysostaphin domains remains unknown. We used hydrogen/deuterium exchange mass spectrometry (H/DX-MS) and site-directed disulfide cross-linking to probe the interface between the lysostaphin catalytic and targeting domains. H/DX-MS-mediated comparison of peptides from full-length lysostaphin and the separated domains identified four peptides of lower solvent accessibility in the full-length protein. Cross-linking analysis using cysteine pair substitutions within those peptides showed that two pairs of cysteines can form disulfide bonds, supporting the domain association role of the targeted peptides. The cross-linked mutant exhibited a binding capacity to S. aureus that was similar to that of the wild-type protein but reduced bacteriolytic activity probably because of restraint in conformation. The diminished activity was further reduced with increasing NaCl concentrations that can cause contractions of bacterial peptidoglycan. The lytic activity, however, could be fully recovered by reducing the disulfide bonds. These results suggest that lysostaphin may require dynamic association of the two domains for coordinating substrate binding and target cleavage on the elastic peptidoglycan. Our study will help develop site-specific PEGylated lysostaphin to treat systemic S. aureus infections. PMID:23380729

  18. Structural Dynamics of Soluble Chloride Intracellular Channel Protein CLIC1 Examined by Amide Hydrogen-Deuterium Exchange Mass Spectrometry (DXMS)† (United States)

    Stoychev, Stoyan H.; Nathaniel, Christos; Fanucchi, Sylvia; Brock, Melissa; Li, Sheng; Asmus, Kyle; Woods, Virgil L.; Dirr, Heini W.


    Chloride intracellular channel protein 1 (CLIC1) functions as an anion channel in plasma and nuclear membranes when its soluble monomeric form converts to an integral-membrane form. The transmembrane region of CLIC1 is located in its thioredoxin-like domain 1 but the mechanism whereby the protein converts to its membrane conformation has yet to be determined. Since channel formation in membranes is enhanced at low pH (5 to 5.5), a condition that is found at the surface of membranes, the structural dynamics of soluble CLIC1 was studied at pH 7 and at pH 5.5 in the absence of membranes by amide hydrogen-deuterium exchange mass spectrometry (DXMS). Rapid hydrogen exchange data indicate that CLIC1 displays a similar core structure at these pH values. Domain 1 is less stable than the all-helical domain 2 and, while the structure of domain 1 remains intact, its conformational flexibility is further increased in an acidic environment (pH 5.5). In the absence of membrane, an acidic environment appears to prime the solution structure of CLIC1 by destabilising domain 1 in order to lower the activation energy barrier for its conversion to the membrane-insertion conformation. The significantly enhanced H/D-exchange rates at pH 5.5 displayed by two segments (peptides 11-31 and 68-82) could be due to the protonation of acidic residues in salt bridges. One of these segments (peptide 11-31) includes part of the transmembrane region which, in the solution structure, consists of helix α1. This helix is intrinsically stable and is most likely retained in the membrane conformation. Strand β2, another element of the transmembrane region, displays a propensity to form a helical structure and has putative N- and C-capping motifs, suggesting that it too most likely forms a helix in a lipid bilayer. PMID:19650640

  19. Study of fragmentation pattern and adsorption of 9-O-(triphenylsilyl)-10,11-dihydrocinchonidine on platinum by hydrogen/deuterium exchange using electrospray ionization ion-trap tandem mass spectrometry. (United States)

    Szöllosi, György; Bucsi, Imre; Cserényi, Szabolcs; Bartók, Mihály


    We have studied the adsorption on a platinum (Pt) catalyst of two compounds utilizable as a chiral basic catalyst and a chiral modifier, dihydrocinchonidine (DHCD), and a new cinchona alkaloid derivative containing a bulky group, the Ph3SiO-DHCD molecule. The method of choice was the detection by electrospray ionization (ESI) ion-trap tandem mass spectrometry (MS/MS) of hydrogen/deuterium (H/D) exchange at room temperature, in tetrahydrofuran, at a D2 pressure of 1 bar. Based on the ESI-MS/MS spectrum of the new compound, we propose a mechanism for the formation of the silatropylium cation containing a Si-O bond. From the fragmentation pattern of Ph3SiO-DHCD it was confirmed that ESI-ion-trap MS/MS can be used to study the adsorption processes of complicated carbon compounds by investigating their H/D exchange reactions. In the case of Ph3SiO-DHCD, the results demonstrate that H/D exchange takes place mainly on the quinoline skeleton. However, the strong pi-bonded adsorption of the quinoline skeleton parallel with the imaginary plane of Pt is not preferred because the bulky Ph3Si group inhibits the multiple pi-bonded adsorption of the Ph3SiO-DHCD. Because of this hindrance the molecule was adsorbed tilted via the nonbonding electron pair of the N atom and C2' atom of the quinoline skeleton; consequently, mainly alkaloid-d1 and alkaloid-d2 are formed. 2005 John Wiley & Sons, Ltd.

  20. Structure and Dynamics of NBD1 from CFTR Characterized Using Crystallography and Hydrogen/Deuterium Exchange Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Lewis, H.A.; Wang, C.; Zhao, X.; Hamuro, Y.; Conners, K.; Kearins, M.C.; Lu, F.; Sauder, J.M.; Molnar, K.S.; Coales, S.J.; Maloney, P.C.; Guggino, W.B.; Wetmore, D.R.; Weber, P.C.; Hunt, J.F. (SGX); (ExSAR); (Cystic); (JHU-MED); (Columbia)


    The {Delta}F508 mutation in nucleotide-binding domain 1 (NBD1) of the cystic fibrosis transmembrane conductance regulator (CFTR) is the predominant cause of cystic fibrosis. Previous biophysical studies on human F508 and {Delta}F508 domains showed only local structural changes restricted to residues 509-511 and only minor differences in folding rate and stability. These results were remarkable because {Delta}F508 was widely assumed to perturb domain folding based on the fact that it prevents trafficking of CFTR out of the endoplasmic reticulum. However, the previously reported crystal structures did not come from matched F508 and {Delta}F508 constructs, and the {Delta}F508 structure contained additional mutations that were required to obtain sufficient protein solubility. In this article, we present additional biophysical studies of NBD1 designed to address these ambiguities. Mass spectral measurements of backbone amide {sup 1}H/{sup 2}H exchange rates in matched F508 and {Delta}F508 constructs reveal that {Delta}F508 increases backbone dynamics at residues 509-511 and the adjacent protein segments but not elsewhere in NBD1. These measurements also confirm a high level of flexibility in the protein segments exhibiting variable conformations in the crystal structures. We additionally present crystal structures of a broader set of human NBD1 constructs, including one harboring the native F508 residue and others harboring the {Delta}F508 mutation in the presence of fewer and different solubilizing mutations. The only consistent conformational difference is observed at residues 509-511. The side chain of residue V510 in this loop is mostly buried in all non-{Delta}F508 structures but completely solvent exposed in all {Delta}F508 structures. These results reinforce the importance of the perturbation {Delta}F508 causes in the surface topography of NBD1 in a region likely to mediate contact with the transmembrane domains of CFTR. However, they also suggest that increased

  1. Liquid Chromatography Electrospray Ionization Tandem Mass Spectrometric (LC/ESI-MS/MS Study for the Identification and Characterization of In Vivo Metabolites of Cisplatin in Rat Kidney Cancer Tissues: Online Hydrogen/Deuterium (H/D Exchange Study.

    Directory of Open Access Journals (Sweden)

    Raju Bandu

    Full Text Available In vivo rat kidney tissue metabolites of an anticancer drug, cisplatin (cis-diamminedichloroplatinum [II] (CP which is used for the treatment of testicular, ovarian, bladder, cervical, esophageal, small cell lung, head and neck cancers, have been identified and characterized by using liquid chromatography positive ion electrospray ionization tandem mass spectrometry (LC/ESI-MS/MS in combination with on line hydrogen/deuterium exchange (HDX experiments. To identify in vivo metabolites, kidney tissues were collected after intravenous administration of CP to adult male Sprague-Dawley rats (n = 3 per group. The tissue samples were homogenized and extracted using newly optimized metabolite extraction procedure which involves liquid extraction with phosphate buffer containing ethyl acetate and protein precipitation with mixed solvents of methanol-water-chloroform followed by solid-phase clean-up procedure on Oasis HLB 3cc cartridges and then subjected to LC/ESI-HRMS analysis. A total of thirty one unknown in vivo metabolites have been identified and the structures of metabolites were elucidated using LC-MS/MS experiments combined with accurate mass measurements. Online HDX experiments have been used to further support the structural characterization of metabolites. The results showed that CP undergoes a series of ligand exchange biotransformation reactions with water and other nucleophiles like thio groups of methionine, cysteine, acetylcysteine, glutathione and thioether. This is the first research approach focused on the structure elucidation of biotransformation products of CP in rats, and the identification of metabolites provides essential information for further pharmacological and clinical studies of CP, and may also be useful to develop various effective new anticancer agents.

  2. Liquid Chromatography Electrospray Ionization Tandem Mass Spectrometric (LC/ESI-MS/MS) Study for the Identification and Characterization of In Vivo Metabolites of Cisplatin in Rat Kidney Cancer Tissues: Online Hydrogen/Deuterium (H/D) Exchange Study. (United States)

    Bandu, Raju; Ahn, Hyun Soo; Lee, Joon Won; Kim, Yong Woo; Choi, Seon Hee; Kim, Hak Jin; Kim, Kwang Pyo


    In vivo rat kidney tissue metabolites of an anticancer drug, cisplatin (cis-diamminedichloroplatinum [II]) (CP) which is used for the treatment of testicular, ovarian, bladder, cervical, esophageal, small cell lung, head and neck cancers, have been identified and characterized by using liquid chromatography positive ion electrospray ionization tandem mass spectrometry (LC/ESI-MS/MS) in combination with on line hydrogen/deuterium exchange (HDX) experiments. To identify in vivo metabolites, kidney tissues were collected after intravenous administration of CP to adult male Sprague-Dawley rats (n = 3 per group). The tissue samples were homogenized and extracted using newly optimized metabolite extraction procedure which involves liquid extraction with phosphate buffer containing ethyl acetate and protein precipitation with mixed solvents of methanol-water-chloroform followed by solid-phase clean-up procedure on Oasis HLB 3cc cartridges and then subjected to LC/ESI-HRMS analysis. A total of thirty one unknown in vivo metabolites have been identified and the structures of metabolites were elucidated using LC-MS/MS experiments combined with accurate mass measurements. Online HDX experiments have been used to further support the structural characterization of metabolites. The results showed that CP undergoes a series of ligand exchange biotransformation reactions with water and other nucleophiles like thio groups of methionine, cysteine, acetylcysteine, glutathione and thioether. This is the first research approach focused on the structure elucidation of biotransformation products of CP in rats, and the identification of metabolites provides essential information for further pharmacological and clinical studies of CP, and may also be useful to develop various effective new anticancer agents.

  3. Different conformational dynamics of β-arrestin1 and β-arrestin2 analyzed by hydrogen/deuterium exchange mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Yun, Youngjoo; Kim, Dong Kyun [School of Pharmacy, Sungkyunkwan University, Suwon (Korea, Republic of); Seo, Min-Duk [College of Pharmacy & Department of Molecular Science and Technology, Ajou University, Suwon (Korea, Republic of); Kim, Kyeong-Man [College of Pharmacy, Chonnam National University, Gwang-Ju (Korea, Republic of); Chung, Ka Young, E-mail: [School of Pharmacy, Sungkyunkwan University, Suwon (Korea, Republic of)


    Highlights: • The conformational dynamics of β-arrestin1 or β-arrestin2 were analyzed by HDX-MS. • β-Strands II through IV were more dynamic in β-arrestin2 than in β-arrestin1. • The middle loop was less dynamic in β-arrestin2 than in β-arrestin1. • Upon pre-activation by the R169E mutation, β-arrestins became more dynamic. • Pre-activation affected a wider region of β-arrestin1 compared to β-arrestin2. - Abstract: Arrestins have important roles in G protein-coupled receptor (GPCR) signaling including desensitization of GPCRs and G protein-independent signaling. There have been four arrestins identified: arrestin1, arrestin2 (e.g. β-arrestin1), arrestin3 (e.g. β-arrestin2), and arrestin4. β-Arrestin1 and β-arrestin2 are ubiquitously expressed and regulate a broad range of GPCRs, while arrestin1 and arrestin4 are expressed in the visual system. Although the functions of β-arrestin1 and β-arrestin2 widely overlap, β-arrestin2 has broader receptor selectivity, and a few studies have suggested that β-arrestin1 and β-arrestin2 have distinct cellular functions. Here, we compared the conformational dynamics of β-arrestin1 and β-arrestin2 by hydrogen/deuterium exchange mass spectrometry (HDX-MS). We also used the R169E mutant as a pre-activation model system. HDX-MS data revealed that β-strands II through IV were more dynamic in β-arrestin2 in the basal state, while the middle loop was more dynamic in β-arrestin1. With pre-activation, both β-arrestin1 and β-arrestin2 became more flexible, but broader regions of β-arrestin1 became flexible compared to β-arrestin2. The conformational differences between β-arrestin1 and β-arrestin2 in both the basal and pre-activated states might determine their different receptor selectivities and different cellular functions.

  4. Two tools for applying chromatographic retention data to the mass-based identification of peptides during hydrogen/deuterium exchange experiments by nano-liquid chromatography/matrix-assisted laser desorption/ionization mass spectrometry. (United States)

    Gershon, P D


    Two tools are described for integrating LC elution position with mass-based data in hydrogen-deuterium exchange (HDX) experiments by nano-liquid chromatography/matrix-assisted laser desorption/ionization mass spectrometry (nanoLC/MALDI-MS, a novel approach to HDX-MS). The first of these, 'TOF2H-Z Comparator', highlights peptides in HDX experiments that are potentially misidentified on the basis of mass alone. The program first calculates normalized values for the organic solvent concentration responsible for the elution of ions in nanoLC/MALDI HDX experiments. It then allows the solvent gradients for the multiple experiments contributing to an MS/MS-confirmed peptic peptide library to be brought into mutual alignment by iteratively re-modeling variables among LC parameters such as gradient shape, solvent species, fraction duration and LC dead time. Finally, using the program, high-probability chromatographic outliers can be flagged within HDX experimental data. The role of the second tool, 'TOF2H-XIC Comparator', is to normalize the LC chromatograms corresponding to all deuteration timepoints of all HDX experiments of a project, to a common reference. Accurate normalization facilitates the verification of chromatographic consistency between all ions whose spectral segments contribute to particular deuterium uptake plots. Gradient normalization in this manner revealed chromatographic inconsistencies between ions whose masses were either indistinguishable or separated by precise isotopic increments. Copyright © 2010 John Wiley & Sons, Ltd.

  5. Distinct structures of scrapie prion protein (PrPSc)-seeded versus spontaneous recombinant prion protein fibrils revealed by hydrogen/deuterium exchange. (United States)

    Smirnovas, Vytautas; Kim, Jae-Il; Lu, Xiaojun; Atarashi, Ryuichiro; Caughey, Byron; Surewicz, Witold K


    The detailed structures of prion disease-associated, partially protease-resistant forms of prion protein (e.g. PrP(Sc)) are largely unknown. PrP(Sc) appears to propagate itself by autocatalyzing the conformational conversion and oligomerization of normal prion protein (PrP(C)). One manifestation of PrP(Sc) templating activity is its ability, in protein misfolding cyclic amplification reactions, to seed the conversion of recombinant prion protein (rPrP) into aggregates that more closely resemble PrP(Sc) than spontaneously nucleated rPrP amyloids in terms of proteolytic fragmentation and infrared spectra. The absence of posttranslational modifications makes these rPrP aggregates more amenable to detailed structural analyses than bona fide PrP(Sc). Here, we compare the structures of PrP(Sc)-seeded and spontaneously nucleated aggregates of hamster rPrP by using H/D exchange coupled with mass spectrometry. In spontaneously formed fibrils, very slow H/D exchange in region approximately 163-223 represents a systematically H-bonded cross-beta amyloid core structure. PrP(Sc)-seeded aggregates have a subpopulation of molecules in which this core region extends N-terminally as far as to residue approximately 145, and there is a significant degree of order within residues approximately 117-133. The formation of tightly H-bonded structures by these more N-terminal residues may account partially for the generation of longer protease-resistant regions in the PrP(Sc)-seeded rPrP aggregates; however, part of the added protease resistance is dependent on the presence of SDS during proteolysis, emphasizing the multifactorial influences on proteolytic fragmentation patterns. These results demonstrate that PrP(Sc) has a distinct templating activity that induces ordered, systematically H-bonded structure in regions that are dynamic and poorly defined in spontaneously formed aggregates of rPrP.

  6. Metabolite identification of triptolide by data-dependent accurate mass spectrometric analysis in combination with online hydrogen/deuterium exchange and multiple data-mining techniques. (United States)

    Du, Fuying; Liu, Ting; Liu, Tian; Wang, Yongwei; Wan, Yakun; Xing, Jie


    Triptolide (TP), the primary active component of the herbal medicine Tripterygium wilfordii Hook F, has shown promising antileukemic and anti-inflammatory activity. The pharmacokinetic profile of TP indicates an extensive metabolic elimination in vivo; however, its metabolic data is rarely available partly because of the difficulty in identifying it due to the absence of appropriate ultraviolet chromophores in the structure and the presence of endogenous interferences in biological samples. In the present study, the biotransformation of TP was investigated by improved data-dependent accurate mass spectrometric analysis, using an LTQ/Orbitrap hybrid mass spectrometer in conjunction with the online hydrogen (H)/deuterium (D) exchange technique for rapid structural characterization. Accurate full-scan MS and MS/MS data were processed with multiple post-acquisition data-mining techniques, which were complementary and effective in detecting both common and uncommon metabolites from biological matrices. As a result, 38 phase I, 9 phase II and 8 N-acetylcysteine (NAC) metabolites of TP were found in rat urine. Accurate MS/MS data were used to support assignments of metabolite structures, and online H/D exchange experiments provided additional evidence for exchangeable hydrogen atoms in the structure. The results showed the main phase I metabolic pathways of TP are hydroxylation, hydrolysis and desaturation, and the resulting metabolites subsequently undergo phase II processes. The presence of NAC conjugates indicated the capability of TP to form reactive intermediate species. This study also demonstrated the effectiveness of LC/HR-MS(n) in combination with multiple post-acquisition data-mining methods and the online H/D exchange technique for the rapid identification of drug metabolites. Copyright © 2011 John Wiley & Sons, Ltd.

  7. Stainless-Steel Ball-Milling Method for Hydro-/Deutero-genation using H2O/D2O as a Hydrogen/Deuterium Source. (United States)

    Sawama, Yoshinari; Kawajiri, Takahiro; Niikawa, Miki; Goto, Ryota; Yabe, Yuki; Takahashi, Tohru; Marumoto, Takahisa; Itoh, Miki; Kimura, Yuuichi; Monguchi, Yasunari; Kondo, Shin-ichi; Sajiki, Hironao


    A one-pot continuous-flow method for hydrogen (deuterium) generation and subsequent hydrogenation (deuterogenation) was developed using a stainless-steel (SUS304)-mediated ball-milling approach. SUS304, especially zero-valent Cr and Ni as constituents of the SUS304, and mechanochemical processing played crucial roles in the development of the reactions. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Performance of a hydrogen/deuterium polarized gas target in a storage ring

    NARCIS (Netherlands)

    van Buuren, L.D.; Szczerba, D.; van den Brand, J.F.J.; Bulten, H.J.; Klous, S.; Mul, F.A.; Poolman, H.R.; Simani, M.C.


    The performance of a hydrogen/deuterium polarized gas target in a storage ring is presented. The target setup consisted of an atomic beam source, a cryogenic storage cell and a Breit-Rabi polarimeter. High frequency transition units were constructed to produce vector polarized hydrogen and

  9. Longitudinal Lelectroproduction of Charged Pions on Hydrogen, Deuterium, and Helium 3

    Energy Technology Data Exchange (ETDEWEB)

    Gaskell, David [Oregon State Univ., Corvallis, OR (United States)


    Conventional pictures of nuclear interactions, in which the pion mediates the long/medium range part of the nuclear force, predict an enhancement of the virtual pion cloud in nuclei relative to that in the free nucleon. Jefferson Lab Experiment E91003 measured charged pion electroproduction from Hydrogen, Deuterium, and Helium-3. The longitudinal cross section, which in the limit of pole dominance can be viewed as the quasifree knockout of a virtual pion, was extracted via a Rosenbluth separation. The longitudinal cross sections from Deuterium and Helium-3 were compared to Hydrogen to look for signatures of the nuclear pions.

  10. The ground state properties of spin-aligned atomic hydrogen, deuterium, and tritium (United States)

    Etters, R. D.; Dugan, J. V., Jr.; Palmer, R. W.


    The internal energy, pressure, and compressibility of ground-state, spin-aligned atomic hydrogen, deuterium, and tritium are calculated assuming that all pair interactions occur via the atomic triplet (spin-aligned) potential. The conditions required to obtain atomic hydrogen and its isotopes in bulk are discussed; such a development would be of value in propulsion systems because of the light mass and energetic recombination of atomic hydrogen. Results show that atomic triplet hydrogen and deuterium remain gaseous at 0 K, and that tritium forms a liquid with a binding energy of approximately -0.75 K per atom at a molar volume of 130 cu cm per mole. The pair distribution function for these systems is calculated, and the predicted superfluid behavior of atomic triplet hydrogen and tritium is briefly discussed.

  11. Individual Differences in Reactions to Inequitable Exchanges. (United States)

    Ellis, Barbara B.; Penner, Louis A.


    Investigates the role of sociopathic tendencies in reactions to inequitable exchanges in 273 males and females classified as high or low in sociopathy. Subjects read narratives of inequitable exchanges and assumed the role of the exploiter and the role of the victim in each. (Author/RH)

  12. Optimization of Feasibility Stage for Hydrogen/Deuterium Exchange Mass Spectrometry. (United States)

    Hamuro, Yoshitomo; Coales, Stephen J


    The practice of HDX-MS remains somewhat difficult, not only for newcomers but also for veterans, despite its increasing popularity. While a typical HDX-MS project starts with a feasibility stage where the experimental conditions are optimized and the peptide map is generated prior to the HDX study stage, the literature usually reports only the HDX study stage. In this protocol, we describe a few considerations for the initial feasibility stage, more specifically, how to optimize quench conditions, how to tackle the carryover issue, and how to apply the pepsin specificity rule. Two sets of quench conditions are described depending on the presence of disulfide bonds to facilitate the quench condition optimization process. Four protocols are outlined to minimize carryover during the feasibility stage: (1) addition of a detergent to the quench buffer, (2) injection of a detergent or chaotrope to the protease column after each sample injection, (3) back-flushing of the trap column and the analytical column with a new plumbing configuration, and (4) use of PEEK (or PEEK coated) frits instead of stainless steel frits for the columns. The application of the pepsin specificity rule after peptide map generation and not before peptide map generation is suggested. The rule can be used not only to remove falsely identified peptides, but also to check the sample purity. A well-optimized HDX-MS feasibility stage makes subsequent HDX study stage smoother and the resulting HDX data more reliable. Graphical Abstract ᅟ.

  13. Quantum interference effects in laser spectroscopy of muonic hydrogen, deuterium, and helium-3 (United States)

    Amaro, Pedro; Franke, Beatrice; Krauth, Julian J.; Diepold, Marc; Fratini, Filippo; Safari, Laleh; Machado, Jorge; Antognini, Aldo; Kottmann, Franz; Indelicato, Paul; Pohl, Randolf; Santos, José Paulo


    Quantum interference between energetically close states is theoretically investigated, with the state structure being observed via laser spectroscopy. In this work, we focus on hyperfine states of selected hydrogenic muonic isotopes, and on how quantum interference affects the measured Lamb shift. The process of photon excitation and subsequent photon decay is implemented within the framework of nonrelativistic second-order perturbation theory. Due to its experimental interest, calculations are performed for muonic hydrogen, deuterium, and helium-3. We restrict our analysis to the case of photon scattering by incident linear polarized photons and the polarization of the scattered photons not being observed. We conclude that while quantum interference effects can be safely neglected in muonic hydrogen and helium-3, in the case of muonic deuterium there are resonances with close proximity, where quantum interference effects can induce shifts up to a few percent of the linewidth, assuming a pointlike detector. However, by taking into account the geometry of the setup used by the CREMA collaboration, this effect is reduced to less than 0.2% of the linewidth in all possible cases, which makes it irrelevant at the present level of accuracy.

  14. A very light and thin liquid hydrogen/deuterium heat pipe target for COSY experiments (United States)

    Abdel-Bary, M.; Abdel-Samad, S.; Kilian, K.


    A liquid hydrogen/deuterium heat pipe (HP) target is used at the COSY external experiments TOF, GEM and MOMO. The target liquid is produced at a cooled condenser and guided through a central tube assisted by gravitation into the target cell. An aluminum condenser is used instead of copper, which requires less material, improves conductivities and provides shorter cooling down time. Residual condenser temperature fluctuations in the order of ≈0.4 K are reduced by using thermal resistances between the cooling machine and the condenser of the heat pipe combined with a controlled heating power. A new design with only a 7-mm-diameter HP has been developed. The diameter of the condenser part remains at 16 mm to provide enough condensation area. The small amount of material ensures short cooling down times. A cold gas deuterium HP target has been designed and developed which allows protons with energy ⩽1 MeV to be measured. A 7-mm-diameter HP is used to fill a cooling jacket around the D 2 gas cell with LH 2. The D 2 gas is stabilized at 200 mbar to allow for thin windows. Its density is increased by factor 15 compared to room temperature.

  15. Forging Colloidal Nanostructures via Cation Exchange Reactions (United States)


    Among the various postsynthesis treatments of colloidal nanocrystals that have been developed to date, transformations by cation exchange have recently emerged as an extremely versatile tool that has given access to a wide variety of materials and nanostructures. One notable example in this direction is represented by partial cation exchange, by which preformed nanocrystals can be either transformed to alloy nanocrystals or to various types of nanoheterostructures possessing core/shell, segmented, or striped architectures. In this review, we provide an up to date overview of the complex colloidal nanostructures that could be prepared so far by cation exchange. At the same time, the review gives an account of the fundamental thermodynamic and kinetic parameters governing these types of reactions, as they are currently understood, and outlines the main open issues and possible future developments in the field. PMID:26891471

  16. Propionate exchange reactions in methanogenic ecosystems. (United States)

    Boone, D R


    Propionate degradation was measured with [1-C]- and [2-C]propionate in an anaerobic digestor. When [1-C]propionate was used, label disappeared more rapidly from the propionate pool than when [2-C]propionate was used. This indicated that an exchange reaction involving the carboxyl group of propionate occurred. Labeled propionate added to digestor samples which were equilibrated with H(2) lost label from the carboxyl group but not from the methylene group.

  17. Competing Noncovalent Host-guest Interactions and H/D Exchange: Reactions of Benzyloxycarbonyl-Proline Glycine Dipeptide Variants with ND3 (United States)

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


    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.

  18. Propionate Exchange Reactions in Methanogenic Ecosystems † (United States)

    Boone, David R.


    Propionate degradation was measured with [1-14C]- and [2-14C]propionate in an anaerobic digestor. When [1-14C]propionate was used, label disappeared more rapidly from the propionate pool than when [2-14C]propionate was used. This indicated that an exchange reaction involving the carboxyl group of propionate occurred. Labeled propionate added to digestor samples which were equilibrated with H2 lost label from the carboxyl group but not from the methylene group. PMID:16346651

  19. Amplitude analysis for hypercharge exchange reactions

    CERN Document Server

    Barger, V


    The s channel helicity non-flip amplitudes for the line reversed reactions pi N to K( Sigma , Lambda ) and KN to pi ( Sigma , Lambda ) are determined directly from cross-section and polarization data at 4 GeV/c. Rigorous bounds are obtained on the magnitudes of the flip amplitudes, whose phases are assumed to be given by an exchange degenerate K*-K** Regge trajectory. The solution for the non-flip amplitude is unique and shows the following characteristics: (i) Im K* ( Delta lambda =0) has a 'cross-over' zero at t approximately=-0.15 in both Sigma and Lambda reactions, (ii) Im K** ( Delta lambda =0) has an approximate double zero near t approximately=-0.6 in Sigma reactions and a positive minimum there in Lambda reactions, (iii) Re K* ( Delta lambda =0) and Re K** ( Delta lambda =0) are less peripheral in character than their imaginary counter-part and have similar behaviour at alpha =0 to simple Regge poles. (12 refs).

  20. Asymmetric H-D exchange reactions of fluorinated aromatic ketones

    KAUST Repository

    Zhao, Yujun


    Chiral bicyclic guanidine catalyzes the asymmetric H-D exchange reactions. Up to 30% ee was achieved. DFT calculations were employed to elucidate and explain the origin of the reaction\\'s stereoselectivity. © 2012 The Royal Society of Chemistry.

  1. Heterogeneous Catalysis: Deuterium Exchange Reactions of Hydrogen and Methane (United States)

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


    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…

  2. Charge Exchange and Chemical Reactions with Trapped Th$^{3+}$

    CERN Document Server

    Churchill, L R; Chapman, M S


    We have measured the reaction rates of trapped, buffer gas cooled Th$^{3+}$ 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$^{3+}$ make them more prone to loss. Our results show that reactions of Th$^{3+}$ 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$^{3+}$ with oxygen and methane proceed primarily via charge exchange, while simultaneous charge exchange and chemical reaction occurs between Th$^{3+}$ and carbon dioxide. Loss rates of Th$^{3+}$ in helium are consistent with reaction with impurities in the gas. Reaction rates of Th$^{3+}$ with nitrogen and argon depend on the internal electronic configuration of the Th$^{3+}$.

  3. Microdroplet fusion mass spectrometry for fast reaction kinetics. (United States)

    Lee, Jae Kyoo; Kim, Samuel; Nam, Hong Gil; Zare, Richard N


    We investigated the fusion of high-speed liquid droplets as a way to record the kinetics of liquid-phase chemical reactions on the order of microseconds. Two streams of micrometer-size droplets collide with one another. The droplets that fused (13 μm in diameter) at the intersection of the two streams entered the heated capillary inlet of a mass spectrometer. The mass spectrum was recorded as a function of the distance x between the mass spectrometer inlet and the droplet fusion center. Fused droplet trajectories were imaged with a high-speed camera, revealing that the droplet fusion occurred approximately within a 500-μm radius from the droplet fusion center and both the size and the speed of the fused droplets remained relatively constant as they traveled from the droplet fusion center to the mass spectrometer inlet. Evidence is presented that the reaction effectively stops upon entering the heated inlet of the mass spectrometer. Thus, the reaction time was proportional to x and could be measured and manipulated by controlling the distance x. Kinetic studies were carried out in fused water droplets for acid-induced unfolding of cytochrome c and hydrogen-deuterium exchange in bradykinin. The kinetics of the former revealed the slowing of the unfolding rates at the early stage of the reaction within 50 μs. The hydrogen-deuterium exchange revealed the existence of two distinct populations with fast and slow exchange rates. These studies demonstrated the power of this technique to detect reaction intermediates in fused liquid droplets with microsecond temporal resolution.

  4. Charge exchange reactions as tests for structures of exotic nuclei

    CERN Document Server

    Karataglidis, S


    Charge exchange reactions serve as alternative tests of the structures of exotic nuclei. Of particular relevance is the (p, n) reaction, which is related to the Gamow-Teller matrix element. The (p, n) reaction is also related to (p, p′) in the case of transitions to the isobaric analogue state (IAS). There are few measurements of (p, n) reactions using exotic beams. We revisit the case of 6He(p, n)6Li and discuss apparent discrepancies with other available data.

  5. Development and Application of Ligand-Exchange Reaction Method ...

    African Journals Online (AJOL)

    Purpose: This paper presents an improved kinetic-spectrophotometric procedure for determining clonazepam (CZP) in pharmaceutical formulations and human serum. Methods: The method is based on ligand-exchange reaction. The reaction was followed spectrophotometrically by measuring the rate of change of ...

  6. Pinpointing changes in higher-order protein structure by hydrogen/deuterium exchange coupled to electron transfer dissociation mass spectrometry

    DEFF Research Database (Denmark)

    Rand, Kasper Dyrberg


    and new options for method optimization are discussed and exemplified. In addition, the real-world applicability of the HDX-ETD method to pinpoint conformational changes in a large 75 kDa protein complex of therapeutic interest is demonstrated. This feature highlights how the conformation and interactions...

  7. Continuous Consecutive Reactions with Inter-Reaction Solvent Exchange by Membrane Separation. (United States)

    Peeva, Ludmila; Da Silva Burgal, Joao; Heckenast, Zsofia; Brazy, Florine; Cazenave, Florian; Livingston, Andrew


    Pharmaceutical production typically involves multiple reaction steps with separations between successive reactions. Two processes which complicate the transition from batch to continuous operation in multistep synthesis are solvent exchange (especially high-boiling- to low-boiling-point solvent), and catalyst separation. Demonstrated here is membrane separation as an enabling platform for undertaking these processes during continuous operation. Two consecutive reactions are performed in different solvents, with catalyst separation and inter-reaction solvent exchange achieved by continuous flow membrane units. A Heck coupling reaction is performed in N,N-dimethylformamide (DMF) in a continuous membrane reactor which retains the catalyst. The Heck reaction product undergoes solvent exchange in a counter-current membrane system where DMF is continuously replaced by ethanol. After exchange the product dissolved in ethanol passes through a column packed with an iron catalyst, and undergoes reduction (>99 % yield). © 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  8. Analysis of data for hypercharge-exchange reactions

    CERN Document Server

    Irving, A C; Martin, A D


    The properties of the experimental data on the hypercharge- exchange reactions pi N to K Sigma , K Lambda and KN to pi Sigma , pi Lambda in the region (4/16)GeV/c are surveyed, with attention to line-reversal inequalities, reaction energy dependences in terms of effective trajectories, phase-energy properties, and SU/sub 3/ for exchanges. The s-channel helicity nonflip amplitudes at 4 and 14 GeV/c are determined, assuming an exchange degenerate K/sub V/*-K/sub T/* Regge- pole approximation for the flip amplitudes. In the impact-parameter representation only the imaginary parts of the pi N to KY nonflip amplitudes (or in terms of exchanges Im K/sub V/*) are found to be peripheral. All other nonflip amplitude components are central. An SU /sub 3/ comparison is made with K/sup -/p to eta Lambda , eta ' Lambda data. (28 refs).

  9. A stochastic modeling of isotope exchange reactions in glutamine synthetase (United States)

    Kazmiruk, N. V.; Boronovskiy, S. E.; Nartsissov, Ya R.


    The model presented in this work allows simulation of isotopic exchange reactions at chemical equilibrium catalyzed by a glutamine synthetase. To simulate the functioning of the enzyme the algorithm based on the stochastic approach was applied. The dependence of exchange rates for 14C and 32P on metabolite concentration was estimated. The simulation results confirmed the hypothesis of the ascertained validity for preferred order random binding mechanism. Corresponding values of K0.5 were also obtained.

  10. Perspective: Exchange reactions in thiolate-protected metal clusters

    Directory of Open Access Journals (Sweden)

    Yoshiki Niihori


    Full Text Available Thiolate-protected metal clusters can exchange ligands or metal atoms with other substances such as coexisting ligands, complexes, and metal clusters in solution. Using these reactions, it is possible to synthesize metal clusters with new physical and chemical properties. Although the occurrence of such reactions was recognized nearly 20 years ago, their details were not well understood. In recent years, techniques for the precise synthesis of metal clusters and their characterization have progressed considerably and, as a result, details of these reactions have been clarified. In this perspective, we focus on the most-studied thiolate-protected gold clusters and provide a summary of recent findings as well as future expectations concerning the exchange reactions of these clusters.

  11. Lock-exchange experiments with an autocatalytic reaction front (United States)

    Malham, I. Bou; Jarrige, N.; Martin, J.; Rakotomalala, N.; Talon, L.; Salin, D.


    A viscous lock-exchange gravity current corresponds to the reciprocal exchange of two fluids of different densities in a horizontal channel. The resulting front between the two fluids spreads as the square root of time, with a diffusion coefficient reflecting the buoyancy, viscosity, and geometrical configuration of the current. On the other hand, an autocatalytic reaction front between a reactant and a product may propagate as a solitary wave, namely, at a constant velocity and with a stationary concentration profile, resulting from the balance between molecular diffusion and chemical reaction. In most systems, the fluid left behind the front has a different density leading to a lock-exchange configuration. We revisit, with a chemical reaction, the classical situation of lock-exchange. We present an experimental analysis of buoyancy effects on the shape and the velocity of the iodate arsenous acid autocatalytic reaction fronts, propagating in horizontal rectangular channels and for a wide range of aspect ratios (1/3 to 20) and cylindrical tubes. We do observe stationary-shaped fronts, spanning the height of the cell and propagating along the cell axis. Our data support the contention that the front velocity and its extension are linked to each other and that their variations scale with a single variable involving the diffusion coefficient of the lock-exchange in the absence of chemical reaction. This analysis is supported by results obtained with lattice Bathnagar-Gross-Krook (BGK) simulations Jarrige et al. [Phys. Rev. E 81, 06631 (2010)], in other geometries (like in 2D simulations by Rongy et al. [J. Chem. Phys. 127, 114710 (2007)] and experiments in cylindrical tubes by Pojman et al. [J. Phys. Chem. 95, 1299 (1991)]), and for another chemical reaction Schuszter et al. [Phys. Rev. E 79, 016216 (2009)].

  12. Isotope exchange reactions involving HCO+ with CO: A theoretical approach (United States)

    Mladenović, M.; Roueff, E.


    Aims: We aim to investigate fractionation reactions involved in the 12C/13C, 16O/18O, and 17O balance. Methods: Full-dimensional rovibrational calculations were used to compute numerically exact rovibrational energies and thermal equilibrium conditions to derive the reaction rate coefficients. A nonlinear least-squares method was employed to represent the rate coefficients by analytic functions. Results: New exothermicities are derived for 30 isotopic exchange reactions of HCO+ with CO. For each of the reactions, we provide the analytic three-parameter Arrhenius-Kooij formula for both the forward reaction and backward reaction rate coefficients, that can further be used in astrochemical kinetic models. Rotational constants derived here for the 17O containing forms of HCO+ may assist detection of these cations in outer space.

  13. Geometric phase effects in ultracold hydrogen exchange reaction (United States)

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


    The role of the geometric phase effect on chemical reaction dynamics is explored by examining the hydrogen exchange process in the fundamental H+HD reaction. Results are presented for vibrationally excited HD molecules in the v = 4 vibrational level and for collision energies ranging from 1 μK to 100 K. It is found that, for collision energies below 3 K, inclusion of the geometric phase leads to dramatic enhancement or suppression of the reaction rates depending on the final quantum state of the HD molecule. The effect was found to be the most prominent for rotationally resolved integral and differential cross sections but it persists to a lesser extent in the vibrationally resolved and total reaction rate coefficients. However, no significant GP effect is present in the reactive channel leading to the D+H2 product or in the D+H2 (v=4,j=0) \\to HD+H reaction. A simple interference mechanism involving inelastic (nonreactive) and exchange scattering amplitudes is invoked to account for the observed GP effects. The computed results also reveal a shape resonance in the H+HD reaction near 1 K and the GP effect is found to influence the magnitude of the resonant part of the cross section. Experimental detection of the resonance may allow a sensitive probe of the GP effect in the H+HD reaction.

  14. Nucleon charge-exchange reactions at intermediate energy

    Energy Technology Data Exchange (ETDEWEB)

    Alford, W.P. [Western Ontario Univ., London, ON (Canada). Dept. of Physics]|[TRIUMF, Vancouver, BC (Canada); Spicer, B.M. [Melbourne Univ., Parkville, VIC (Australia). School of Physics


    An historical review of the development of ideas pertaining to Gamow-Teller giant resonances is given, and a description of the emergence of techniques for the study of charge exchange reactions - particularly the technical advances which yielded the recent volume of new date. The present status of charge exchange reactions is reviewed and assessed. Evidence is presented from the {sup 14}C(p,n) reaction for the dominance of the spin-isospin component of the nucleon-nucleon interaction in intermediate energy reactions. In (p,n) reactions the Gamow-Teller giant resonance dominates the spectra, with higher multipoles contributing. By contrast, in (n,p) reactions in the heavier nuclei, the Gamow-Teller transitions are substantially Pauli-blocked and the spin dipole resonance dominates, with contributions from higher multipoles. Discussions of the multipole decomposition process, used to obtain from the data the contributions of the different multipoles, and the contributions of the multipoles, are given. 226 refs., 19 figs.

  15. Investor Reaction to Mandatory Offers on the Warsaw Stock Exchange

    Directory of Open Access Journals (Sweden)

    Szymon Okoń


    Full Text Available The following paper aims to assess investor reaction to mandatory offers on the Warsaw Stock Exchange, which is important because knowledge about these reactions can be used to make better investment decisions. This paper highlights the importance of procedure in making a mandatory offer and its grounds in the Polish legal system. Additionally, it presents empirical research on the reactions of investors to mandatory offers on the Warsaw Stock Exchange. It has been provided that mandatory offers have a significant impact on the price of a company’s shares listed on the Warsaw Stock Exchange. Knowledge about the reactions of investors to a mandatory offer may be used when selecting securities for an investment portfolio. The findings may provide guidance in deciding whether to begin or end investment in the company, both for individual and institutional investors. The event study methodology approach used in the paper is regarded as valuable and can be the basis for further research in other areas of the capital market research, especially in the context of information efficiency.

  16. H-D exchange in metal carbene complexes: Structure of cluster (μ-H)(μ-OCD3)Os3(CO)9{:C(CD3)NC2H8O} (United States)

    Savkov, Boris; Maksakov, Vladimir; Kuratieva, Natalia


    X-ray and spectroscopic data for the new complex (μ-H)(μ-OCH3)Os3(CO)9{:C(CD3)NC2H8O} (2) obtained in the reaction of the (μ-H)(μ-Cl)Os3(CO)9{:C(CH3)NC2H8O} (1) with NaOCD3 in CD3OD solution are reported. It is shown that cluster 1 has the property of CH-acidity inherent of Fisher type carbenes. This had demonstrated using hydrogen deuterium exchange reaction in the presence of a strong base. Bridging chlorine to metoxide ligand substitution takes place during the reaction. The molecular structure of 2 is compared with known analogues.

  17. Exciting baryon resonances in isobar charge-exchange reactions (United States)

    Benlliure, J.; Rodriguez-Sanchez, J. L.; Vargas, J.; Alavarez-Pol, H.; Aumann, T.; Atkinson, J.; Ayyad, Y.; Beceiro, S.; Boretzky, K.; Chatillon, A.; Cortina, D.; Diaz, P.; Estrade, A.; Geissel, H.; Lenske, H.; Litvinov, Y.; Mostazo, M.; Paradela, C.; Pietri, S.; Prochazka, A.; Takechi, M.; Vidaña, I.; Weick, H.; Winfield, J.


    Isobaric charge-exchange reactions induced by different tin isotopes have been investigated at GSI. The high-resolving power of the FRS spectrometer made it possible to separate elastic and inelastic components in the missing-energy spectra of the ejectiles. The inelastic component was associated to the in-medium excitation of nucleon resonances such as the Delta and Roper resonances. These data are expected to contribute to better understand the in-medium properties of baryon resonances but also to investigate the abundance of protons and neutrons at the nuclear periphery.

  18. Alloyed copper chalcogenide nanoplatelets via partial cation exchange reactions. (United States)

    Lesnyak, Vladimir; George, Chandramohan; Genovese, Alessandro; Prato, Mirko; Casu, Alberto; Ayyappan, S; Scarpellini, Alice; Manna, Liberato


    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.

  19. Geometric Phase Appears in the Ultracold Hydrogen Exchange Reaction. (United States)

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


    Quantum reactive scattering calculations for the hydrogen exchange reaction H+H_{2}(v=4,j=0)→H+H_{2}(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.

  20. Population of 13Be with a Nucleon-Exchange Reaction (United States)

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


    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.

  1. Charge-exchange reactions with a secondary triton beam

    CERN Document Server

    Sherrill, B M; Austin, S M; Bazin, D; Berg, A; Berg, G P A; Caggiano, J; Daito, I; Fujimura, H; Fujita, Y; Fujiwara, M; Hara, K; Harakeh, M N; Jänecke, J; Kawabata, T; Navin, A; Roberts, D A; Steiner, M


    A secondary triton beam from fragmentation of 560-MeV alpha-particles has been used in a high-resolution (t, sup 3 He) charge-exchange experiment at intermediate bombarding energies. The experiment was carried out at the National Superconducting Cyclotron Laboratory using a sup 4 He beam from the K1200 cyclotron. The radioactive triton beam of (0.5-1.0)x10 sup 6 particles/s with a mean energy of 350 MeV was produced in a production target of the A1200 fragment separator and transported to the target position of the S800 magnetic spectrometer. Ray-tracing and dispersion-matching techniques were employed to detect sup 3 He particles from the sup 1 sup 2 C(t, sup 3 He) sup 1 sup 2 B reaction near 0 deg. . An energy resolution of DELTA E approx 160 keV or DELTA E/E approx 4.6x10 sup - sup 4 (FWHM) was achieved. This is an improvement over our previous results and opens the possibility for studying high-resolution (n,p)-type reactions at intermediate bombarding energies. (author)

  2. Ion-Isotopic Exchange Reaction Kinetics using Anion Exchange Resins Dowex 550A LC and Indion-930A

    Directory of Open Access Journals (Sweden)

    P.U. Singare


    Full Text Available The present paper deals with the characterization of ion exchange resins Dowex 550A LC and Indion-930A based on kinetics of ion-isotopic exchange reactions for which the short lived radioactive isotopes 131I and 82Br were used as a tracers. The study was performed for different concentration of ionic solution varying from 0.001 mol/L to 0.004 mol/L and temperature in the range of 30.0 °C to 45.0 °C. The results indicate that as compared to bromide ion-isotopic exchange reaction, iodide exchange reaction take place at the faster rate. For both the ion-isotopic exchange reactions, under identical experimental conditions, the values of specific reaction rate increases with increase in the ionic concentration and decreases with rise in temperature. It was observed that at 35.00C, 1.000 g of ion exchange resins and 0.002 mol/L labeled iodide ion solution for iodide ion-isotopic exchange reaction, the values of specific reaction rate (min-1, amount of ion exchanged (mmol, initial rate of ion exchange (mmol/min and log Kd were 0.270, 0.342, 0.092 and 11.8 respectively for Dowex 550A LC resin, which was higher than the respective values of 0.156, 0.241, 0.038 and 7.4 as that obtained for Indion-930A resins. From the results, it appears that Dowex 550A LC resins show superior performance over Indion-930A resins under identical experimental conditions.

  3. Investigation of the role of the micro-porous layer in polymer electrolyte fuel cells with hydrogen deuterium contrast neutron radiography. (United States)

    Cho, Kyu Taek; Mench, Matthew M


    In this study, the high resolution hydrogen-deuterium contrast radiography method was applied to elucidate the impact of the micro-porous layer (MPL) on water distribution in the porous fuel cell media. At the steady state, deuterium replaced hydrogen in the anode stream, and the large difference in neutron attenuation of the D(2)O produced at the cathode was used to track the produced water. It was found that the water content peaked in the cathode-side diffusion media (DM) for the cell without MPL, but with an MPL on the anode and cathode DM, the peak water amount was pushed toward the anode, resulting in a relatively flattened water profile through components and demonstrating a liquid barrier effect. Additionally, the dynamic water behavior in diffusion media was analyzed to understand the effect of a MPL and operating conditions. The water content in the DM changed with applied current, although there is a significant amount of residual liquid content that does not appear to be part of capillary channels. The effect of the MPL on irreducible saturation in DM and cell performance was also investigated.

  4. Cryogenic tritium-hydrogen-deuterium and deuterium-tritium layer implosions with high density carbon ablators in near-vacuum hohlraums

    Energy Technology Data Exchange (ETDEWEB)

    Meezan, N. B., E-mail:; Hopkins, L. F. Berzak; Pape, S. Le; Divol, L.; MacKinnon, A. J.; Döppner, T.; Ho, D. D.; Jones, O. S.; Khan, S. F.; Ma, T.; Milovich, J. L.; Pak, A. E.; Ross, J. S.; Thomas, C. A.; Benedetti, L. R.; Bradley, D. K.; Celliers, P. M.; Clark, D. S.; Field, J. E.; Haan, S. W. [Lawrence Livermore National Laboratory, P.O. Box 808, Livermore, California 94551-0808 (United States); and others


    High Density Carbon (or diamond) is a promising ablator material for use in near-vacuum hohlraums, as its high density allows for ignition designs with laser pulse durations of <10 ns. A series of Inertial Confinement Fusion (ICF) experiments in 2013 on the National Ignition Facility [Moses et al., Phys. Plasmas 16, 041006 (2009)] culminated in a deuterium-tritium (DT) layered implosion driven by a 6.8 ns, 2-shock laser pulse. This paper describes these experiments and comparisons with ICF design code simulations. Backlit radiography of a tritium-hydrogen-deuterium (THD) layered capsule demonstrated an ablator implosion velocity of 385 km/s with a slightly oblate hot spot shape. Other diagnostics suggested an asymmetric compressed fuel layer. A streak camera-based hot spot self-emission diagnostic (SPIDER) showed a double-peaked history of the capsule self-emission. Simulations suggest that this is a signature of low quality hot spot formation. Changes to the laser pulse and pointing for a subsequent DT implosion resulted in a higher temperature, prolate hot spot and a thermonuclear yield of 1.8 × 10{sup 15} neutrons, 40% of the 1D simulated yield.

  5. Kinetics and Mechanism of the Ligand Exchange Reaction Between ...

    African Journals Online (AJOL)


    Visible spectrophotometry is used to study the kinetics of ligand exchange in the system Ni(salpn)/H2salen with or without triethylamine (NEt3) and ... coordination chemistry.4,5 However, the kinetics of polydentate ligands exchange ..... chlorides and tetraaza Schiff bases: synthesis and characterization of some novel tin(IV) ...

  6. The labeling of unsaturated gamma-hydroxybutyric acid by heavy isotopes of hydrogen: iridium complex-mediated H/D exchange by C-H bond activation vs reduction by boro-deuterides/tritides

    Czech Academy of Sciences Publication Activity Database

    Marek, Aleš; Pedersen, M. H. F.; Vogensen, S. B.; Clausen, R. P.; Frolund, B.; Elbert, Tomáš


    Roč. 59, č. 12 (2016), s. 476-483 ISSN 0362-4803 Institutional support: RVO:61388963 Keywords : C-H activation * borotritides * hydrogen/deuterium exchange * iridium catalyst * tritium-labeled gamma-hydroxybutyric acid Subject RIV: CC - Organic Chemistry Impact factor: 1.745, year: 2016

  7. Theoretical investigation of isotope exchange reaction in tritium-contaminated mineral oil in vacuum pump. (United States)

    Dong, Liang; Xie, Yun; Du, Liang; Li, Weiyi; Tan, Zhaoyi


    The mechanism of the isotope exchange reaction between molecular tritium and several typical organic molecules in vacuum pump mineral oil has been investigated by density functional theory (DFT), and the reaction rates are determined by conventional transition state theory (TST). The tritium-hydrogen isotope exchange reaction can proceed with two different mechanisms, the direct T-H exchange mechanism and the hyrogenation-dehydrogenation exchange mechanism. In the direct exchange mechanism, the titrated product is obtained through one-step via a four-membered ring hydrogen migration transition state. In the hyrogenation-dehydrogenation exchange mechanism, the T-H exchange could be accomplished by the hydrogenation of the unsaturated bond with tritium followed by the dehydrogenation of HT. Isotope exchange between hydrogen and tritium is selective, and oil containing molecules with OH and COOH groups can more easily exchange hydrogen for tritium. For aldehydes and ketones, the ability of T-H isotope exchange can be determined by the hydrogenation of T2 or the dehydrogenation of HT. The molecules containing one type of hydrogen provide a single product, while the molecules containing different types of hydrogens provide competitive products. The rate constants are presented to quantitatively estimate the selectivity of the products. Copyright © 2015 Elsevier B.V. All rights reserved.

  8. An Asymmetric Runaway Domain Swap Antithrombin Dimer as a Key Intermediate for Polymerization Revealed by Hydrogen/Deuterium-Exchange Mass Spectrometry

    DEFF Research Database (Denmark)

    Trelle, Morten Beck; Pedersen, Shona; Østerlund, Eva Christina


    Antithrombin deficiency is associated with increased risk of venous thrombosis. In certain families, this condition is caused by pathogenic polymerization of mutated antithrombin in the blood. To facilitate future development of pharmaceuticals against antithrombin polymerization, an improved und...... strongly supports a β4A-β5A β-hairpin runaway domain swap mechanism for antithrombin polymerization. HDX-MS thus holds exceptional promise as an enabling analytical technique in the efforts toward future pharmacological intervention with protein polymerization and associated diseases....

  9. Removal of N-Linked Glycosylations at Acidic pH by PNGase A Facilitates Hydrogen/Deuterium Exchange Mass Spectrometry Analysis of N-Linked Glycoproteins

    DEFF Research Database (Denmark)

    Jensen, Pernille Foged; Comamala Grau, Gerard; Trelle, Morten Beck


    -HDX) and the utility of this approach is demonstrated during analysis of the monoclonal antibody Trastuzumab for which it has been shown that the native conformational dynamics is dependent on the N-linked glycan. In summary, the HDX-MS workflow with integrated PNGase A deglycosylation enables analysis of the native...

  10. Conformational preludes to the latency transition in PAI-1 as determined by atomistic computer simulations and hydrogen/deuterium-exchange mass spectrometry

    DEFF Research Database (Denmark)

    Petersen, Michael; Madsen, Jeppe B; Jørgensen, Thomas J D


    as ligand binding in this region can accelerate or decelerate the conformational inactivation. Plasticity in this region may thus be mechanistically linked to the conformational change, possibly through facilitation of further unfolding of the hydrophobic core, as previously reported. This study provides...... a promising example of how computer simulations can help tether out mechanisms of serpin function and dysfunction at a spatial and temporal resolution that is far beyond the reach of any experiment....

  11. Conditions on exchange mechanisms for polarization effects in inclusive reactions

    CERN Document Server

    Salin, P


    In the framework of Mueller-Regge phenomenology the conditions under which one could expect to observe polarization effects in the fragmentation region for inclusive relations are investigated. On the basis of kinematical considerations and parity relations only, it is found that this requires exchange of states with mixed naturalities. (9 refs).

  12. Evaluation of Soil Reaction, Exchangeable Acidity and Cation ...

    African Journals Online (AJOL)

    Adequate application of both organic and inorganic fertilizers will improve the organic matter content which will increase the level of CEC of the soils and also liming was recommended to rise the pH of the soils for enhanced production capacity in the study area. Keywords: Exchangeable Acidity, Soil, Pedons and Fertility ...

  13. Synthesis and ligand exchange reactions of (pentamethylcyclopentadienyl)lanthanum aryloxides

    NARCIS (Netherlands)

    Heeres, H.J.; Teuben, J.H.

    Cp*La(OAr)2 (Cp* = η5-C5Me5) is easily accessible by the reaction of La(OAr)3 with Cp*Li. Addition of THF yields the adduct Cp*La(OAr)2(THF)2. Both compounds disproportionate in solution with formation of equilibrium mixtures with comparable amounts of Cp*La(OAr)2, La(OAr)3 and Cp*2LaOAr. The

  14. Examining the reaction of monetary policy to exchange rate changes: A nonlinear ARDL approach (United States)

    Manogaran, Lavaneesvari; Sek, Siok Kun


    Previous studies showed the exchange rate changes can have significant impacts on macroeconomic performance. Over fluctuation of exchange rate may lead to economic instability. Hence, monetary policy rule tends to react to exchange rate changes. Especially, in emerging economies where the policy-maker tends to limit the exchange rate movement through interventions. In this study, we seek to investigate how the monetary policy rule reacts to exchange rate changes. The nonlinear autoregressive distributed lag (NARDL) model is applied to capture the asymmetric effect of exchange rate changes on monetary policy reaction function (interest rate). We focus the study in ASEAN5 countries (Indonesia, Malaysia, Philippines, Thailand and Singapore). The results indicated the existence of asymmetric effect of exchange rates changes on the monetary reaction function for all ASEAN5 countries in the long-run. Where, in majority of the cases the monetary policy is reacting to the appreciation and depreciation of exchange rate by raising the policy rate. This affirms the intervention of policymakers with the `fear of floating' behavior.

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

    Energy Technology Data Exchange (ETDEWEB)

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


    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.

  16. State-to-state quantum dynamics of the H + HBr reaction: competition between the abstraction and exchange reactions. (United States)

    Xie, Changjian; Jiang, Bin; Xie, Daiqian


    Quantum state-to-state dynamics for the H + HBr(υ(i) = 0, j(i) =0) reaction was studied on an accurate ab intio potential energy surface for the electronic ground state of BrH(2). Both the H + HBr → H(2) + Br abstraction reaction and the H' + HBr → H'Br + H exchange reaction were investigated up to a collision energy of 2.0 eV. It was found that the abstraction channel is dominant at lower collision energies, while the exchange channel becomes dominant at higher collision energies. The total integral cross section of the abstraction reaction at a collision energy of 1.6 eV was found to be 1.37 Å(2), which is larger than a recent quantum mechanical result (1.06 Å(2)) and still significantly smaller than the experimental value (3 ± 1 Å(2)). Meanwhile, similar to the previous theoretical study, our calculations also predicted much hotter product rotational state distributions than those from the experimental study. This suggests that further experimental investigations are highly desirable to elucidate the dynamic properties of the title reactions.

  17. Energetics and control of ultracold isotope-exchange reactions between heteronuclear dimers in external fields (United States)

    Tomza, Michal


    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.

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

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


    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.

  19. Preparation of radioactive acetyl-l-carnitine by an enzymatic exchange reaction

    Energy Technology Data Exchange (ETDEWEB)

    Emaus, R.; Bieber, L.L.


    A rapid method for the preparation of (1-/sup 14/C)acetyl-L-carnitine is described. The method involves exchange of (1-/sup 14/C)acetic acid into a pool of unlabeled acetyl-L-carnitine using the enzymes acetyl-CoA synthetase and carnitine acetyltransferase. After isotopic equilibrium is attained, radioactive acetylcarnitine is separated from the other reaction components by chromatography on Dowex 1 (C1/sup -/) anion exchange resin. One of the procedures used to verify the product (1-/sup 14/C)acetyl-L-carnitine can be used to synthesize (3S)-(5-/sup 14/C)citric acid.

  20. Symmetry and the geometric phase in ultracold hydrogen-exchange reactions. (United States)

    Croft, J F E; Hazra, J; Balakrishnan, N; Kendrick, B K


    Quantum reactive scattering calculations are reported for the ultracold hydrogen-exchange reaction and its non-reactive atom-exchange isotopic counterparts, proceeding from excited rotational states. It is shown that while the geometric phase (GP) does not necessarily control the reaction to all final states, one can always find final states where it does. For the isotopic counterpart reactions, these states can be used to make a measurement of the GP effect by separately measuring the even and odd symmetry contributions, which experimentally requires nuclear-spin final-state resolution. This follows from symmetry considerations that make the even and odd identical-particle exchange symmetry wavefunctions which include the GP locally equivalent to the opposite symmetry wavefunctions which do not. It is shown how this equivalence can be used to define a constant which quantifies the GP effect and can be obtained solely from experimentally observable rates. This equivalence reflects the important role that discrete symmetries play in ultracold chemistry and highlights the key role that ultracold reactions can play in understanding fundamental aspects of chemical reactivity more generally.

  1. Synthesis and anion-exchange reactions of a new anionic clay, α-magnesium hydroxide. (United States)

    Nethravathi, C; Rajamathi, Jacqueline T; George, Preeta; Rajamathi, Michael


    A new anionic clay, α-magnesium hydroxide, was synthesized by hydrolysis of magnesium acetate in propylene glycol. The structure of this α-hydroxide is similar to that of hydrotalcites. It consists of positively charged magnesium hydroxide layers arising out of partial protonation of the hydroxyl groups of the [Mg(OH)(2)] layers and loosely held anions in the interlayer region. As expected it ages readily in water to give β-magnesium hydroxide, brucite. While anion-exchange reactions of α-magnesium hydroxide could not be carried out in aqueous medium a number of anion-exchange reactions could be carried out successfully in ethanol medium. Copyright © 2010 Elsevier Inc. All rights reserved.

  2. Activity of some disiloxanes toward the cation exchange resin-catalyst in the siloxane equilibration reaction

    Directory of Open Access Journals (Sweden)



    Full Text Available The relative activities of four disiloxanes toward the cation exchange resin, which was used as an equilibration catalyst, were determined in such a way that the equilibrium initially present in an arbitrary chosen equilibrate was disturbed by adding the respective disiloxanes to it, and then by recording the viscosity of the equilibrating mixtures as a function of reaction time. As a result, a set of different viscosity-reaction time relationships was obtained, which implies different activities of disiloxanes toward the catalyst. In this way the following decreasing order of acitivites was established: 1,3-tetramethyldisiloxane > 1,3-divinyltetramethyldisiloxane > hexamethyldisiloxane > 1,3-bis(3-carboxypropyltetramethyldisiloxane.

  3. Phenomenological characteristics of absorption in charge- and hypercharge-exchange reactions

    CERN Document Server

    Sadoulet, B


    The author tries to explain in a unique framework charge- and hypercharge-exchange reactions above 3 GeV/c. His approach is based on exchange degenerate and SU(3) symmetric Regge poles to which absorption corrections are applied. In the absence of a firm theoretical basis for the corrections he adopts the approach of fixing the Regge poles through theoretical and phenomenological considerations; he then determines what kind of absorption he should apply. At intermediate energy (around 5 GeV/c) his results indicate complete absorption of the s-wave amplitude. Of the two terms 1 and e /sup -i pi alpha / of the Regge signature factor, the latter should be more strongly absorbed. This effect may explain especially the breaking of line-reversal symmetry for hypercharge-exchange reactions, pi /sup -/p to pi /sup 0/n polarization data, and the difference of peripherality of rho - omega and A/sub 2/-f/sub 0/ contributions. In addition, K-exchange in pp to Lambda Lambda has been studied. (50 refs).

  4. Macroscopic models for charge exchange reactions in N not = Z nuclei

    Energy Technology Data Exchange (ETDEWEB)

    Stringari, S.; Lipparini, E.


    Vlasov equations in the isospin channels are derived in the framework of the time dependent Hartree-Fock theory. The local equilibrium (hydrodynamic) approximation is then considered and applied to study isovector giant resonances excited in charge exchange reactions and -/ inclusive capture in N not = Z nuclei. The theoretical predictions well account for the observed energy splitting between different isospin fragments and for the quenching of the Z/ = +1 strength.

  5. Isotope exchange reactions on ceramic breeder materials and their effect on tritium inventory

    Energy Technology Data Exchange (ETDEWEB)

    Nishikawa, M.; Baba, A. [Kyushu Univ., Fukuoka (Japan). Faculty of Engineering; Kawamura, Y.; Nishi, M.


    Though lithium ceramic materials such as Li{sub 2}O, LiAlO{sub 2}, Li{sub 2}ZrO{sub 3}, Li{sub 2}TiO{sub 3} and Li{sub 4}SiO{sub 4} are considered as breeding materials in the blanket of a D-T fusion reactor, the release behavior of the bred tritium in these solid breeder materials has not been fully understood. The isotope exchange reaction rate between hydrogen isotopes in the purge gas and tritium on the surface of breeding materials have not been quantified yet, although helium gas with hydrogen or deuterium is planned to be used as the blanket purge gas in the recent blanket designs. The mass transfer coefficient representing the isotope exchange reaction between H{sub 2} and D{sub 2}O or that between D{sub 2} and H{sub 2}O in the ceramic breeding materials bed is experimentally obtained in this study. Effects of isotope exchange reactions on the tritium inventory in the bleeding blanket is discussed based on data obtained in this study where effects of diffusion of tritium in the grain, absorption of water in the bulk of grain, and adsorption of water on the surface of grain, together with two types of isotope exchange reactions are considered. The way to estimate the tritium inventory in a Li{sub 2}ZrO{sub 3} blanket used in this study shows a good agreement with data obtained in such in-situ experiments as MOZART, EXOTIC-5, 6 and TRINE experiments. (author)

  6. Properties of ionic liquids on Au surfaces: non-conventional anion exchange reactions with carbonate. (United States)

    Ratel, Mathieu; Branca, Mathieu; Breault-Turcot, Julien; Zhao, Sandy Shuo; Chaurand, Pierre; Schmitzer, Andreea R; Masson, Jean-Francois


    A simple anion metathesis in diluted aqueous carbonate at room temperature affords 1-(12-mercaptododecyl)-3-methyl-imidazolium carbonate (MDMI-HCO(3)) from MDMI salts self-assembled on gold films and nanoparticles. The properties of MDMI-SAM differ from MDMI in solution, for which the anion exchange reaction does not proceed. This journal is © The Royal Society of Chemistry 2011

  7. Moving Towards a State of the Art Charge-Exchange Reaction Code (United States)

    Poxon-Pearson, Terri; Nunes, Filomena; Potel, Gregory


    Charge-exchange reactions have a wide range of applications, including late stellar evolution, constraining the matrix elements for neutrinoless double β-decay, and exploring symmetry energy and other aspects of exotic nuclear matter. Still, much of the reaction theory needed to describe these transitions is underdeveloped and relies on assumptions and simplifications that are often extended outside of their region of validity. In this work, we have begun to move towards a state of the art charge-exchange reaction code. As a first step, we focus on Fermi transitions using a Lane potential in a few body, Distorted Wave Born Approximation (DWBA) framework. We have focused on maintaining a modular structure for the code so we can later incorporate complications such as nonlocality, breakup, and microscopic inputs. Results using this new charge-exchange code will be shown compared to the analysis in for the case of 48Ca(p,n)48Sc. This work was supported in part by the National Nuclear Security Administration under the Stewardship Science Academic Alliances program through the U.S. DOE Cooperative Agreement No. DE- FG52-08NA2855.

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

    Energy Technology Data Exchange (ETDEWEB)

    McLane, V.


    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Vrakking, Marcus Johannes Jacobus [Univ. of California, Berkeley, CA (United States)


    The hydrogen exchange reaction H + H2 → H2 + 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 + H2 reaction. A crossed molecular beam arrangement is used, in which a photolytic D atom beam is crossed by a pulsed beam of H2 molecules. DH molecules formed in the D + H2 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 6.8 103 molecules/cc. This thesis does not contain experimental results for the D + H2 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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Vrakking, M.J.J.


    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.

  11. A solid-state cation exchange reaction to form multiple metal oxide heterostructure nanowires. (United States)

    Chen, Y H; Huang, C W; Yeh, P H; Chen, J Y; Lin, T Y; Chang, C F; Wu, W W


    Metal oxide nanostructures have been investigated extensively due to their wide range of physical properties; zinc oxide is one of the most promising materials. It exhibits fascinating functional properties and various types of morphologies. In particular, ZnO heterostructures have attracted great attention because their performance can be modified and further improved by the addition of other materials. In this study, we successfully transformed ZnO nanowires (NWs) into multiple ZnO/Al 2 O 3 heterostructure NWs via a solid-state cation exchange reaction. The experiment was carried out in situ via an ultrahigh vacuum transmission electron microscope (UHV-TEM), which was equipped with a video recorder. Moreover, we analyzed the structure and composition of the heterostructure NWs by Cs-corrected STEM equipped with EDS. Based on these experimental results, we inferred a cation exchange reaction ion path model. Additionally, we investigated the defects that appeared after the cation reaction, which resulted from the remaining zinc ions. These multiple heterostructure ZnO/Al 2 O 3 NWs exhibited excellent UV sensing sensitivity and efficiency.

  12. Novel Hydrophobic Pt/Inorganic Catalyst Used in Hydrogen Isotope Exchange Reaction

    Directory of Open Access Journals (Sweden)

    JIA Qing-qing1;HU Shi-lin1;FENG Xiao-yan2;LIU Ya-ming1


    Full Text Available To improve the performance of hydrophobic catalyst and extend its using range, this research adopted the porous columnar inorganic carriers (ø=5 mm to prepare the hydrophobic catalyst used in hydrogen isotopes exchange reaction, the hydrophilic carriers became hydrophobic with the nanostructured CeO2 coating and the catalyst were then fabricated by convenient impregnation method. The samples were characterized by XRD、SEM、EDX、XPS and CO adsorption. The catalytic activity were tested through catalytic exchange reaction between hydrogen and saturated water vapor to investigate the effect of micro structured CeO2 on the catalyst properties. It turned out that the nano-CeO2 coating could build favorable hydrophobic environment for the catalysts and had almost no influence on the pore structure properties of carriers. Although the hydrophobic coating would lead to the decrease of Pt particle dispersion and metallic Pt content, it could make the Pt particles mostly deposit on the surface layer of the catalysts, which would make more Pt particle participate in the reaction at the same time. The catalytic activity of the novel Pt/inorganic catalyst could reach to 80% of the mature Pt/organic catalyst. After being flushed by water for 12 weeks, the catalytic activity of Pt/inorganic catalyst decreased less than 5%. The novel hydrophobic catalyst with good activity and stability was practical and had great application prospects.

  13. Excitation of Nucleon Resonances in Heavy-Ion Charge-Exchange Reactions (United States)

    Benlliure, J.; Vargas, J.; Alvarez-Pol, H.; Aumann, T.; Atkinson, J.; Ayyad, Y.; Beceiro, S.; Borezky, K.; Chatillon, A.; Cortina, D.; Diaz, P.; Estrade, A.; Geissel, H.; Lenske, H.; Litvinov, Y.; Mostazo, M.; Paradela, C.; Pietri, S.; Prochazka, A.; Taieb, J.; Takechi, M.; Vidaña, I.; Weick, H.; Winfield, J.

    Isobaric charge-exchange reactions induced by different tin isotopes have been investigated at GSI. The high-resolving power of the FRS spectrometer made it possible to separate elastic and inelastic components in the missing-energy spectra of the ejectiles. The inelastic component was associated to the in-medium excitation of nucleon resonances such as the Delta and Roper resonances. These data are expected to contribute to better understand the role of subnuclear degrees of freedom in three body forces or the missing strength in Gamow-Teller transitions but also to investigate the abundance of protons and neutrons at the nuclear periphery.

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

    CERN Document Server

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


    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 Cd2+ or Hg2+, 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 Cd2+ and Hg2+ 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 t...

  15. Mineral carbonation of gaseous carbon dioxide using a clay-hosted cation exchange reaction. (United States)

    Kang, Il-Mo; Roh, Ki-Min


    The mineral carbonation method is still a challenge in practical application owing to: (1) slow reaction kinetics, (2) high reaction temperature, and (3) continuous mineral consumption. These constraints stem from the mode of supplying alkaline earth metals through mineral acidification and dissolution. Here, we attempt to mineralize gaseous carbon dioxide into calcium carbonate, using a cation exchange reaction of vermiculite (a species of expandable clay minerals). The mineralization is operated by draining NaCI solution through vermiculite powders and continuously dropping into the pool of NaOH solution with CO2 gas injected. The mineralization temperature is regulated here at 293 and 333 K for 15 min. As a result of characterization, using an X-ray powder diffractometer and a scanning electron microscopy, two types of pure CaCO3 polymorphs (vaterite and calcite) are identified as main reaction products. Their abundance and morphology are heavily dependent on the mineralization temperature. Noticeably, spindle-shaped vaterite, which is quite different from a typical vaterite morphology (polycrystalline spherulite), forms predominantly at 333 K (approximately 98 wt%).

  16. Modeling of hydrogen/deuterium dynamics and heat generation on palladium nanoparticles for hydrogen storage and solid-state nuclear fusion. (United States)

    Tanabe, Katsuaki


    We modeled the dynamics of hydrogen and deuterium adsorbed on palladium nanoparticles including the heat generation induced by the chemical adsorption and desorption, as well as palladium-catalyzed reactions. Our calculations based on the proposed model reproduce the experimental time-evolution of pressure and temperature with a single set of fitting parameters for hydrogen and deuterium injection. The model we generated with a highly generalized set of formulations can be applied for any combination of a gas species and a catalytic adsorbent/absorbent. Our model can be used as a basis for future research into hydrogen storage and solid-state nuclear fusion technologies.

  17. Modeling of hydrogen/deuterium dynamics and heat generation on palladium nanoparticles for hydrogen storage and solid-state nuclear fusion

    Directory of Open Access Journals (Sweden)

    Katsuaki Tanabe


    Full Text Available We modeled the dynamics of hydrogen and deuterium adsorbed on palladium nanoparticles including the heat generation induced by the chemical adsorption and desorption, as well as palladium-catalyzed reactions. Our calculations based on the proposed model reproduce the experimental time-evolution of pressure and temperature with a single set of fitting parameters for hydrogen and deuterium injection. The model we generated with a highly generalized set of formulations can be applied for any combination of a gas species and a catalytic adsorbent/absorbent. Our model can be used as a basis for future research into hydrogen storage and solid-state nuclear fusion technologies.

  18. Enhanced catalytic performance of copper-exchanged SAPO-34 molecular sieve in methanol-to-olefin reaction. (United States)

    Kim, Sun Jung; Park, Ji Won; Lee, Kwang Young; Seo, Gon; Song, Mee Kyung; Jeong, Soon-Yong


    Methanol-to-olefin (MTO) reaction over copper-exchanged SAPO-34 catalysts was investigated in order to extend their catalyst life. The exchange of copper ions into the cages of an SAPO-34 molecular sieve was confirmed by ESR, XPS, and 129Xe NMR techniques. Copper ions located in its cages considerably reduced its deactivation rate in the MTO reaction, while those dispersed on the external surface of the SAPO-34 molecular sieve accelerated the deactivation due to the limited mass transfer through the pore entrances. The 13C NMR and UV-VIS spectroscopy investigations of the materials occluded on the copper-exchanged SAPO-34 catalysts during the MTO reaction clearly showed that the copper ions exchanged in the cages suppressed the further condensation of alkyl aromatics to large, fused polycyclic aromatic hydrocarbons (PAHs). Theoretical calculations for the SAPO-34 and copper-exchanged SAPO-34 molecular sieves supported this observation because copper ions located in the cages stabilized the alkyl aromatics. Therefore, the exchange of copper ions into the SAPO-34 molecular sieve stabilized the reactive intermediates, alkyl aromatics, of the MTO reaction and suppressed their further condensation to PAHs, thereby slowing the deactivation.

  19. Stock Price Reaction to Announcements of Right Issues and Debenture Issues: Evidence from Colombo Stock Exchange

    Directory of Open Access Journals (Sweden)

    Udani Chathurika Edirisinghe


    Full Text Available This study investigates the stock market reaction for right issues and debenture issues of Colombo Stock Exchange (CSE during the period of 2005 to 2011 while providing evidence for the research question “how do stock prices react to the debt and equity issue announcements of listed companies in CSE?” In investigating the ex-ante and ex-post market reactions the study employees event study methodology, while predicting abnormal returns, based on three alternative normal/expected returns modeling methods, namely Mean Adjusted Model, Market Adjusted Model, and Capital Asset Pricing Model. When testing the alternative hypothesis, whether stock prices significantly reacts to the announcement of right & debenture issues, results of all models show positive market reaction during the 30 days prior to the announcement and react negatively from 2 days after the announcements for right issues, but for debenture issues market reacted negatively during the period prior to debenture issues and continue to do the same during the post event period. Although the magnitude and significance of abnormal return generated through three alternatives methods differ, the pattern of the CAAR of all models are similar. Thus, as far as the speed of the price adjustment is concerned it seems that the CSE is not efficient.

  20. Effect of chelate dynamics on water exchange reactions of paramagnetic aminopolycarboxylate complexes. (United States)

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


    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

  1. A numerical modelling of gas exchange mechanisms between air and turbulent water with an aquarium chemical reaction (United States)

    Nagaosa, Ryuichi S.


    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.

  2. Reprint of: A numerical modelling of gas exchange mechanisms between air and turbulent water with an aquarium chemical reaction (United States)

    Nagaosa, Ryuichi S.


    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.

  3. Non-coherent contributions in charge-exchange reactions and η-η{sup '} mixing

    Energy Technology Data Exchange (ETDEWEB)

    Nekrasov, M.L. [NRC ' ' Kurchatov Institute' ' , Institute for High Energy Physics, Protvino (Russian Federation)


    We analyse K{sup -}p → (η,η{sup '},π{sup 0})Λ on the basis of the fit of data in a wide region of energies, and π{sup -}p → (η,η{sup '})n at the energies of GAMS-4π. We show that disagreements between the data and the predictions of Regge theory may be explained by the mode change of summation of intermediate contributions at increasing energy, from coherent to non-coherent. A method of experimental measurement of the non-coherent contributions is proposed. On the basis of available data on the charge-exchange reactions the η-η{sup '} mixing is estimated. (orig.)

  4. Metastable structures and isotope exchange reactions in polyoxometalate ions provide a molecular view of oxide dissolution (United States)

    Rustad, James R.; Casey, William H.


    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.

  5. Bifluoride-catalysed sulfur(VI) fluoride exchange reaction for the synthesis of polysulfates and polysulfonates (United States)

    Gao, Bing; Zhang, Linda; Zheng, Qinheng; Zhou, Feng; Klivansky, Liana M.; Lu, Jianmei; Liu, Yi; Dong, Jiajia; Wu, Peng; Sharpless, K. Barry


    Polysulfates and polysulfonates possess exceptional mechanical properties making them potentially valuable engineering polymers. However, they have been little explored due to a lack of reliable synthetic access. Here we report bifluoride salts (Q+[FHF]-, where Q+ represents a wide range of cations) as powerful catalysts for the sulfur(VI) fluoride exchange (SuFEx) reaction between aryl silyl ethers and aryl fluorosulfates (or alkyl sulfonyl fluorides). The bifluoride salts are significantly more active in catalysing the SuFEx reaction compared to organosuperbases, therefore enabling much lower catalyst-loading (down to 0.05 mol%). Using this chemistry, we are able to prepare polysulfates and polysulfonates with high molecular weight, narrow polydispersity and excellent functional group tolerance. The process is practical with regard to the reduced cost of catalyst, polymer purification and by-product recycling. We have also observed that the process is not sensitive to scale-up, which is essential for its future translation from laboratory research to industrial applications.

  6. Baryon exchange reactions in. pi. -p scattering at 4 GeV/c. [Differential cross sections

    Energy Technology Data Exchange (ETDEWEB)

    Scharre, D.L.


    An experiment designed to study baryon exchange reactions in ..pi../sup -/p scattering at 4 GeV/c is discussed. The experiment was performed at the Bevatron and utilized a streamer chamber and a downstream spectrometer which consisted of two scintillation counter hodoscopes and a Cerenkov counter to define the fast proton trigger, and two planes of spark chambers to provide improved resolution on the forward track. Analysis of meson production in the reactions ..pi../sup -/p ..-->.. pM/sup -/, ..pi../sup -/p ..-->.. p..pi../sup -/M/sup 0/, ..pi../sup -/p ..-->.. Lambda/sup 0/M/sup 0/ is discussed for backward production of meson systems M/sup -/ and M/sup 0/. Differential cross sections and decay distributions (where applicable) for ..pi../sup -/, rho/sup -/, rho/sup 0/, f/sup 0/, omega/sup 0/, eta/sup 0/, and K*/sup 0/ production are discussed. Upper limits for A/sup -//sub 1/, A/sup -//sub 2/, and B/sup -/ production are given. Baryon resonance production and limits on exotic meson production are briefly discussed.

  7. Hydrogen-exchange mass spectrometry for the study of intrinsic disorder in proteins. (United States)

    Balasubramaniam, Deepa; Komives, Elizabeth A


    Amide hydrogen/deuterium exchange detected by mass spectrometry (HXMS) is seeing wider use for the identification of intrinsically disordered parts of proteins. In this review, we discuss examples of how discovery of intrinsically disordered regions and their removal can aid in structure determination, biopharmaceutical quality control, the characterization of how post-translational modifications affect weak structuring of disordered regions, the study of coupled folding and binding, and the characterization of amyloid formation. This article is part of a Special Issue entitled: Mass spectrometry in structural biology. Copyright © 2012 Elsevier B.V. All rights reserved.

  8. Hydrogen and oxygen isotope exchange reactions between clay minerals and water (United States)

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


    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. Modelling of geochemical reactions and experimental cation exchange in MX 80 bentonite. (United States)

    Montes-H, G; Fritz, B; Clement, A; Michau, N


    Bentonites are widely used for waste repository systems because of their hydrodynamic, surface and chemical-retention properties. MX 80 bentonite (bentonite of Wyoming) contains approximately 85% Na/Ca-montmorillonite and 15% accessory minerals. The dominant presence of Na/Ca-montmorillonite in this clay mineral could cause it to perform exceptionally well as an engineered barrier for a radioactive waste repository because this buffer material is expected to fill up by swelling the void between canisters containing waste and the surrounding ground. However, the Na/Ca-montmorillonite could be transformed to other clay minerals as a function of time under repository conditions. Previous modelling studies based on the hydrolysis reactions have shown that the Na/Ca-montmorillonite-to-Ca-montmorillonite conversion is the most significant chemical transformation. In fact, this chemical process appears to be a simple cation exchange into the engineered barrier. The purpose of the present study was two-fold. Firstly, it was hoped to predict the newly formed products of bentonite-fluid reactions under repository conditions by applying a thermokinetic hydrochemical code (KIRMAT: Kinetic Reactions and Mass Transport). The system modelled herein was considered to consist of a 1-m thick zone of water-saturated engineered barrier. This non-equilibrated system was placed in contact with a geological fluid on one side, which was then allowed to diffuse into the barrier, while the other side was kept in contact with iron-charged water. Reducing initial conditions ( [P(O)2 approximately equals 0] ; Eh=-200 mV) and a constant reaction temperature (100 degrees C) were considered. Secondly, it was hoped to estimate the influence of inter-layer cations (Ca and Na) on the swelling behaviour of the MX 80 bentonite by using an isothermal system of water vapour adsorption and an environmental scanning electron microscope (ESEM) coupled with a digital image analysis (DIA) program. Here, the

  10. Superparamagnetic Ironoxide Nanoparticles via Ligand Exchange Reactions: Organic 1,2-Diols as Versatile Building Blocks for Surface Engineering

    Directory of Open Access Journals (Sweden)

    Wolfgang H. Binder


    Full Text Available A method for the preparation of ligand-covered superparamagnetic iron oxide nanoparticles via exchange reactions is described. 1,2-diol-ligands are used to provide a stable binding of the terminally modified organic ligands onto the surface of γ-Fe2O3-nanoparticles (r∼4 nm. The 1,2-diol-ligands are equipped with variable terminal functional groups (i.e., hydrogen bonding moieties, azido- bromo-, fluorescent moieties and can be easily prepared via osmium tetroxide-catalyzed 1,2-dihydroxylation reactions of the corresponding terminal alkenes. Starting from octylamine-covered γ-Fe2O3-nanoparticles, ligand exchange was effected at 50∘C over 24–48 hours, whereupon complete ligand exchange is taking place as proven by thermogravimetric (TGA- and IR-spectroscopic measurements. A detailed kinetic analysis of the ligand exchange reaction was performed via TGA analysis, demonstrating a complete ligand exchange after 24 hours. The method offers a simple approach for the generation of various γ-Fe2O3-nanoparticles with functional organic shells in a one-step procedure.

  11. Controlled growth of gold nanoparticles in zeolite L via ion-exchange reactions and thermal reduction processes

    KAUST Repository

    Zeng, Shangjing


    The growth of gold nanoparticles in zeolite can be controlled using ion-exchange reactions and thermal reduction processes. We produce a number of different sizes of the gold nanoparticles with the particle size increasing with increased temperature of the final heat treatment. © 2014 Elsevier B.V.

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

    Energy Technology Data Exchange (ETDEWEB)

    Cappuzzello, F.; Bondi, M. [Universita di Catania, Dipartimento di Fisica e Astronomia, Catania (Italy); INFN, Laboratori Nazionali del Sud, Catania (Italy); Cavallaro, M.; Agodi, C.; Carbone, D.; Cunsolo, A. [INFN, Laboratori Nazionali del Sud, Catania (Italy); Foti, A. [Universita di Catania, Dipartimento di Fisica e Astronomia, Catania (Italy); INFN, Sezione di Catania, Catania (Italy)


    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 {sup 40}Ca({sup 18}O,{sup 18}Ne){sup 40}Ar reaction at 270 MeV incident energy show that such cross section factorization reasonably holds for the crucial 0{sup +} → 0{sup +} transition to {sup 40}Ar{sub gs}, at least at very forward angles. (orig.)

  13. H2/D2 exchange reaction on mono-disperse Pt clusters: enhanced activity from minute O2 concentrations

    DEFF Research Database (Denmark)

    Riedel, Jakob Nordheim; Rötzer, Marian David; Jørgensen, Mikkel


    significantly. XPS and ISS before and after reaction suggest little or no sintering during reaction. A reaction pathway is suggested based on DFT. H2 desorption is identified as the rate-limiting step and O2 is confirmed as the source of the increased activity. The binding energy of platinum atoms in a SiO2......The H2/D2 exchange reaction was studied on mono-disperse Pt8 clusters in a μ-reactor. The chemical activity was studied at temperatures varying from room temperature to 180 °C using mass spectrometry. It was found that minute amounts of O2 in the gas stream increased the chemical activity...

  14. Unveiling the structure and composition of titanium oxide nanotubes through ion exchange chemical reactions and thermal decomposition processes

    Directory of Open Access Journals (Sweden)

    Ferreira Odair P.


    Full Text Available In this paper we report the ion exchange reactions and the thermal decomposition of titanium oxide nanotubes, obtained by hydrothermal treatment of TiO2 and NaOH. Based on these results we propose a new composition for the as-prepared nanotubes as Na2Ti3O7.nH2O. Our results also suggest that nanotube walls have structure similar to those observed in the layer of the bulk Na2Ti3O7. Depending on how the washing process is performed on the nanotubes (water or acid solutions the Na+ content can be modified via the exchange reaction of Na+ by H+. Thus, a general chemical formula was also proposed: Na2-xHxTi3O7 .nH2O (0 < x < 2, x being dependent on the washing process.

  15. A meson-exchange isobar model for the {pi}{sup +}d {r_reversible} pp reaction

    Energy Technology Data Exchange (ETDEWEB)

    Canton, L.; Cattapan, G.; Dortmans, P.J.; Pisent, G. [Istituto Nazionale di Fisica Nucleare, Padua (Italy); Svenne, J.P. [Manitoba Univ., Winnipeg, MB (Canada). Dept. of Physics]|[Winnipeg Inst. for Theoretical Physics, Winnipeg, MB (Canada)


    A broad set of observables are calculated for the {pi}{sup +} d {r_reversible} pp reaction with a relatively simple meson-exchange isobar model. The comparison between the calculated results and experimental data (including spin observables), shows that the model gives an overall phenomenologically acceptable description of the reaction around the {Delta} resonance. The effects due to the inclusion of Galilei invariant (pseudovector) recoil term in the {pi}NN vertex, of relativistic corrections to the {rho}-exchange component of the {Delta}N transition potential, and of NN final state interaction in the {pi}{sup +}d {yields} p+p process are also discussed. It is estimated that the model is sufficiently simple to be extended to the case of pion absorption on other light nuclei, in particular {sup 3}He (or tritium). 32 refs., 13 figs.

  16. Controlled state-to-state atom-exchange reaction in an ultracold atom-dimer mixture


    Rui, Jun; Yang, Huan; Liu, Lan; Zhang, De-Chao; Liu, Ya-Xiong; Nan, Jue; Zhao, Bo; Pan, Jian-Wei


    Ultracold molecules offer remarkable opportunities to study chemical reactions at nearly zero temperature. Although significant progresses have been achieved in exploring ultracold bimolecular reactions, the investigations are usually limited to measurements of the overall loss rates of the reactants. Detection of the reaction products will shed new light on understanding the reaction mechanism and provide a unique opportunity to study the state-to-state reaction dynamics. Here we report on t...

  17. A quark model calculation for the short-range contribution in the pion double charge exchange reaction

    Energy Technology Data Exchange (ETDEWEB)

    Zou Bingsong; Jiang Huanqing (Institute of Theoretical Physics and Institute of High Energy Physcis, Academia Sinica, Beijing (CN))


    A quark model calculation for the short-range contribution in the pion double charge exchange (DCX) reaction is presented. In the framework of this new model the angular distributions of {sup 18}O({pi}{sup +},{pi}{sup {minus}}){sup 18}Ne(g.s.) at low energies are calculated and compared with the experimental data. It is found that this model can explain the anomalous'' increasing behavior for the DCX reaction around 50 MeV quite well.

  18. Ab initio R1 mechanism of photostimulated oxygen isotope exchange reaction on a defect TiO{sub 2} surface: The case of terminal oxygen atom exchange

    Energy Technology Data Exchange (ETDEWEB)

    Kevorkyants, Ruslan, E-mail:; Sboev, Mikhail N.; Chizhov, Yuri V.


    Highlights: • DFT R1 mechanism of photostimulated oxygen isotope exchange between {sup 16}O{sup 18}O and terminal oxygen atom of a defect surface of nanocrystalline TiO{sub 2} is proposed. • The mechanism involves four adsorption intermediates and five transition states. • Activation energy of the reaction is 0.24 eV. • G-tensors of O{sub 3}{sup −} intermediates match EPR data on O{sub 2} adsorbed on UV-irradiated TiO{sub 2} surface. - Abstract: Based on density functional theory we propose R1 mechanism of photostimulated oxygen isotope exchange (POIEx) reaction between {sup 16}O{sup 18}O and terminal oxygen atom of a defect TiO{sub 2} surface, which is modeled by amorphous Ti{sub 8}O{sub 16} nanocluster in excited S{sup 1} electronic state. The proposed mechanism involves four adsorption intermediates and five transition states. The computed activation energy of the POIEx equals 0.24 eV. The computed g-tensors of the predicted ozonide O{sub 3}{sup −} chemisorption species match well EPR data on O{sub 2} adsorption on UV-irradiated nanocrystalline TiO{sub 2}. This match serves a mean of justification of the proposed R1 mechanism of the POIEx reaction. In addition, it is found that the proposed R1 POIEx reaction’s mechanism differs from R1 mechanism of thermo-assisted OIEx reaction on a surface of supported vanadium oxide catalyst VO{sub x}/TiO{sub 2} reported earlier.

  19. Reactions of. cap alpha. -hydroxy acid chemical exchange in titanium (3) and vanadyl (2) coordination compounds

    Energy Technology Data Exchange (ETDEWEB)

    Glebov, A.N.; Sal' nikov, Yu.I.; Zakharov, A.V.; Saprykova, Z.A.; Gogolashvili, Eh.L. (Kazanskij Gosudarstvennyj Univ. (USSR))


    For the first time a study was made on the effect of chemical exchange of oxygen-containing ligands (lactic, mandelic, sulfosalicylic acids) on the relaxation period of solvent water protons. Constants of exchange rates of protonated ligand forms were evaluated. The mechanism of the observed processes are proposed.

  20. Kinetic and Mechanistic Studies of the Deuterium Exchange in Classical Keto-Enol Tautomeric Equilibrium Reactions (United States)

    Nichols, Michael A.; Waner, Mark J.


    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…

  1. Possibility of Superconductivity in a Layered Perovskite Niobate, KCa_2Nb_3O_<10>, Synthesized by an Ion Exchange Reaction


    竹澤, 幸; 寺西, 喬; 石川, 宏典; 徳光, 俊章; 戸田, 健司; 上松, 和義; 佐藤, 峰夫; Takezawa, Sachi; Teranishi, Takashi; Ishikawa, Hironori; Tokumitsu, Toshiaki; Toda, Kenji; Uematsu, Kazuyoshi; Sato, Mineo


    We prepared low temperature phase of triple layered perovksite KCa_2Nb_3O_ by an ion-exchange reaction. Li-intercalated low temperature phase, Li_KCa_2Nb_3O_, shows strong diamagnetic signal around at 7.8 K. The magnetic phase transition temperature of Li-intercalated low temperature phase is higher than that of Li-intercalated high temperature phase.

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

    Energy Technology Data Exchange (ETDEWEB)

    Hao, Feng; Lin, Hong; Zhang, Jing [State Key Laboratory of New Ceramics and Fine Processing, Department of Material Science and Engineering, Tsinghua University, Beijing 100084 (China); Li, Jianbao [State Key Laboratory of New Ceramics and Fine Processing, Department of Material Science and Engineering, Tsinghua University, Beijing 100084 (China); Key Laboratory of Ministry of Education for Application Technology of Chemical Materials in Hainan Superior Resources, Hainan Provincial Key Laboratory of Research on Utilization of Si-Zr-Ti Resources, College of Materials Science and Chemical Engineering, Hainan University, Haikou 570228 (China)


    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. (author)

  3. Understanding and Practical Use of Ligand and Metal Exchange Reactions in Thiolate-Protected Metal Clusters to Synthesize Controlled Metal Clusters. (United States)

    Niihori, Yoshiki; Hossain, Sakiat; Sharma, Sachil; Kumar, Bharat; Kurashige, Wataru; Negishi, Yuichi


    It is now possible to accurately synthesize thiolate (SR)-protected gold clusters (Aun (SR)m ) with various chemical compositions with atomic precision. The geometric structure, electronic structure, physical properties, and functions of these clusters are well known. In contrast, the ligand or metal atom exchange reactions between these clusters and other substances have not been studied extensively until recently, even though these phenomena were observed during early studies. Understanding the mechanisms of these reactions could allow desired functional metal clusters to be produced via exchange reactions. Therefore, we have studied the exchange reactions between Aun (SR)m and analogous clusters and other substances for the past four years. The results have enabled us to gain deep understanding of ligand exchange with respect to preferential exchange sites, acceleration means, effect on electronic structure, and intercluster exchange. We have also synthesized several new metal clusters using ligand and metal exchange reactions. In this account, we summarize our research on ligand and metal exchange reactions. © 2017 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Inelastic process observed in charge-exchange reactions of 56Fe at 500 MeV/u

    Directory of Open Access Journals (Sweden)

    Momota S.


    Full Text Available The inelastic (IE component of the reaction product, which is produced through charge-exchange reactions at relativistic energies of E ~ 1 GeV/u, is one of the hopeful probes used to study the nuclear medium effect on Δ excitation. In the present study, the longitudinal-momentum (PL distribution of 56Co, produced by bombarding C-and CH2-target with a primary beam of 56Fe at E=500 MeV/u, was observed by means of the spectrometer at HIMAC facility. The IE peak of 56Co, produced from H and C targets, was successfully observed in energy transfer spectrum. The behaviors of the IE peaks are consistent with those observed in previous experiments. A remarkable reduction of the energy transfer for the IE process was also observed with C target compared with H target. The present results have shown the feasibility to investigate the energy transfer in charge-exchange reactions for heavy reaction system at the energy down to 500 MeV/u.

  5. Quantal Study of the Exchange Reaction for N + N2 using an ab initio Potential Energy Surface (United States)

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


    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.

  6. Red cell exchange to mitigate a delayed hemolytic transfusion reaction in a patient transfused with incompatible red blood cells. (United States)

    Irani, Mehraboon S; Karafin, Matthew S; Ernster, Luke


    A red cell exchange was performed to prevent a potentially fatal hemolytic transfusion reaction in a patient with anti-e who was transfused with e-antigen unscreened red blood cells during liver transplant surgery. A 64-year-old woman with cirrhosis due to hepatitis C was scheduled to receive a liver transplant. She had a previously documented anti-e, an antibody to the Rh(e)-antigen that is known to cause delayed hemolytic transfusion reactions. Pre-operatively and intra-operatively, she had massive hemorrhage which required transfusion of 34 e-antigen unscreened red blood cells (RBCs) most of which were incompatible. The hemoglobin dropped from 9.1 g/dL on post-operative day (POD)1 to 6.6 g/dL on POD6, with no evidence of blood loss. The bilirubin also increased from 5.0 mg/dL on POD 1 to 11.0 mg/dL on POD 6. As she was also becoming more hemodynamically unstable, a red cell exchange with 10 units of e-negative RBCs was performed on POD 6. She improved clinically and was extubated the following day. A few residual transfused e-positive red cells were detected after the red cell exchange until POD 13. This case illustrates how a red cell exchange can mitigate the potentially harmful effects of a delayed hemolytic transfusion reaction caused by red cell antibodies. With massive intraoperative blood loss it may not be possible to have antigen-negative RBCs immediately available, particularly for the e-antigen, which is present in 98% of the donor population. The ability to perform such a procedure may be life-saving in such patients. J. Clin. Apheresis 32:59-61, 2017. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

  7. Synthesis of model humic substances: a mechanistic study using controllable H/D exchange and Fourier transform ion cyclotron resonance mass spectrometry. (United States)

    Zherebker, Alexander Ya; Airapetyan, David; Konstantinov, Andrey I; Kostyukevich, Yury I; Kononikhin, Alexey S; Popov, Igor A; Zaitsev, Kirill V; Nikolaev, Eugene N; Perminova, Irina V


    The products of the oxidative coupling of phenols are frequently used as synthetic analogues to natural humic substances (HS) for biomedical research. However, their molecular compositions and exact structures remain largely unknown. The objective of this study was to develop a novel approach for the molecular-level analysis of phenolic polymerisates that is capable of inventorying molecular constituents and resolving their distinct structural formulas. For this purpose, we have synthesized the model HS using the oxidative coupling of a specifically designed phenylpropanoic monomer, 3-(4-hydroxy-3-methoxyphenyl)-3-oxopropionic acid, to hydroquinone. We have characterized the synthesized model HS using high resolution Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS), (1)H NMR spectroscopy, and controllable hydrogen/deuterium (H/D) exchange. We succeeded in the molecular inventory of the model HS. The assigned molecular formulas occupied the substantial space of CHO compositions in the Van Krevelen diagram with a maximum density found in the regions of tannins and lignins, resembling those of natural HS. To identify the exact structural formulas of the individual constituents in the model HS, we have applied selective H/D exchange of non-labile backbone protons by a choice of basic or acidic catalytic conditions followed by FTICR MS. The determined formulas allowed us to verify the proposed pathways of hydroxylation and carboxylation in the course of the phenolic coupling and to identify the acetylation of aromatic rings as an important side reaction. We conclude that the proposed analytical approach may be used to identify the molecular carriers of biological activity within the phenolic polymerisates and eventually within natural HS.

  8. The molecular mechanism of the ligand exchange reaction of an antibody against a glutathione-coated gold cluster. (United States)

    Rojas-Cervellera, Víctor; Raich, Lluís; Akola, Jaakko; Rovira, Carme


    The labeling of proteins with heavy atom clusters is of paramount importance in biomedical research, but its detailed molecular mechanism remains unknown. Here we uncover it for the particular case of the anti-influenza N9 neuraminidase NC10 antibody against a glutathione-coated gold cluster by means of ab initio QM/MM calculations. We show that the labeling reaction follows an associative double SN2-like reaction mechanism, involving a proton transfer, with low activation barriers only if one of the two distinct peptide/peptidic ligands (the one that occupies the side position) is substituted. Positively charged residues in the vicinity of the incoming thiol result in strong interactions between the antibody and the AuMPC, favoring the ligand exchange reaction for suitable protein mutants. These results pave the way for future investigations aimed at engineering biomolecules to increase their reactivity towards a desired gold atom cluster.

  9. Synthesis of LiAlO{sub 2} and LiGaO{sub 2} by ion exchange reaction

    Energy Technology Data Exchange (ETDEWEB)

    Villafuerte-Castrejon, M.E.; Mondragon, C.; Sanchez-Arjona, A.M. [Universidad Nacional Autonoma de Mexico, Mexico City (Mexico). Inst. de Investigaciones en Materiales; Olguin, M.T.; Bulbulian, S. [Inst. Nacional de Investigaciones Nucleares, Delegacion Miguel Hidalgo, Mexico, D.F. (Mexico); Bosch, P. [Univ. Autonoma Metropolitan-Iztapalapa, Mexico, D.F. (Mexico)


    The complex oxides {beta} and {gamma}-NaAlO{sub 2} polymorphs and NaGaO{sub 2} were reacted by the ion exchange route with molten salts (LiCl and LiNO{sub 3}). Kinetics of the reaction were followed by the X-ray powder diffraction and by neutronic activation analysis using a TRIGA MARG III nuclear reactor. The products of the reactions were polymorphs {beta} and {gamma}-LiAlO{sub 2} and LiGaO{sub 2}. {beta}-LiAlO{sub 2} is the high pressure form, obtained by this method at relative low temperature and at atmospheric pressure. LiGAO{sub 2} was obtained after only one minute of reaction in the molten salt. (orig.) 4 refs.

  10. Study of the pd→→n{pp}s charge-exchange reaction using a polarised deuterium target

    Directory of Open Access Journals (Sweden)

    B. Gou


    Full Text Available The vector and tensor analysing powers, Ay and Ayy, of the pd→→n{pp}s charge-exchange reaction have been measured at a beam energy of 600 MeV at the COSY-ANKE facility by using an unpolarised proton beam incident on an internal storage cell target filled with polarised deuterium gas. The low energy recoiling protons were measured in a pair of silicon tracking telescopes placed on either side of the target. Putting a cut of 3 MeV on the diproton excitation energy ensured that the two protons were dominantly in the S01 state, here denoted by {pp}s. The polarisation of the deuterium gas was established through measurements in parallel of proton–deuteron elastic scattering. By analysing events where both protons entered the same telescope, the charge-exchange reaction was measured for momentum transfers q≥160 MeV/c. These data provide a good continuation of the earlier results at q≤140 MeV/c obtained with a polarised deuteron beam. They are also consistent with impulse approximation predictions with little sign evident for any modifications due to multiple scatterings. These successful results confirm that the ANKE deuteron charge-exchange programme can be extended to much higher energies with a polarised deuterium target than can be achieved with a polarised deuteron beam.

  11. Investigating convergence of the reaction γp→π±Δ and tensor meson a2 exchange at high energy

    Directory of Open Access Journals (Sweden)

    Byung-Geel Yu


    Full Text Available A Regge approach to the reaction processes γp→π−Δ++ and γp→π+Δ0 is presented for the description of existing data up to Eγ=16 GeV. The model consists of the t-channel π(139+ρ(775+a2(1320 exchanges which are reggeized from the relevant Born amplitude. Discussion is given on the minimal gauge prescription for the π exchange to render convergent the divergence of the u-channel Δ-pole in the former process. A new Lagrangian is constructed for the a2NΔ coupling in this work and applied to the process for the first time with the coupling constant deduced from the duality plus vector dominance. It is shown that, while the π exchange dominates over the process, the role of the a2 exchange is crucial rather than the ρ in reproducing the cross sections for total, differential, and photon polarization asymmetry to agree with data at high energy.

  12. On the Mechanism of the Iodide-Triiodide Exchange Reaction in a Solid-State Ionic Liquid. (United States)

    Grossi, Joás; Kohanoff, Jorge J; English, Niall J; Bringa, Eduardo M; Del Pópolo, Mario G


    Efficient charge transport has been observed in iodide-based room-temperature ionic liquids when doped with iodine. To investigate preferred pathways for the iodide (I-)-to-triiodide (I3-) exchange reaction and to clarify the origin of this high ionic conductivity, we have conducted electronic structure calculations in the crystal state of 1-butyl-3-methylimidazolium iodide ([BMIM][I]). Energy barriers for the different stages of the iodine-swapping process, including the reorientation of the I-···I3- moiety, were determined from minimum energy paths as a function of a reaction coordinate. Hirshfeld charges and structural parameters, such as bond lengths and angles, were monitored during the reaction. Several bond-exchange events were observed with energy barriers ranging from 0.17 to 0.48 eV and coinciding with the formation of a twisted I-···I3- complex. Striking similarities were observed in the mechanics and energetics of this charge-transfer process in relation to solid-state superionic conductors.

  13. A computational study of a recreated G protein-GEF reaction intermediate competent for nucleotide exchange: fate of the Mg ion.

    Directory of Open Access Journals (Sweden)

    Mériam Ben Hamida-Rebaï

    Full Text Available Small G-proteins of the superfamily Ras function as molecular switches, interacting with different cellular partners according to their activation state. G-protein activation involves the dissociation of bound GDP and its replacement by GTP, in an exchange reaction that is accelerated and regulated in the cell by guanine-nucleotide exchange factors (GEFs. Large conformational changes accompany the exchange reaction, and our understanding of the mechanism is correspondingly incomplete. However, much knowledge has been derived from structural studies of blocked or inactive mutant GEFs, which presumably closely represent intermediates in the exchange reaction and yet which are by design incompetent for carrying out the nucleotide exchange reaction. In this study we have used comparative modelling to recreate an exchange-competent form of a late, pre-GDP-ejection intermediate species in Arf1, a well-characterized small G-protein. We extensively characterized three distinct models of this intermediate using molecular dynamics simulations, allowing us to address ambiguities related to the mutant structural studies. We observed in particular the unfavorable nature of Mg2+ associated forms of the complex and the establishment of closer Arf1-GEF contacts in its absence. The results of this study shed light on GEF-mediated activation of this small G protein and on predicting the fate of the Mg ion at a critical point in the exchange reaction. The structural models themselves furnish additional targets for interfacial inhibitor design, a promising direction for exploring potentially druggable targets with high biological specificity.

  14. Ion temperatures in HIP-1 and SUMMA from charge-exchange neutral optical emission spectra (United States)

    Patch, R. W.; Lauver, M. R.


    Ion temperatures were obtained from observations of the H sub alpha, D sub alpha, and He 587.6 nm lines emitted from hydrogen, deuterium, and helium plasmas in the SUMMA and HIP-1 mirror devices at Lewis Research Center. Steady state discharges were formed by applying a radially inward dc electric field between cylindrical or annular anodes and hollow cathodes located at the peaks of the mirrors. The ion temperatures were found from the Doppler broadening of the charge-exchange components of spectral lines. A statistical method was developed for obtaining scaling relations of ion temperature as a function of current, voltage, and magnetic flux density. Derivations are given that take into account triangular monochromator slit functions, loss cones, and superimposed charge-exchange processes. In addition, the Doppler broadening was found to be sensitive to the influence of drift on charge-exchange cross section. The effects of finite ion-cyclotron radius, cascading, and delayed emission are reviewed.

  15. An Effective Deuterium Exchange Method for Neutron Crystal Structure Analysis with Unfolding-Refolding Processes. (United States)

    Kita, Akiko; Morimoto, Yukio


    A method of hydrogen/deuterium (H/D) exchange with an unfolding-refolding process has been applied to hen egg-white lysozyme (HWL), and accurate evaluation of its deuteration was carried out by time-of-flight mass spectroscopy. Neutron crystallography requires a suitable crystal with enough deuterium exchanged in the protein to decrease incoherent scattering from hydrogens. It is very expensive to prepare a fully deuterated protein, and therefore a simple H/D exchange technique is desirable for this purpose. Acid or base addition to protein solutions with heating effectively increased the number of deuterium up to more than 20 % of that of all hydrogen atoms, and refolded structures were determined by X-ray structure analysis at 1.8 Å resolution. Refolded HWL had increased deuterium content in its protein core and its native structure, determined at atomic resolution, was fully preserved.

  16. Synthesis and anion exchange reactions of a layered copper-zinc ...

    Indian Academy of Sciences (India)

    A mixed-metal hydroxysalt of formula Cu1.6Zn0.4(OH)3(OAc) ⋅ H2O has been synthesized by an acetate hydrolysis route. Acetate ions can be exchanged with simple inorganic anions such as chloride and nitrate, and organic anions such as benzoate and large surfactant anions such as dodecyl sulphate. Structures of ...

  17. Hydrogen production and deuterium-proton exchange reactions catalyzed by Desulfovibrio nickel(II)-substituted rubredoxins (United States)

    Saint-Martin, Pascal; Lespinat, Paul A.; Fauque, Guy; Berlier, Yves; LeGall, Jean; Moura, Isabel; Teixeira, Miguel; Xavier, Antonio V.; Moura, Jose J. G.


    The nickel tetrahedral sulfur-coordinated core formed upon metal replacement of the native iron in Desulfovibrio sp. rubredoxins is shown to mimic the reactivity pattern of nickel-containing hydrogenases with respect to hydrogen production, deuterium-proton exchange, and inhibition by carbon monoxide. PMID:16594005

  18. Synthesis and anion exchange reactions of a layered copper–zinc ...

    Indian Academy of Sciences (India)


    Abstract. A mixed-metal hydroxysalt of formula Cu1⋅6Zn0⋅4(OH)3(OAc)⋅H2O has been synthesized by an acetate hydrolysis route. Acetate ions can be exchanged with simple inorganic anions such as chloride and nitrate, and organic anions such as benzoate and large surfactant anions such as dodecyl sulphate. Struc-.

  19. Structure Determination of New Layered Perovskite Compound, NaLaTa2O7, Synthesized by Ion-Exchange Reaction


    Toda, Kenji; Uematsu, Kazuyoshi; Sato, Mineo; 戸田, 健司; 上松, 和義; 佐藤, 峰夫


    A new layered perovskite compound, NaLaTa2O7, was synthesized by ion-exchange reaction of the rubidium compound, RbLaTa2O7. The crystal structure of the compound was determined by the Rietveld analysis for powder X-ray diffraction pattern. The crystal structure is analogous to that of the corresponding niobate compound, NaLaNb2O7. This layered perovskite compound is a new member of the Dion-Jacobson series with n=2 for the general formula M[An-1BnO3n+1] (M=alkali metals).

  20. Strong Metal Support Interaction of Pt and Ru Nanoparticles Deposited on HOPG Probed by the H-D Exchange Reaction

    DEFF Research Database (Denmark)

    Fiordaliso, Elisabetta M.; Dahl, Søren; Chorkendorff, Ib


    adsorbed and gas phase at 1 bar is measured before and after annealing. The rate is measured in the temperature range of 40–200 °C at 1 bar, by utilization of the H-D exchange reaction. Experiments are performed on fresh cleaved and sputtered HOPG, which give similar results. We find that annealing......The interaction between metals and support is investigated in the case of 50 Å Pt and 50 Å Ru films deposited on a HOPG substrate. The films are prepared by electron beam physical vapor deposition and annealed in UHV to temperatures up to 700 °C. The equilibrium hydrogen exchange rate between...... the films from 150 up to 700 °C increases the amount of carbon present in the films up to 95%, as derived by surface analysis, indicating the formation of a carbon layer on top of the metal films. The exchange rate decreases dramatically with increasing carbon content on the films for both metals, pointing...

  1. Electrocatalytic reduction of acetone in a proton-exchange-membrane reactor: a model reaction for the electrocatalytic reduction of biomass. (United States)

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


    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. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Theoretical investigation of the thermodynamic structures and kinetic water-exchange reactions of aqueous Al(III)-salicylate complexes (United States)

    Shi, Wenjing; Jin, Xiaoyan; Dong, Shaonan; Bi, Shuping


    Density functional theory (DFT) calculations were performed on the structures and water-exchange reactions of aqueous Al(III)-salicylate complexes. Based on the four models (gas phase (GP); polarizable continuum model (PCM), which estimates the bulk solvent effect; supermolecule model (SM), which considers the explicit solvent effect, and supermolecule-polarizable continuum model (SM-PCM), which accounts for both types of solvent effects), we systematically conducted this study by examining three different properties of the complexes. (1) The microscopic properties of the aqueous Al(III)-salicylate complexes were studied by optimizing their various structures (including the possible 1:1 mono- and bidentate complexes, cis and trans isomers of the 1:2 bidentate complexes and 1:3 bidentate complexes) at the B3LYP/6-311+G(d, p) level. (2) The 27Al and 13C NMR chemical shifts were calculated using the GIAO method at the HF/6-311+G(d, p) level. The calculation results show that the values obtained with the SM-PCM models are in good agreement with the experimental data available in the literature, indicating that the models we employed are appropriate for Al(III)-salicylate complexes. (3) The water-exchange reactions of 1:1 mono- and bidentate Al(III)-salicylate complexes were simulated using supermolecule models at the B3LYP/6-311+G(d, p) level. The logarithm of the water-exchange rate constant (log kex) of the 1:1 bidentate complex predicted using the "log kex-dAl-OH2" correlation is 4.0, which is in good agreement with the experimental value of 3.7, whereas the calculated range of log kex of the 1:1 monodentate complexes is 1.3-1.9. By effectively combining the results for the thermodynamic static structures with the simulations of the kinetic water-exchange reactions, this work promotes further understanding of the configurations and formation mechanism of Al(III)-salicylate complexes.

  3. Room Temperature Cation Exchange Reaction in Nanocrystals for Ultrasensitive Speciation Analysis of Silver Ions and Silver Nanoparticles. (United States)

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


    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.

  4. An alternative preparation method for ion exchanged catalysts: Solid state redox reaction

    DEFF Research Database (Denmark)

    Schneider, E.; Hagen, A.; Grunwaldt, J.-D.


    infrared Fourier transform spectroscopy (DRIFTS). The evolution of hydrogen was detected at temperatures above 620 K. The source of hydrogen was the solid state redox reaction of the metal with protons of the support. The samples exhibit catalytic activity in ethane aromatization indicating that zinc...

  5. Further links between the maximum hardness principle and the hard/soft acid/base principle: insights from hard/soft exchange reactions. (United States)

    Chattaraj, Pratim K; Ayers, Paul W; Melin, Junia


    Ayers, Parr, and Pearson recently showed that insight into the hard/soft acid/base (HSAB) principle could be obtained by analyzing the energy of reactions in hard/soft exchange reactions, i.e., reactions in which a soft acid replaces a hard acid or a soft base replaces a hard base [J. Chem. Phys., 2006, 124, 194107]. We show, in accord with the maximum hardness principle, that the hardness increases for favorable hard/soft exchange reactions and decreases when the HSAB principle indicates that hard/soft exchange reactions are unfavorable. This extends the previous work of the authors, which treated only the "double hard/soft exchange" reaction [P. K. Chattaraj and P. W. Ayers, J. Chem. Phys., 2005, 123, 086101]. We also discuss two different approaches to computing the hardness of molecules from the hardness of the composing fragments, and explain how the results differ. In the present context, it seems that the arithmetic mean of fragment softnesses is the preferable definition.

  6. Plasma Deposited Thin Iron Oxide Films as Electrocatalyst for Oxygen Reduction Reaction in Proton Exchange Membrane Fuel Cells

    Directory of Open Access Journals (Sweden)

    Lukasz JOZWIAK


    Full Text Available The possibility of using plasma deposited thin films of iron oxides as electrocatalyst for oxygen reduction reaction (ORR in proton exchange membrane fuel cells (PEMFC was examined. Results of energy-dispersive X-ray spectroscopy (EDX and X-ray photoelectron spectroscopy (XPS analysis indicated that the plasma deposit consisted mainly of FeOX structures with the X parameter close to 1.5. For as deposited material iron atoms are almost exclusively in the Fe3+ oxidation state without annealing in oxygen containing atmosphere. However, the annealing procedure can be used to remove the remains of carbon deposit from surface. The single cell test (SCT was performed to determine the suitability of the produced material for ORR. Preliminary results showed that power density of 0.23 mW/cm2 could be reached in the tested cell.DOI:

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

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


    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. Copyright 2004 John Wiley and Sons, Ltd.

  8. Cytocompatible in situ cross-linking of degradable LbL films based on thiol-exchange reaction. (United States)

    Yang, Sung Ho; Choi, Jinsu; Palanikumar, L; Choi, Eun Seong; Lee, Juno; Kim, Juan; Choi, Insung S; Ryu, Ja-Hyoung


    Formation of both mechanically durable and programmably degradable layer-by-layer (LbL) films in a biocompatible fashion has potential applications in cell therapy, tissue engineering, and drug-delivery systems, where the films are interfaced with living cells. In this work, we developed a simple but versatile method for generating in situ cross-linked and responsively degradable LbL films, based on the thiol-exchange reaction, under highly cytocompatible conditions (aqueous solution at pH 7.4 and room temperature). The cytocompatibility of the processes was confirmed by coating individual yeast cells with the cross-linked LbL films and breaking the films on demand, while maintaining the cell viability. In addition, the processes were applied to the controlled release of an anticancer drug in the HeLa cells.

  9. Hydrogen bonding induced proton exchange reactions in dense D2-NH3 and D2-CH4 mixtures. (United States)

    Borstad, Gustav M; Yoo, Choong-Shik


    We have investigated high-pressure behaviors of simple binary mixtures of NH3 and D2 to 50 GPa and CH4 and D2 to 30 GPa using confocal micro-Raman spectroscopy. The spectral data indicate strong proton exchange reactions occur in dense D2-NH3 mixture, producing different isotopes of ammonia such as NH3, NH2D, NHD2, and ND3. In contrast, the proton exchange process in dense D2-CH4 mixture is highly limited, and no vibration feature is apparent for deuterated methane. The vibrational modes of H2 isotopes in D2-NH3 are blue shifted from those of pure H2 isotopes, whereas the modes of D2-CH4 show overall agreement with those in pure D2 and CH4. In turn, this result advocates the presence of strong repulsion and thereby internal pressure in D2-NH3 mixture, which are absent in D2-CH4. In fact, the bond length of hydrogen molecules in D2-NH3, calculated from the present spectral data, is shorter than that observed in pure hydrogen - supporting the enhanced intermolecular interaction in the mixture. Comparing the present spectral results with those previously observed in D2-H2O mixtures further suggests that the strength of repulsive interaction or the magnitude of internal pressure in the mixtures is proportional to the strength of hydrogen bonding in H2O, NH3, and CH4 in decreasing order. Hence, we suggest that the proton exchange is assisted by hydrogen bonding in these molecules.

  10. Perturbative QCD versus pion exchange and hadronic FSI effects in the γγ→ π+π- reaction (United States)

    Szczurek, A.; Speth, J.


    The interplay of pQCD, pion exchange and FSI effects is studied for the γγ→ π+π- reaction in the region of 2 GeV < Wγγ< 6 GeV. We find strong interference effects between pQCD and soft pion-exchange amplitudes up to Wγγ˜ 4 GeV. We discuss to which extend the conventional hadronic FSI effects could cloud the pQCD effects. We study multiple soft and hard scattering effects as well as the coupling between final state hadronic channels. We show how the perturbative effects in γγ→ ρρ may mix with perturbative effects in γγ→ π+π-. The effects discussed in this paper improve the agreement with the new data of the DELPHI and ALEPH Collaborations. We give estimates of the onset of the pQCD regime. Predictions for γγ→ π0π0 are presented.

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

    Energy Technology Data Exchange (ETDEWEB)

    Mugridge, Jeffrey; Bergman, Robert; Raymond, Kenneth


    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.

  12. Conformational lability in the class II MHC 310 helix and adjacent extended strand dictate HLA-DM susceptibility and peptide exchange. (United States)

    Painter, Corrie A; Negroni, Maria P; Kellersberger, Katherine A; Zavala-Ruiz, Zarixia; Evans, James E; Stern, Lawrence J


    HLA-DM is required for efficient peptide exchange on class II MHC molecules, but its mechanism of action is controversial. We trapped an intermediate state of class II MHC HLA-DR1 by substitution of αF54, resulting in a protein with increased HLA-DM binding affinity, weakened MHC-peptide hydrogen bonding as measured by hydrogen-deuterium exchange mass spectrometry, and increased susceptibility to DM-mediated peptide exchange. Structural analysis revealed a set of concerted conformational alterations at the N-terminal end of the peptide-binding site. These results suggest that interaction with HLA-DM is driven by a conformational change of the MHC II protein in the region of the α-subunit 3(10) helix and adjacent extended strand region, and provide a model for the mechanism of DM-mediated peptide exchange.

  13. Conformational lability in the class II MHC 310 helix and adjacent extended strand dictate HLA-DM susceptibility and peptide exchange (United States)

    Painter, Corrie A.; Negroni, Maria P.; Kellersberger, Katherine A.; Zavala-Ruiz, Zarixia; Evans, James E.; Stern, Lawrence J.


    HLA-DM is required for efficient peptide exchange on class II MHC molecules, but its mechanism of action is controversial. We trapped an intermediate state of class II MHC HLA-DR1 by substitution of αF54, resulting in a protein with increased HLA-DM binding affinity, weakened MHC-peptide hydrogen bonding as measured by hydrogen-deuterium exchange mass spectrometry, and increased susceptibility to DM-mediated peptide exchange. Structural analysis revealed a set of concerted conformational alterations at the N-terminal end of the peptide-binding site. These results suggest that interaction with HLA-DM is driven by a conformational change of the MHC II protein in the region of the α-subunit 310 helix and adjacent extended strand region, and provide a model for the mechanism of DM-mediated peptide exchange. PMID:22084083

  14. Ion exchange equilibrium constants

    CERN Document Server

    Marcus, Y


    Ion Exchange Equilibrium Constants focuses on the test-compilation of equilibrium constants for ion exchange reactions. The book first underscores the scope of the compilation, equilibrium constants, symbols used, and arrangement of the table. The manuscript then presents the table of equilibrium constants, including polystyrene sulfonate cation exchanger, polyacrylate cation exchanger, polymethacrylate cation exchanger, polysterene phosphate cation exchanger, and zirconium phosphate cation exchanger. The text highlights zirconium oxide anion exchanger, zeolite type 13Y cation exchanger, and

  15. Hydrogen isotope exchange experiments with Mt Mazama ash (United States)

    Nolan, G. S.; Bindeman, I. N.; Palandri, J. L.


    minor (~20%) hydroxyl loss. 5) Native ash dried to <3% water and ~-145% ∂2H), and reacted with the 650 % prepared water evinces a much higher rate of 2H incorporation compared to rates with the native ash under all the same conditions. Given linearity of ∂2H exchange through time and modeling the reaction as (pseudo) first order in concentration of deuterium yields the following isotopic half life values: for 70° C 1.43 years, for 40° C 4.1 years, and for 25 °C 12.1 years. An Arrhenius treatment yields an activation energy of 32-38 kjoules. 6) A second order kinetic treatment can be used to follow the reaction. A calculation using the reaction constant k at 25 °C assuming native ash exposed to -60 % ∂2H water indicates it would take 2 years to rise from a starting value of -150 to approximately -100 % ∂2H. Results of these experiments put quantitative limits on reliability of ∂2H in ash in paleo-climate studies that are primarily controlled by the isotopic environments and temperatures. We hypothesize that hydrogen-deuterium exchange occurs in native ash exposed to isotopically labeled water. The effect is mediated through surface correlated water in addition to diffusion with both having a rate determining effect. There is nothing to suggest that deuterium-hydrogen exchange is selective for molecular or SiOH hydrogen in the ash.

  16. EPR study on the ligand-exchange reaction between bis(diethyldiselenocarbamato)copper(II) and bis(octyldithiocarbonato)copper(II) (United States)

    Yordanov, Nicola D.; Dimitrova, Anna


    EPR study on the ligand-exchange reaction between bis(diethyldiselenocarbamato)copper(II), Cu(Et 2dsc) 2, and bis(octyldithiocarbonato)copper(II), Cu(octxant) 2, in CH 2Cl 2, CHCl 3, CCl 4, C 6H 6 and C 6H 5·CH 3 is reported for the first time. Mixing of equimolar amounts of the parents (chromophores CuSe 4 and CuS 4, respectively) in C 6H 6, C 6H 5·CH 3 and CH 2Cl 2 makes EPR signals of both parents superimposed by the spectrum of a mixed-chelate Cu(xant)(dsc) complex (chromophore CuS 2Se 2). A new additional EPR spectrum appears in CHCl 3 or CCl 4 due to a five-coordinate mixed-ligand complex with the chromophore Cu(S 3Se)S as follows by comparing the g-values of parents and mixed-ligand complexes. The appearance of this complex could be explained having in mind donor-acceptor properties of complexes, solvents and the resultant reaction of Cu(octxant) 2 with the ester of diselenocarbamic acid yielded in Cu(Et 2dsc) 2 destruction by CCl 4 or CHCl 3.

  17. Additional Evidence That Transaldolase Exchange, Isotope Discrimination During the Triose-Isomerase Reaction, or Both Occur in Humans (United States)

    Basu, Rita; Chandramouli, Visvanthan; Schumann, William; Basu, Ananda; Landau, Bernard R.; Rizza, Robert A.


    OBJECTIVE To determine whether deuterium enrichment on carbons 5 and 3 (C5/C3) in plasma glucose is influenced by processes other than gluconeogenesis and, if so, whether these processes are altered by type 2 diabetes. RESEARCH DESIGN AND METHODS In this study, 10 obese diabetic and 10 obese nondiabetic subjects were infused intravenously with [3,5-2H2] galactose enriched at a C5-to-C3 ratio of 1.0 as well as the enrichment of deuterium on C5 and C3 of plasma glucose, measured with nuclear magnetic resonance using the acetaminophen glucuronide method. RESULTS The ratio of deuterium enrichment on C5 and C3 of glucose was deuterium at the level of the triose-isomerase reaction, or both occur in humans. This also indicates that the net effect of these processes on the C5-to-C3 ratio is the same in people with and without type 2 diabetes. The possible effects of transaldolase exchange or selective retention of deuterium (or tritium) at the level of the triose-isomerase reaction on tracee labeling and tracer metabolism should be considered when the deuterated water method is used to measure gluconeogenesis or [3-3H] glucose is used to measure glucose turnover in humans. PMID:19366865

  18. Experimental investigation of the reaction of helium ions with dimethyl ether: stereodynamics of the dissociative charge exchange process. (United States)

    Cernuto, Andrea; Tosi, Paolo; Martini, Luca Matteo; Pirani, Fernando; Ascenzi, Daniela


    The fate of dimethyl ether (DME, CH3OCH3) in collisions with He+ ions is of high relevance for astrochemical models aimed at reproducing the abundances of complex organic molecules in the interstellar medium. Here we report an investigation on the reaction of He+ ions with DME carried out using a Guided Ion Beam Mass Spectrometer (GIB-MS), which allows the measurement of reactive cross-sections and branching ratios (BRs) as a function of the collision energy. We obtain insights into the dissociative charge (electron) exchange mechanism by investigating the nature of the non-adiabatic transitions between the relevant potential energy surfaces (PESs) in an improved Landau-Zener approach. We find that the large interaction anisotropy could induce a pronounced orientation of the polar DME molecule in the electric field generated by He+ so that at short distances the collision complex is confined within pendular states, a particular case of bending motion, which gives rise to intriguing stereodynamic effects. The positions of the intermolecular potential energy curve crossings indicate that He+ captures an electron from an inner valence orbital of DME, thus causing its dissociation. In addition to the crossing positions, the symmetry of the electron density distribution of the involved DME orbitals turns out to be a further major point affecting the probability of electron transfer. Thus, the anisotropy of the intermolecular interaction and the electron densities of the orbitals involved in the reaction are the key "ingredients" for describing the dynamics of this dissociative charge transfer.

  19. Swi5-Sfr1 protein stimulates Rad51-mediated DNA strand exchange reaction through organization of DNA bases in the presynaptic filament.

    KAUST Repository

    Fornander, Louise H


    The Swi5-Sfr1 heterodimer protein stimulates the Rad51-promoted DNA strand exchange reaction, a crucial step in homologous recombination. To clarify how this accessory protein acts on the strand exchange reaction, we have analyzed how the structure of the primary reaction intermediate, the Rad51/single-stranded DNA (ssDNA) complex filament formed in the presence of ATP, is affected by Swi5-Sfr1. Using flow linear dichroism spectroscopy, we observe that the nucleobases of the ssDNA are more perpendicularly aligned to the filament axis in the presence of Swi5-Sfr1, whereas the bases are more randomly oriented in the absence of Swi5-Sfr1. When using a modified version of the natural protein where the N-terminal part of Sfr1 is deleted, which has no affinity for DNA but maintained ability to stimulate the strand exchange reaction, we still observe the improved perpendicular DNA base orientation. This indicates that Swi5-Sfr1 exerts its activating effect through interaction with the Rad51 filament mainly and not with the DNA. We propose that the role of a coplanar alignment of nucleobases induced by Swi5-Sfr1 in the presynaptic Rad51/ssDNA complex is to facilitate the critical matching with an invading double-stranded DNA, hence stimulating the strand exchange reaction.

  20. Mass-independent isotopic fractionation of tin in a chemical exchange reaction (United States)

    Fujii, T.; Moynier, F.


    Tin isotopes were fractionated by the liquid-liquid extraction technique with a crown ether, dicyclohexano-18- crown-6 (DC18C6). Tin dichloride was dissolved in HCl to create solutions, 0.1 mol dm-3 (M) Sn(II) in various [HCl]. The organic phase was 0.1 M DC18C6 in 1,2-dichloroethane. A 5 cm3 aqueous solution and a 5 cm3 organic solution were mixed in a glass vial with a stirrer bar, and the glass vial was sealed. The two phases were stirred by a magnetic stirrer, and after the equilibrium, the two phases were separated by centrifugation. An aliquot of the upper aqueous solution was taken for analysis. These procedures were carried out at room temperature. The Sn concentration in the equilibrated aqueous phase was analyzed by ICP-AES. In order to avoid any matrix effect, possible trace of organic materials from DC18C6 was separated from the Sn on a micro-column anion-exchange resin in HBr/HNO3. An aliquot of the aqueous phase was once dried by heating and then dissolved into a HBr solution. Sn was strongly adsorbed while organic materials went through. Finally Sn was collected in a HNO3 solution. A solution containing 300 ppb of Sn in 0.05 M HNO3 was prepared for isotopic analysis. Isotopic ratios of Sn in all samples were analyzed with the MC-ICP-MS Nu plasma 500 HR at ENS Lyon coupled with a desolvating nebulizer Nu DSN-100 (with a typical precision of <100 ppm). The instrumental mass bias was controlled by bracketing each of the samples with standards. Because 120Sn is the most abundant isotopes, the isotope ratios have been measured as mSn/120Sn (m : 116, 117, 118, 119, 122, and 124). 114Sn and 115Sn were not analyzed due to their low abundances. Possible interferences with Cd on the masses 116, with Te on the mass 120, 122 and 124 were verified to be under the detection of the ICP-MS. Odd atomic mass isotopes (117Sn and 119Sn) showed deficits of enrichment comparing to the even atomic mass isotopes (116Sn, 118Sn, 122Sn, and 124Sn). This odd-even staggering

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

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


    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.

  2. Modification of polyamide-CdS-CdSe composite material films with Ag using a cation–cation exchange reaction

    Energy Technology Data Exchange (ETDEWEB)

    Krylova, V.; Žalenkienė, S.; Dukstienė, N. [Department of Physical and Inorganic Chemistry, Kaunas University of Technology, Radvilenu st. 19, LT-50254, Kaunas (Lithuania); Baltrusaitis, J., E-mail: [Department of Chemical and Biomolecular Engineering, Lehigh University, B336 Iacocca Hall, 111 Research Drive, Bethlehem, PA 18015 (United States)


    Highlights: • We investigated deposition of a mixed CdSe-CdS-Ag{sub 2}Se-Ag{sub 2}S on polyamide. • A single chalcogen precursor – K{sub 2}SeS{sub 2}O{sub 6} – was used. • AAS showed five- to ten-fold excess of chalcogens diffused into PA. • Addition of AgNO{sub 3} resulted in subsurface Ag{sub 2}Se–Ag{sub 2}S formation. - Abstract: Thin mixed CdSe-CdS-Ag{sub 2}Se-Ag{sub 2}S films were deposited on a polyamide 6 (PA) surface by successfully using a cation-exchange reaction between Cd{sup 2+} and Ag{sup +} to convert CdSe-CdS into Ag{sub 2}Se-Ag{sub 2}S. These were deposited using a K{sub 2}SeS{sub 2}O{sub 6} precursor solution at 60 °C followed by cadmium acetate (Cd(CH{sub 3}COO){sub 2}). An aqueous AgNO{sub 3} solution was used as the Ag source. XRD patterns showed a complex PA-Cd-S-Se-Ag film crystalline composition with CdS, CdSe, Ag{sub 2}S and Ag{sub 2}Se peaks. Calculated dislocation density ranged within 5–15 × 10{sup 13} lines·m{sup −2} indicating high quality atomic layers. Atomic Absorption Spectroscopy (AAS) showed five- to ten-fold excess of chalcogens to metals in the thin films formed. No chalcogenides were observed on the sample surface during XPS analysis after Ag exchange due to the desorption of CdS and CdSe layers, not diffused into the bulk of the polymer suggesting that silver chalcogenides were located subsurface, as opposed to the outermost layer, likely comprised of Ag{sub 2}O.

  3. Tuning a High Transmission Ion Guide to Prevent Gas-Phase Proton Exchange During H/D Exchange MS Analysis (United States)

    Guttman, Miklos; Wales, Thomas E.; Whittington, Dale; Engen, John R.; Brown, Jeffery M.; Lee, Kelly K.


    Hydrogen/deuterium exchange (HDX) mass spectrometry (MS) for protein structural analysis has been adopted for many purposes, including biopharmaceutical development. One of the benefits of examining amide proton exchange by mass spectrometry is that it can readily resolve different exchange regimes, as evidenced by either binomial or bimodal isotope patterns. By careful analysis of the isotope pattern during exchange, more insight can be obtained on protein behavior in solution. However, one must be sure that any observed bimodal isotope patterns are not artifacts of analysis and are reflective of the true behavior in solution. Sample carryover and certain stationary phases are known as potential sources of bimodal artifacts. Here, we describe an additional undocumented source of deuterium loss resulting in artificial bimodal patterns for certain highly charged peptides. We demonstrate that this phenomenon is predominantly due to gas-phase proton exchange between peptides and bulk solvent within the initial stages of high-transmission conjoined ion guides. Minor adjustments of the ion guide settings, as reported here, eliminate the phenomenon without sacrificing signal intensity. Such gas-phase deuterium loss should be appreciated for all HDX-MS studies using such ion optics, even for routine studies not focused on interpreting bimodal spectra.

  4. Reactive copolymers based on N-vinyl lactams with pyridyl disulfide side groups via RAFT polymerization and postmodification via thiol-disulfide exchange reaction

    NARCIS (Netherlands)

    Peng, Huan; Rübsam, Kristin; Huang, Xiaobin; Jakob, Felix; Karperien, Marcel; Schwaneberg, Ulrich; Pich, Andrij


    Herein, we report the synthesis of a series of novel pyridyl disulfide (PDS)-functionalized statistical reactive copolymers that enable facile access to complex polymeric architectures through highly selective thiol-disulfide exchange reaction with thiol-containing ligands or proteins. Functional

  5. Precision evaluation of the Ga-71(nu(e),e(-)) solar neutrino capture rate from the (He-3,t) charge-exchange reaction

    NARCIS (Netherlands)

    Frekers, D.; Adachi, T.; Akimune, H.; Alanssari, M.; Brown, B. A.; Cleveland, B. T.; Ejiri, H.; Fujita, H.; Fujita, Y.; Fujiwara, M.; Gavrin, V. N.; Harakeh, M. N.; Hatanaka, K.; Holl, M.; Iwamoto, C.; Lennarz, A.; Okamoto, A.; Okamura, H.; Suzuki, T.; Tamii, A.


    A precision measurement of the Ga-71(He-3,t)Ge-71 charge-exchange reaction was performed. By using a rather complete set of theoretical form factors to describe the cross-section angular distributions over a large angular range, the Gamow-Teller strength distribution up to the effective

  6. Catalytic C-H bond activation at nanoscale Lewis acidic aluminium fluorides: H/D exchange reactions at aromatic and aliphatic hydrocarbons. (United States)

    Prechtl, Martin H G; Teltewskoi, Michael; Dimitrov, Anton; Kemnitz, Erhard; Braun, Thomas


    Nanoscopic amorphous Lewis acidic aluminium fluorides, such as aluminium chlorofluoride (ACF) and high-surface aluminium fluoride (HS-AlF(3)), are capable of activating C-H bonds of aliphatic hydrocarbons. H/D exchange reactions are catalysed under mild conditions (40 °C). Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Presolvated Electron Reactions with Methyl Acetoacetate: Electron Localization, Proton-Deuteron Exchange, and H-Atom Abstraction

    Directory of Open Access Journals (Sweden)

    Alex Petrovici


    Full Text Available 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 methyl acetoacetate (MAA, CH3-CO-CH2-COOCH3 at 77 K and subsequent reactions of the anion radical (CH3-CO•−-CH2-COOCH3 in the 77 to ca. 170 K temperature range 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-COOCH3. The ESR spectrum of CH3-C(•OH-CH2-COOCH3 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-COOCH3 in D2O glass shows only the line components due to proton hyperfine couplings of CH3 group. This is expected since the methylene protons in MAA are readily exchangeable in D2O. On stepwise annealing to higher temperatures (ca. 150 to 170 K, CH3-C(•OH-CH2-COOCH3 undergoes bimolecular H-atom abstraction from MAA to form the more stable radical, CH3-CO-CH•-COOCH3. Theoretical calculations using density functional theory (DFT support the radical assignments.

  8. Reaction

    African Journals Online (AJOL)



    May 11, 2011 ... Open-heart surgery and coronary artery bypass grafting in Western Africa. Frank Edwin1,2,&, Kwabena Frimpong-Boateng1 .... Frimpong-Boateng K, Amoah AG, Barwasser HM, Kallen C. Cardiopulmonary bypass in sickle cell anaemia without exchange transfusion.Eur J Cardiothorac Surg. 1998 Nov ...

  9. Two approaches to the clinical dilemma of treating TTP with therapeutic plasma exchange in patients with a history of anaphylactic reactions to plasma. (United States)

    Sidhu, Davinder; Snyder, Edward L; Tormey, Christopher A


    Thrombotic thrombocytopenic purpura (TTP) is a rare but serious disease caused by autoantibody-mediated deficiency in von Willebrand factor (VWF) cleaving protease, ADAMTS-13. The primary acute treatment is therapeutic plasma exchange (TPE). However, some patients can develop allergic/anaphylactic reactions to the replacement (i.e., donor) plasma over time. Two potential treatment strategies for patients with TTP who demonstrate severe allergic reactions to plasma used for exchange were examined. Two patients with TTP exacerbations who developed severe allergic reactions to donor plasma were identified. One patient's TPE was re-initiated with Octaplas, a lot-batched solvent and detergent treated, type-specific, pooled donor plasma product. The other patient was exchanged with primarily albumin, followed by slow incremental exposures to donor plasma to mitigate exposures and allergic risks. Both patients were assessed for anaphylaxis. Both treatment strategies were successful in preventing any further clinically significant allergic/anaphylactic reactions and facilitated both patients' TTP remissions. Based on our experience with two similar patients with TTP exacerbations and history of anaphylactic reactions to plasma during TPE, we have identified two possible treatment protocols to achieve remission in this clinical dilemma. Substituting Octaplas for standard plasma or, alternatively, using albumin with slowly increasing amounts of standard plasma may help to mitigate the risk of further anaphylactic adverse events. J. Clin. Apheresis 32:158-162, 2017. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

  10. Size dependent reactivity of metal nanoparticles and alloys supported on HOPG, probed by the H-D exchange and the NH3 decomposition reactions

    DEFF Research Database (Denmark)

    Fiordaliso, Elisabetta Maria

    the exchange reaction on the nanoparticles and on alloys have been summarized in two scientific articles which have been recently published [1, 2]. The exchange reaction is carried out on supported catalysts. The effect of the interaction between metals and support on the catalytic activity has been......, Rh and Pt thin films, on Ru nanoparticles and on Ir/Ru alloys. Preliminary results indicated that Ru is the most active among the selected metals, but no definitive conclusions can be drawn on the effect of the particle diameter on the decomposition rate. In the case of the Ru/Ir alloys, it is found......This thesis presents the results obtained from experiments performed in an Ultra High Vacuum (UHV) apparatus, named Parallel Screening, consisting of a preparation chamber combined to a High Pressure Cell (HPC) for testing catalytic activity at 1 bar. Two catalytic reactions have been carried out...

  11. Molecular dynamics investigation of water-exchange reactions on lanthanide ions in water/1-ethyl-3-methylimidazolium trifluoromethylsufate ([EMIm][OTf]). (United States)

    Tu, Yi-Jung; Lin, Zhijin; Allen, Matthew J; Cisneros, G Andrés


    We report a kinetic study of the water exchange on lanthanide ions in water/[1-ethyl-3-methylimidazolium][trifluoromethylsufate] (water/[EMIm][OTf]). The results from 17O-NMR measurements show that the water-exchange rates in water/[EMIm][OTf] increase with decreasing size of the lanthanide ions. This trend for water-exchange is similar to the previously reported trend in water/1-ethyl-3-methylimidazolium ethyl sulfate (water/[EMIm][EtSO4]) but opposite to that in water. To gain atomic-level insight into these water-exchange reactions, molecular dynamics simulations for lanthanide ions in water/[EMIm][OTf] have been performed using the atomic-multipole-optimized-energetics-for-biomolecular-application polarizable force field. Our molecular dynamics simulations reproduce the experimental water-exchange rates in terms of the trend and provide possible explanations for the observed experimental behavior. The smaller lanthanide ions in water/[EMIm][OTf] undergo faster water exchange because the smaller lanthanide ions coordinate to the first shell [OTf]- anions more tightly, resulting in a stronger screening effect for the second-shell water. The screening effect weakens the interaction of the lanthanide ions with the second-shell water molecules, facilitating the dissociation of water from the second-shell and subsequent association of water molecules from the outer solvation shells.

  12. 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 (United States)

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


    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.

  13. Exchanged naturality contributions from high-energy polarization measurements in two-body inclusive and exclusive reactions

    CERN Document Server

    Ader, J P


    In the paper, dealing with high-energy quasi-two-body or multiparticle production, the authors focus on what can be learned about exchanged naturality amplitudes from final polarization measurements with polarized or unpolarized beam amd/or target. The separation of t- channel (boson exchange) and u-channel (baryon exchange) exchanges into components of natural and unnatural parity and the measure of naturality interferences are extensively studied in all cases which are now or will be soon available with present experimental techniques. Special attention is paid to the transversity amplitudes which are shown to be always naturality conserving. (19 refs).

  14. General Tritium Labelling of Gentamicin C by catalytic hydrogen exchange Reaction with Tritiated Water; Marcado general con tritio de la Gentamicina C por intercambio catalitico con agua triatiada

    Energy Technology Data Exchange (ETDEWEB)

    Suarez, C.; Diaz, D.; Paz, D.


    Gentamicin C was labelled with tritium by means of a PtO2 catalyzed hydrogen exchange reaction. Under the conditions of the exchange (100 mg of gentamicin, basic form, 0,3 ml H2O-3H, and 50 mg of prereduced PtO2) the radiochemical yield was 0,24, 0,38 and 0,48 % at 120 degree celsius, for 8, 16 and 24 hours respectively. Chemical yield for purified gentamicin was about 60 %. Purification was accomplished with a cellulose column eluted with the lower phase of chloroform-methanol 17 % ammonium hydroxide (2:1:1, v/v) . Chemical purity, determined by HPLC, was 96,5 % and radiochemical one was 95. Main exchange degradation products show biological activity. (Author) 12 refs.

  15. $\\beta$- decay of $^{58}$Zn. A critical test for the charge-exchange reaction as a probe for the $\\beta$- decay strength distribution

    CERN Multimedia


    % IS353 \\\\ \\\\ Due to its importance in fundamental physics and astrophysics, a great effort both theoretically and experimentally is devoted to study Gamow Teller (GT)-strength. The GT-strength and its distribution play a key role in late stellar evolution. During the pre-supernova core-collapse of massive stars, the electron capture and nuclear $\\beta$ -decay determine the electron-to-baryon ratio, which influences the infall dynamics and the mass of the final core. The cross-section of the charge-exchange reaction at forward angles with energies above 100~MeV is expected to be proportional to the squares of Fermi and GT matrix elements. This proportionality should provide a Q-value free method to probe the weak interaction strength and renormalization effects in nuclei. Thus charge-exchange reactions are often used to determine the experimental GT-strength. However, the connection between the GT-strength and the cross-section of the charge-exchange reaction is partially model-dependent and the question aris...

  16. A study of the coordination shell of aluminum(III) and magnesium(II) in model protein environments: thermodynamics of the complex formation and metal exchange reactions. (United States)

    Rezabal, Elixabete; Mercero, Jose M; Lopez, Xabier; Ugalde, Jesus M


    Al(III) toxicity in living organisms is based on competition with other metal cations. Mg(II) is one of the most affected cations, since the size similarity dominates over the charge identity. The slow ligand exchange rates for Al(III) render the ion useless as a metal ion at the active sites of enzymes and provide a mechanism by which Al(III) inhibits Mg(II) dependent biochemical processes. Al(III) cation interactions with relevant bioligands have been studied in a protein-model environment in gas and aqueous phases using density functional theory methods. The protein model consists of the metal cation bound to two chosen bioligands (functional groups of the amino acid side chains, one of them being always an acetate) and water molecules interacting with the cation to complete its first coordination shell. Analogous Mg(II) complexes are calculated and compared with the Al(III) ones. Formation energies of the complexes are calculated in both phases and magnesium/aluminum exchange energies evaluated. The effect of different dielectric media is also analyzed. The presence of an acetate ligand in the binding site is found to promote both, complex formation and metal exchange reactions. In addition, buried binding sites (with low dielectric constant) of the protein favor metal exchange, whereas fully solvated environments of high dielectric constant require the presence of two anionic ligands for metal exchange to occur.

  17. Ratiometric analysis in hyperpolarized NMR (I): test of the two-site exchange model and the quantification of reaction rate constants. (United States)

    Li, Lin Z; Kadlececk, Stephen; Xu, He N; Daye, Dania; Pullinger, Benjamin; Profka, Harrilla; Chodosh, Lewis; Rizi, Rahim


    Conventional methods for the analysis of in vivo hyperpolarized (13) C NMR data from the lactate dehydrogenase (LDH) reaction usually make assumptions on the stability of rate constants and/or the validity of the two-site exchange model. In this study, we developed a framework to test the validity of the assumption of stable reaction rate constants and the two-site exchange model in vivo via ratiometric fitting of the time courses of the signal ratio L(t)/P(t). Our analysis provided evidence that the LDH enzymatic kinetics observed by hyperpolarized NMR are in near-equilibrium and satisfy the two-site exchange model for only a specific time window. In addition, we quantified both the forward and reverse exchange rate constants of the LDH reaction for the transgenic and mouse xenograft models of breast cancer using the ratio fitting method developed, which includes only two modeling parameters and is less sensitive to the influence of instrument settings/protocols, such as flip angles, degree of polarization and tracer dosage. We further compared the ratio fitting method with a conventional two-site exchange modeling method, i.e. the differential equation fitting method, using both the experimental and simulated hyperpolarized NMR data. The ratio fitting method appeared to fit better than the differential equation fitting method for the reverse rate constant on the mouse tumor data, with less relative errors on average, whereas the differential equation fitting method also resulted in a negative reverse rate constant for one tumor. The simulation results indicated that the accuracy of both methods depends on the width of the transport function, noise level and rate constant ratio; one method may be more accurate than the other based on the experimental/biological conditions aforementioned. We were able to categorize our tumor models into specific conditions of the computer simulation and to estimate the errors of rate quantification. We also discussed possible

  18. Carbon isotope exchange between gaseous CO2 and thin solution films: Artificial cave experiments and a complete diffusion-reaction model (United States)

    Hansen, Maximilian; Scholz, Denis; Froeschmann, Marie-Louise; Schöne, Bernd R.; Spötl, Christoph


    Speleothem stable carbon isotope (δ13C) records provide important paleoclimate and paleo-environmental information. However, the interpretation of these records in terms of past climate or environmental change remains challenging because of various processes affecting the δ13C signals. A process that has only been sparsely discussed so far is carbon isotope exchange between the gaseous CO2 of the cave atmosphere and the dissolved inorganic carbon (DIC) contained in the thin solution film on the speleothem, which may be particularly important for strongly ventilated caves. Here we present a novel, complete reaction diffusion model describing carbon isotope exchange between gaseous CO2 and the DIC in thin solution films. The model considers all parameters affecting carbon isotope exchange, such as diffusion into, out of and within the film, the chemical reactions occurring within the film as well as the dependence of diffusion and the reaction rates on isotopic mass and temperature. To verify the model, we conducted laboratory experiments under completely controlled, cave-analogue conditions at three different temperatures (10, 20, 30 °C). We exposed thin (≈0.1 mm) films of a NaHCO3 solution with four different concentrations (1, 2, 5 and 10 mmol/l, respectively) to a nitrogen atmosphere containing a specific amount of CO2 (1000 and 3000 ppmV). The experimentally observed temporal evolution of the pH and δ13C values of the DIC is in good agreement with the model predictions. The carbon isotope exchange times in our experiments range from ca. 200 to ca. 16,000 s and strongly depend on temperature, film thickness, atmospheric pCO2 and the concentration of DIC. For low pCO2 (between 500 and 1000 ppmV, as for strongly ventilated caves), our time constants are substantially lower than those derived in a previous study, suggesting a potentially stronger influence of carbon isotope exchange on speleothem δ13C values. However, this process should only have an

  19. Resonance Effects in Mixed Hydrogen-Deuterium Crystals

    DEFF Research Database (Denmark)

    Powell, B. M.; Nielsen, Mourits


    Neutron scattering measurements of the impurity induced resonance mode caused by orthodeuterium as a substitutional impurity in solid h.c.p. parahydrogen are found to be in qualitative agreement with simple mass defect theory predictions. The samples studied contained 11-, 10-, and 6 at.% deuterium...... and the observations were made along the [100] and the [110] directions in the basal plane. Some discrepancies are found to exist in the detailed quantitative comparison of the phonon shifts and widths and in the intensity of the resonance mode...

  20. The spin-parity structure of the $(K^{-}\\pi^{+})$ and $(\\overline{K}^{0}\\pi^{+}\\pi^{-})$ systems produced in charged exchange reactions

    CERN Document Server

    Sotiriou, D S


    Partial wave analyses have been performed for the $(K^-\\pi^+)$ and $(K^{-O}\\pi^+\\pi^-)$ systems produced in the reactions $K^-p\\to K^-\\pi^+$ n and $K^-p\\to K^{-O}\\pi^+\\pi^-$ n, respectively. It is found that the S-wave $(K^-\\pi^+)$ system is consistent with a Breit-Wigner shape peaked at 1.3 GeV and 0.6 GeV wide . The low mass $(K^{-O}\\pi^+\\pi^-)$ system composed mainly of $J^P$ = $o^-$ , $l^+$ and $2^+$ states, resembles in its structure the $(K^{\\pi}{\\pi}^-)$ ­ system produced in diffractive reactions. This implies, in particular , that the presence of unnatural spin-parity states produced by natural parity exchanges cannot be considered as an exclusive characteristic of diffractive processes. A method of analysing the $(N^{\\pi})$ systems is described.

  1. Ion-Exchange Reaction Of A-Site In A2Ta2O6 Pyrochlore Crystal Structure

    Directory of Open Access Journals (Sweden)

    Matsunami M.


    Full Text Available Na+ or K+ ion rechargeable battery is started to garner attention recently in Place of Li+ ion cell. It is important that A+ site ion can move in and out the positive-electrode materials. When K2Ta2O6 powder had a pyrochlore structure was only dipped into NaOH aqueous solution at room temperature, Na2Ta2O6 was obtained. K2Ta2O6 was fabricated from a tantalum sheet by a hydrothermal synthesize with KOH aqueous solution. When Na2Ta2O6 was dipped into KOH aqueous solution, K2Ta2O6 was obtained again. If KTaO3 had a perovskite structure was dipped, Ion-exchange was not observed by XRD. Because a lattice constant of pyrochlore structure of K-Ta-O system is bigger than perovskite, K+ or Na+ ion could shinny through and exchange between Ta5+ and O2− ion site in a pyrochlore structure. K+ or Na+ ion exchange of A2Ta2O6 pyrochlore had reversibility. Therefore, A2Ta2O6 had a pyrochlore structure can be expected such as Na+ ion rechargeable battery element.

  2. Identification of the protein kinase A regulatory RIalpha-catalytic subunit interface by amide H/2H exchange and protein docking. (United States)

    Anand, Ganesh S; Law, Dennis; Mandell, Jeffrey G; Snead, Aaron N; Tsigelny, Igor; Taylor, Susan S; Ten Eyck, Lynn F; Komives, Elizabeth A


    An important goal after structural genomics is to build up the structures of higher-order protein-protein complexes from structures of the individual subunits. Often structures of higher order complexes are difficult to obtain by crystallography. We have used an alternative approach in which the structures of the individual catalytic (C) subunit and RIalpha regulatory (R) subunit of PKA were first subjected to computational docking, and the top 100,000 solutions were subsequently filtered based on amide hydrogen/deuterium (H/2H) exchange interface protection data. The resulting set of filtered solutions forms an ensemble of structures in which, besides the inhibitor peptide binding site, a flat interface between the C-terminal lobe of the C-subunit and the A- and B-helices of RIalpha is uniquely identified. This holoenzyme structure satisfies all previous experimental data on the complex and allows prediction of new contacts between the two subunits.

  3. A reactant-coordinate-based wave packet method for full-dimensional state-to-state quantum dynamics of tetra-atomic reactions: Application to both the abstraction and exchange channels in the H + H2O reaction. (United States)

    Zhao, Bin; Sun, Zhigang; Guo, Hua


    An efficient and accurate wave packet method is proposed for the calculation of the state-to-state S-matrix elements in bimolecular reactions involving four atoms. This approach propagates an initial state specific wave packet in reactant Jacobi coordinates. The projection in product channels is carried out on projection planes, which have one less degree of freedom, by transforming both the time-dependent wave packet and final product states into a set of intermediate coordinates. This reactant-coordinate-based method is more efficient than product-coordinate-based methods because it typically requires a smaller number of basis functions or grid points and allows the determination of S-matrix elements for multiple product channels from a single propagation. This method is demonstrated in calculating the (Jtot = 0) state-to-state S-matrix elements for both the abstraction and exchange channels of the H + H2O reaction.

  4. Calculating constants of the rates of the reactions of excitation, ionization, and atomic exchange: A model of a shock oscillator with a change of the Hamiltonian of the system (United States)

    Tsyganov, D. L.


    A new model for calculating the rates of reactions of excitation, ionization, and atomic exchange is proposed. Diatomic molecule AB is an unstructured particle M upon the exchange of elastic-vibrational (VT) energy, i.e., a model of a shock forceful oscillator with a change in Hamiltonian (SFOH). The SFOH model is based on the quantum theory of strong perturbations. The SFOH model allows generalization in simulating the rates of the reactions of excitation, ionization, and atomic exchange in the vibrational-vibrational (VV) energy exchange of diatomic molecules, and the exchange of VV- and VT-energy of polyatomic molecules. The rate constants of the excitation of metastables A 3Σ u +, B 3Π g , W 3Δ u , B'3Σ u -, a'3Σ u -, and the ionization of a nitrogen molecules from ground state X2Σ g + upon a collision with a heavy structureless particle (a nitrogen molecule), are found as examples.

  5. Determination of labile Fe(II) species complexed with seawater extractable organic matter under seawater conditions based on the kinetics of ligand-exchange reactions with ferrozine. (United States)

    Iwai, Hisanori; Fukushima, Masami; Yamamoto, Mitsuo


    A fertilizer, comprised of a mixture of steel slag and compost, was used to restore seaweed beds in barren coastal areas. Complex Fe(II) species, supplied by steel slag, play a significant role in supplying Fe(II) to coastal areas and stimulating seaweed growth. Seawater extractable organic matter (SWEOM) from compost is generally assumed to serve as a chelator of Fe(II) in the fertilizer. It is considered that the bioavailability of Fe(II)-SWEOM complexes is higher in the dissociable (labile) species. In the present study, a method for determining labile species of Fe(II)-SWEOM complexes in seawater (pH 8.0, I = 0.7) was developed. The method is based on a ligand-exchange reaction between SWEOM and ferrozine (FZ). Because Fe(II) is readily oxidized to Fe(III) under normal seawater conditions, ascorbic acid was added as an antioxidant. The coloring for the Fe-FZ complex in the presence of SWEOM was retarded. This retarding can be attributed to a ligand-exchange reaction between FZ and labile Fe(II)-SWEOM complexes. Conditional binding constants for the labile Fe(II)-SWEOM complexes and binding capacities of labile sites in SWEOM to Fe(II) were evaluated for a variety of total Fe(II) concentrations.

  6. Synthesis and radioiodination of di-iodo-Evan's blue via isotopic exchange reaction in the molten state and evaluation of the kinetics

    Energy Technology Data Exchange (ETDEWEB)

    El-Azony, K.M. [Research Center Juelich (Germany). Inst. of Nuclear Chemistry]|[Hot Lab. Center, Cairo (Egypt). Radioactive Isotopes and Generators Dept.; Bier, D.; Coenen, H.H. [Research Center Juelich (Germany). Inst. of Nuclear Chemistry


    Many aryl halides were synthesized from aryl amines such as iodo-trypan, iodo-methylene blue and iodo-toluidine. Methylene blue and toludine blue are phenothiazinium dyes and were used to localize parathyroid glands visually during surgery. Radioiodination of these compounds by using iodine-123 analogues for scintgraphic localization of parathyroids was reported. Radiolabelled dyes administered may also localize in tumor tissues. Evan's blue dye was used to study altered sarcolemmal permeability in dystrophic muscle fibers, and in animals to study muscular dystrophy. In this work Diiodo-Evan's blue was synthesized via Sandmeyer reaction and characterized by mass spectrum analysis. A procedure for labelling DIEB with Na{sup 131}I via isotopic exchange in molten medium was developed. The labelling conditions studied for the isotopic exchange of {sup 131}I-for-I in DIEB included the effect of temperature and solvents (melt of acetamide, benzoic and pivalic acid). Kinetic studies were performed to obtain [{sup 131}I] DIEB with more reliable reaction conditions. Quality control for the final product ([{sup 131}I] DIEB) was performed by HPLC. (orig.)

  7. Anion-exchange reactions on a robust phosphonium photopolymer for the controlled deposition of ionic gold nanoclusters. (United States)

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


    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.

  8. Synthesis and hydrolysis of ATP and the phosphate-ATP exchange reaction in soluble mitochondrial F1 in the presence of dimethylsulfoxide. (United States)

    Tuena de Gómez-Puyou, M; Pérez-Hernández, G; Gómez-Puyou, A


    increase in water activity. The effect of solvent is fully reversible. In comparison to other enzymes, F1 seems unique in that solvent controls the equilibrium that exists within an enzyme population. This results from the effect of solvent on the partition of Pi between the catalytic site and the medium, and the large energetic barrier that prevents release of ATP from the catalytic site. In the presence of dimethylsulfoxide and Pi, ATP is continuously hydrolyzed and synthesized with formation and uptake of Pi from the medium. This process is essentially an exchange reaction analogous to the phosphate-ATP exchange reaction that is catalyzed by the ATP synthase in coupled energy transducing membranes.

  9. Search for $\\Sigma$ Hypernuclear States using the Strangeness Exchange Reactions $(K^{-},\\pi^{-})$ and $(K^{-},\\pi^{+})$

    CERN Multimedia


    In previous $\\Lambda$ hypernuclei experiments details of the $\\Lambda$ nucleus interaction have been deduced, the most outstanding being a very small spin orbit interaction in p$^{-}$ and sd shell $\\Lambda$ hypernuclei. This kind of information is decisive in the understanding of the baryon interaction and will contribute to distinguish between the boson exchange and the QCD motivated picture of the baryon baryon interaction. To further exploit the hyperon nucleus interaction one has to investigate hypernuclei with hyperons of different quark configuration, i.e. $\\Sigma$ hypernuclei. Since the $\\Sigma\\$ particle can, in contrast to the $\\Lambda$, decay by strong interaction in the nucleus, the existence of narrow states was not obvious. A small momentum transfer guarantees that the spectra are dominated by a few strong transitions to narrow hypernuclear states with the same spin and space quantum numbers as the target nucleus. Therefore a new kaon beamline was built with a lower momentum of 400~MeV/c and a co...

  10. Solution-phase deuterium/hydrogen exchange at a specific residue using nozzle-skimmer and electron capture dissociation mass spectrometry. (United States)

    Hagman, Charlotte; Tsybin, Yury O; Håkansson, Per


    Information about protein conformation can be obtained with hydrogen/deuterium exchange (HDX) mass spectrometry. The isotopic solution-phase exchange of specific amide hydrogen atoms can be followed using low-vacuum nozzle-skimmer collision-induced dissociation (CID). In this study, the nozzle-skimmer technique was complemented by electron capture dissociation (ECD) Fourier transform ion cyclotron resonance mass spectrometry (FTICRMS). The solution-phase exchange at a specific residue is monitored by comparing isotopic distributions of two consecutive b- or c-type ions. While nozzle-skimmer fragmentation takes place in the low-vacuum region of the mass spectrometer, ECD occurs at ultra-high vacuum within the mass analyzer cell of the FTICR mass spectrometer. The dissociations take place at 10(-4) and 10(-9) mbar, respectively. Low-vacuum nozzle-skimmer fragmentation can result in intramolecular exchange between product ions and solvent molecules in the gas phase. Consequently, the solution-phase information about protein or peptide conformation is lost. It was not possible to monitor isotopic solution-phase exchange at the eighth residue in substance P, (Phe)8, with nozzle-skimmer CID. By using the in-cell ECD fragmentation method, the solution-phase exchange at the (Phe)8 residue was preserved during mass spectrometric analysis. This result shows the complementary aspects of applying fragmentation at low and at high vacuum, when studying isotopic exchange in solution at specific residues using FTICRMS. Copyright 2006 John Wiley & Sons, Ltd.

  11. Ligand Exchange Reactions of a Monomeric Zirconium Carbonate Complex with Carboxylic Acids Studied by Extended X-ray Absorption Fine Structure, UV Absorption and Raman Spectrophotometry. (United States)

    Takasaki, Fumiyuki; Fujiwara, Kazuhiko; Kikuchi, Tomomi; Tanno, Takenori; Nakajima, Yasushi; Toyoda, Yasunori; Ogawa, Nobuaki


    Ligand exchange reactions of a monomeric zirconium carbonate complex with carboxylic acids were studied by means of extended X-ray absorption fine structure (EXAFS), UV absorption spectrophotometry and Raman spectrometry. Three carboxylic acids, gluconic acid, and L-tartaric acid and citric acid, which are mono-, di- and tri-carboxylic acids, respectively, were employed in this study. These three carboxylic acids gave different spectral signatures and concentration dependences, respectively. In the gluconic acid system, the peaks on Fourier transform of EXAFS spectrum and Raman spectrum caused by carbonate ion coordinating to zirconium atom were obviously decreased with increasing gluconic acid concentration compared to the other two carboxylic acid systems. This indicates the high association ability of gluconic acid to zirconium, which was revealed by UV spectrophotometric analysis.

  12. Perturbative QCD versus pion exchange and hadronic FSI effects in the {gamma}{gamma}{yields}{pi}{sup +}{pi}{sup -} reaction

    Energy Technology Data Exchange (ETDEWEB)

    Szczurek, A. E-mail:; Speth, J


    The interplay of pQCD, pion exchange and FSI effects is studied for the {gamma}{gamma}{yields}{pi}{sup +}{pi}{sup -} reaction in the region of 2 GeV exchange amplitudes up to W{sub {gamma}}{sub {gamma}}{approx} 4 GeV. We discuss to which extend the conventional hadronic FSI effects could cloud the pQCD effects. We study multiple soft and hard scattering effects as well as the coupling between final state hadronic channels. We show how the perturbative effects in {gamma}{gamma}{yields}{rho}{rho} may mix with perturbative effects in {gamma}{gamma}{yields}{pi}{sup +}{pi}{sup -}. The effects discussed in this paper improve the agreement with the new data of the DELPHI and ALEPH Collaborations. We give estimates of the onset of the pQCD regime. Predictions for {gamma}{gamma}{yields}{pi}{sup 0}{pi}{sup 0} are presented.

  13. Determination of insecticides in water using in situ halide exchange reaction-assisted ionic liquid dispersive liquid-liquid microextraction followed by high-performance liquid chromatography. (United States)

    Li, Songqing; Gao, Haixiang; Zhang, Jiaheng; Li, Yubo; Peng, Bing; Zhou, Zhiqiang


    A dispersive liquid-liquid microextraction (DLLME) method using in situ halide exchange reaction to form ionic liquid (IL) extraction phase was developed to determine four insecticides (i.e. methoxyfenozide, tetrachlorvinphos, thiamethoxam, and diafenthiuron) in water samples. The preconcentration procedure, followed by high-performance liquid chromatography and variable wavelength detectors (VWD), enabled the formation of the immiscible IL extraction phase; the insecticides were transferred into the IL phase simultaneously, which enhanced the efficiency and sufficiency, greatly shortening the operation time. The experimental parameters affecting the extraction efficiency including volume of extraction IL, extraction and centrifugation times, volume of the sample solution and exchanging reagent, and addition of organic solvent and salt were investigated and optimized. Under optimized conditions, the extractions yielded recoveries of the target analytes from 82 to 102%. The calibration curves were linear, and the correlation coefficient ranged from 0.9990 to 0.9999 under the concentration levels of 5-200 μg/L. The relative standard deviation (n=6) was 2.9-4.6%. The limits of detection (LODs) for the four insecticides were between 0.98 and 2.54 μg/L. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. $k^{*0}$(890) polarization measurements in the hypercharge exchange reaction $\\pi^{-}p \\to k^{*0}(890)\\Lambda^{0}/\\Sigma^{0}$ at 10 GeV/c

    CERN Document Server

    Picciarelli, V; Armstrong, A G; Bröring, A; Cluskey, A; Costa, A; Donald, A; Edwards, D N; Edwards, M; Evangelista, A; French, A; Ghidini, A; Gordon, A; Houlden, A; Hughes, A; Lewis, A; Mandelli, A; Mättig, P; Miller, A; Mitaroff, A; Müller, A; Palano, A; Palazzi-Cerrina, C; Paul, A; Pensotti, A; Perini, A; Pregernig, Ludwig F; Ruhmer, A; Strub, A; Thompson, A; Turnbull, A; Woodworth, A A; Zito, A


    K*/sup 0/(890) production in the hypercharge exchange reaction pi /sup -/p to K*/sup 0/(890) Lambda /sup 0// Sigma /sup 0/ at 10 GeV/c (28448 events) is discussed. An amplitude analysis in the t' range up to 1 Ge V/sup 2/ shows that the production mechanism is dominated by Natural Parity Exchange ( approximately 84%). Comparisons are made with predictions from a Regge model and a quark model.

  15. Simple setup for gas-phase h/d exchange mass spectrometry coupled to electron transfer dissociation and ion mobility for analysis of polypeptide structure on a liquid chromatographic time scale

    DEFF Research Database (Denmark)

    Mistarz, Ulrik Hvid; Brown, Jeffery M; Haselmann, Kim F


    with liquid chromatography and a chip-based automated nanoESI interface, allowing for online gas-phase HDX-MS analysis of peptides and proteins separated on a liquid chromatographic time scale at increased throughput. Furthermore, online gas-phase HDX-MS could be performed in tandem with ion mobility......Gas-phase hydrogen/deuterium exchange (HDX) is a fast and sensitive, yet unharnessed analytical approach for providing information on the structural properties of biomolecules, in a complementary manner to mass analysis. Here, we describe a simple setup for ND3-mediated millisecond gas-phase HDX...... gas immediately upstream or downstream of the primary skimmer cone. The approach was implemented on three commercially available mass spectrometers and required no or minor fully reversible reconfiguration of gas-inlets of the ion source. Results from gas-phase HDX-MS of peptides using the aqueous ND3...

  16. Synthesis and characterization of high performing Fe-N-C catalyst for oxygen reduction reaction (ORR) in Alkaline Exchange Membrane Fuel Cells (United States)

    Hossen, Md Mosaddek; Artyushkova, Kateryna; Atanassov, Plamen; Serov, Alexey


    In this article, three different Fe-N-C oxygen reduction reaction (ORR) catalysts derived from different organic molecules i.e. Fe-NMG, Fe-NMP, Fe-MBZ have been synthesized, characterized by physical-chemical methods and studied in the reaction of oxygen reduction (ORR). It is found that Fe-NMG shows higher ORR performance than Fe-NMP and Fe-MBZ, by both rotating ring disk electrode (RRDE) and fuel cell tests. From characterization and surface analysis, it can be explained that the presence of higher amount of surface oxides and pyridinic nitrogen is the main reason for better performance towards ORR in alkaline media. To achieve the highest performance in alkaline exchange membrane fuel cell (AEMFC), the optimization of catalyst layer composition using various concentrations of ionomer (Tokuyama, AS4) was performed. At the optimum cathode layer configuration utilizing Fe-NMG produces the peak power density of 218 mWcm-2, which is one of the highest values presented in the open literature.

  17. Additional evidence that transaldolase exchange, isotope discrimination during the triose-isomerase reaction, or both occur in humans: effects of type 2 diabetes. (United States)

    Basu, Rita; Chandramouli, Visvanthan; Schumann, William; Basu, Ananda; Landau, Bernard R; Rizza, Robert A


    To determine whether deuterium enrichment on carbons 5 and 3 (C5/C3) in plasma glucose is influenced by processes other than gluconeogenesis and, if so, whether these processes are altered by type 2 diabetes. In this study, 10 obese diabetic and 10 obese nondiabetic subjects were infused intravenously with [3,5-(2)H(2)] galactose enriched at a C5-to-C3 ratio of 1.0 as well as the enrichment of deuterium on C5 and C3 of plasma glucose, measured with nuclear magnetic resonance using the acetaminophen glucuronide method. The ratio of deuterium enrichment on C5 and C3 of glucose was deuterium at the level of the triose-isomerase reaction, or both occur in humans. This also indicates that the net effect of these processes on the C5-to-C3 ratio is the same in people with and without type 2 diabetes. The possible effects of transaldolase exchange or selective retention of deuterium (or tritium) at the level of the triose-isomerase reaction on tracee labeling and tracer metabolism should be considered when the deuterated water method is used to measure gluconeogenesis or [3-(3)H] glucose is used to measure glucose turnover in humans.

  18. Submolecular regulation of cell transformation by deuterium depleting water exchange reactions in the tricarboxylic acid substrate cycle. (United States)

    Boros, László G; D'Agostino, Dominic P; Katz, Howard E; Roth, Justine P; Meuillet, Emmanuelle J; Somlyai, Gábor


    The naturally occurring isotope of hydrogen ((1)H), deuterium ((2)H), could have an important biological role. Deuterium depleted water delays tumor progression in mice, dogs, cats and humans. Hydratase enzymes of the tricarboxylic acid (TCA) cycle control cell growth and deplete deuterium from redox cofactors, fatty acids and DNA, which undergo hydride ion and hydrogen atom transfer reactions. A model is proposed that emphasizes the terminal complex of mitochondrial electron transport chain reducing molecular oxygen to deuterium depleted water (DDW); this affects gluconeogenesis as well as fatty acid oxidation. In the former, the DDW is thought to diminish the deuteration of sugar-phosphates in the DNA backbone, helping to preserve stability of hydrogen bond networks, possibly protecting against aneuploidy and resisting strand breaks, occurring upon exposure to radiation and certain anticancer chemotherapeutics. DDW is proposed here to link cancer prevention and treatment using natural ketogenic diets, low deuterium drinking water, as well as DDW production as the mitochondrial downstream mechanism of targeted anti-cancer drugs such as Avastin and Glivec. The role of (2)H in biology is a potential missing link to the elusive cancer puzzle seemingly correlated with cancer epidemiology in western populations as a result of excessive (2)H loading from processed carbohydrate intake in place of natural fat consumption. Published by Elsevier Ltd.

  19. Investor Reaction to Market Surprises on the Istanbul Stock Exchange Investor Reaction to Market Surprises on the Istanbul Stock Exchange = İstanbul Menkul Kıymetler Borsasında Piyasa Sürprizlerine Yatırımcı Tepkisi

    Directory of Open Access Journals (Sweden)

    Yaman Ömer ERZURUMLU


    Full Text Available This paper examines the reaction of investors to the arrival of unexpected information on the Istanbul Stock Exchange. The empirical results suggest that the investor reaction following unexpected news on the ISE100 is consistent with Overreaction Hypothesis especially after unfavorable market surprises. Interestingly such pattern does not exist for ISE30 index which includes more liquid and informationally efficient securities. A possible implication of this study for investors is that employing a semi contrarian investment strategy of buying losers in ISE100 may generate superior returns. Moreover, results are supportive of the last regulation change of Capital Market Board of Turkey which mandates more disclosure regarding the trading of less liquid stocks with lower market capitalization.

  20. Use of deuterium labeling by high-temperature solid-state hydrogen-exchange reaction for mass spectrometric analysis of bradykinin biotransformation. (United States)

    Kopylov, Arthur T; Myasoedov, Nikolay F; Dadayan, Alexander K; Zgoda, Victor G; Medvedev, Alexei E; Zolotarev, Yurii A


    Studies of molecular biodegradation by mass spectrometry often require synthetic compounds labeled with stable isotopes as internal standards. However, labeling is very expensive especially when a large number of compounds are needed for analysis of biotransformation. Here we describe an approach for qualitative and quantitative analysis using bradykinin (BK) and its in vitro degradation metabolites as an example. Its novelty lies in the use of deuterated peptides which are obtained by a high-temperature solid-state exchange (HSCIE) reaction. Deuterated and native BK were analyzed by positive electrospray ionization high-resolution mass spectrometry (ESI-HRMS) using an Orbitrap Fusion mass spectrometer. High-energy collision-induced dissociation (HCD) experiments were performed on [M+H](+) and [M+2H](2+) ions in targeted-MS(2) mode with adjusted normalized HCD value. After the HSCIE reaction, each amino acid residue of the deuterated peptide contained deuterium atoms and the average degree of substitution was 5.5 atoms per the peptide molecule. The deuterated peptide demonstrated the same chromatographic mobility as the unlabeled counterpart, and lack of racemization during substitution with deuterium. Deuterium-labeled and unlabeled BKs were incubated with human plasma and their corresponding fragments BK(1-5) and BK(1-7), well known as the major metabolites, were detected. Quantitative assays demonstrated applicability of the heavy peptide for both sequencing and quantification of generated fragments. Applicability of the HSCIE deuterated peptide for analysis of routes of its degradation has been shown in in vitro experiments. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

  1. Ion-exchange separation of radioiodine and its application to production of {sup 124}I by alpha particle induced reactions on antimony

    Energy Technology Data Exchange (ETDEWEB)

    Shuza Uddin, Md. [Forschungszentrum Juelich (Germany). Inst. fuer Neurowissenschaften und Medizin, INM-5: Nuklearchemie; Atomic Energy Research Establishment, Inst. of Nuclear Science and Technology, Dhaka (Bangladesh); Qaim, Seyed M.; Spahn, Ingo; Spellerberg, Stefan; Scholten, Bernhard; Coenen, Heinz H. [Forschungszentrum Juelich (Germany). Inst. fuer Neurowissenschaften und Medizin, INM-5: Nuklearchemie; Hermanne, Alex [Vrije Univ. Brussel (Belgium). Cyclotron Lab.; Hossain, Syed Mohammod [Atomic Energy Research Establishment, Inst. of Nuclear Science and Technology, Dhaka (Bangladesh)


    The basic parameters related to radiochemical separation of iodine from tellurium and antimony by anion-exchange chromatography using the resin Amberlyst A26 were studied. The separation yield of {sup 124}I amounted to 96% and the decontamination factor from {sup 121}Te and {sup 122}Sb was > 10{sup 4}. The method was applied to the production of {sup 124}I via the {sup 123}Sb(α, 3n) reaction. In an irradiation of 110 mg of {sup nat}Sb{sub 2}O{sub 3} (thickness ∝0.08 g/cm{sup 2}) with 38 MeV α-particles at 1.2 μA beam current for 4 h, corresponding to the beam energy range of E{sub α} = 37 → 27 MeV, the batch yield of {sup 124}I obtained was 12.42 MBq and the {sup 125}I and {sup 126}I impurities amounted to 3.8% and 0.7%, respectively. The experimental batch yield of {sup 124}I amounted to 80% of the theoretically calculated value but the level of the radionuclidic impurities were in agreement with the theoretical values. About 96% of the radioiodine was in the form of iodide and the inactive impurities (Te, Sb, Sn) were below the permissible level. Due to the relatively high level of radionuclidic impurity the {sup 124}I produced would possibly be useful only for restricted local consumption or for animal experiments.

  2. Effect of solvent on the lithium-bromine exchange of aryl bromides: reactions of n-butyllithium and tert-butyllithium with 1-bromo-4-tert-butylbenzene at 0 degrees C. (United States)

    Bailey, William F; Luderer, Mark R; Jordan, Kevin P


    The outcome of reactions of 1-bromo-4-tert-butylbenzene (1), a representative aryl bromide, with n-BuLi or t-BuLi at 0 degrees C in a variety of solvent systems has been investigated. The products of reactions of 1 with n-BuLi vary significantly with changes in solvent composition: 1 does not react with n-BuLi in pure heptane; the exchange reaction to give (4-tert-butylphenyl)lithium, which is slow in pure diethyl ether, is virtually quantitative in heptane containing a small quantity of THF; and the reaction of 1 with n-BuLi in THF leads to considerable coupling. Lithium-bromine exchange is the virtually exclusive outcome of reactions of 1 with t-BuLi in every solvent studied except pure heptane: the presence of a small quantity of any of a variety of structurally diverse ethers (Et(2)O, THF, THP, MTBE) in the predominantly hydrocarbon medium affords (4-tert-butylphenyl)lithium, assayed as tert-butylbenzene, in yields exceeding 97%. The only side products observed from reactions of 1 with t-BuLi are small amounts of benzyne-derived hydrocarbons.

  3. Isotopic Exchange HPLC-HRMS/MS Applied to Cyclic Proanthocyanidins in Wine and Cranberries (United States)

    Longo, Edoardo; Rossetti, Fabrizio; Scampicchio, Matteo; Boselli, Emanuele


    Cyclic B-type proanthocyanidins in red wines and grapes have been discovered recently. However, proanthocyanidins of a different chemical structure (non-cyclic A-type proanthocyanidins) already known to be present in cranberries and wine possess an identical theoretical mass. As a matter of fact, the retention times and the MS/MS fragmentations found for the proposed novel cyclic B-type tetrameric proanthocyanidin in red wine and the known tetrameric proanthocyanidin in a cranberry extract are herein shown to be identical. Thus, hydrogen/deuterium (H/D) exchange was applied to HPLC-HRMS/MS to confirm the actual chemical structure of the new oligomeric proanthocyanidins. The comparison of the results in water and deuterium oxide and between wine and cranberry extract indicates that the cyclic B-type tetrameric proanthocyanidin is the actual constituent of the recently proposed novel tetrameric species ([C60H49O24]+, m/z 1153.2608). Surprisingly, the same compound was also identified as the main tetrameric proanthocyanidin in cranberries. Finally, a totally new cyclic B-type hexameric proanthocyanidin ([C90H73O36]+, m/z 1729.3876) belonging to this novel class was identified for the first time in red wine. [Figure not available: see fulltext.

  4. Ric-8A, a G protein chaperone with nucleotide exchange activity induces long-range secondary structure changes in Gα. (United States)

    Kant, Ravi; Zeng, Baisen; Thomas, Celestine J; Bothner, Brian; Sprang, Stephen R


    Cytosolic Ric-8A has guanine nucleotide exchange factor (GEF) activity and is a chaperone for several classes of heterotrimeric G protein α subunits in vertebrates. Using Hydrogen-Deuterium Exchange-Mass Spectrometry (HDX-MS) we show that Ric-8A disrupts the secondary structure of the Gα Ras-like domain that girds the guanine nucleotide-binding site, and destabilizes the interface between the Gαi1 Ras and helical domains, allowing domain separation and nucleotide release. These changes are largely reversed upon binding GTP and dissociation of Ric-8A. HDX-MS identifies a potential Gα interaction site in Ric-8A. Alanine scanning reveals residues crucial for GEF activity within that sequence. HDX confirms that, like G protein-coupled receptors (GPCRs), Ric-8A binds the C-terminus of Gα. In contrast to GPCRs, Ric-8A interacts with Switches I and II of Gα and possibly at the Gα domain interface. These extensive interactions provide both allosteric and direct catalysis of GDP unbinding and release and GTP binding.

  5. Microscopic insight into role of protein flexibility during ion exchange chromatography by nuclear magnetic resonance and quartz crystal microbalance approaches. (United States)

    Hao, Dongxia; Ge, Jia; Huang, Yongdong; Zhao, Lan; Ma, Guanghui; Su, Zhiguo


    Driven by the prevalent use of ion exchange chromatography (IEC) for polishing therapeutic proteins, many rules have been formulated to summarize the different dependencies between chromatographic data and various operational parameters of interest based on statically determined interactions. However, the effects of the unfolding of protein structures and conformational stability are not as well understood. This study focuses on how the flexibility of proteins perturbs retention behavior at the molecular scale using microscopic characterization approaches, including hydrogen-deuterium (H/D) exchange detected by NMR and a quartz crystal microbalance (QCM). The results showed that a series of chromatographic retention parameters depended significantly on the adiabatic compressibility and structural flexibility of the protein. That is, softer proteins with higher flexibility tended to have longer retention times and stronger affinities on SP Sepharose adsorbents. Tracing the underlying molecular mechanism using NMR and QCM indicated that an easily unfolded flexible protein with a more compact adsorption layer might contribute to the longer retention time on adsorbents. The use of NMR and QCM provided a previously unreported approach for elucidating the effect of protein structural flexibility on binding in IEC systems. Copyright © 2016. Published by Elsevier B.V.

  6. Microfluidic chemical reaction circuits (United States)

    Lee, Chung-cheng [Irvine, CA; Sui, Guodong [Los Angeles, CA; Elizarov, Arkadij [Valley Village, CA; Kolb, Hartmuth C [Playa del Rey, CA; Huang, Jiang [San Jose, CA; Heath, James R [South Pasadena, CA; Phelps, Michael E [Los Angeles, CA; Quake, Stephen R [Stanford, CA; Tseng, Hsian-rong [Los Angeles, CA; Wyatt, Paul [Tipperary, IE; Daridon, Antoine [Mont-Sur-Rolle, CH


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

  7. Proton translocation in cytochrome c oxidase: insights from proton exchange kinetics and vibrational spectroscopy. (United States)

    Ishigami, Izumi; Hikita, Masahide; Egawa, Tsuyoshi; Yeh, Syun-Ru; Rousseau, Denis L


    Cytochrome c oxidase is the terminal enzyme in the electron transfer chain. It reduces oxygen to water and harnesses the released energy to translocate protons across the inner mitochondrial membrane. The mechanism by which the oxygen chemistry is coupled to proton translocation is not yet resolved owing to the difficulty of monitoring dynamic proton transfer events. Here we summarize several postulated mechanisms for proton translocation, which have been supported by a variety of vibrational spectroscopic studies. We recently proposed a proton translocation model involving proton accessibility to the regions near the propionate groups of the heme a and heme a3 redox centers of the enzyme based by hydrogen/deuterium (H/D) exchange Raman scattering studies (Egawa et al., PLoS ONE 2013). To advance our understanding of this model and to refine the proton accessibility to the hemes, the H/D exchange dependence of the heme propionate group vibrational modes on temperature and pH was measured. The H/D exchange detected at the propionate groups of heme a3 takes place within a few seconds under all conditions. In contrast, that detected at the heme a propionates occurs in the oxidized but not the reduced enzyme and the H/D exchange is pH-dependent with a pKa of ~8.0 (faster at high pH). Analysis of the thermodynamic parameters revealed that, as the pH is varied, entropy/enthalpy compensation held the free energy of activation in a narrow range. The redox dependence of the possible proton pathways to the heme groups is discussed. This article is part of a Special Issue entitled: Vibrational spectroscopies and bioenergetic systems. Copyright © 2014 Elsevier B.V. All rights reserved.

  8. Determination of thermodynamic and kinetic properties of biomolecules by mass spectrometry.


    Gülbakan Basri; Barylyuk Konstantin; Zenobi Renato


    Over the past two decades mass spectrometry (MS) has transformed the life sciences. The advances in understanding biomolecule structure and function by MS is progressing at an accelerated pace. MS has also largely been applied to study thermodynamic and kinetic structure of biomolecules. Herein we highlight the recent discussions about native mass spectrometry and studies about determining stable gas phase structures hydrogen/deuterium exchange studies about reaction kinetics and determinatio...

  9. Enumeration of non-labile oxygen atoms in dissolved organic matter by use of ¹⁶O/ ¹⁸O exchange and Fourier transform ion-cyclotron resonance mass spectrometry. (United States)

    Kostyukevich, Yury; Kononikhin, Alexey; Zherebker, Alexander; Popov, Igor; Perminova, Irina; Nikolaev, Eugene


    We report a simple approach for enumeration of non-labile oxygen atoms in individual molecules of dissolved organic matter (DOM), using acid-catalyzed (16)O/(18)O exchange and ultrahigh-resolution Fourier-transform ion-cyclotron-resonance mass spectrometry (FTICR-MS). We found that by dissolving DOM in H2 (18)O at 95 °C for 20 days it is possible to replace all oxygen atoms of DOM molecules (excluding oxygen from ether groups) with (18)O. The number of exchanges in each molecule can be determined using high-resolution FTICR. Using the proposed method we identified the number of non-labile oxygen atoms in 231 molecules composing DOM. Also, using a previously developed hydrogen-deuterium (H/D)-exchange approach we identified the number of labile hydrogen atoms in 450 individual molecular formulas. In addition, we observed that several backbone hydrogen atoms can be exchanged for deuterium under acidic conditions. The method can be used for structural and chemical characterization of individual DOM molecules, comparing different DOM samples, and investigation of biological pathways of DOM in the environment.

  10. Amide H/2H exchange reveals communication between the cAMP and catalytic subunit-binding sites in the R(I)alpha subunit of protein kinase A. (United States)

    Anand, Ganesh S; Hughes, Carrie A; Jones, John M; Taylor, Susan S; Komives, Elizabeth A


    The changes in backbone hydrogen/deuterium (H/2H) exchange in the regulatory subunit (R(I)alpha(94-244)) of cyclic AMP-dependent protein kinase A (PKA) were probed by MALDI-TOF mass spectrometry. The three naturally occurring states of the regulatory subunit were studied: (1) free R(I)alpha(94-244), which likely represents newly synthesized protein, (2) R(I)alpha(94-244) bound to the catalytic (C) subunit, or holoenzyme, and (3) R(I)alpha(94-244) bound to cAMP. Protection from amide exchange upon C-subunit binding was observed for the helical subdomain, including the A-helix and B-helix, pointing to regions adjacent to those shown to be important by mutagenesis. In addition, C-subunit binding caused changes in observed amide exchange in the distal cAMP-binding pocket. Conversely, cAMP binding caused protection in the cAMP-binding pocket and increased exchange in the helical subdomain. These results suggest that the mutually exclusive binding of either cAMP or C-subunit is controlled by binding at one site transmitting long distance changes to the other site.

  11. Study of fluorine doped (Nb,Ir)O{sub 2} solid solution electro-catalyst powders for proton exchange membrane based oxygen evolution reaction

    Energy Technology Data Exchange (ETDEWEB)

    Kadakia, Karan Sandeep [Chemical and Petroleum Engineering, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); Jampani, Prashanth H., E-mail: [Bioengineering, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); Velikokhatnyi, Oleg I.; Datta, Moni Kanchan [Bioengineering, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); Center for Complex Engineered Multifunctional Materials, University of Pittsburgh, PA 15261 (United States); Patel, Prasad [Chemical and Petroleum Engineering, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); Chung, Sung Jae [Mechanical Engineering and Materials Science, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); Park, Sung Kyoo [Bioengineering, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); Poston, James A.; Manivannan, Ayyakkannu [US Department of Energy, National Energy Technology Laboratory, Morgantown, WV 26507 (United States); Kumta, Prashant N. [Chemical and Petroleum Engineering, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); Bioengineering, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); Center for Complex Engineered Multifunctional Materials, University of Pittsburgh, PA 15261 (United States); Mechanical Engineering and Materials Science, Swanson School of Engineering, University of Pittsburgh, PA 15261 (United States); Department of Oral Biology, School of Dental Medicine, University of Pittsburgh, PA 15217 (United States)


    Graphical abstract: High surface area (∼300 m{sup 2}/g) nanostructured powders of nominal composition (Nb{sub 1−x}Ir{sub x})O{sub 2} and (Nb{sub 1−x}Ir{sub x})O{sub 2}:10F have been synthesized and tested as oxygen evolution electro-catalysts for PEM based water electrolysis using a simple two-step chemical synthesis procedure. Superior electrochemical activity was demonstrated by fluorine doped compositions of (Nb{sub 1−x}Ir{sub x})O{sub 2} with an optimal composition (Nb{sub 0.75}Ir{sub 0.25})O{sub 2}:10F (x = 0.25) demonstrating on-par performance with commercial hydrated IrO{sub 2} and nanostructured in-house chemically synthesized IrO{sub 2}. Using first principles calculations, the electronic structure modification resulting in ∼75 at.% reduction (experimentally observed) in noble metal content without loss in catalytic performance and stability has been established. - Highlights: • (Nb{sub 1−x}Ir{sub x})O{sub 2}:10F nanopowder electrocatalysts have been wet chemically synthesized. • (Nb{sub 0.75}Ir{sub 0.25})O{sub 2}:10F exhibits superior electrochemical activity than pure IrO{sub 2}. • Stability of the (Nb,Ir)O{sub 2}:10F nanomaterials is comparable to pure (Nb,Ir)O{sub 2}. • High surface area F doped (Nb,Ir)O{sub 2} are promising OER anode electro-catalysts. - Abstract: High surface area (∼300 m{sup 2}/g) nanostructured powders of (Nb{sub 1−x}Ir{sub x})O{sub 2} and (Nb{sub 1−x}Ir{sub x})O{sub 2}:10F (∼100 m{sup 2}/g) have been examined as promising oxygen evolution reaction (OER) electro-catalysts for proton exchange membrane (PEM) based water electrolysis. Nb{sub 2}O{sub 5} and 10 wt.% F doped Nb{sub 2}O{sub 5} powders were prepared by a low temperature sol-gel process which were then converted to solid solution (Nb,Ir)O{sub 2} and 10 wt.% F doped (Nb,Ir)O{sub 2} [(NbIr)O{sub 2}:10F] electro-catalysts by soaking in IrCl{sub 4} followed by heat treatment in air. Electro-catalyst powders of optimal composition (Nb{sub 0.75}Ir

  12. Development of a cryogenic target system with optimal access to reaction detectors

    Energy Technology Data Exchange (ETDEWEB)

    Abd El-Bary Dewidar, M.M.


    A liquid hydrogen/deuterium target is used at COSY of the FZ-Juelich in the external experiments TOF, GEM and MOMO. The combination of 1mm diameter beam from COSY with the small target provides the necessary very well defined interaction vertex within few mm{sup 3}. The target liquid is made on a cooled condenser and guided through a central tube assisted by gravitation into the target cell. There the liquid is kept below boiling temperature by evaporation cooling. The vapor rises up to the condenser through a very well isolated concentric center tube. This circulation provides a stable dynamic equilibrium. The target container should have as small as possible material between the reaction volume and the detectors in order to minimize secondary interactions of reaction products. In order to reduce unnecessary material, a very thin target cell is fabricated by galvanization technique. An aluminum condenser is now used instead of copper. This decreased the material from 100 g to 20 g. It provides better thermal properties and performance. The cool down time from 300K to LH{sub 2}/LD{sub 2} is improved to 38 minutes instead of 52 minutes for copper. (orig.)

  13. Effective and selective extraction of noble metal nanoparticles from environmental water through a noncovalent reversible reaction on an ionic exchange resin. (United States)

    Li, Lingxiangyu; Leopold, Kerstin; Schuster, Michael


    Capable of preserving the size and shape of nanoparticles, a novel method to effectively and selectively extract noble metal nanoparticles even at the 80 ng L(-1) level from real environmental water was designed and performed using a noncovalent reversible adsorption onto an ionic exchange resin.

  14. Epitope mapping of a monoclonal antibody against human thrombin by H/D-exchange mass spectrometry reveals selection of a diverse sequence in a highly conserved protein. (United States)

    Baerga-Ortiz, Abel; Hughes, Carrie A; Mandell, Jeffrey G; Komives, Elizabeth A


    The epitope of a monoclonal antibody raised against human thrombin has been determined by hydrogen/deuterium exchange coupled to MALDI mass spectrometry. The antibody epitope was identified as the surface of thrombin that retained deuterium in the presence of the monoclonal antibody compared to control experiments in its absence. Covalent attachment of the antibody to protein G beads and efficient elution of the antigen after deuterium exchange afforded the analysis of all possible epitopes in a single MALDI mass spectrum. The epitope, which was discontinuous, consisting of two peptides close to anion-binding exosite I, was readily identified. The epitope overlapped with, but was not identical to, the thrombomodulin binding site, consistent with inhibition studies. The antibody bound specifically to human thrombin and not to murine or bovine thrombin, although these proteins share 86% identity with the human protein. Interestingly, the epitope turned out to be the more structured of two surface regions in which higher sequence variation between the three species is seen.

  15. Hydrogen-exchange stability analysis of Bergerac-Src homology 3 variants allows the characterization of a folding intermediate in equilibrium (United States)

    Viguera, Ana-Rosa; Serrano, Luis


    Amide hydrogen/deuterium exchange rates have been determined for two mutants of α-spectrin Src homology 3 domain (WT), containing an elongated stable (SHH) and unstable (SHA) distal loop. SHA, similarly to WT, follows a two-state transition, whereas SHH apparently folds via a three-state mechanism. Native-state amide hydrogen exchange is effective in ascribing energetic readjustments observed in kinetic experiments to species stabilized within the denatured base and distinguishing those from high-energy barrier crossings. Comparison of ΔGex and mex parameters for amide protons of these mutants demonstrates the existence of an intermediate and allows the identification of protons protected in this state. The consolidation of a form containing a prefolded long β-hairpin induces the switch to a three-state mechanism in an otherwise two-state folder. It can be inferred that the unbalanced high stability of individual elements of secondary structure in a polypeptide could ultimately complicate its folding mechanism. PMID:12719536

  16. Barter exchanges

    DEFF Research Database (Denmark)

    Sudzina, Frantisek

    Although barter is often perceived as something that proceeded money, barter is still used. The focus of the paper is on barter exchanges. Barter exchanges are used both in developing countries as well as in developed countries (including the U.S.). They are used by both organizations...... and individuals. They usually allow to exchange good but some include also services. Some exchanges allow only for bi-directional barter, i.e. when only two parties are involved in the exchange. But probably most of the barter exchanges use barter money; this makes it easier to exchange goods and services...

  17. Analysis of the charge-exchange reaction $pp \\rightarrow (p\\pi^{+}) (p\\pi^{-}$ and of \\delta^{++}\\delta^{0}$ production at the CERN ISR

    CERN Document Server

    Goggi, Giorgio V; Conta, C; Fraternali, M; Impellizzeri, F; Mantovani, G C; Pastore, F; Rimoldi, A; Rossini, B


    The results of a systematic analysis of charge-exchange double dissociation in proton-proton collisions at the CERN Intersecting Storage Rings are presented. The data cover the entire ISR energy range between square root s=23 GeV and square root s=63 GeV at five standard energies. Double resonance production is observed in the Delta /sup ++/ Delta /sup 0/ and Delta /sup ++/N/sup 0/(1688) final states. The mass spectra of the p pi /sup -/ system show more pronounced resonant signals in the backward Jackson hemisphere. A detailed analysis ofdifferential cross sections shows a forward peak typical of absorbed pion exchanges decreasing as s/sup -1.81+or-0.06/, followed by a much gentler exponential behaviour associated with a trajectory typical of rho -A/sub 2/ exchange. The high-energy transition to this regime is also indicated by a dramatic change in the s-dependence of total cross sections as compared with low-energy data. (20 refs).

  18. Ion Exchange and Antibiofouling Properties of Poly(ether sulfone) Membranes Prepared by the Surface Immobilization of Brønsted Acidic Ionic Liquids via Double-Click Reactions. (United States)

    Yi, Zhuan; Liu, Cui-Jing; Zhu, Li-Ping; Xu, You-Yi


    Brønsted acidic ionic liquids (BAILs) are unique ionic liquids that display chemical structures similar to zwitterions, and they were typically used as solvents and catalysts. In this work, an imidazole-based BAIL monolayer was fabricated onto poly(ether sulfone) (PES) membranes via surface clicking reactions, and the multifunctionality, including ion exchange and biofouling resistance to proteins and bacteria, was demonstrated, which was believed to be one of few works in which BAIL had been considered to be a novel fouling resistance layer for porous membranes. The successful immobilization of the BAILs onto a membrane surface was confirmed by X-ray photoelectron spectroscopy analysis, contact angle measurement, and ζ potential determination. The results from Raman spectroscopy showed that, as a decisive step prior to zwitterion, the BAIL was deprotonated in aqueous solution, and biofouling resistance to proteins and bacteria was found. However, BAIL displayed ion exchange ability at lower pH, and surface hydrophilicity/hydrophobicity of membranes could be tuned on purpose. Our results have demonstrated that the BAIL grafted onto membranes will not only act as an antibiofouling barrier like zwitterions but also provide a platform for surface chemical tailoring by ion exchange, the property of which will become especially important in acidic solutions where the fouling resistance performances of zwitterions are greatly weakened.

  19. Accurate concentration measurements using surface-enhanced Raman and deuterium exchanged dye pairs. (United States)

    Deb, Shirshendu K; Davis, Brandon; Ben-Amotz, Dor; Davisson, V Jo


    Quantitative applications of surface-enhanced resonance Raman scattering (SERRS) are often limited by the reproducibility of SERRS intensities, given the difficulty of controlling analyte-substrate interactions and the associated local field enhancement. As demonstrated here, SERRS from dye molecules even within the same structural class that compete with similar substrates display distinct spectral intensities that are not proportional to analyte concentrations, which limits their use as internal standardization probes and/or for multiplex analysis. Recently, we demonstrated that isotopic variants of rhodamine 6G (R6G), namely R6G-d0 and R6G-d4, can be used for internal standards in SERRS experiments with a linear optical response from picomolar to micromolar concentrations (of total analytes). Here we extend these results by describing a straightforward method for obtaining isotopomeric pairs of other Raman active dyes by hydrogen-deuterium exchange conditions for substitution at electron rich aromatic heterocycles. Most of the known SERRS active probes can be converted into the corresponding isotopomeric molecule by this exchange method, which significantly expands the scope of the isotopic edited internal standard (IEIS) approach. The relative quantification using IEIS enables accurate, reproducible (residual standard deviation+/-2.2%) concentration measurements over a range of 200 pM to 2 microM. These studies enable easy access to a variety of isotopically substituted Raman active dyes and establish the generality of the methodology for quantitative SERRS measurements. For the first time, three rhodamine 6G isotopomers have been created and show distinct Raman spectra, demonstrating the principle of the approach for application as a multiplex technique in biomolecular detection/quantification.

  20. Density functional theory studies on the solvent effects in Al(H2O)63+water-exchange reactions: the number and arrangement of outer-sphere water molecules. (United States)

    Liu, Li; Zhang, Jing; Dong, Shaonan; Zhang, Fuping; Wang, Ye; Bi, Shuping


    Density functional theory (DFT) calculations combined with cluster models are performed at the B3LYP/6-311+G(d,p) level for investigating the solvent effects in Al(H 2 O) 6 3+ water-exchange reactions. A "One-by-one" method is proposed to obtain the most representative number and arrangement of explicit H 2 Os in the second hydration sphere. First, all the possible ways to locate one explicit H 2 O in second sphere (N m ' = 1) based on the gas phase structure (N m ' = 0) are examined, and the optimal pathway (with the lowest energy barrier) for N m ' = 1 is determined. Next, more explicit H 2 Os are added one by one until the inner-sphere is fully hydrogen bonded. Finally, the optimal pathways with N m ' = 0-7 are obtained. The structural and energetic parameters as well as the lifetimes of the transition states are compared with the results obtained with the "Independent-minimum" method and the "Independent-average" method, and all three methods show that the pathway with N m ' = 6 may be representative. Our results give a new idea for finding the representative pathway for water-exchange reactions in other hydrated metal ion systems.

  1. Measurement of yield of residues produced in {sup 12}C+{sup nat}Y reaction and subsequent separation of {sup 97}Ru from Y target using cation exchange resin

    Energy Technology Data Exchange (ETDEWEB)

    Maiti, Moumita [Indian Institute of Technology Roorkee, Uttarakhand (India). Dept. of Physics; Lahiri, Susanta [Saha Institute of Nuclear Physics, Kolkata (India). Chemical Sciences Div.


    This paper reports the yield of no-carrier-added (NCA) radionuclides produced in {sup 12}C{sup 6+} induced reaction on natural yttrium target at 10 different incident energies in the range of 40 to 75 MeV by the stacked-foil technique, followed by off-line γ-ray spectroscopy. It also reports the radiochemical separation of NCA {sup 97}Ru from the bulk yttrium target. {sup 97}Ru was produced in the yttrium matrix through {sup 89}Y({sup 12}C,4n){sup 97,97m}Rh(EC){sup 97}Ru and {sup 89}Y({sup 12}C,p3n){sup 97}Ru reactions along with the radioisotopes {sup 98}Rh, {sup 97}Rh, {sup 97m}Rh, {sup 93}Tc, {sup 94}Tc, {sup 95}Tc and {sup 93m}Mo. Irradiated target was allowed to cool for the complete decay of short-lived residues and {sup 97}Ru was then separated from the bulk yttrium using the cation exchanger DOWEX-50WX4 in an ion exchange column as well as via solid-liquid extraction (SLX). A total of ∝ 88% NCA {sup 97}Ru was separated in column chromatography without any contamination of bulk, whereas quantitative separation of NCA Ru was achieved in SLX.

  2. Synthesis and crystal structure of Mg{sub 0.5}NbO{sub 2}: An ion-exchange reaction with Mg{sup 2+} between trigonal [NbO{sub 2}]{sup -} layers

    Energy Technology Data Exchange (ETDEWEB)

    Miura, Akira, E-mail: [Center for Crystal Science and Technology, University of Yamanashi (Japan); Takei, Takahiro; Kumada, Nobuhiro [Center for Crystal Science and Technology, University of Yamanashi (Japan)


    A new layered niobate, Mg{sub 0.5}NbO{sub 2}, was synthesized from LiNbO{sub 2} through a cation-exchange reaction with Mg{sup 2+} at 450-550 Degree-Sign C. This is the first example of a topotactic reaction with an aliovalent cation between trigonal [NbO{sub 2}]{sup -} layers. It is proposed to be isostructural with LiNbO{sub 2} (space group; P6{sub 3}/mmc) with lattice parameters of a=2.9052(6) A, c=10.625(15) A. The lattice parameters and formation energy of Mg{sub 0.5}NbO{sub 2} crystallized in LiNbO{sub 2} form and other layered CaNb{sub 2}O{sub 4} one were calculated by density functional theory. - Graphical abstract: A new layered niobate, Mg{sub 0.5}NbO{sub 2}, was synthesized from LiNbO{sub 2} through a cation-exchange reaction with Mg{sup 2+} at 450-550 Degree-Sign C. It is isostructural with LiNbO{sub 2} with lattice parameters of a=2.9052(6) A, c=10.625(15) A. Mg{sup 2+} are described in spheres located between [NbO{sub 2}]{sup -} trigonal layers and its occupancy is 0.5. Highlights: Black-Right-Pointing-Pointer A new layered niobate, Mg{sub 0.5}NbO{sub 2}, was synthesized from LiNbO{sub 2}. Black-Right-Pointing-Pointer Cation-exchange reaction converted two monovalent Li{sup +} into one divalent Mg{sup 2+} at 450-550 Degree-Sign C. Black-Right-Pointing-Pointer Mg{sub 0.5}NbO{sub 2} was isostructural with LiNbO{sub 2} (space group; P6{sub 3}/mmc). Black-Right-Pointing-Pointer Its lattice parameters were a=2.9052(6) A and c=10.625(15) A. Black-Right-Pointing-Pointer Synthesized Mg{sub 0.5}NbO{sub 2} was calculated to be thermodynamically more favorable.

  3. Differential cross section of the pion-nucleon charge-exchange reaction in the momentum range from 148 to 323 MeV/c

    CERN Document Server

    Sadler, M E; Abaev, V V; Allgower, C; Barker, A; Bekrenev, V; Bircher, C; Briscoe, W J; Cadman, R; Carter, C; Clajus, M; Comfort, J R; Craig, K; Daugherity, M; Draper, B; Grosnick, D P; Hayden, S; Huddleston, J; Isenhower, D; Jerkins, M; Joy, M; Knecht, N; Koetke, D D; Kozlenko, N; Kruglov, S; Kycia, T; Lolos, G J; Lopatin, I; Manley, D M; Manweiler, R; Marusic, A; McDonald, S; Nefkens, B M K; Olmsted, J; Papandreou, Z; Peaslee, D; Peterson, J; Phaisangittisakul, N; Prakhov, S N; Price, J W; Ramírez, A; Robinson, C; Shafi, A; Spinka, H; Stanislaus, S; Starostin, A; Staudenmaier, H M; Strakovsky, I I; Supek, I; Tippens, W B; Watson, S


    Measured values of the differential cross section for pion-nucleon charge exchange are presented at momenta 148, 174, 188, 212, 238, 271, 298, and 323 MeV/c, a region dominated by the Delta resonance. Complete angular distributions were obtained using the Crystal Ball detector at the Alternating Gradient Synchrotron (AGS) at Brookhaven National Laboratory (BNL). Statistical uncertainties of the differential cross sections are typically 2-6%, exceptions being the results at the lowest momentum and at the most forward measurements of the five lowest momenta. We estimate the systematic uncertainties to be 3-6%.

  4. Differential cross sections of the charge-exchange reaction pi- p --> pi0 n in the momentum range from 103 to 178 MeV/c

    CERN Document Server

    Mekterović, D; Abaev, V; Bekrenev, V; Bircher, C; Briscoe, W J; Cadman, R V; Clajus, M; Comfort, J R; Craig, K; Grosnick, D; Isenhover, D; Jerkins, M; Joy, M; Knecht, N; Koetke, D D; Kozlenko, N; Kulbardis, A; Kruglov, S; Lolos, G; Lopatin, I; Manley, D M; Manweiler, R; Marušić, A; McDonald, S; Nefkens, B M K; Olmsted, J; Papandreou, Z; Peaslee, D; Peterson, J; Phaisangittisakul, N; Prakhov, S N; Price, J W; Ramírez, A; Sadler, M E; Shafi, A; Spinka, H; Stanislaus, S; Starostin, A; Staudenmaier, H M; Strakovsky, I; Tippens, W B; Watson, S


    Measured values of the differential cross sections for pion-nucleon charge exchange, pi- p --> pi0 n, are presented for pi- momenta of 103, 112, 120, 130, 139, 152, and 178 MeV/c. Complete angular distributions were obtained by using the Crystal Ball detector at the Alternating Gradient Synchrotron at Brookhaven National Laboratory. Statistical uncertainties of the differential cross sections vary from 3% to 6% in the backward angle region, and from 6% to about 20% in the forward region with the exception of the two most forward angles. The systematic uncertainties are estimated to be about 3% for all momenta.

  5. Proof of concept of the CaO/Ca(OH)2 reaction in a continuous heat-exchanger BFB reactor for thermochemical heat storage in CSP plants (United States)

    Rougé, Sylvie; Criado, Yolanda A.; Huille, Arthur; Abanades, J. Carlos


    The CaO/Ca(OH)2 hydration/dehydration reaction has long been identified as a attractive method for storing CSP heat. However, the technology applications are still at laboratory scale (TG or small fixed beds). The objective of this work is to investigate the hydration and dehydration reactions performance in a bubbling fluidized bed (BFB) which offers a good potential with regards to heat and mass transfers and upscaling at industrial level. The reactions are first investigated in a 5.5 kW batch BFB, the main conditions are the bed temperature (400-500°C), the molar fraction of steam in the fluidizing gas (0-0.8), the fluidizing gas velocity (0.2-0.7 m/s) and the mass of lime in the batch (1.5-3.5 kg). To assist in the interpretation of the experimental results, a standard 1D bubbling reactor model is formulated and fitted to the experimental results. The results indicate that the hydration reaction is mainly controlled by the slow kinetics of the CaO material tested while significant emulsion-bubble mass-transfer resistances are identified during dehydration due to the much faster dehydration kinetics. In the continuity of these preliminary investigations, a continuous 15.5 kW BFB set-up has been designed, manufactured and started with the objective to operate the hydration and dehydration reactions in steady state during a few hours, and to investigate conditions of faster reactivity such as higher steam molar fractions (up to 1), temperatures (up to 600°C) and velocities (up to 1.5 m/s).

  6. Removal of Nickel and Vanadium from heavy Crude Oils by Ligand Exchange Reactions: Final Report CRADA No. TC-0400-92

    Energy Technology Data Exchange (ETDEWEB)

    Reynolds, John G. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Paul, Robert H. [Phillips Petroleum Company, Bartlesville, OK (United States)


    This was a collaborative agreement to develop new methods for the removal of nickel and vanadium from heavy crude oils utilizing chemical agents in a pre-treatment or before downstream processing step. The project was motivated by the need to utilize more heavy crude oils in refining. The result expected would decrease America's dependence on foreign oil, and protect against potential foreign oil embargoes. This project attempted to: a) find any or several chemical agents which removed Ni and/ or V from heavy crude oils in a pre-treatment step; b) understand the fundamental chemical reactions which accomplish this; c) measure the intrinsic kinetic reaction rates relevant to scale-up and utilization in the refinery; and d) scale-up to refinery utilization.

  7. Triple Regge exchange mechanisms of four-pion continuum production in the p p →p p π+π-π+π- reaction (United States)

    Kycia, Radosław; Lebiedowicz, Piotr; Szczurek, Antoni; Turnau, Jacek


    We consider exclusive multiperipheral production of four charged pions in proton-proton collisions at high energies with simultaneous exchange of three Pomerons/Reggeons. The amplitude(s) for the genuine 2 →6 process are written in the Regge approach. The calculation is performed with the help of the GenEx Monte Carlo code. Some corrections at low invariant masses in the two-body subsystems are necessary for application of the Regge formalism. We estimate the corresponding cross section and present differential distributions in rapidity, transverse momenta and two- and four-pion invariant masses. The cross section and the distributions depend on the value of the cutoff parameter of a form factor correcting amplitudes for off-shellness of t -channel pions. A rather large cross section is found for the whole phase space (σ ˜1 - 5 μ b , including absorption corrections). Relatively large four-pion invariant masses are populated in the considered diffractive mechanism compared to other mechanisms discussed so far in the context of four-pion production. We investigate whether the triple Regge exchange processes could be identified with the existing LHC detectors. We consider the case of ATLAS and ALICE cuts. The ATLAS (or CMS) has a better chance to identify the process in the region of large invariant masses M4 π>10 GeV . In the case of the ALICE experiment the considered mechanism competes with other mechanisms (production of σ σ , ρ ρ pairs or single resonances) and cannot be unambiguously identified.

  8. Combining H/D exchange mass spectroscopy and computational docking reveals extended DNA-binding surface on uracil-DNA glycosylase (United States)

    Roberts, Victoria A.; Pique, Michael E.; Hsu, Simon; Li, Sheng; Slupphaug, Geir; Rambo, Robert P.; Jamison, Jonathan W.; Liu, Tong; Lee, Jun H.; Tainer, John A.; Ten Eyck, Lynn F.; Woods, Virgil L.


    X-ray crystallography provides excellent structural data on protein–DNA interfaces, but crystallographic complexes typically contain only small fragments of large DNA molecules. We present a new approach that can use longer DNA substrates and reveal new protein–DNA interactions even in extensively studied systems. Our approach combines rigid-body computational docking with hydrogen/deuterium exchange mass spectrometry (DXMS). DXMS identifies solvent-exposed protein surfaces; docking is used to create a 3-dimensional model of the protein–DNA interaction. We investigated the enzyme uracil-DNA glycosylase (UNG), which detects and cleaves uracil from DNA. UNG was incubated with a 30 bp DNA fragment containing a single uracil, giving the complex with the abasic DNA product. Compared with free UNG, the UNG–DNA complex showed increased solvent protection at the UNG active site and at two regions outside the active site: residues 210–220 and 251–264. Computational docking also identified these two DNA-binding surfaces, but neither shows DNA contact in UNG–DNA crystallographic structures. Our results can be explained by separation of the two DNA strands on one side of the active site. These non-sequence-specific DNA-binding surfaces may aid local uracil search, contribute to binding the abasic DNA product and help present the DNA product to APE-1, the next enzyme on the DNA-repair pathway. PMID:22492624

  9. Stereodirectional Origin of anti-Arrhenius Kinetics for a Tetraatomic Hydrogen Exchange Reaction: Born-Oppenheimer Molecular Dynamics for OH + HBr. (United States)

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


    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

  10. 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 (United States)

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


    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.

  11. Activated carbon from orange peels as supercapacitor electrode and catalyst support for oxygen reduction reaction in proton exchange membrane fuel cell

    Directory of Open Access Journals (Sweden)

    M. Dhelipan


    Full Text Available Activated carbon is synthesized using orange peel as precursor through chemical activation using H3PO4 and its ability as electrocatalyst support for ORR reaction is examined. The prepared material was subjected to various structural, compositional, morphological and electrochemical studies. For ORR activity, the platinum loaded on activated carbon (Pt/OP-AC was investigated by cyclic voltammograms (CVs recorded in N2 and O2 saturated 0.1 M aqueous HClO4. For supercapacitor performance, three electrode systems was tested in aqueous H2SO4 for feasibility determination and showed electrochemical double layer capacitance (EDLC behaviour which is expected for activated carbon like materials. Electrochemical surface area (ECSA of the activated carbon from orange peel is measured using CV. The physical properties of the prepared carbon are studied using SEM (scanning electron microscope, XRD (X-ray diffraction, Fourier transform infrared (FT-IR spectroscopy and Raman spectroscopy. The AC derived from orange peels delivered a high specific capacitance of 275 F g−1 at 10 mV s-1 scan rate. Hence, this study suggested that orange peels may be considered not only as a potential alternative source for synthesizing carbon supported catalyst for fuel cell application but also highlight the production of low-cost carbon for further applications like supercapacitors.

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

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


    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.

  13. Predicting the distribution of whey protein fouling in a plate heat exchanger using the kinetic parameters of the thermal denaturation reaction of β-lactoglobulin and the bulk temperature profiles. (United States)

    Blanpain-Avet, P; André, C; Khaldi, M; Bouvier, L; Petit, J; Six, T; Jeantet, R; Croguennec, T; Delaplace, G


    Fouling of plate heat exchangers (PHE) is a severe problem in the dairy industry, notably because the relationship between the build-up of protein fouling deposits and the chemical reactions taking place in the fouling solution has not yet been fully elucidated. Experiments were conducted at pilot scale in a corrugated PHE, and fouling deposits were generated using a model β-lactoglobulin (β-LG) fouling solution for which the β-LG thermal denaturation reaction constants had been previously determined experimentally. Then 18 different bulk temperature profiles within the PHE were imposed. Analysis of the fouling runs shows that the dry deposit mass per channel versus the ratio R=kunf/kagg (with kunf and kagg representing, respectively, the unfolding and aggregation rate constants computed from both the identification of the β-LG thermal denaturation process and knowledge of the imposed bulk temperature profile into the PHE channel) is able to gather reasonably well the experimental fouling mass data into a unique master curve. This type of representation of the results clearly shows that the heat-induced reactions (unfolding and aggregation) of the various β-LG molecular species in the bulk fluid are essential to capture the trend of the fouling mass distribution inside a PHE. This investigation also illustrates unambiguously that the release of the unfolded β-LG (also called β-LG molten globule) within the bulk fluid (and the absence of its consumption in the form of aggregates) is a key phenomenon that controls the extent of protein fouling as well as its location inside the PHE. Copyright © 2016 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

  14. Mechanism of single metal exchange in the reactions of [M4(SPh)10]2- (M = Zn or Fe) with CoX2 (X = Cl or NO3) or FeCl2. (United States)

    Autissier, Valerie; Henderson, Richard A


    The kinetics of the reactions between [Zn4(SPh)10](2-) and an excess of MX2 (M = Co, X = NO3 or Cl; M = Fe, X = Cl), in which a Zn(II) is replaced by M(II), have been studied in MeCN at 25.0 degrees C. (1)H NMR spectroscopy shows that the ultimate product of the reactions is an equilibrium mixture of clusters of composition [Zn(n)M(4-n)(SPh)10](2-), and this is reflected in the multiphasic absorbance-time curves observed over protracted times (several minutes) using stopped-flow spectrophotometry to study the reactions. The kinetics of only the first phase have been determined, corresponding to the equilibrium formation of [Zn3M(SPh)10](2-). The effects of varying the concentrations of cluster, MX2, and ZnCl2 on the kinetics have been investigated. The rate law is consistent with the equilibrium nature of the metal exchange process and indicates a mechanism for the formation of [Zn3M(SPh)10](2-) involving two coupled equilibria. In the initial step binding of MX2 to a bridging thiolate in [Zn4(SPh)10](2-) results in breaking of a Zn-bridging thiolate bond. In the second step replacement of the cluster Zn involves transfer of the bridging thiolates from the Zn to M, with breaking of a Zn-bridged thiolate bond being rate-limiting. The kinetics for the reaction of ZnCl2 with [Zn3M(SPh)10](2-) (M = Fe or Co)} depends on the identity of M. This behavior indicates attack of ZnCl2 at a M-mu-SPh-Zn bridged thiolate. Similar studies on the analogous reactions between [Fe4(SPh)10](2-) and an excess of CoX2 (X = NO3 or Cl) in MeCN exhibit simpler kinetics but these are also consistent with the same mechanism.

  15. The Dynamics of Multilateral Exchange (United States)

    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.

  16. Exchange Network (United States)

    The Environmental Information Exchange Network (EIEN) is an Internet-based system used by state, tribal and territorial partners to securely share environmental and health information with one another and EPA.

  17. Study of the elastic scattering and of the (p,n) charge exchange reaction with neutron-rich light exotic beams; Etude de la diffusion elastique et de la reaction d`echange de charge (p,n) avec des faisceaux exotiques legers riches en neutrons

    Energy Technology Data Exchange (ETDEWEB)

    Cortina Gil, D.


    We have measured at GANIL, with the high resolution spectrometer SPEG, the elastic scattering of several neutron rich secondary beams ({sup 6}He, {sup 10}Be and {sup 11}Be) on a polypropylene target and the charge exchange reaction p({sup 6}He, {sup 6}Li)n. These exotic beams were produced by nuclear fragmentation and re-focalized with the SISSI device (superconducting solenoids). The signature of a halo structure in these nuclei has been analysed. Special attention has been paid to several aspects of the associated calculations namely, the proton and neutron density distributions and the small binding energy for the last nucleons in these exotic nuclei. Break-up mechanisms are seen to play an important role in these nuclei. 100 refs.

  18. Optimization of collision/reaction gases for determination of 90Sr in atmospheric particulate matter by inductively coupled plasma tandem mass spectrometry after direct introduction of air via a gas-exchange device (United States)

    Suzuki, Yoshinari; Ohara, Ryota; Matsunaga, Kirara


    Nuclear power plant accidents release radioactive strontium 90 (90Sr) into the environment. Monitoring of 90Sr, although important, is difficult and time consuming because it emits only beta radiation. We have developed a new analytical system that enables real-time analysis of 90Sr in atmospheric particulate matter with an analytical run time of only 10 min. Briefly, after passage of an air sample through an impactor, a small fraction of the sample is introduced into a gas-exchange device, where the air is replaced by Ar. Then the sample is directly introduced into an inductively coupled plasma tandem mass spectrometry (ICP-MS/MS) system equipped with a collision/reaction cell to eliminate isobaric interferences on 90Sr from 90Zr+, 89Y1H+, and 90Y+. Experiments with various reaction gas conditions revealed that these interferences could be minimized under the following optimized conditions: 1.0 mL min- 1 O2, 10.0 mL min- 1 H2, and 1.0 mL min- 1 NH3. The estimated background equivalent concentration and estimated detection limit of the system were 9.7 × 10- 4 and 3.6 × 10- 4 ng m- 3, respectively, which are equivalent to 4.9 × 10- 6 and 1.8 × 10- 6 Bq cm- 3. Recoveries of Sr in PM2.5 measured by real-time analysis compared to those obtained by simultaneously collection on filter was 53 ± 23%, and using this recovery, the detection limit as PM2.5 was estimated to be 3.4 ± 1.5 × 10- 6 Bq cm- 3. That is, this system enabled detection of 90Sr at concentrations < 5 × 10- 6 Bq cm- 3 even considering the insufficient fusion/vaporization/ionization efficiency of Sr in PM2.5.

  19. V-doped TiO2 supported Pt as a promising oxygen reduction reaction catalyst: Synthesis, characterization and in-situ evaluation in proton exchange membrane fuel cell (United States)

    Bharti, Abha; Cheruvally, Gouri


    This study deals with the synthesis and characterization of V-doped, TiO2 supported Pt catalyst (Pt/V-TiO2) for oxygen reduction reaction (ORR) and its in-situ performance investigation in proton exchange membrane (PEM) fuel cell. Pt/V-TiO2 nanocomposite catalyst is prepared via a facile sol-gel and microwave assisted, modified chemical reduction route and its performance is compared with the undoped TiO2 supported catalyst, Pt/TiO2 prepared in an identical way. The prepared Pt/V-TiO2 and Pt/TiO2 catalysts are employed as cathode catalyst in PEM fuel cell and compared with standard Pt/C catalyst. Their comparative studies are conducted with physical and electrochemical techniques. In-situ electrochemical characterization studies show improved ORR catalytic activity of Pt/V-TiO2 compared to Pt/TiO2. Furthermore, both Pt/TiO2 and Pt/V-TiO2 are more stable than Pt/C when subjected to 6000 voltammetric cycles in the range of 0.2-1.2 V vs. standard hydrogen electrode in operating fuel cell conditions, losing only nanocomposite material as a potential cathode catalyst for PEM fuel cell with immense scope for further investigation.

  20. Effect of solvent and temperature on the lithium-bromine exchange of vinyl bromides: reactions of n-butyllithium and t-butyllithium with (E)-5-bromo-5-decene. (United States)

    Bailey, William F; Luderer, Mark R; Uccello, Daniel P; Bartelson, Ashley L


    The outcome of reactions of (E)-5-bromo-5-decene (1), a representative vinyl bromide, with t-BuLi or n-BuLi at 0 degrees C and room temperature, respectively, in a variety of solvent systems has been investigated. Vinyl bromide 1 does not react with t-BuLi in pure heptane; however, the presence of even small quantities of an ether in a predominantly heptane medium resulted in virtually complete consumption of 1 at 0 degrees C, resulting in nearly the same distribution of products, including 60-80% of (Z)-5-decenyllithium, regardless of the solvent composition. Vinyl bromide 1 reacts slowly with n-BuLi at room temperature in a variety of ether and heptane-ether mixtures to afford a mixture of products including significant quantities of recovered starting material. The results of these experiments demonstrate that lithium-bromine exchange between a vinyl bromide and either t-BuLi or n-BuLi at temperatures significantly above -78 degrees C is not an efficient method for the generation of a vinyllithium.

  1. The effect of hydrogen/deuterium introduction on photoluminescence of 3C-SiC crystals

    Energy Technology Data Exchange (ETDEWEB)

    Lee, B.K.; Steckl, A.J. [Univ. of Cincinnati, OH (United States). Nanoelectronics Lab.; Zavada, J.M. [Army Research Office, Research Triangle Park, NC (United States); Wilson, R.G. [Hughes Research Labs., Malibu, CA (United States)


    The effect of the incorporation and annealing of deuterium in 3C-SiC on its photoluminescence is reported. A 3C-SiC crystal has been implanted with 100 kev deuterium and subsequently annealed at temperatures between 1015 C and 1220 C for 1 to 5 minutes. SIMS depth profiles indicate hydrogen is strongly trapped by defects generated through ion bombardment, but a gradual damage repairing occurs during annealing. Photoluminescence was measured with 488 nm Ar laser excitation for sample temperatures from 89 K to 400 K. The PL peak wavelength of 540 nm at room temperature has shifted to 538 nm at 89 K. The peak PL intensity decreases with measurement temperature while its full width at half maximum (FWHM) exhibits an increasing trend. PL data were taken at five annealing stages. The post-implantation peak PL intensity and its integrated area increase initially with annealing temperature and time. After the final annealing at 1218 C for 2 minute, PL intensity and its integrated area exhibit a decrease in level.

  2. The Ionic Hydrogen/Deuterium Bonds between Diammoniumalkane Dications and Halide Anions

    NARCIS (Netherlands)

    Demireva, M.; Oomens, J.; Berden, G.; Williams, E.R.


    Halide-anion binding to 1,12-dodecanediammonium, tetramethyl-1,12-dodecanediammmonium, and tetramethyl-1,7-heptanediammonium has been investigated with infrared multiple-photon dissociation (IRMPD) spectroscopy in the 1000-2250cm(-1) spectral region and with theory. Both charged ammonium groups in

  3. Muon molecular formation and transfer rate in solid hydrogen-deuterium mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Jacot-Guillarmod, R. [Fribourg Univ. (Switzerland); Bailey, J.M. [Chester Technology (United Kingdom); Beer, G.A.; Knowles, P.E.; Mason, G.R.; Olin, A. [Victoria Univ., BC (Canada); Beveridge, J.L.; Marshall, G.M.; Mulhauser, F. [British Columbia Univ., Vancouver, BC (Canada). TRIUMF Facility; Fujiwara, M.C. [British Columbia Univ., Vancouver, BC (Canada); Huber, T.M. [Gustavus Adolphus Coll., St. Peter, MN (United States); Kammel, P.; Zmeskal, J. [Oesterreichische Akademie der Wissenschaften, Vienna (Austria); Kunselman, A.R. [Wyoming Univ., Laramie, WY (United States); Martoff, C.J. [Temple Univ., Philadelphia, PA (United States); Petitjean, C. [Paul Scherrer Inst. (PSI), Villigen (Switzerland); Wozniak, J. [Akademia Gorniczo-Hutnicza, Cracow (Poland). Inst. of Physics and Nuclear Technology


    In an experiment at TRIUMF to study muon-catalyzed fusion and associated atomic and molecular effects, negative muons were stopped in a solid protium hydrogen layer containing a small amount of deuterium. Most of the resulting {mu}H atoms disappeared by formation of HH{mu} molecules or by muon transfer to a deuteron. The {mu}D can drift almost freely through the hydrogen layer due to the Ramsauer-Townsend effect and may even leave the layer. If a thin neon layer is frozen atop the hydrogen, the exiting muonic atoms will very rapidly release their muon to a neon atom. The analysis of the time structure of the neon X-rays is used to determine the rates of the slower processes involved in the evolution of the {mu}H. This analysis has been performed with the help of Monte Carlo calculations, which simulate the kinetics of both {mu}H and {mu}D atoms in the hydrogen mixtures. (orig.). 23 refs.

  4. Hydrogen exchange

    DEFF Research Database (Denmark)

    Jensen, Pernille Foged; Rand, Kasper Dyrberg


    Hydrogen exchange (HX) monitored by mass spectrometry (MS) is a powerful analytical method for investigation of protein conformation and dynamics. HX-MS monitors isotopic exchange of hydrogen in protein backbone amides and thus serves as a sensitive method for probing protein conformation...... and dynamics along the entire protein backbone. This chapter describes the exchange of backbone amide hydrogen which is highly quenchable as it is strongly dependent on the pH and temperature. The HX rates of backbone amide hydrogen are sensitive and very useful probes of protein conformation......, as they are distributed along the polypeptide backbone and form the fundamental hydrogen-bonding networks of basic secondary structure. The effect of pressure on HX in unstructured polypeptides (poly-dl-lysine and oxidatively unfolded ribonuclease A) and native folded proteins (lysozyme and ribonuclease A) was evaluated...

  5. Exchange Options

    NARCIS (Netherlands)

    Jamshidian, F.


    The contract is described and market examples given. Essential theoretical developments are introduced and cited chronologically. The principles and techniques of hedging and unique pricing are illustrated for the two simplest nontrivial examples: the classical Black-Scholes/Merton/Margrabe exchange

  6. Extension of a Kinetic-Theory Approach for Computing Chemical-Reaction Rates to Reactions with Charged Particles (United States)

    Liechty, Derek S.; Lewis, Mark J.


    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.

  7. Determination of thermodynamic and kinetic properties of biomolecules by mass spectrometry. (United States)

    Gülbakan, Basri; Barylyuk, Konstantin; Zenobi, Renato


    Over the past two decades, mass spectrometry (MS) has transformed the life sciences. The advances in understanding biomolecule structure and function by MS is progressing at an accelerated pace. MS has also largely been applied to study thermodynamic and kinetic structure of biomolecules. Herein, we highlight the recent discussions about native mass spectrometry and studies about determining stable gas phase structures, hydrogen/deuterium exchange studies about reaction kinetics and determination of binding constants of biomolecules with their ligands. Copyright © 2014 Elsevier Ltd. All rights reserved.

  8. The investigation of the bio-oil produced by hydrothermal liquefaction of Spirulina platensis using ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry. (United States)

    Kostyukevich, Yury; Vlaskin, Mikhail; Vladimirov, Gleb; Zherebker, Alexander; Kononikhin, Alexey; Popov, Igor; Nikolaev, Eugene


    We report the investigation of the hydrothermal liquefaction products of the Spirulina platensis microalgae by using the Fourier transform ion cyclotron resonance mass spectrometry. The hydrothermal liquefaction produced two fractions: one with boiling temperature below 300℃ and the dense residue that remained in the reactor. It was observed that N 2 and N classes of compounds that dominate in the positive ESI Fourier transform ion cyclotron resonance spectra for both fractions, and that the light fraction is considerably more saturated then the heavy one. The performed hydrogen/deuterium exchange reaction indicated the presence of the onium compounds in the bio-oil.

  9. Electron transfer reactions

    CERN Document Server

    Cannon, R D


    Electron Transfer Reactions deals with the mechanisms of electron transfer reactions between metal ions in solution, as well as the electron exchange between atoms or molecules in either the gaseous or solid state. The book is divided into three parts. Part 1 covers the electron transfer between atoms and molecules in the gas state. Part 2 tackles the reaction paths of oxidation states and binuclear intermediates, as well as the mechanisms of electron transfer. Part 3 discusses the theories and models of the electron transfer process; theories and experiments involving bridged electron transfe

  10. Scraped surface heat exchangers. (United States)

    Rao, Chetan S; Hartel, Richard W


    Scraped surface heat exchangers (SSHEs) are commonly used in the food, chemical, and pharmaceutical industries for heat transfer, crystallization, and other continuous processes. They are ideally suited for products that are viscous, sticky, that contain particulate matter, or that need some degree of crystallization. Since these characteristics describe a vast majority of processed foods, SSHEs are especially suited for pumpable food products. During operation, the product is brought in contact with a heat transfer surface that is rapidly and continuously scraped, thereby exposing the surface to the passage of untreated product. In addition to maintaining high and uniform heat exchange, the scraper blades also provide simultaneous mixing and agitation. Heat exchange for sticky and viscous foods such as heavy salad dressings, margarine, chocolate, peanut butter, fondant, ice cream, and shortenings is possible only by using SSHEs. High heat transfer coefficients are achieved because the boundary layer is continuously replaced by fresh material. Moreover, the product is in contact with the heating surface for only a few seconds and high temperature gradients can be used without the danger of causing undesirable reactions. SSHEs are versatile in the use of heat transfer medium and the various unit operations that can be carried out simultaneously. This article critically reviews the current understanding of the operations and applications of SSHEs.

  11. HK97 Maturation Studied by Crystallography and H/[superscript 2]H Exchange Reveals the Structural Basis for Exothermic Particle Transitions

    Energy Technology Data Exchange (ETDEWEB)

    Gertsman, Ilya; Komives, Elizabeth A.; Johnson, John E. (Scripps); (UCSD)


    HK97 is an exceptionally amenable system for characterizing major conformational changes associated with capsid maturation in double-stranded DNA bacteriophage. HK97 undergoes a capsid expansion of {approx}20%, accompanied by major subunit rearrangements during genome packaging. A previous 3.44-{angstrom}-resolution crystal structure of the mature capsid Head II and cryo-electron microscopy studies of other intermediate expansion forms of HK97 suggested that, primarily, rigid-body movements facilitated the maturation process. We recently reported a 3.65-{angstrom}-resolution structure of the preexpanded particle form Prohead II (P-II) and found that the capsid subunits undergo significant refolding and twisting of the tertiary structure to accommodate expansion. The P-II study focused on major twisting motions in the P-domain and on refolding of the spine helix during the transition. Here we extend the crystallographic comparison between P-II and Head II, characterizing the refolding events occurring in each of the four major domains of the capsid subunit and their effect on quaternary structure stabilization. In addition, hydrogen/deuterium exchange, coupled to mass spectrometry, was used to characterize the structural dynamics of three distinct capsid intermediates: P-II, Expansion Intermediate, and the nearly mature Head I. Differences in the solvent accessibilities of the seven quasi-equivalent capsid subunits, attributed to differences in secondary and quaternary structures, were observed in P-II. Nearly all differences in solvent accessibility among subunits disappear after the first transition to Expansion Intermediate. We show that most of the refolding is coupled to this transformation, an event associated with the transition from asymmetric to symmetric hexamers.

  12. Segmented heat exchanger (United States)

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


    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.

  13. Electronic device for measuring the polarization parameter in the {pi}{sup -}p {yields} {pi}{sup 0}n charge exchange reaction on a polarized proton target; Un appareillage electronique destine a la mesure du parametre de polarisation dans la reaction d'echange de charge {pi}{sup -}p {yields} {pi}{sup 0}n sur cible de protons polarises

    Energy Technology Data Exchange (ETDEWEB)

    Brehin, S. [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires


    An electronic apparatus has been constructed to measure the polarization parameter P{sub 0}(t) in {pi}{sup -}p {yields} {pi}{sup 0}n charge exchange scattering at 5.9 GeV/c and 11,2 GeV/c on polarized proton target. This device insures triggering of a heavy plate spark chamber, allowing visualisation of {gamma} rays from the {pi}{sup 0} decays when the associated neutron offers suitable characteristics in direction and energy. The neutron is detected by an array of 32 counters and his energy is measured by a time of flight method. Electronic circuits of this apparatus are described as test and calibration methods used. (author) [French] Un appareillage electronique a ete realise pour mesurer le parametre de polarisation P{sub 0}(t) dans la reaction d'echange de charge {pi}{sup -}p {yields} {pi}{sup 0}n a 5,9 GeV/c et 11,2 GeV/c sur une cible de protons polarises. Ce dispositif assure le declenchement d'une chambre a etincelles a plaques lourdes, permettant de visualiser les {gamma} de desitegration du {pi}{sup 0}, lorsque le neutron associe presente les caracteristiques convenables en direction et en energie. Le neutron est detecte par un ensemble de 32 compteurs et son energie est mesuree par une methode de temps de vol. Les circuits composant cet appareillage sont decrits ainsi que les methodes d'etalonnage et de verification utilisees. (auteur)

  14. Fabrication of Cationic Exchange Polystyrene Nanofibers for Drug ...

    African Journals Online (AJOL)

    Purpose: To prepare polystyrene nanofiber ion exchangers (PSNIE) with surface cation exchange functionality using a new method based on electrospinning and also to optimize crosslinking and sulfonation reactions to obtain PSNIE with maximum ion exchange capacity (IEC). Method: The nanofibers were prepared from ...

  15. Tritium Labeled Gentamicin C: II.- Bioradiactive Degradation Products of Gentamicin by Catalytic H2O-3H Exchange Reaction; Getamicina C Tritiada: II.- Productos de Degradacion Radiactivos y Bioactivos en el Intercambio Catalitico con H2O-3H

    Energy Technology Data Exchange (ETDEWEB)

    Suarez, C.; Diaz, A.; Paz, D.; Jimeno, M. L.


    The main bio radioactive degradation products from catalytic hydrogen exchange of gentamicin C, (C1 + C2 + Cla) in basic form, are generated by N-demethylation in 3{sup -}N and 6-N positions. Their structures were confirmed by 1HNMR and 13CNMR. These derivatives were fractionated by chromatography on silica gel. Antibacterial activities were similar to those of the parent antibiotics. Tritium exchange, under vacuum or nitrogen, is highly increased (4:1) when gentamicin are in basic form. In contrast with gentamicin sulfate, hydrolytic sub products as gramine, genta mines, garosamine and purpurosamines are practically absent. To properly optimize the exchange process, the composition of the gentamicin C complex must be taken into account. The exchange decreases in the order C2 > C1> Cla. Because of 6'-N-demethyl gentamicin C1 is C2, the radiochemical yield of C2 appears enhanced in the H2O-3H exchange of a mixture of them. Radioactivity distribution among the components and subunits of these three gentamicin were studied by strong and mild hydrolysis, and by methanolysis. (Author) 18 refs.

  16. DSMC Modeling of Flows with Recombination Reactions (United States)


    Reactions S. Gimelshein, I. Wysong Air Force Research Laboratory (AFMC) AFRL/RQRC 10 E. Saturn Blvd. Edwards AFB, CA 93524-7680 Air Force Research ...dis- sociation and exchange reactions for diatomic , and sometimes for polyatomic, molecules. The recombination reaction was largely avoided in the DSMC...believed to provide adequate accuracy to the VT energy exchange of diatomic molecules. As shown in Fig. 4(a), the use of that model results in good

  17. Acid-catalysed deuterium exchange of aromatic protons. Pt. 3; Accelerated exchange by microwave irradiation

    Energy Technology Data Exchange (ETDEWEB)

    Koeves, G.J. (Centre of Forensic Sciences, Toronto, ON (Canada))


    Conventional acid-catalysed [sup 2]H/[sup 1]H exchange in aromatic rings requires long reaction times, high temperatures and pressure. This paper reports that accelerated deuterium exchange can be achieved in a microwave oven. Experiments were carried out on benzodiazepines, tricyclic antidepressants and phenothiazines. The reaction time was decreased from days to minutes, the preparatory work was simpler than with conventional heating and the labelled products were cleaner. (author).

  18. Nonadiabatic ionic--covalent transitions. Exponential-linear model for the charge exchange and neutralization reactions Na+H arrow-right-left Na/sup +/+H/sup -/

    Energy Technology Data Exchange (ETDEWEB)

    Errea, L.F.; Mendez, L.; Mo, O.; Riera, A.


    A previous study of charge exchange processes taking place through ionic--covalent transitions is extended to the case of Na+H and Na/sup +/+H/sup -/ collisions. A five-state molecular expansion, with the inclusion of two-electron translation factors, is employed to calculate the charge exchange and neutralization cross sections. Transitions at the first two pseudocrossings between the energy curves, practically determine the cross sections in the energy range 0.16--5 keV amu/sup -1/. We also show that the widely used multichannel Landau--Zener theory is totally inadequate, to treat these transitions.

  19. Reaction Automata


    Okubo, Fumiya; Kobayashi, Satoshi; YOKOMORI, Takashi


    Reaction systems are a formal model that has been introduced to investigate the interactive behaviors of biochemical reactions. Based on the formal framework of reaction systems, we propose new computing models called reaction automata that feature (string) language acceptors with multiset manipulation as a computing mechanism, and show that reaction automata are computationally Turing universal. Further, some subclasses of reaction automata with space complexity are investigated and their la...

  20. Reactor for exothermic reactions (United States)

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


    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 to 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.

  1. Totalization Data Exchange (TDEX) (United States)

    Social Security Administration — The Totalization Data Exchange (TDEX) process is an exchange between SSA and its foreign country partners to identify deaths of beneficiaries residing abroad. The...

  2. A combined experimental, theoretical, and Van't Hoff model study for identity methyl, proton, hydrogen atom, and hydride exchange reactions. Correlation with three-center four-, three-, and two-electron systems (United States)

    Buck, Henk M.

    We have studied carbon transfer reactions following an SN2 reaction profile. With ab initio calculations and experimental geometries concerning the nature of the various complexes indicated as stable, intermediate, and transition state we were able to show the additional value of van't Hoff's tetrahedral configuration by changing its geometry via a trigonal pyramid into a trigonal bipyramid. The ratio of the apical bond and corresponding tetrahedral bond distances is then nearly 1.333. The relevance of this approach has also been shown for identity proton-(hydrogen atom-, and hydride-) in-line reactions. The use of this geometrical transmission will be demonstrated for the hydrogen bonding distances in e.g., DNA duplexes and other biological (supra) molecular systems.

  3. When Ligand Exchange Leads to Ion Exchange: Nanocrystal Facets Dictate the Outcome. (United States)

    Hewavitharana, Indika K; Brock, Stephanie L


    This study demonstrates that ligand exchange of nanocrystals (NCs) is not always an innocuous process, but can lead to facile (room temperature) ion exchange, depending on the surface crystal faceting. Rock salt PbTe NCs prepared as cubes with neutral facets undergo room-temperature ligand exchange with sulfide ions, whereas cuboctahedron-shaped particles with neutral {100} and polar {111} facets are transformed to PbS, driven by ion exchange along the ⟨111⟩ direction. Likewise, cation exchange (with Ag + ) occurs rapidly for cuboctahedra, whereas cubes remain inert. This dramatic difference is attributed to the relative surface area of {111} facets that promote rapid ion exchange and shows how facet engineering is a powerful knob for the control of reaction pathways in nanoparticles.

  4. Catalytic performance of the exchanged Y faujasites by Ce{sup 3+}, La{sup 3}+, UO{sub 2}{sup 2+}, Co{sup 2+}, Sr{sup 2+}, Pb{sup 2+}, Tl{sup +} and NH{sup 4+} cations in the disproportionation reaction of toluene; Performances catalytiques de faujasites Y echangees par des cations de Ce{sup 3+}, La{sup 3+}, UO{sub 2}{sup 2+}, Co{sup 2+}, Sr{sup 2+}, Pb{sup 2+}, Tl{sup +} et NH{sub 4}{sup +} dans la reaction de dismutation du toluene

    Energy Technology Data Exchange (ETDEWEB)

    Amokrane, S. [Universite des sciences et de la technologie Houari Boumediene, Departement genie chimique et cryogenie, Faculte de Genie mecanique et genie des procedes, Alger (Algeria); Nibou, D. [Universite des sciences et de la technologie Houari Boumediene, faculte de genie mecanique et genie des procedes, Departement sciences des materiaux, Alger (Algeria)


    The catalytic performance of exchanged Y faujasites by Ce{sup 3+}, La{sup 3+}, UO{sub 2}{sup 2+}, Co{sup 2+}, Sr{sup 2+}, Pb{sup 2+}, Tl{sup +} and NH{sup 4+} ions were studied in a disproportionation reaction in the gaseous phase. It was shown that total acidity generated by exchanged ions is responsible of the catalytic activity. Rare earths (cerium, lanthanum and uranium) catalysts have appreciable performance and allowed one to obtain an important xylenes proportion at 400 to 450 C. The decrease of xylenes and trimethyl-benzenes proportion in studied catalysts shows the implication of xylenes in toluene disproportionation reaction. (authors)

  5. Drug Reactions (United States)

    ... or diabetes. But medicines can also cause unwanted reactions. One problem is interactions, which may occur between ... more serious. Drug allergies are another type of reaction. They can be mild or life-threatening. Skin ...

  6. Hydra: software for tailored processing of H/D exchange data from MS or tandem MS analyses

    Directory of Open Access Journals (Sweden)

    Bennett Melissa


    Full Text Available Abstract Background Hydrogen/deuterium exchange mass spectrometry (H/DX-MS experiments implemented to characterize protein interaction and protein folding generate large quantities of data. Organizing, processing and visualizing data requires an automated solution, particularly when accommodating new tandem mass spectrometry modes for H/DX measurement. We sought to develop software that offers flexibility in defining workflows so as to support exploratory treatments of H/DX-MS data, with a particular focus on the analysis of very large protein systems and the mining of tandem mass spectrometry data. Results We present a software package ("Hydra" that supports both traditional and exploratory treatments of H/DX-MS data. Hydra's software architecture tolerates flexible data analysis procedures by allowing the addition of new algorithms without significant change to the underlying code base. Convenient user interfaces ease the organization of raw data files and input of peptide data. After executing a user-defined workflow, extracted deuterium incorporation values can be visualized in tabular and graphical formats. Hydra also automates the extraction and visualization of deuterium distribution values. Manual validation and assessment of results is aided by an interface that aligns extracted ion chromatograms and mass spectra, while providing a means of rapidly reprocessing the data following manual adjustment. A unique feature of Hydra is the automated processing of tandem mass spectrometry data, demonstrated on a large test data set in which 40,000 deuterium incorporation values were extracted from replicate analysis of approximately 1000 fragment ions in one hour using a typical PC. Conclusion The customizable workflows and user-friendly interfaces of Hydra removes a significant bottleneck in processing and visualizing H/DX-MS data and helps the researcher spend more time executing new experiments and interpreting results. This increased

  7. Nuclear reactions an introduction

    CERN Document Server

    Paetz gen. Schieck, Hans


    Nuclei and nuclear reactions offer a unique setting for investigating three (and in some cases even all four) of the fundamental forces in nature. Nuclei have been shown – mainly by performing scattering experiments with electrons, muons, and neutrinos – to be extended objects with complex internal structures: constituent quarks; gluons, whose exchange binds the quarks together; sea-quarks, the ubiquitous virtual quark-antiquark pairs and, last but not least, clouds of virtual mesons, surrounding an inner nuclear region, their exchange being the source of the nucleon-nucleon interaction.   The interplay between the (mostly attractive) hadronic nucleon-nucleon interaction and the repulsive Coulomb force is responsible for the existence of nuclei; their degree of stability, expressed in the details and limits of the chart of nuclides; their rich structure and the variety of their interactions. Despite the impressive successes of the classical nuclear models and of ab-initio approaches, there is clearly no ...

  8. The single-process biochemical reaction of Rubisco: a unified theory and model with the effects of irradiance, CO₂ and rate-limiting step on the kinetics of C₃ and C₄ photosynthesis from gas exchange. (United States)

    Farazdaghi, Hadi


    Photosynthesis is the origin of oxygenic life on the planet, and its models are the core of all models of plant biology, agriculture, environmental quality and global climate change. A theory is presented here, based on single process biochemical reactions of Rubisco, recognizing that: In the light, Rubisco activase helps separate Rubisco from the stored ribulose-1,5-bisphosphate (RuBP), activates Rubisco with carbamylation and addition of Mg²(+), and then produces two products, in two steps: (Step 1) Reaction of Rubisco with RuBP produces a Rubisco-enediol complex, which is the carboxylase-oxygenase enzyme (Enco) and (Step 2) Enco captures CO₂ and/or O₂ and produces intermediate products leading to production and release of 3-phosphoglycerate (PGA) and Rubisco. PGA interactively controls (1) the carboxylation-oxygenation, (2) electron transport, and (3) triosephosphate pathway of the Calvin-Benson cycle that leads to the release of glucose and regeneration of RuBP. Initially, the total enzyme participates in the two steps of the reaction transitionally and its rate follows Michaelis-Menten kinetics. But, for a continuous steady state, Rubisco must be divided into two concurrently active segments for the two steps. This causes a deviation of the steady state from the transitional rate. Kinetic models are developed that integrate the transitional and the steady state reactions. They are tested and successfully validated with verifiable experimental data. The single-process theory is compared to the widely used two-process theory of Farquhar et al. (1980. Planta 149, 78-90), which assumes that the carboxylation rate is either Rubisco-limited at low CO₂ levels such as CO₂ compensation point, or RuBP regeneration-limited at high CO₂. Since the photosynthesis rate cannot increase beyond the two-process theory's Rubisco limit at the CO₂ compensation point, net photosynthesis cannot increase above zero in daylight, and since there is always respiration at

  9. VT Telephone Exchange Boundaries (United States)

    Vermont Center for Geographic Information — (Link to Metadata) The UtilityTelecom_EXCHANGE represents Vermont Telephone Exchange boundaries as defined by the VT Public Service Board. The original data was...

  10. Ligand Exchange Kinetics of Environmentally Relevant Metals

    Energy Technology Data Exchange (ETDEWEB)

    Panasci, Adele Frances [Univ. of California, Davis, CA (United States)


    The interactions of ground water with minerals and contaminants are of broad interest for geochemists but are not well understood. Experiments on the molecular scale can determine reaction parameters (i.e. rates of ligand exchange, activation entropy, activation entropy, and activation volume) that can be used in computations to gain insight into reactions that occur in natural groundwaters. Experiments to determine the rate of isotopic ligand exchange for three environmentally relevant metals, rhodium (Rh), iron (Fe), and neptunium (Np), are described. Many environmental transformations of metals (e.g. reduction) in soil occur at trivalent centers, Fe(III) in particular. Contaminant ions absorb to mineral surfaces via ligand exchange, and the reversal of this reaction can be dangerous, releasing contaminants into the environment. Ferric iron is difficult to study spectroscopically because most of its complexes are paramagnetic and are generally reactive toward ligand exchange; therefore, Rh(III), which is diamagnetic and less reactive, was used to study substitution reactions that are analogous to those that occur on mineral oxide surfaces. Studies on both Np(V) and Np(VI) are important in their own right, as 237Np is a radioactive transuranic element with a half-life of 2 million years.


    African Journals Online (AJOL)

    For Nigeria at the inception of SAP, a major strategic importance in the nexus of the exchange rate policy was the reduction of the parallel market premium given the existence of the market side by side the official markets. The Hamdala, a group of Hausa `currency sellers' came into existence as a reaction to the need to act ...

  12. Ideal Heat Exchange System (United States)

    Tsirlin, A. M.


    The requirements with which a heat exchange system should comply in order that at certain values of the total contact surface and heat load the entropy production in it should be minimal have been determined. It has been shown that this system can serve as a standard for real systems of irreversible heat exchange. We have found the conditions for physical realizability of a heat exchange system in which heat exchange occurs by a law linear with respect to the temperature difference between contacting flows. Analogous conditions are given without deriving for the case of heat exchange by the Fourier law.

  13. Resolution exchange simulation. (United States)

    Lyman, Edward; Ytreberg, F Marty; Zuckerman, Daniel M


    We extend replica-exchange simulation in two ways and apply our approaches to biomolecules. The first generalization permits exchange simulation between models of differing resolution--i.e., between detailed and coarse-grained models. Such "resolution exchange" can be applied to molecular systems or spin systems. The second extension is to "pseudoexchange" simulations, which require little CPU usage for most levels of the exchange ladder and also substantially reduce the need for overlap between levels. Pseudoexchanges can be used in either replica or resolution exchange simulations. We perform efficient, converged simulations of a 50-atom peptide to illustrate the new approaches.

  14. Ion Exchange Formation via Sulfonated Bicomponent Nonwovens (United States)

    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.

  15. Reaction product imaging

    Energy Technology Data Exchange (ETDEWEB)

    Chandler, D.W. [Sandia National Laboratories, Livermore, CA (United States)


    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}.

  16. 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 (United States)

    Yaldagard, Maryam; Seghatoleslami, Naser; Jahanshahi, Mohsen


    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.

  17. Adaptively Compressed Exchange Operator

    CERN Document Server

    Lin, Lin


    The Fock exchange operator plays a central role in modern quantum chemistry. The large computational cost associated with the Fock exchange operator hinders Hartree-Fock calculations and Kohn-Sham density functional theory calculations with hybrid exchange-correlation functionals, even for systems consisting of hundreds of atoms. We develop the adaptively compressed exchange operator (ACE) formulation, which greatly reduces the computational cost associated with the Fock exchange operator without loss of accuracy. The ACE formulation does not depend on the size of the band gap, and thus can be applied to insulating, semiconducting as well as metallic systems. In an iterative framework for solving Hartree-Fock-like systems, the ACE formulation only requires moderate modification of the code, and can be potentially beneficial for all electronic structure software packages involving exchange calculations. Numerical results indicate that the ACE formulation can become advantageous even for small systems with tens...

  18. Laser Processed Heat Exchangers (United States)

    Hansen, Scott


    The Laser Processed Heat Exchanger project will investigate the use of laser processed surfaces to reduce mass and volume in liquid/liquid heat exchangers as well as the replacement of the harmful and problematic coatings of the Condensing Heat Exchangers (CHX). For this project, two scale unit test articles will be designed, manufactured, and tested. These two units are a high efficiency liquid/liquid HX and a high reliability CHX.

  19. Microsoft Exchange 2013 cookbook

    CERN Document Server

    Van Horenbeeck, Michael


    This book is a practical, hands-on guide that provides the reader with a number of clear, step-by-step exercises.""Microsoft Exchange 2013 Cookbook"" is targeted at network administrators who deal with the Exchange server in their day-to-day jobs. It assumes you have some practical experience with previous versions of Exchange (although this is not a requirement), without being a subject matter expert.

  20. Microtube strip heat exchanger (United States)

    Doty, F. D.


    During the last quarter, Doty Scientific, Inc. (DSI) continued to make progress on the microtube strip (MTS) heat exchanger. The DSI completed a heat exchanger stress analysis of the ten-module heat exchanger bank; and performed a shell-side flow inhomogeneity analysis of the three-module heat exchanger bank. The company produced 50 tubestrips using an in-house CNC milling machine and began pressing them onto tube arrays. The DSI revised some of the tooling required to encapsulate a tube array and press tubestrips into the array to improve some of the prototype tooling.

  1. Transbilayer distribution and mobility of phosphatidylcholine in intact erythrocyte membranes. A study with phosphatidylcholine exchange protein

    NARCIS (Netherlands)

    van Meer, G.|info:eu-repo/dai/nl/068570368; Poorthuis, B.J.H.M.; Wirtz, K.W.A.|info:eu-repo/dai/nl/068427956; op den Kamp, J.A.F.; van Deenen, L.L.M.


    The exchange of phosphatidylcholine between intact human or rat erythrocytes and rat liver microsomes was greatly stimulated by phosphatidylcholine-specific exchange proteins from rat liver and beef liver. It was found, however, that compared to the exchange reaction between phospholipid vesicles

  2. Transbilayer distribution and mobility of phosphatidylcholine in intact erythrocyte membranes. A study with phosphatidylcholine exchange protein

    NARCIS (Netherlands)

    van Meer, G.; Poorthuis, B. J.; Wirtz, K. W.; Op den Kamp, J. A.; van Deenen, L. L.


    1. The exchange of phosphatidylcholine between intact human or rat erythrocytes and rat liver microsomes was greatly stimulated by phosphatidylcholine-specific exchange proteins from rat liver and beef liver. It was found, however, that compared to the exchange reaction between phospholipid vesicles

  3. Method for conducting exothermic reactions (United States)

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


    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 to 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.


    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...

  5. GRUNDTVIG in transnational exchange

    DEFF Research Database (Denmark)

    Grundtvig in transnational exchange is the report from the seminar in december 2015 in cooperation with University of Cape Town and University of Hamburg.......Grundtvig in transnational exchange is the report from the seminar in december 2015 in cooperation with University of Cape Town and University of Hamburg....

  6. Optimization of Heat Exchangers

    Energy Technology Data Exchange (ETDEWEB)

    Ivan Catton


    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.

  7. Education and Industry Exchange (United States)

    Webb, Gerald A.


    Through an exchange plan a school representative worked at the personnel counter of a local company, and a supervisor from that company worked with counselors, faculty, administrators, and students from the local school. The exchange of ideas and insights were of benefit to the school and the company. (KP)

  8. cycloaddition reactions

    Indian Academy of Sciences (India)


    models of regioselectivity in pericyclic reactions. In addition, local hard and soft acid base (HSAB) princi- ples have been also employed to predict the observed regioselectivity.2 In recent years, the conceptual density functional theory has been remarkably successful in explaining the reactivity and site selectivity.3 The.

  9. Heat exchanger design handbook

    CERN Document Server

    Thulukkanam, Kuppan


    Completely revised and updated to reflect current advances in heat exchanger technology, Heat Exchanger Design Handbook, Second Edition includes enhanced figures and thermal effectiveness charts, tables, new chapter, and additional topics--all while keeping the qualities that made the first edition a centerpiece of information for practicing engineers, research, engineers, academicians, designers, and manufacturers involved in heat exchange between two or more fluids.See What's New in the Second Edition: Updated information on pressure vessel codes, manufacturer's association standards A new c

  10. Anion exchange membrane (United States)

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


    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.

  11. Data Exchange Inventory System (DEXI) (United States)

    Social Security Administration — Enterprise tool used to identify data exchanges occurring between SSA and our trading partners. DEXI contains information on both incoming and outgoing exchanges and...

  12. Microplate Heat Exchanger Project (United States)

    National Aeronautics and Space Administration — We propose a microplate heat exchanger for cryogenic cooling systems used for continuous flow distributed cooling systems, large focal plane arrays, multiple cooling...

  13. Exchange Risk Management Policy

    CERN Document Server


    At the Finance Committee of March 2005, following a comment by the CERN Audit Committee, the Chairman invited the Management to prepare a document on exchange risk management policy. The Finance Committee is invited to take note of this document.

  14. HUD Exchange Grantee Database (United States)

    Department of Housing and Urban Development — The About Grantees section of the HUD Exchange brings up contact information, reports, award, jurisdiction, and location data for organizations that receive HUD...

  15. NASA Earth Exchange (NEX) (United States)

    National Aeronautics and Space Administration — The NASA Earth Exchange (NEX) represents a new platform for the Earth science community that provides a mechanism for scientific collaboration and knowledge sharing....

  16. Anion exchange polymer electrolytes (United States)

    Kim, Yu Seung; Kim, Dae Sik


    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.

  17. Proton channels and exchangers in cancer. (United States)

    Spugnini, Enrico Pierluigi; Sonveaux, Pierre; Stock, Christian; Perez-Sayans, Mario; De Milito, Angelo; Avnet, Sofia; Garcìa, Abel Garcìa; Harguindey, Salvador; Fais, Stefano


    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. Copyright © 2014 Elsevier B.V. All rights reserved.

  18. Cryptographic Combinatorial Securities Exchanges (United States)

    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.

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


    Abhijeet Kapoor; Alex Travesset


    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 identifi...

  20. Development and Application of Ligand-Exchange Reaction Method ...

    African Journals Online (AJOL)


    rpm to separate the protein precipitate. The supernatant was collected in a 50 mL standard volumetric flask and filled up to the mark with the same solvent. The serum sample contained 200.0 µg mL-1 of CZP. Aliquots of this solution were transferred into vessels spanning the concentration range listed in Table 5. For kinetic ...

  1. A degradable polydopamine coating based on disulfide-exchange reaction (United States)

    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.


    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

  2. Thermodynamics of ion exchange equilibrium for some uni ...

    African Journals Online (AJOL)

    The study on thermodynamics of ion exchange equilibrium for uni-univalent Cl-/I-, Cl-/Br-, and uni-divalent Cl-/SO42-, Cl-/C2O42- reaction systems was carried out using ion exchange resin Indion FF-IP. The equilibrium constant K was calculated by taking into account the activity coefficient of ions both in solution as well as ...

  3. Exchanging Description Logic Knowledge Bases

    NARCIS (Netherlands)

    Arenas, M.; Botoeva, E.; Calvanese, D.; Ryzhikov, V.; Sherkhonov, E.


    In this paper, we study the problem of exchanging knowledge between a source and a target knowledge base (KB), connected through mappings. Differently from the traditional database exchange setting, which considers only the exchange of data, we are interested in exchanging implicit knowledge. As

  4. Spallation reactions; Reactions de spallation

    Energy Technology Data Exchange (ETDEWEB)

    Cugon, J.


    Spallation reactions dominate the interactions of hadrons with nuclei in the GeV range (from {approx} 0.1 to {approx} 10 GeV). They correspond to a sometimes important ejection of light particles leaving most of the time a residue of mass commensurate with the target mass. The main features of the experimental data are briefly reviewed. The most successful theoretical model, namely the intranuclear cascade + evaporation model, is presented. Its physical content, results and possible improvements are critically discussed. Alternative approaches are shortly reviewed. (author). 84 refs.

  5. Modified ion exchange resins - synthesis and properties. Pt. 1

    Energy Technology Data Exchange (ETDEWEB)

    Doescher, F.; Klein, J.; Pohl, F.; Widdecke, H.


    Sulfomethylated resins are prepared by polymer analogous reactions, starting from macroporous poly(styrene-co-divinylbenzene) matrices. Different reaction paths are discussed and used in the synthesis. Sulfomethylation can be achieved by reaction of a chloromethylated resin with dimethyl sulfide and sodium sulfonate or alternatively by oxidation of polymer-bound thiol groups. Both methods give high conversions as shown by IR spectra and titration of the sulfonic acid groups. Poly(1-(4-hydroxysulfomethylphenyl)ethylene) (3) is obtained by reaction of poly(1-(4-hydroxyphenyl)ethylene) (2) resin with formaldehyde/sodium sulfonate. The thermal stability, catalytic activity, and ion exchange equilibria of the sulfomethylated resin are investigated.

  6. Microgravity condensing heat exchanger (United States)

    Thomas, Christopher M. (Inventor); Ma, Yonghui (Inventor); North, Andrew (Inventor); Weislogel, Mark M. (Inventor)


    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 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.

  7. Ion exchange phenomena

    Energy Technology Data Exchange (ETDEWEB)

    Bourg, I.C.; Sposito, G.


    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).

  8. Heat exchanger panel (United States)

    Warburton, Robert E. (Inventor); Cuva, William J. (Inventor)


    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.

  9. Microscale Regenerative Heat Exchanger (United States)

    Moran, Matthew E.; Stelter, Stephan; Stelter, Manfred


    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.

  10. Deuterium Exchange in the Systems of H2O+/H2O and H3O+/H2O (United States)

    Anicich, V. G.; Sen, A. D.


    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.

  11. Flows and chemical reactions in heterogeneous mixtures

    CERN Document Server

    Prud'homme, Roger


    This book - a sequel of previous publications 'Flows and Chemical Reactions' and 'Chemical Reactions in Flows and Homogeneous Mixtures' - is devoted to flows with chemical reactions in heterogeneous environments.  Heterogeneous media in this volume include interfaces and lines. They may be the site of radiation. Each type of flow is the subject of a chapter in this volume. We consider first, in Chapter 1, the question of the generation of environments biphasic individuals: dusty gas, mist, bubble flow.  Chapter 2 is devoted to the study at the mesoscopic scale: particle-fluid exchange of mom

  12. Nature's Heat Exchangers. (United States)

    Barnes, George


    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)

  13. Basic Exchange Rate Theories

    NARCIS (Netherlands)

    J.G.M. van Marrewijk (Charles)


    textabstractThis four-chapter overview of basic exchange rate theories discusses (i) the elasticity and absorption approach, (ii) the (long-run) implications of the monetary approach, (iii) the short-run effects of monetary and fiscal policy under various economic conditions, and (iv) the transition

  14. Technology Performance Exchange

    Energy Technology Data Exchange (ETDEWEB)


    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.

  15. Telephone Exchange Maintenance

    CERN Document Server


    Urgent maintenance work on CERN telephone exchanges will be performed on 24 March from 6 a.m. to 8 a.m. Telephone services may be disrupted or even interrupted during this time. For more details, please contact us by email at

  16. Baltic Exchange toodi Tallinna

    Index Scriptorium Estoniae


    Viimane osa merekonteineritesse kokkupakitud Londoni laevandus- ja merebörsi Baltic Exchange'i endise peakorteri detailidest jõudis 2007. a. juunis Tallinna. Hoone detailid ostnud ärimehed Heiti Hääl ja Eerik-Niiles Kross plaanivad leida hoonele koha Tallinna kesklinnas. E.-N. Krossi kommentaar

  17. Heat exchanger. Varmeveksler

    Energy Technology Data Exchange (ETDEWEB)

    Rosman, I.E.; Wagner, W.R.


    The invention concerns a manifold for a plate-type heat exchanger, and includes a side channel connected the inlet of the manifold. The plates can be designed as an integral assembly together with the integrated side- and external end-manifolds as well. 16 drawings.

  18. Chemical exchange program analysis.

    Energy Technology Data Exchange (ETDEWEB)

    Waffelaert, Pascale


    As part of its EMS, Sandia performs an annual environmental aspects/impacts analysis. The purpose of this analysis is to identify the environmental aspects associated with Sandia's activities, products, and services and the potential environmental impacts associated with those aspects. Division and environmental programs established objectives and targets based on the environmental aspects associated with their operations. In 2007 the most significant aspect identified was Hazardous Materials (Use and Storage). The objective for Hazardous Materials (Use and Storage) was to improve chemical handling, storage, and on-site movement of hazardous materials. One of the targets supporting this objective was to develop an effective chemical exchange program, making a business case for it in FY07, and fully implementing a comprehensive chemical exchange program in FY08. A Chemical Exchange Program (CEP) team was formed to implement this target. The team consists of representatives from the Chemical Information System (CIS), Pollution Prevention (P2), the HWMF, Procurement and the Environmental Management System (EMS). The CEP Team performed benchmarking and conducted a life-cycle analysis of the current management of chemicals at SNL/NM and compared it to Chemical Exchange alternatives. Those alternatives are as follows: (1) Revive the 'Virtual' Chemical Exchange Program; (2) Re-implement a 'Physical' Chemical Exchange Program using a Chemical Information System; and (3) Transition to a Chemical Management Services System. The analysis and benchmarking study shows that the present management of chemicals at SNL/NM is significantly disjointed and a life-cycle or 'Cradle-to-Grave' approach to chemical management is needed. This approach must consider the purchasing and maintenance costs as well as the cost of ultimate disposal of the chemicals and materials. A chemical exchange is needed as a mechanism to re-apply chemicals on site. This

  19. Counterflow Regolith Heat Exchanger (United States)

    Zubrin, Robert; Jonscher, Peter


    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.

  20. Fast anion-exchange in highly luminescent nanocrystals of cesium lead halide perovskites (CsPbX3, X=Cl, Br, I).


    G. Nedelcu L. Protesescu S. Yakunin M. I. Bodnarchuk M. Grotevent and M. V. Kovalenko


    Postsynthetic chemical transformations of colloidal nanocrystals, such as ion-exchange reactions, provide an avenue to compositional fine-tuning or to otherwise inaccessible materials and morphologies. While cation-exchange is facile and commonplace, anion-exchange reactions have not received substantial deployment. Here we report fast, low-temperature, deliberately partial, or complete anion-exchange in highly luminescent semiconductor nanocrystals of cesium lead halide perovskites (CsPbX3, ...

  1. Analytical applications of ion exchangers

    CERN Document Server

    Inczédy, J


    Analytical Applications of Ion Exchangers presents the laboratory use of ion-exchange resins. This book discusses the development in the analytical application of ion exchangers. Organized into 10 chapters, this book begins with an overview of the history and significance of ion exchangers for technical purposes. This text then describes the properties of ion exchangers, which are large molecular water-insoluble polyelectrolytes having a cross-linked structure that contains ionic groups. Other chapters consider the theories concerning the operation of ion-exchange resins and investigate th

  2. Fe atom exchange between aqueous Fe2+ and magnetite. (United States)

    Gorski, Christopher A; Handler, Robert M; Beard, Brian L; Pasakarnis, Timothy; Johnson, Clark M; Scherer, Michelle M


    The reaction between magnetite and aqueous Fe(2+) has been extensively studied due to its role in contaminant reduction, trace-metal sequestration, and microbial respiration. Previous work has demonstrated that the reaction of Fe(2+) with magnetite (Fe(3)O(4)) results in the structural incorporation of Fe(2+) and an increase in the bulk Fe(2+) content of magnetite. It is unclear, however, whether significant Fe atom exchange occurs between magnetite and aqueous Fe(2+), as has been observed for other Fe oxides. Here, we measured the extent of Fe atom exchange between aqueous Fe(2+) and magnetite by reacting isotopically "normal" magnetite with (57)Fe-enriched aqueous Fe(2+). The extent of Fe atom exchange between magnetite and aqueous Fe(2+) was significant (54-71%), and went well beyond the amount of Fe atoms found at the near surface. Mössbauer spectroscopy of magnetite reacted with (56)Fe(2+) indicate that no preferential exchange of octahedral or tetrahedral sites occurred. Exchange experiments conducted with Co-ferrite (Co(2+)Fe(2)(3+)O(4)) showed little impact of Co substitution on the rate or extent of atom exchange. Bulk electron conduction, as previously invoked to explain Fe atom exchange in goethite, is a possible mechanism, but if it is occurring, conduction does not appear to be the rate-limiting step. The lack of significant impact of Co substitution on the kinetics of Fe atom exchange, and the relatively high diffusion coefficients reported for magnetite suggest that for magnetite, unlike goethite, Fe atom diffusion is a plausible mechanism to explain the rapid rates of Fe atom exchange in magnetite.

  3. Iron Atom Exchange between Hematite and Aqueous Fe(II). (United States)

    Frierdich, Andrew J; Helgeson, Maria; Liu, Chengshuai; Wang, Chongmin; Rosso, Kevin M; Scherer, Michelle M


    Aqueous Fe(II) has been shown to exchange with structural Fe(III) in goethite without any significant phase transformation. It remains unclear, however, whether aqueous Fe(II) undergoes similar exchange reactions with structural Fe(III) in hematite, a ubiquitous iron oxide mineral. Here, we use an enriched (57)Fe tracer to show that aqueous Fe(II) exchanges with structural Fe(III) in hematite at room temperature, and that the amount of exchange is influenced by particle size, pH, and Fe(II) concentration. Reaction of 80 nm-hematite (27 m(2) g(-1)) with aqueous Fe(II) at pH 7.0 for 30 days results in ∼5% of its structural Fe(III) atoms exchanging with Fe(II) in solution, which equates to about one surface iron layer. Smaller, 50 nm-hematite particles (54 m(2) g(-1)) undergo about 25% exchange (∼3× surface iron) with aqueous Fe(II), demonstrating that structural Fe(III) in hematite is accessible to the fluid in the presence of Fe(II). The extent of exchange in hematite increases with pH up to 7.5 and then begins to decrease as the pH progresses to 8.0, likely due to surface site saturation by sorbed Fe(II). Similarly, when we vary the initial amount of added Fe(II), we observe decreasing amounts of exchange when aqueous Fe(II) is increased beyond surface saturation. This work shows that Fe(II) can catalyze iron atom exchange between bulk hematite and aqueous Fe(II), despite hematite being the most thermodynamically stable iron oxide.

  4. Data Exchange Inventory (DEXI) System (United States)

    Social Security Administration — DEXI is an intranet application used by SSA users to track all incoming and outgoing data exchanges between SSA and our data exchange partners. Information such as...

  5. Dynamical Clustering of Exchange Rates


    Fenn, Daniel J.; Porter, Mason A.; Mucha, Peter J; Mark McDonald; Stacy Williams; Johnson, Neil F.; Jones, Nick S


    We use techniques from network science to study correlations in the foreign exchange (FX) market over the period 1991--2008. We consider an FX market network in which each node represents an exchange rate and each weighted edge represents a time-dependent correlation between the rates. To provide insights into the clustering of the exchange rate time series, we investigate dynamic communities in the network. We show that there is a relationship between an exchange rate's functional role withi...

  6. Serial tempering without exchange. (United States)

    Nymeyer, Hugh


    Serial tempering is a computational method that turns the temperature T (or more generally any independent λ parameter) into a dynamical variable. It is shown that, under conditions for which this variable is fast, serial tempering is equivalent to the umbrella sampling method with a single effective potential. This equivalence is demonstrated using both a small one-dimensional system and a small solvated peptide. The suggestion is then made to replace the serial tempering protocol with the equivalent umbrella sampling calculation. This approach, serial tempering without exchange (STeWiE), has the same performance as serial tempering in the limit that exchanges are frequent, is simpler to implement, and has fewer adjustable parameters than conventional serial tempering. The equivalence of serial tempering and STeWiE also provides a convenient route for estimating and optimizing the performance of serial tempering simulations and other generalized-ensemble methods.

  7. Lipid exchange by ultracentrifugation

    DEFF Research Database (Denmark)

    Drachmann, Nikolaj Düring; Olesen, Claus


    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 lipids 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...

  8. Reaction Kinetics of HBr with HO2: A New Channel for Isotope Scrambling Reactions. (United States)

    Church, Jonathan R; Skodje, Rex T


    The gas phase reaction kinetics of HBr with the HO2 radical are investigated over the temperature range of T = 200-1500 K using a theoretical approach based on transition state theory. The parameters for the potential energy surface are computed using density functional theory with the M11 exchange functional. The rate coefficient for the HBr + HO2 → Br + H2O2 abstraction channel is found to be somewhat larger than previous estimates at low temperatures due to quantum tunneling. The present study reveals the existence of a novel exchange pathway, HBr + H'O2 → H'Br + HO2, which exhibits a much lower reaction barrier than does the abstraction route. The transition state for this process is a symmetrical planar five-membered-ring-shaped structure. At low temperatures, this concerted double hydrogen transfer reaction is several orders of magnitude faster than the abstraction channel. The exchange process may be observed using isotope scrambling reactions; such reactions may contribute to observed isotope abundances in the atmosphere. The rate coefficients for the isotopically labeled reactions are computed.

  9. Exchange rate rebounds after foreign exchange market interventions (United States)

    Hoshikawa, Takeshi


    This study examined the rebounds in the exchange rate after foreign exchange intervention. When intervention is strongly effective, the exchange rate rebounds at next day. The effect of intervention is reduced slightly by the rebound after the intervention. The exchange rate might have been 67.12-77.47 yen to a US dollar without yen-selling/dollar-purchasing intervention of 74,691,100 million yen implemented by the Japanese government since 1991, in comparison to the actual exchange rate was 103.19 yen to the US dollar at the end of March 2014.

  10. O3 and NOx Exchange

    NARCIS (Netherlands)

    Loubet, B.; Castell, J.F.; Laville, P.; Personne, E.; Tuzet, A.; Ammann, C.; Emberson, L.; Ganzeveld, L.; Kowalski, A.S.; Merbold, L.; Stella, P.; Tuovinen, J.P.


    This discussion was based on the background document “Review on modelling atmosphere-biosphere exchange of Ozone and Nitrogen oxides”, which reviews the processes contributing to biosphere-atmosphere exchange of O3 and NOx, including stomatal and non-stomatal exchange of O3 and NO, NO2.

  11. The stability of exchange networks

    NARCIS (Netherlands)

    Doğan, G.; Assen, M. van; Rijt, A. van de; Buskens, V.W.


    Economic and sociological exchange theories predict divisions of exchange benefits given an assumed fixed network of exchange relations. Since network structure has been found to have a large impact on actors’ payoffs, actors have strong incentives for network change.Weanswer the question what

  12. Integrated foreign exchange risk management

    DEFF Research Database (Denmark)

    Aabo, Tom; Høg, Esben; Kuhn, Jochen


    Empirical research has focused on export as a proxy for exchange rate exposure and the use of foreign exchange derivatives as an instrument to deal with this exposure. This empirical study applies an integrated foreign exchange risk management approach with a particular focus on the role of impor...

  13. Integrated Foreign Exchange Risk Management

    DEFF Research Database (Denmark)

    Aabo, Tom; Høg, Esben; Kuhn, Jochen

    Empirical research has focused on export as a proxy for the exchange rate exposure and the use of foreign exchange derivatives as the instrument to deal with this exposure. This empirical study applies an integrated foreign exchange risk management approach with a particular focus on the role...

  14. Timing Foreign Exchange Markets

    Directory of Open Access Journals (Sweden)

    Samuel W. Malone


    Full Text Available To improve short-horizon exchange rate forecasts, we employ foreign exchange market risk factors as fundamentals, and Bayesian treed Gaussian process (BTGP models to handle non-linear, time-varying relationships between these fundamentals and exchange rates. Forecasts from the BTGP model conditional on the carry and dollar factors dominate random walk forecasts on accuracy and economic criteria in the Meese-Rogoff setting. Superior market timing ability for large moves, more than directional accuracy, drives the BTGP’s success. We explain how, through a model averaging Monte Carlo scheme, the BTGP is able to simultaneously exploit smoothness and rough breaks in between-variable dynamics. Either feature in isolation is unable to consistently outperform benchmarks throughout the full span of time in our forecasting exercises. Trading strategies based on ex ante BTGP forecasts deliver the highest out-of-sample risk-adjusted returns for the median currency, as well as for both predictable, traded risk factors.

  15. Paste heat exchange

    Energy Technology Data Exchange (ETDEWEB)


    The subject of coal paste heat exchangers is discussed in this letter report from Gelsenberg A.G. to I.G. Farbenindustrie A.G. Gelsenberg had given little consideration to the heating of coal paste by means of regeneration (heat exchange) because of the lack of experience in paste regeneration with bituminous coal, especially at 700 atmospheres. At the I.G. Farben plant at Poelitz, paste regeneration was carried out so that low concentration coal paste was heated in the regenerator together with the process gas, and the remaining coal was fed into the cold pass of the preheater in a thicker paste. Later tests proved this process viable. Gelsenberg heated normal coal paste and the gas in heat exchangers with the goal of relieving the preheater. Good results were achieved without change in design. The coal paste was heated with process gas in the regenerator at up to 315 degrees with constant pressure difference, so that after three months no decrease in K-values and no deposition or thickening was observed. Through the omission of paste gas, the pressure difference of the system became more constant and did not rise above the former level. The temperature also was more controllable, the chamber smoother running. Principal thermal data are given in a table. 1 table, 1 graph.

  16. The exchangeability of shape

    Directory of Open Access Journals (Sweden)

    Kaba Dramane


    Full Text Available Abstract 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.

  17. Therapeutic plasma exchange in Casablanca. (United States)

    Tazi, I; Merimi, F; Majd, A; Benchemsi, N


    Therapeutic plasma exchange (TPE) is an extracorporeal blood purification method for the treatment of diseases in which pathological proteins have to be eliminated. In the aim to demonstrate our single center activity, we analyzed our data since 2 years. Between years 2002 and 2005, 104 TPE procedures were performed on 42 patients. Median age and male/female ratio were 32 (range, 17-56) and 24/18, respectively. Departments those referred the majority of the TPE were neurology (n=32), nephrology (n=5) and intensive care unit (n=5). The most common indications were: polyradiculoneuropathies (53%), myasthenia gravis (17%) and Guillain-Barré syndrome (12%). The median TPE procedure per patient was 2.3 (range, 1-10). In the majority of patients, vascular access was provided by puncture of two large, durable peripheral antecubital veins. The procedures were performed with the "Haemonetic Ultralight" discontinuous flow cell separator devices. Citrate solution was used as an anticoagulant in all cases. The substitution fluids most often used in our unit are Albumin 20% solution (92 times), Albumin 4% (10 times) and fresh frozen plasma (twice). Seventy five percent of the patients showed improvement, 7% remained the same and 18% worsened. Thirteen adverse reactions were recorded. The creation of a national registry by the local society is a vital move to improve TPE practice in our country.

  18. evaluation of total annual costs of heat exchanger networks using

    African Journals Online (AJOL)


    This study presents pinch analysis of some heat exchanger networks (HENs) problems using Hint integration. (HINT) software ... after solving the first problem using RPA based heat integration gave a minimum total annual cost (TAC) of $237,. 510 /yr. which ... reaction, run pumps, and effect the separation and compressors.

  19. thermodynamics of ion exchange equilibrium for some uni

    African Journals Online (AJOL)


    equilibrium constant K was calculated by taking into account the activity coefficient of ions both in solution as well as in the resin phase. For uni-univalent ion exchange reaction systems, the equilibrium constant K' were also calculated by considering mole fraction of ions in the resin phase. The K values calculated for ...

  20. Simultaneous Disulfide and Boronic Acid Ester Exchange in Dynamic Combinatorial Libraries

    DEFF Research Database (Denmark)

    Diemer, Sanna L.; Kristensen, Morten; Rasmussen, Brian


    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...

  1. Nuclear Transparency and Single Particle Spectral Functions from Quasielastic A(e,e'p) Reactions up to Q2=8.1 GeV2

    Energy Technology Data Exchange (ETDEWEB)

    McKee, David Wayne [New Mexico State Univ., Las Cruces, NM (United States)


    High statistics elastic and quasielastic scattering measurements were performed on hydrogen, deuterium, carbon, and iron at squared momentum transfers up to 8.1 GeV2. Both the nuclear transparency and the single particle spectral functions were extracted by means of comparison with a Plane- Wave Impulse Approximation calculation. Our data provide no evidence of the onset of color transparency within our kinematic range.

  2. ion exchange equilibrium for some uni-univalent and uni-divalent ...

    African Journals Online (AJOL)


    equilibrium constant K was calculated by taking into account the activity coefficient of ions both in solution as well as in the resin phase. The K values calculated for uni-univalent and uni-divalent anion exchange reaction systems was observed to increase with rise in temperature, indicating the endothermic exchange ...

  3. Sulfur Isotope Exchange between S-35 Labeled Inorganic Sulfur-Compounds in Anoxic Marine-Sediments

    DEFF Research Database (Denmark)



    of isotope exchange, specific radioactivities of the reduced sulfur pools were poorly defined and could not be used to calculate their rates of formation. Such isotope exchange reactions between the reduced inorganic sulfur compounds will affect the stable isotope distribution and are expected to decrease...

  4. Radiotracer application for characterization of nuclear grade anion exchange resins Tulsion A-23 and Dowex SBR LC

    Energy Technology Data Exchange (ETDEWEB)

    Singare, P.U. [Bhavan' s College, Mumbai (India). Dept. of Chemistry


    Radio isotopic tracer technique as one of the versatile nondestructive technique is employed to evaluate the performance of nuclear grade anion exchange resins Tulsion A-23 and Dowex SBR LC. The evaluation was made on the basis of ion-isotopic exchange reaction kinetics by using {sup 131}I and {sup 82}Br radioactive tracer isotopes. It was observed that for both the resins, the values of specific reaction rate (min{sup -1}), amount of ion exchanged (mmol) and initial rate of ion exchange (mmol/min) were calculated to be lower for bromide ion-isotopic exchange reaction than that for iodide ion-isotopic exchange reaction. It was observed that for iodide ion-isotopic exchange reaction under identical experimental conditions of 30.0 C, 1.000 g of ion exchange resins and 0.001 mol/L labeled iodide ion solution, the values of specific reaction rate (min{sup -1}), amount of iodide ion exchanged (mmol), initial rate of iodide ion exchange (mmol/min) and log K{sub d} were calculated as 0.377, 0.212, 0.080 and 15.5 respectively for Dowex SBR LC resin, which was higher than 0.215, 0.144, 0.031 and 14.1 respectively as that obtained for Tulsion A23 resins. Also at a constant temperature of 30.0 C, as the concentration of labeled iodide ion solution increases from 0.001 mol/L to 0.004 mol/L, the percentage of iodide ions exchanged increases from 84.75 % to 90.20 % for Dowex SBR LC resins which was higher than increases from 57.66 % to 62.38 % obtained for Tulsion A23 resins. The identical trend was observed for the two resins during bromide ion-isotopic exchange reaction. The overall results indicate superior performance of Dowex SBR LC over Tulsion A23 resins under identical experimental conditions.

  5. 10 CFR Appendix E to Part 110 - Illustrative List of Chemical Exchange or Ion Exchange Enrichment Plant Equipment and Components... (United States)


    ... (exchange rate half-time of less than 10 seconds) and are capable of operating at a temperature in the range... between the isotopes of uranium causes small changes in chemical reaction equilibria that can be used as a..., immiscible liquid phases (aqueous and organic) are countercurrently contacted to give the cascading effect of...

  6. Ion source parameters and hydrogen scrambling in the ECD of selectively deuterated peptides

    DEFF Research Database (Denmark)

    Duchateau, Magalie; Jørgensen, Thomas J. D.; Robine, Ophélie


    Hydrogen/deuterium exchange monitored by mass spectrometry (HDX-MS) has become an important method to study protein dynamics in solution. Recently, electron-based fragmentation methods (ECD and ETD) have been utilized in HDX-MS/MS experiments as experimental tools to increase the spatial resoluti...

  7. Conformational changes in the G protein Gs induced by the β2 adrenergic receptor

    DEFF Research Database (Denmark)

    Chung, Ka Young; Rasmussen, Søren Gøgsig Faarup; Liu, Tong


    the receptor-binding surface and the nucleotide-binding pocket of Gs that undergo higher levels of hydrogen-deuterium exchange than would be predicted from the crystal structure of the β(2)AR-Gs complex. Together with X-ray crystallographic and electron microscopic data of the β(2)AR-Gs complex (from refs 2, 3...

  8. Investigating the Role of Artemin Glycosylation

    DEFF Research Database (Denmark)

    Danwen, Qiu; Code, Christian; Quan, Chao


    to examine the relative activity and pharmacokinetic properties of ART as a function of glycosylation. In order to reveal the conformational impact of glycosylation on ART, hydrogen/deuterium exchange mass spectrometry (HDX-MS) was employed in addition to differential scanning calorimetry. The colloidal...

  9. Sorption and binary exchange of nitrate, sulfate, and uranium on an anion-exchange resin. (United States)

    Gu, Baohua; Ku, Yee-Kyoung; Jardine, Philip M


    Competitive ion-exchange reactions were studied on a strong-base anion-exchange resin to remove NO3- and uranium from a contaminated groundwater containing high levels of NO3- (approximately 140 mM), SO4(2-) (approximately 10 mM), and U(VI) (approximately 0.2 mM). Results indicate that although SO4(2-) carries divalent negative charges, it showed the least selectivity for sorption by the Purolite A-520E resin, which is functionalized with triethylamine exchange sites. Nitrate was the most strongly sorbed. Sorption selectivity followed the order of NO3- > Cl- > SO4(2-) under the experimental conditions. Nitrate competitively sorbed and displaced previously sorbed SO4(2-) in a column flow-through experiment and resulted in a high elution front of SO4(2-) in the effluent. Although the concentration of uranium in groundwater is orders of magnitude lower than that of NO3- or SO4(2-), it was found to be strongly sorbed by the anion-exchange resin. Because the most stable uranium species in oxic and suboxic environments is the UO2(2+) cation, its strong sorption by anion-exchange resins is hypothesized to be the result of the co-ion effect of NO3- by forming anionic UO2(NO3)3- complexes in the resin matrix. These observations point out a potential alternative remediation strategy that uses strong-base anion-exchange resins to remove uranium from this site-specific groundwater, which has a low pH and a relatively high NO3- concentration.

  10. Cryogenic regenerative heat exchangers

    CERN Document Server

    Ackermann, Robert A


    An in-depth survey of regenerative heat exchangers, this book chronicles the development and recent commercialization of regenerative devices for cryogenic applications. Chapters cover historical background, concepts, practical applications, design data, and numerical solutions, providing the latest information for engineers to develop advanced cryogenic machines. The discussions include insights into the operation of a regenerator; descriptions of the cyclic and fluid temperature distributions in a regenerator; data for various matrix geometries and materials, including coarse and fine bronze, stainless steel-woven wire mesh screens, and lead spheres; and unique operating features of cryocoolers that produce deviations from ideal regenerator theory.

  11. Vanadium proton exchange membrane water electrolyser (United States)

    Noack, Jens; Roznyatovskaya, Nataliya; Pinkwart, Karsten; Tübke, Jens


    In order to reverse the reactions of vanadium oxygen fuel cells and to regenerate vanadium redox flow battery electrolytes that have been oxidised by atmospheric oxygen, a vanadium proton exchange membrane water electrolyser was set up and investigated. Using an existing cell with a commercial and iridium-based catalyst coated membrane, it was possible to fully reduce V3.5+ and V3+ solutions to V2+ with the formation of oxygen and with coulomb efficiencies of over 96%. The cell achieved a maximum current density of 75 mA/cm2 during this process and was limited by the proximity of the V(III) reduction to the hydrogen evolution reaction. Due to the specific reaction mechanisms of V(IV) and V(III) ions, V(III) solutions were reduced with an energy efficiency of 61%, making this process nearly twice as energy efficient as the reduction of V(IV) to V(III). Polarisation curves and electrochemical impedance spectroscopy were used to further investigate the losses of half-cell reactions and to find ways of further increasing efficiency and performance levels.

  12. Anaphylaxis-Like Reactions (United States)

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

  13. Catalysis of Photochemical Reactions. (United States)

    Albini, A.


    Offers a classification system of catalytic effects in photochemical reactions, contrasting characteristic properties of photochemical and thermal reactions. Discusses catalysis and sensitization, examples of catalyzed reactions of excepted states, complexing ground state substrates, and catalysis of primary photoproducts. (JM)

  14. On Thermonuclear Reaction Rates


    Haubold, H. J.; Mathai, A. M.


    Nuclear reactions govern major aspects of the chemical evolution of galaxies and stars. Analytic study of the reaction rates and reaction probability integrals is attempted here. Exact expressions for the reaction rates and reaction probability integrals for nuclear reactions in the cases of nonresonant, modified nonresonant, screened nonresonant and resonant cases are given. These are expressed in terms of H-functions, G-functions and in computable series forms. Computational aspects are als...

  15. Atmospheric gas phase reactions (United States)

    Platt, Ulrich

    This chapter introduces the underlying physicochemical principles and the relevance of atmospheric gas phase reactions. In particular, reaction orders, the concept of elementary reactions, definition of and factors determining reaction rates (kinetic theory of chemical reactions), and photochemical reactions are discussed. Sample applications of the pertinent reaction pathways in tropospheric chemistry are presented, particularly reactions involving free radicals (OH, NO3, halogen oxides) and their roles in the self-cleaning of the troposphere. The cycles of nitrogen and sulfur species as well as the principles of tropospheric ozone formation are introduced. Finally, the processes governing the stratospheric ozone layer (Chapman Cycle and extensions) are discussed.

  16. Oxygen exchange between nitrate molecules during nitrite oxidation by Nitrobacter. (United States)

    DiSpirito, A A; Hooper, A B


    During oxidation of nitrite, cells of Nitrobacter winogradskyi are shown to catalyze the active exchange of oxygen atoms between exogenous nitrate molecules (production of 15N16/18O3- during incubation of 14N16/18O3-, 15N16O3-, and 15N16O2- in H216O). Little, if any, exchange of oxygens between nitrate and water also occurs (production of 15N16/18O3- during incubation of 15N16O3- and 14N16O2- in H218O). 15N species of nitrate were assayed by 18O-isotope shift in 15N NMR. Taking into account the O-exchange reactions which occur during nitrite oxidation, H2O is seen to be the source of O in nitrate produced by oxidation of nitrite by N. winogradskyi. The data do not establish whether the nitrate-nitrate O exchange is catalyzed by nitrite oxidase (H2O + HNO2----HNO3 + 2H+ + 2e-) or nitrate reductase (HNO3 + 2H+ + 2e-----HNO2 + H2O) or both enzymes in consort. The nitrate-nitrate exchange reaction suggests the existence of an oxygen derivative of a H2O-utilizing oxidoreductase.

  17. Developing bulk exchange spring magnets

    Energy Technology Data Exchange (ETDEWEB)

    Mccall, Scott K.; Kuntz, Joshua D.


    A method of making a bulk exchange spring magnet by providing a magnetically soft material, providing a hard magnetic material, and producing a composite of said magnetically soft material and said hard magnetic material to make the bulk exchange spring magnet. The step of producing a composite of magnetically soft material and hard magnetic material is accomplished by electrophoretic deposition of the magnetically soft material and the hard magnetic material to make the bulk exchange spring magnet.

  18. Characteristics of model heat exchanger (United States)

    Kolínský, Jan


    The aim of this paper is thermal analysis of model water to water heat exchanger at different mass flow rates. Experimental study deals with determination of total heat transfer - power of the heat exchanger. Furthermore the paper deals with analysis of heat exchanger charakcteristic using a definition of thermal efficiency. It is demonstrated that it is advisable to monitor the dependence of thermal efficiency and flow ratio.

  19. What Drives Stock Exchange Integration?

    National Research Council Canada - National Science Library

    Ekaterina Dorodnykh


    .... After a broad discussion of the existent literature, the investigation combines a large number of potentially relevant determinants for the explanation of whether stock exchanges are participating...

  20. Mastering Microsoft Exchange Server 2013

    CERN Document Server

    Elfassy, David


    The bestselling guide to Exchange Server, fully updated for the newest version Microsoft Exchange Server 2013 is touted as a solution for lowering the total cost of ownership, whether deployed on-premises or in the cloud. Like the earlier editions, this comprehensive guide covers every aspect of installing, configuring, and managing this multifaceted collaboration system. It offers Windows systems administrators and consultants a complete tutorial and reference, ideal for anyone installing Exchange Server for the first time or those migrating from an earlier Exchange Server version.Microsoft

  1. Hybrid Heat Exchangers (United States)

    Tu, Jianping Gene; Shih, Wei


    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.

  2. The Radioecology Exchange

    Energy Technology Data Exchange (ETDEWEB)

    Barnett, Catherine L.; Beresford, Nicholas A.; Patel, Sabera; Wells, Claire; Howard, Brenda J. [NERC Centre for Ecology and Hydrology, CEH Lancaster, Lancaster Environment Centre, Library Av., Bailrigg, Lancaster, LA1 4AP (United Kingdom); Mora, Juan Carlos; Real, Almudena [Centro de Investigaciones Energeticas, Medioambientales y Tecnologicas (CIEMAT), Avenida complutense 22, Madrid, 28040 (Spain); Beaugelin-Seiller, Karine; Gilbin, Rodolphe; Hinton, Thomas [IRSN-Institut de Radioprotection et de Surete Nucleaire, 31, Avenue de la Division Leclerc, 92260 Fontenay-Aux-Roses (France); Vesterbacka, Pia; Muikku, Maarit; Outola, Iisa [Radiation and Nuclear Safety Authority, P.O. Box 14, FI-00881 Helsinki (Finland); Skuterud, Lavrans; AlbumYtre-Eide, Martin [Norwegian Radiation Protection Authority, Grini Naeringspark 13, Oesteraas, 1332 (Norway); Bradshaw, Clare; Stark, Karolina; Jaeschke, Ben [Stockholms Universitet, Universitetsvaegen 10, Stockholm, 10691 (Sweden); Oughton, Deborah; Skipperud, Lindis [NMBU Norwegian University of Life Science P.O. Box 5003N-1432 Aas, Oslo (Norway); Vandenhove, Hildegarde; Vanhoudt, Nathalie [SCK.CEN, Studiecentrum voor Kernenergie/Centre d' Etude de l' Energie Nucleaire, Avenue Herrmann-Debroux 40, BE-1160 Brussels (Belgium); Willrodt, Christine; Steiner, Martin [Bundesamt fuer Strahlenschutz, Willy-Brandt-Strasse 5, 38226 Salzgitter (Germany)


    The Radioecology Exchange ( was created in 2011 under the EU FP7 STAR (Strategy for Allied Radioecology) network of excellence. The project aims to integrate the research efforts on radioecology of nine European organisations into a sustainable network. The web site (together with associated Twitter feeds and Facebook page) currently provides the gateway to project outputs and other on-line radiation protection and radioecological resources. In 2013, the EU FP7 COMET (Coordination and implementation of a pan-European instrument for radioecology) project commenced; it aims to strengthen research on the impact of radiation on man and the environment. COMET includes the STAR partners with the addition of one Japanese and two Ukrainian research institutes. As STAR and COMET interact closely together and with the European Radioecology Alliance (, the Radioecology Exchange will be modified to become an international 'hub' for information related to radioecology. Project specific information will be hosted on separate web sites and This paper will present an overview of the resources hosted on the Radioecology Exchange inviting other scientists to contribute. Highlighted aspects of the site include: Social media (News blog, Twitter, Facebook) - Items announcing project outputs, training courses, jobs, studentships etc. Virtual laboratory - Information which encourages integration through joint research and integrated use of data and sample materials. These pages will focus on three categories: (1) Methodological: descriptions and video clips of commonly used analytical methods and protocols and the procedures used in STAR and COMET; (2) Informative: databases made available by STAR/COMET partners together with details of sample archives held. Fact-sheets on radio-ecologically important radionuclides and 'topical descriptions' which show absorbed

  3. Studies concerning the anion ex-change resins catalyzed esterification of epichlorohydrin with organic acids

    Directory of Open Access Journals (Sweden)

    E.I. Muresan


    Full Text Available The paper studies the esterification of carboxylic acids with epichlorohydrin over two macroporous strong base anion exchange resins with different polymer matrix. For both resins, the influence of reaction parameters (temperature, catalyst loading, molar ratio on the reaction rate and the yields of the two isomeric esters were investigated.

  4. Line reversal, SU$_{3}, and exchange degeneracy in K$\\pm$N charge exchange at 4 GeV/c

    CERN Document Server

    Elvekjaer, F


    The recent data on charge exchange reactions K/sup +/n to K/sup 0/p and K/sup -/p to K/sup 0/n are discussed. The data are shown to be consistent with SU/sub 3/ octet symmetry for helicity flip rho and A /sub 2/ quantum-number exchange. The sizeable breaking of line reversal symmetry is not consistent with the standard model which blames the s-channel helicity-non flip amplitude, while supposing that the flip amplitude is EXD and Regge pole like. A model of alpha broken EXD poles may work for the flip amplitude. (20 refs).

  5. 78 FR 69910 - Joint Industry Plan; BATS Exchange, Inc., BATS-Y Exchange, Inc., BOX Options Exchange LLC, C2... (United States)


    ... COMMISSION Joint Industry Plan; BATS Exchange, Inc., BATS-Y Exchange, Inc., BOX Options Exchange LLC, C2... LLC, NYSE Arca, Inc. and Topaz Exchange, LLC; Notice of Filing of Proposed National Market System Plan... and Exchange Commission (``Commission'') the proposed National Market System (``NMS'') Plan Governing...

  6. Liquid/liquid heat exchanger (United States)

    Miller, C. G.


    Conceptual design for heat exchanger, utilizing two immiscible liquids with dissimilar specific gravities in direct contact, is more efficient mechanism of heat transfer than conventional heat exchangers with walls or membranes. Concept could be adapted for collection of heat from solar or geothermal sources.

  7. Educators Exchange: A Program Evaluation. (United States)

    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…

  8. Risk Balance in Exchange Protocols

    NARCIS (Netherlands)

    M.T. Dashti (Mohammad); Y. Wang (Yanjing); I. Cervesato


    htmlabstractWe study the behaviour of rational agents in exchange protocols which rely on trustees. We allow malicious parties to compromise the trustee by paying a cost and, thereby, present a game analysis that advocates exchange protocols which induce balanced risks on the participants. We also

  9. Professional Exchange: Mapping the Future. (United States)

    Dingman, Robert L.


    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)

  10. Heat exchanger leakage problem location

    Directory of Open Access Journals (Sweden)

    Jícha Miroslav


    Full Text Available Recent compact heat exchangers are very often assembled from numerous parts joined together to separate heat transfer fluids and to form the required heat exchanger arrangement. Therefore, the leak tightness is very important property of the compact heat exchangers. Although, the compact heat exchangers have been produced for many years, there are still technological problems associated with manufacturing of the ideal connection between the individual parts, mainly encountered with special purpose heat exchangers, e.g. gas turbine recuperators. This paper describes a procedure used to identify the leakage location inside the prime surface gas turbine recuperator. For this purpose, an analytical model of the leaky gas turbine recuperator was created to assess its performance. The results obtained are compared with the experimental data which were acquired during the recuperator thermal performance analysis. The differences between these two data sets are used to indicate possible leakage areas.

  11. Transendothelial lipoprotein exchange and microalbuminuria

    DEFF Research Database (Denmark)

    Jensen, Jan Skov; Feldt-Rasmussen, Bo; Jensen, Kurt Svarre


    OBJECTIVE: Microalbuminuria associates with increased risk of atherosclerosis in individuals without diabetes. We hypothesized that transendothelial lipoprotein exchange is elevated among such individuals, possibly explaining increased intimal lipoprotein accumulation and thus atherosclerosis....... METHODS: Using an in vivo isotope technique, transendothelial exchange of low density lipoprotein (LDL) was measured in 77 non-diabetic individuals. Autologous 131-iodinated LDL was reinjected intravenously, and the 1-h fractional escape rate was calculated as index of transendothelial exchange. RESULTS......: There was no difference in transendothelial LDL exchange between subjects with microalbuminuria versus normoalbuminuria (mean (95% confidence interval) 3.8%/h (3.3-4.3%/h) versus 4.2%/h (3.7-4.7%/h); P=0.33). In contrast, there was a positive correlation between transendothelial LDL exchange and (logarithmically...

  12. Next Generation Microchannel Heat Exchangers

    CERN Document Server

    Ohadi, Michael; Dessiatoun, Serguei; Cetegen, Edvin


    In Next Generation Microchannel Heat Exchangers, the authors’ focus on the new generation highly efficient heat exchangers and presentation of novel data and technical expertise not available in the open literature.  Next generation micro channels offer record high heat transfer coefficients with pressure drops much less than conventional micro channel heat exchangers. These inherent features promise fast penetration into many mew markets, including high heat flux cooling of electronics, waste heat recovery and energy efficiency enhancement applications, alternative energy systems, as well as applications in mass exchangers and chemical reactor systems. The combination of up to the minute research findings and technical know-how make this book very timely as the search for high performance heat and mass exchangers that can cut costs in materials consumption intensifies.

  13. High Temperature Heat Exchanger Project

    Energy Technology Data Exchange (ETDEWEB)

    Anthony E. Hechanova, Ph.D.


    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

  14. Spin isovector giant resonances in (n,p) reactions

    Energy Technology Data Exchange (ETDEWEB)

    Spicer, B.M.


    The present status of the study of spin-flip isovector giant resonances, using the (n,p) charge exchange reaction, is reviewed. After a brief history of the discovery of these giant resonances, a critical appraisal of the interpretation of the data in terms of giant resonances is given, along with some of the theoretical advances that impact on the interpretation of these data. A sampling of the results obtained for typical targets is given, followed by the interpretation of these results. A brief statement is made concerning the way forward in experimental technique for nuclear structure research using charge exchange reactions. 54 refs., 18 figs.

  15. Fault-Tolerant Heat Exchanger (United States)

    Izenson, Michael G.; Crowley, Christopher J.


    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.

  16. Transport of divalent cations: cation exchange capacity of intact xylem vessels. (United States)

    Van de Geijn, S C; Petit, C M


    The cation exchange capacity of the intact xylem vessels in cut shoots of papyrus (Cyperus papyrus spec.) has been determined. The cation exchange capacity is independent of the cation concentration in the transpiration stream, and is equal for Ca and Co. The high value of the cation exchange capacity (0.6 to 1 x 10(-7) equivalents per square centimeter vessel wall surface) leads to the hypothesis that the porous structure of the vessel wall, and not only the inner vessel wall surface, acts as a cation exchanger.Differences between anion ([(32)P]phosphate, [(45)Ca]EDTA(2-), [(115)Cd(m)]-EDTA(2-)), and cation ([(45)Ca](2+), [(115)Cd(m)](2+)) movement are explained in terms of transport with the transpiration flux or by exchange reactions. The competition between exchange sites and natural or synthetic ligands for the divalent cations is discussed.

  17. Electrically switched ion exchange

    Energy Technology Data Exchange (ETDEWEB)

    Lilga, M.A. [Pacific Northwest National Lab., Richland, WA (United States); Schwartz, D.T.; Genders, D.


    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.

  18. Tandem cathode for proton exchange membrane fuel cells

    DEFF Research Database (Denmark)

    Siahrostami, Samira; Björketun, Mårten E.; Strasser, Peter


    tandem cathode design where the full oxygen reduction, involving four electron-transfer steps, is divided into formation (equilibrium potential 0.70 V) followed by reduction (equilibrium potential 1.76 V) of hydrogen peroxide. The two part reactions contain only two electron-transfer steps and one......The efficiency of proton exchange membrane fuel cells is limited mainly by the oxygen reduction reaction at the cathode. The large cathodic overpotential is caused by correlations between binding energies of reaction intermediates in the reduction of oxygen to water. This work introduces a novel...... reaction intermediate each, and they occur on different catalyst surfaces. As a result they can be optimized independently and the fundamental problem associated with the four-electron catalysis is avoided. A combination of density functional theory calculations and published experimental data is used...

  19. NMR and dynamics of biopolymers

    Energy Technology Data Exchange (ETDEWEB)

    Lian, L.Y.; Barsukov, I.L. [Leicester Univ. (United Kingdom)


    Several basic experimental analytical NMR techniques that are frequently used for the qualitative and quantitative analysis of dynamic and exchange processes, focusing on proteins systems, are described: chemical exchange (slow exchange, fast exchange, intermediate exchange), heteronuclear relaxation measurements (relaxation parameters, strategy of relaxation data analysis, experimental results and examples, motional model interpretation of relaxation data, homonuclear relaxation); slow large-scale exchange and hydrogen-deuterium exchange are also studied: mechanisms of hydrogen exchange in a native protein, methods for measuring amide exchange rates by NMR, interpretation of amide exchange rates. 9 fig., 3 tab., 56 ref.

  20. [Adverse reactions to insulin]. (United States)

    Liñana, J J; Montoro, F J; Hernández, M D; Basomba, A


    The prevalence of allergic reactions to insuline has decreased during the last few years. Probably this is due to the use of the newly-developed recombinant human insuline. At present, adverse reactions to insuline occur in 5-10% of patients on therapy with insuline. Adverse reactions may be local (more frequent) or systemic (rare). Insuline resistance consists in a different type of immunological reaction. Diagnosis of allergy to insuline is based on clinical history and cutaneous and serological tests. Treatment depends upon the severity of the reaction. When insuline is indispensable despite a previous allergic reaction, a desensitization protocol may be implemented.

  1. Why are GGAs so accurate for reaction kinetics on surfaces? Systematic comparison of hybrid vs. nonhybrid DFT for representative reactions (United States)

    Mahler, Andrew; Janesko, Benjamin G.; Moncho, Salvador; Brothers, Edward N.


    "Jacob's Ladder" of approximate exchange-correlation (XC) functionals in Kohn-Sham density functional theory are widely accepted to have systematic errors in reaction barriers. The first-rung local spin-density approximation (LDA) typically predicts barriers below generalized gradient approximations, which in turn predict barriers below experiment and below fourth-rung hybrid functionals incorporating a fraction of exact exchange. We show that several reactions from previous literature reports, as well as new simulations of carbon-carbon coupling in the Fischer-Tropsch process, do not follow this conventional picture. We introduce the AB9 test set of nine abnormal reaction barriers, in which density gradient corrections and exact exchange admixture tend to lower rather than to raise predicted barriers. Comparisons of normal and abnormal reactions rationalize this phenomenon in terms of how density gradient and exact-exchange corrections stabilize transition states relative to reaction intermediates. Multireference diagnostics confirm that this behavior is not merely a consequence of multireference character. Benchmarks of the AB9 set, using the best available ab initio reference values, highlight the role of symmetry breaking and show surprisingly good performance from both the LDA and "Rung 3.5" functionals. This motivates benchmarks of the AB9 set in future XC functional development.

  2. Custom, contract, and kidney exchange. (United States)

    Healy, Kieran; Krawiec, Kimberly D


    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.



    Podobeková, Veronika; Peráčková, Jana


    The article discusses utilization of heat from waste water in sewage. During the year, temperature of water in sewage ranges between 10 °C and 20 °C and the heat from sewage could be used for heating, cooling and hot water preparation in building. The heat is extracted through a transfer surface area of the heat exchanger into the heat pump, which is able to utilize the low–potential energy. Different design and types of the heat exchangers in sewage are dealt with: heat exchangers embedded i...

  4. Relational and XML Data Exchange

    CERN Document Server

    Arenas, Marcelo


    Data exchange is the problem of finding an instance of a target schema, given an instance of a source schema and a specification of the relationship between the source and the target. Such a target instance should correctly represent information from the source instance under the constraints imposed by the target schema, and it should allow one to evaluate queries on the target instance in a way that is semantically consistent with the source data. Data exchange is an old problem that re-emerged as an active research topic recently, due to the increased need for exchange of data in various for

  5. Heat exchanger using graphite foam (United States)

    Campagna, Michael Joseph; Callas, James John


    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.

  6. Ion Exchange Selectivity of Nafion Films on Electrode Surfaces. (United States)


    linked, while -10- -. * "* ... .. . *. *.Ref ion is not. The Gibbs-Donnan equation (the fundamental thermodynamic equation for exchange reactions ( evidenced by the nearly complete disappearance of the Fe3+/2+ voltamoetric wave. (To minimize hydrolysis and couplexation effects, 0.25 M HClO4 this point clear why Nation has such high affinities for these complexes. While from a thermodynamic point of view, Nafion appears to be an ideal

  7. Dimerisation of isobutene on acidic ion-exchange resins


    Honkela, Maija


    Dimerisation of isobutene produces diisobutenes that can be hydrogenated to isooctane (2,2,4-trimethyl pentane). Isooctane can be used as a high octane gasoline component. The aim of this work was to study the selective production of diisobutenes through the dimerisation of isobutene on ion-exchange resin catalysts and to construct kinetic models for the reactions in the system for reactor design purposes. High selectivities for diisobutenes were obtained in the presence of polar componen...

  8. Quantum-State Controlled Chemical Reactions of Ultracold Potassium-Rubidium Molecules

    National Research Council Canada - National Science Library

    S. Ospelkaus; K.-K. Ni; D. Wang; M. H. G. de Miranda; B. Neyenhuis; G. Queméméner; P. S. Julienne; J. L. Bohn; D. S. Jin; J. Ye


    ...? Starting with an optically trapped near-quantum-degenerate gas of polar 40 K 87 Rb molecules prepared in their absolute ground state, we report experimental evidence for exothermic atom-exchange chemical reactions...

  9. Engineering of enzymatic reactions and reactors for lipid modification and synthesis

    DEFF Research Database (Denmark)

    Xu, Xuebing


    Progress in enzymic lipid modification and synthesis in the past 20 yr is discussed, with particular reference to: enzymic hydrolysis; enzymic esterification; enzymic acidolysis; enzymic alcoholysis; enzymic ester-ester exchange; reaction and reactor optimization; product development; and process...

  10. Allergic reactions (image) (United States)

    Allergic reaction can be provoked by skin contact with poison plants, chemicals and animal scratches, as well as ... mildew, dust, nuts and shellfish, may also cause allergic reaction. Medications such as penicillin and other antibiotics are ...

  11. Cosmetic tattoo pigment reaction

    National Research Council Canada - National Science Library

    Greywal, Tanya; Cohen, Philip R


    BackgroundCutaneous reactions to tattoos are most commonly granulomatous or lichenoid.PurposeWe describe a woman who developed a lymphocytic reaction following a cosmetic tattoo procedure with black dye...

  12. Effects of Surfactants on the Rate of Chemical Reactions

    Directory of Open Access Journals (Sweden)

    B. Samiey


    Full Text Available Surfactants are self-assembled compounds that depend on their structure and electric charge can interact as monomer or micelle with other compounds (substrates. These interactions which may catalyze or inhibit the reaction rates are studied with pseudophase, cooperativity, and stoichiometric (classical models. In this review, we discuss applying these models to study surfactant-substrate interactions and their effects on Diels-Alder, redox, photochemical, decomposition, enzymatic, isomerization, ligand exchange, radical, and nucleophilic reactions.

  13. Chemical transport reactions

    CERN Document Server

    Schäfer, Harald


    Chemical Transport Reactions focuses on the processes and reactions involved in the transport of solid or liquid substances to form vapor phase reaction products. The publication first offers information on experimental and theoretical principles and the transport of solid substances and its special applications. Discussions focus on calculation of the transport effect of heterogeneous equilibria for a gas motion between equilibrium spaces; transport effect and the thermodynamic quantities of the transport reaction; separation and purification of substances by means of material transport; and

  14. Reaction Time (Polish language)


    Iermakov, Sergii


    Reaction time is the interval time between the presentation of a stimulus and the initiation of the muscular response to that stimulus.If there is only one possible response (simple reaction time) it will only take a short time to react. If there are several possible responses (choice reaction time) then it will take longer to determine which response to carry out.

  15. Laser enhanced chemical reactions (United States)

    Included is the discussion of infrared diode lasers used to study time dependent dynamic events. Also, hot atom excitation of vibrational states of polyatomic molecules, bimolecular quenching and reactions of O(sup 1)D, bimolecular reaction studies of the OH + CO yields H + CO2 system, and the chemical dynamics of the reaction between chlorine atoms and deuterated cyclohexane are covered briefly.

  16. (MIRC) reaction w

    Indian Academy of Sciences (India)

    Sudesh Kumari

    as eco-friendly reaction media in catalyst free organic synthesis.7 Ethylene glycol has promising physical ... these properties it is used as a promising green media in many catalysed/ uncatalysed organic reactions ..... Ruijter E, Scheffelaar R and Orru R V A 2011 Multi- component Reaction Design in the Quest for Molecular ...

  17. Pu Anion Exchange Process Intensification

    Energy Technology Data Exchange (ETDEWEB)

    Taylor-Pashow, K. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)


    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. Liquid droplet heat exchanger studies (United States)

    Bruckner, A. P.; Hedges, D. E.; Yungster, S.


    Recent analytical and experimental investigations of the liquid droplet heat exchanger (LDHX) concept for space power applications are described. The performance of the LDHX is compared to that of a conventional heat exchanger for heat rejection applications in a Brayton cycle, using the mass-specific heat exchanger effectiveness as a figure of merit. It is shown that the LDHX has an order of magnitude advantage over the conventional heat exchanger. Furthermore, significant improvement in cycle efficiency and power to mass ratio is possible. Two-phase flow experiments in a laboratory scale LDHX, using air and water as the two media, show very good agreement with the quasi-one-dimensional model used in the parametric studies.

  19. Estimating Foreign Exchange Reserve Adequacy

    Directory of Open Access Journals (Sweden)

    Abdul Hakim


    Full Text Available Accumulating foreign exchange reserves, despite their cost and their impacts on other macroeconomics variables, provides some benefits. This paper models such foreign exchange reserves. To measure the adequacy of foreign exchange reserves for import, it uses total reserves-to-import ratio (TRM. The chosen independent variables are gross domestic product growth, exchange rates, opportunity cost, and a dummy variable separating the pre and post 1997 Asian financial crisis. To estimate the risky TRM value, this paper uses conditional Value-at-Risk (VaR, with the help of Glosten-Jagannathan-Runkle (GJR model to estimate the conditional volatility. The results suggest that all independent variables significantly influence TRM. They also suggest that the short and long run volatilities are evident, with the additional evidence of asymmetric effects of negative and positive past shocks. The VaR, which are calculated assuming both normal and t distributions, provide similar results, namely violations in 2005 and 2008.

  20. VLER Health Exchange by Area (United States)

    Department of Veterans Affairs — “Connect Your Docs” through the Virtual Lifetime Electronic Record (VLER) Health Exchange program. This program gives VA and community health care providers secure...

  1. Counterflow Regolith Heat Exchanger Project (United States)

    National Aeronautics and Space Administration — 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...

  2. Manipulating the reaction path of the CO2 hydrogenation reaction in molecular sieves


    Borgschulte A.; Callini E.; Stadie N.; Arroyo Y.; Rossell M. D.; Erni R.; Geerlings H.; Zuettel A.; Ferri D.


    We demonstrate that the kinetics of the Sabatier reaction catalysed by sorption catalysts depends on the nanostructure of the catalyst–sorbent system. The catalysts are prepared by ion exchange of a nickel nitrate solution in two zeolites with different pore sizes. Besides their different pore sizes — which enables or hinders the adsorption of the reactants intermediates and products in the inner of the crystallites — the catalyst systems have slightly different size distributions of the Ni p...

  3. Study of the Reaction $np \\rightarrow np \\pi^+ \\pi^-$ at Intermediate Energies

    CERN Document Server

    Jerusalimov, A P; Troyan, A Yu; Belyaev, A V; Plekhanov, E B


    The reaction $np \\rightarrow np \\pi^+ \\pi^-$ was studied at the various momenta of incident neutrons. It was shown that the characteristics of the reaction at the momenta above 3 GeV/c could be described by the model of reggeized $\\pi$ exchange (OPER). At the momenta below 3 GeV/c, it was necessary to use additionally the mechanism of one baryon exchange (OBE).

  4. International Prices and Exchange Rates


    Gopinath, Gita; Burstein, Ariel


    We survey the recent empirical and theoretical developments in the literature on the relation between prices and exchange rates. After updating some of the major findings in the empirical literature we present a simple framework to interpret this evidence. We review theoretical models that generate insensitivity of prices to exchange rate changes through variable markups, both under flexible prices and nominal rigidities, first in partial equilibrium and then in general equilibrium.

  5. Exchange rate determination in Vietnam


    Thai-Ha Le


    This study investigates the determinants of the exchange rate in Vietnam and suggests policy implications. Gregory-Hansen cointegration tests and generalised variance decomposition (VDC) analysis were applied to monthly data from July 2004 to December 2013. The model was built based on the three popular approaches to exchange rate determination, which are purchasing power parity (PPP) approach, balance of payment (BOP) approach, and monetary and portfolio approach. This study finds that the p...

  6. Shared Year Exchange in Nursing

    DEFF Research Database (Denmark)

    Vedsegaard, Helle Wendner; Wederkinck, Elisabeth


    Beskrivelse af Shared Year Exchange in Nursing, et udviklingsporjekt omhandlende udvikling, beskrivelse og implementering af et fælles studieår for sygeplejerskestuderende ved Metropol og La Trobe University Australien.......Beskrivelse af Shared Year Exchange in Nursing, et udviklingsporjekt omhandlende udvikling, beskrivelse og implementering af et fælles studieår for sygeplejerskestuderende ved Metropol og La Trobe University Australien....

  7. Econometric Analysis of Croatia’s Proclaimed Foreign Exchange Rate

    Directory of Open Access Journals (Sweden)

    Mance Davor


    Full Text Available The officially proclaimed foreign exchange policy of the Croatian National Bank (CNB is a managed float with a discretionary right of intervention on the Croatian kuna/euro foreign exchange (FX market in order to maintain price stability. This paper examines the validity of three monetary policy hypotheses: the stability of the nominal exchange rate, the stability of exchange rate changes, and the exchange rate to inflation pass-through effect. The CNB claims a direct FX to inflation rate pass-through channel for which we find no evidence, but we find a strong link between FX rate changes and changes in M4, as well as between M4 changes and inflation. Changes in foreign investment Granger cause changes in monetary aggregates that further Granger cause inflation. Changes in FX rate Granger cause a reaction in M4 that indirectly Granger causes a further rise in inflation. Vector Autoregression Impulse Response Functions of changes in FX rate, M1, M4, and CPI confirm the Granger causalities in the established order.

  8. Simultaneous Disulfide and Boronic Acid Ester Exchange in Dynamic Combinatorial Libraries

    Directory of Open Access Journals (Sweden)

    Sanna L. Diemer


    Full Text Available 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.

  9. Mechanism and Dynamics of Molecular Exchange at the Silica/Binary Solvent Mixtures Interface. (United States)

    Karnes, John J; Benjamin, Ilan


    Nonequilibrium molecular dynamics simulations of acetonitrile/methanol mixtures in contact with a hydroxylated silica surface are used to elucidate the mechanism of molecular exchange at a hydrophilic liquid/solid interface. The different hydrogen-bonding ability of the two solvents provides a driving force for the adsorption/desorption process, which is followed by examining several structural and energetic properties of the system. Two different reaction coordinates for the hydrogen bonding exchange are defined and are used to identify transition states in which the methanol attains a well-defined orientation. The reaction coordinates are used to examine the mechanism and dynamics of the exchange. We find that the exchange process involves multiple recrossing of the transition state and can progress via two different mechanisms, depending whether the methanol first acts as a hydrogen bond donor or acceptor at the silica surface.

  10. Plausibility of potassium ion-exchanged ZSM-5 as soot combustion catalysts. (United States)

    Lu, Chenxi; Liu, Taizheng; Shi, Qiaolan; Li, Qian; Xin, Ying; Zheng, Lei; Zhang, Zhaoliang


    Potassium (K) ion-exchanged ZSM-5 zeolites were investigated for catalytic soot combustion. X-ray absorption fine-structure (XAFS), Raman, in situ IR and NH3-temperature programmed desorption (NH3-TPD) confirmed the location of K+ at the ion-exchanged sites. Temperature-programmed oxidation (TPO) reactions showed that K-ZSM-5 decreased ignition tempeatures of soot combustion and increased selectivity to CO2. The improved activity for soot combustion by increasing K+-exchanged amounts via decreasing the Si/Al ratio reinforced the K+ ions participating in soot combustion. 18O2 isotopic isothermal reactions suggested the activation of gaseous oxygen by the K+ ions. This demonstrated a new appliction of alkali metal exchanged zeolites and the strategy for enhancement of catalytic soot combustion activity.

  11. Researches on Preliminary Chemical Reactions in Spark-Ignition Engines (United States)


    working conditions of the engine influencing the gas-state conditions in the cylinder through the varia- tion in the rate of heat exchange , but also and...and Kooymann, L. P.: Reactions chimiques ~realables dans un moteur a essence. Chaleur et Industrie, vol. 20, 1939, pp. 120-125. 39NACA Technical

  12. The Pt(111)/Electrolyte Interface under Oxygen Reduction Reaction Conditions

    DEFF Research Database (Denmark)

    Bondarenko, A.S.; Stephens, Ifan; Hansen, Heine Anton


    The Pt(111)/electrolyte interface has been characterized during the oxygen reduction reaction (ORR) in 0.1 M HClO4 using electrochemical impedance spectroscopy. The surface was studied within the potential region where adsorption of OH* and O* species occur without significant place exchange...

  13. Production of radioactive nuclides in inverse reaction kinematics

    NARCIS (Netherlands)

    Traykov, E.; Rogachevskiy, A.; Bosswell, M.; Dammalapati, U.; Dendooven, P.G.; Dermois, O.C.; Jungmann, K.P.; Onderwater, C.J.G.; Sohani, M.; Willmann, L.; Wilschut, H.W.E.M.; Young, A.R.


    Efficient production of short-lived radioactive isotopes in inverse reaction kinematics is an important technique for various applications. It is particularly relevant when the isotope of interest is only a few nucleons away from a stable isotope. In this article production via charge exchange and

  14. Enzymatic fatty acid exchange in digalactosyldiacylglycerol. (United States)

    Persson, M; Svensson, I; Adlercreutz, P


    Six different lipases were screened for their ability of acidolysis between digalactosyldiacylglycerol (DGDG) and heptadecanoic acid in toluene. Lipases from Geotrichum candidum, Alcaligenes sp. and Penicillium camembertii did not catalyse the acidolysis reaction. Rhizopus arrhizus and Rhizomucor miehei (Lipozyme) catalysed the acidolysis but produced a mixture of DGMG, DGDG, acyl-DGMG and acyl-DGDG. The extra acyl group is bound to the primary hydroxyl of the digalactosyl moiety. Candida antarctica also catalysed the acidolysis but the TLC analysis showed bands with higher Rf values than acyl-DGDG, these probably being different tetra and higher esters. R. arrhizus lipase was the most promising enzyme under the conditions used, with no tetra esters being formed and giving the highest reaction rate of the enzymes investigated. Low water activity (0.06 or 0.11) and high fatty acid concentration (400 mM) increased the formation of acyl-DGDG whilst higher water activities (0.33 and 0.54) increased the amount of DGMG when R. arrhizus lipase was used as catalyst. At a water activity of 0.11 and a fatty acid concentration of 400 mM a yield of 24% modified DGDG was obtained. In this product the fatty acid originally present in the sn-1 position had been exchanged by heptadecanoic acid.

  15. Conversion of ion exchange resin to various functional resins and the application in the field of pharmaceutical sciences (United States)

    Nakayama, Morio

    Ion exchange resins are widely used for separating ions in the solution, desalination, removal of impurities, and etc. Giving a new function to these ion exchange resins enables the application in more various fields. Until now, we carried out the research work about the following 5 project.: (1) Conversion of ion exchange resins into selective adsorbents by using low molecular reagents, which possess capabilities of a selective reaction with target ions, ion exchange reaction with the ion exchange resin and strong physical adsorption to the ion exchange resin. (2) Synthesis of resins for ion exchange high performance liquid chromatography (IEHPLC) and the analysis of biomaterials. (3) Development of insoluble macromolecular Sn(II) complex based on the aminophosphonic acid type ion exchange resin and its application to the 99mTc labeling of proteins. (4) Development of a new 68Ge-68Ga generator using N-methylglucamine type organic polymer as the adsorbent for 68Ge and production of 68Ga for PET. (5) Preparation of an ion-exchangeable polymer bead wrapped with bilayer membrane structures. In this paper, the application of various functional resins prepared based on ion exchange resin in the field of pharmaceutical sciences has been summarized.

  16. Ion exchange equilibrium for some uni-univalent and uni-divalent ...

    African Journals Online (AJOL)

    The study on thermodynamics of ion exchange equilibrium for uni-univalent Cl-/I-, Cl-/Br-, and uni-divalent Cl-/SO42-, Cl-/C2O42- reaction systems was carried out using ion exchange resin Duolite A-102 D. The equilibrium constant K was calculated by taking into account the activity coefficient of ions both in solution as well ...

  17. Hypersensitivity reactions to heparins. (United States)

    Gonzalez-Delgado, Purificación; Fernandez, Javier


    This article provides an update on hypersensitivity reactions to heparins and novel oral anticoagulants, with special emphasis on diagnostic methods and management of patients. Although heparins are drugs widely used, hypersensitivity reactions are uncommon. Cutaneous delayed hypersensitivity reactions after subcutaneous administration affects up to 7.5% of patients. Heparin-induced thrombocytopenia is another unusual but severe condition in which early recognition is crucial. Immediate hypersensitivity reactions to heparins have been also reported, but with the novel oral anticoagulants are much more uncommon, although reports of exanthemas have been notified.Skin tests and subcutaneous provocation test are useful tools in the diagnosis of hypersensitivity reactions, except in heparin-induced thrombocytopenia in which biopsy of lesional skin and in-vitro tests are the modalities of choice to confirm the diagnosis.Management of hypersensitivity reactions includes finding an alternative depending on the type of reaction. Fondaparinux and novel oral anticoagulants may be safe alternatives. Delayed skin lesions after subcutaneous heparin are the most common type of hypersensitivity reactions, followed by life-threatening heparin-induced thrombocytopenia. Immediate reactions are uncommon. Allergologic studies may be useful to find an alternative option in patients with skin lesions in which heparin-induced thrombocytopenia has been previously excluded, as well as in heparin immediate reactions.

  18. Fair Exchange in Strand Spaces

    Directory of Open Access Journals (Sweden)

    Joshua D. Guttman


    Full Text Available Many cryptographic protocols are intended to coordinate state changes among principals. Exchange protocols coordinate delivery of new values to the participants, e.g. additions to the set of values they possess. An exchange protocol is fair if it ensures that delivery of new values is balanced: If one participant obtains a new possession via the protocol, then all other participants will, too. Fair exchange requires progress assumptions, unlike some other protocol properties. The strand space model is a framework for design and verification of cryptographic protocols. A strand is a local behavior of a single principal in a single session of a protocol. A bundle is a partially ordered global execution built from protocol strands and adversary activities. The strand space model needs two additions for fair exchange protocols. First, we regard the state as a multiset of facts, and we allow strands to cause changes in this state via multiset rewriting. Second, progress assumptions stipulate that some channels are resilient-and guaranteed to deliver messages-and some principals are assumed not to stop at certain critical steps. This method leads to proofs of correctness that cleanly separate protocol properties, such as authentication and confidentiality, from invariants governing state evolution. G. Wang's recent fair exchange protocol illustrates the approach.

  19. Pu Anion Exchange Process Intensification

    Energy Technology Data Exchange (ETDEWEB)

    Taylor-Pashow, Kathryn M. L. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)


    This research is focused on improving the efficiency of the anion exchange process for purifying plutonium. While initially focused on plutonium, the technology could also be applied to other ion-exchange processes. Work in FY17 focused on the improvement and optimization of porous foam columns that were initially developed in FY16. These foam columns were surface functionalized with poly(4-vinylpyridine) (PVP) to provide the Pu specific anion-exchange sites. Two different polymerization methods were explored for maximizing the surface functionalization with the PVP. The open-celled polymeric foams have large open pores and large surface areas available for sorption. The fluid passes through the large open pores of this material, allowing convection to be the dominant mechanism by which mass transport takes place. These materials generally have very low densities, open-celled structures with high cell interconnectivity, small cell sizes, uniform cell size distributions, and high structural integrity. These porous foam columns provide advantages over the typical porous resin beads by eliminating the slow diffusion through resin beads, making the anion-exchange sites easily accessible on the foam surfaces. The best performing samples exceeded the Pu capacity of the commercially available resin, and also offered the advantage of sharper elution profiles, resulting in a more concentrated product, with less loss of material to the dilute heads and tails cuts. An alternate approach to improving the efficiency of this process was also explored through the development of a microchannel array system for performing the anion exchange.

  20. Electrically Switched Cesium Ion Exchange

    Energy Technology Data Exchange (ETDEWEB)

    JPH Sukamto; ML Lilga; RK Orth


    This report discusses the results of work to develop Electrically Switched Ion Exchange (ESIX) for separations of ions from waste streams relevant to DOE site clean-up. ESIX combines ion exchange and electrochemistry to provide a selective, reversible method for radionuclide separation that lowers costs and minimizes secondary waste generation typically associated with conventional ion exchange. In the ESIX process, an electroactive ion exchange film is deposited onto. a high surface area electrode, and ion uptake and elution are controlled directly by modulating the potential of the film. As a result, the production of secondary waste is minimized, since the large volumes of solution associated with elution, wash, and regeneration cycles typical of standard ion exchange are not needed for the ESIX process. The document is presented in two parts: Part I, the Summary Report, discusses the objectives of the project, describes the ESIX concept and the approach taken, and summarizes the major results; Part II, the Technology Description, provides a technical description of the experimental procedures and in-depth discussions on modeling, case studies, and cost comparisons between ESIX and currently used technologies.

  1. Preparation of Cd/Pb Chalcogenide Heterostructured Janus Particles via Controllable Cation Exchange

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Jianbing; Chernomordik, Boris D.; Crisp, Ryan W.; Kroupa, Daniel M.; Luther, Joseph M.; Miller, Elisa M.; Gao, Jianbo; Beard, Matthew C.


    We developed a strategy for producing quasi-spherical nanocrystals of anisotropic heterostructures of Cd/Pb chalcogenides. The nanostructures are fabricated via a controlled cation exchange reaction where the Cd2+ cation is exchanged for the Pb2+ cation. The cation exchange reaction is thermally activated and can be controlled by adjusting the reaction temperature or time. We characterized the particles using TEM, XPS, PL, and absorption spectroscopy. With complete exchange, high quality Pb-chalcogenide quantum dots are produced. In addition to Cd2+, we also find suitable conditions for the exchange of Zn2+ cations for Pb2+ cations. The cation exchange is anisotropic starting at one edge of the nanocrystals and proceeds along the <111> direction producing a sharp interface at a (111) crystallographic plane. Instead of spherical core/shell structures, we produced and studied quasi-spherical CdS/PbS and CdSe/PbSe Janus-type heterostructures. Nontrivial PL behavior was observed from the CdS(e)/PbS(e) heterostructures as the Pb:Cd ratio is increased.

  2. Exchange bias effect in Ti doped nanocrystalline SrFeO3-δ

    Directory of Open Access Journals (Sweden)

    A. Sendil Kumar


    Full Text Available Materials of Ti doped nanocrystalline SrFeO3-δ were synthesized through solid state reaction. Detailed magnetization measurements were carried out in zero field cooled (ZFC and field cooled (FC conditions. Compounds of SrFe1-xTixO3-δ (x = 0.1 to 0.3 are found to be spin glass and parent compound is a helical antiferromagnet. Non magnetic Ti4+ reduces the strength of exchange interactions and the curvature of hysteresis is changed towards concave nature. Exchange bias is observed below the peak temperature (irreversibility in magnetization (TIrr in ZFC-FC of SrFe1-xTixO3-δ (x = 0 to 0.3. The coercivity and exchange bias field values are found to be decreases with increase in temperature. Observed exchange bias effect is attributed to competition between antiferromagnetic superexchange and ferromagnetic double exchange interactions.

  3. Exchange kinetics by inversion transfer: integrated analysis of the phosphorus metabolite kinetic exchanges in resting human skeletal muscle at 7 T. (United States)

    Ren, Jimin; Yang, Baolian; Sherry, A Dean; Malloy, Craig R


    To develop an inversion pulse-based, chemical exchange saturation transfer-like method for detection of (31) P magnetization exchanges among all nuclear magnetic resonance visible metabolites suitable for providing an integrated kinetic analysis of phosphorus exchange reactions in vivo. The exchange kinetics by inversion transfer (EKIT) sequence includes application of a frequency-selective inversion pulse arrayed over the range of relevant (31) P frequencies, followed by a constant delay and a hard readout pulse. A series of EKIT spectra, each given by a plot of Z-magnetization for each metabolite of interest versus frequency of the inversion pulse, can be generated from this single data set. EKIT spectra reflect chemical exchange due to known biochemical reactions, cross-relaxation effects, and relayed magnetization transfers due to both processes. The rate constants derived from EKIT data collected on resting human skeletal muscle were: ATP synthesis via ATP synthase (0.050 ± 0.016 s(-1) ), ATP synthesis via creatine kinase (0.264 ± 0.023 s(-1) ), and cross-relaxation between neighboring spin pairs within ATP (0.164 ± 0.022 s(-1) ). EKIT provides a simple, alternative method to detect chemical exchange, cross relaxation, and relayed magnetization transfer effects in human skeletal muscle at 7 T. © 2014 Wiley Periodicals, Inc.

  4. Reaction kinetics of polybutylene terephthalate polycondensation reaction

    NARCIS (Netherlands)

    Darda, P. J.; Hogendoorn, J. A.; Versteeg, G. F.; Souren, F.


    The kinetics of the forward polycondensation reaction of polybutylene terephthalate (PBT) has been investigated using thermogravimetric analysis (TGA). PBT - prepolymer with an initial degree of polymerization of 5.5 was used as starting material. The PBT prepolymer was prepared from dimethyl

  5. Reactions at Solid Surfaces

    CERN Document Server

    Ertl, Gerhard


    Expanding on the ideas first presented in Gerhard Ertl's acclaimed Baker Lectures at Cornell University, Reactions at Solid Surfaces comprises an authoritative, self-contained, book-length introduction to surface reactions for both professional chemists and students alike. Outlining our present understanding of the fundamental processes underlying reactions at solid surfaces, the book provides the reader with a complete view of how chemistry works at surfaces, and how to understand and probe the dynamics of surface reactions. Comparing traditional surface probes with more modern ones, and brin

  6. Desosamine in multicomponent reactions

    NARCIS (Netherlands)

    Achatz, Sepp; Dömling, Alexander


    Desosamine occurring ubiquitously in natural products is introduced into isocyanide based multicomponent reaction chemistry. Corresponding products are of potential interest for the design of novel antibiotics. © 2006.

  7. Pervaporation with ion exchange membranes

    Energy Technology Data Exchange (ETDEWEB)

    Boeddeker, K.W.; Wenzlaff, A.


    Sorption and pervaporation of aqueous-organic solvent systems (water-ethanol; water-carboxylic acids) with commercial ion exchange membranes are compared to obtain information on polymersolvent interaction vs. coupling. Close agreement between sorption selectivity and pervaporation selectivity indicates coupling. If pervaporation is less selective than sorption, polymer-solvent interaction overtakes coupling, the limit of de-coupling being phase separation within the sorbate as signaled by a sudden increase in permeability of the lesser interacting component. As long as sorption and pervaporation operate in parallel, favoring enrichment of the same component, coupling enhances the separation effect. If pervaporation counteracts sorption, coupling is detrimental to the separation effect. Potential applications include the dehydration of pre-concentrated water-ethanol using anion exchange membranes, and the enrichment of acetic acid from dilute aqueous solution by pervaporative removal of water through cation exchange membranes.

  8. Analysis of Exchange Interaction and Electron Delocalization as Intramolecular Determinants of Intermolecular Electron-Transfer Kinetics. (United States)

    Bominaar, E. L.; Achim, C.; Borshch, S. A.; Girerd, J.-J.; Münck, E.


    During the past decades, spectroscopic characterization of exchange interactions and electron delocalization has developed into a powerful tool for the recognition of metal clusters in metalloproteins. By contrast, the biological relevance of these interactions has received little attention thus far. This paper presents a theoretical study in which this problem is addressed. The rate constant for intermolecular electron-transfer reactions which are essential in many biological processes is investigated. An expression is derived for the dependence of the rate constant for self-exchange on the delocalization degree of the mixed-valence species. This result allows us to rationalize published kinetic data. In the simplest case of electron transfer from an exchange-coupled binuclear mixed-valence donor to a diamagnetic acceptor, the rate constant is evaluated, taking into account spin factors and exchange energies in the initial and final state. The theoretical analysis indicates that intramolecular spin-dependent electron delocalization (double exchange) and Heisenberg-Dirac-van Vleck (HDvV) exchange have an important impact on the rate constant for intermolecular electron transfer. This correlation reveals a novel relationship between magnetochemistry and electrochemistry. Contributions to the electron transfer from the ground and excited states of the exchange-coupled dimer have been evaluated. For clusters in which these states have different degrees of delocalization, the excited-state contributions to electron transfer may become dominant at potentials which are less reductive than the potential at which the rate constant for the transfer from the ground state is maximum. The rate constant shows a steep dependence on HDvV exchange, which suggests that an exchange-coupled cluster can act as a molecular switch for exchange-controlled electron gating. The relevance of this result is discussed in the context of substrate specificity of electron-transfer reactions in

  9. Complex Heat Exchangers for Improved Performance (United States)

    Bran, Gabriela Alejandra

    propagates along the channel. However, the sinusoidal behavior on one of the fluids does not fully translate to the other gets damped by the wall and the heat transfer coefficients that can be barely seen on the other flow. A scaling analysis and a parametric study were performed to determine the influence the different parameters on the system have on the time a heat exchanger takes to reach steady state. The results show the dependency of tst* (time a system takes to reach steady state) on the dimensionless parameters M, C, NTUh, NTUc, and Cw. t st* depends linearly on C and Cw, and it is a power function of M. It was also shown that tst* has a logarithmic dependency on NTUh and NTUc. A correlation was generated to approximate the time a system takes to reach steady state for systems where C w behavior during the system start-up was presented. In order to achieve the desired outlet steam temperature at a reasonable time, the system must operate at high gas mass flow rates. If the inlet temperature of the gas suffers a step change, it affects the reaction rate as well as the outlet steam temperature. A small perturbation on the gas mass flow rate has an effect on the profile shape. However, the maximum temperature reached by the gas due to reaction is not affected, and consequently, it has little effect on the steam temperature. Axial conduction in the reactor heat exchanger was also investigated, specifically in the gas section. Axial conduction cannot be assumed to be negligible in the reactor heat exchanger because of the iron-based catalytic bed. Results in this section show that axial conduction is detrimental for the system. It was found that for Peclet number greater than 100, axial conduction can be neglected. An alternative solution to address axial conduction was proposed, namely to include a well-insulated non-reacting section (without a catalytic bed) upstream of the reactor. The modified reactor heat exchanger was a novel solution to avoid the negative effect

  10. Oscillating-Coolant Heat Exchanger (United States)

    Scotti, Stephen J.; Blosser, Max L.; Camarda, Charles J.


    Devices useful in situations in which heat pipes inadequate. Conceptual oscillating-coolant heat exchanger (OCHEX) transports heat from its hotter portions to cooler portions. Heat transported by oscillation of single-phase fluid, called primary coolant, in coolant passages. No time-averaged flow in tubes, so either heat removed from end reservoirs on every cycle or heat removed indirectly by cooling sides of channels with another coolant. Devices include leading-edge cooling devices in hypersonic aircraft and "frost-free" heat exchangers. Also used in any situation in which heat pipe used and in other situations in which heat pipes not usable.


    Directory of Open Access Journals (Sweden)



    Full Text Available The experience of recentyears showsthat it hasa fundamentalroleformation mechanismof the exchange rateinmacroeconomic stabilization. Global economiccrises, oil shockshave shownthe difficultyoffloatingsustainabilitybyparticipants in the system. EuropeanMonetary System, focused onconcertedfloatingcurrenciestoECU, was formedunder the conditionsin which somecountries have adoptedregional monetaryarrangements(EU countries, with suchbasescurrencyregimeshybridthat combinesspecific mechanismsto those offixedratefree floating. This paperaims to demonstratethe important role thatithasthe choice ofexchange rateregimeas abasic elementin thefoundationofmacroeconomic stabilizationinstruments. Consideredan expression of thestateof the domestic economyandinternationalcompetitiveness, the exchange rate is determined bya complex set ofexternal factorsorinternalstabilityisa prerequisite forthe crisis.

  12. Proton exchange membrane fuel cells

    CERN Document Server

    Qi, Zhigang


    Preface Proton Exchange Membrane Fuel CellsFuel CellsTypes of Fuel CellsAdvantages of Fuel CellsProton Exchange Membrane Fuel CellsMembraneCatalystCatalyst LayerGas Diffusion MediumMicroporous LayerMembrane Electrode AssemblyPlateSingle CellStackSystemCell Voltage Monitoring Module (CVM)Fuel Supply Module (FSM)Air Supply Module (ASM)Exhaust Management Module (EMM)Heat Management Module (HMM)Water Management Module (WMM)Internal Power Supply Module (IPM)Power Conditioning Module (PCM)Communications Module (COM)Controls Module (CM)SummaryThermodynamics and KineticsTheoretical EfficiencyVoltagePo

  13. [Histone variants and histone exchange]. (United States)

    Wu, Nan; Gui, Jian-Fang


    Histones, as the basic components of nucleosome, are essential to chromatin structure and function. To adapt to various states of chromatin, corresponding histone variants are incorporated in nucleosome, and certain modifications also occur on the variants' tails. These variants change the conformation and stability of nucleosome to facilitate transcriptional activation or deactivation, DNA repairing, heterochromatin formation, and others. During histone exchange, chromatin remodeling complex facilitates histone variant deposition into nucleosome, and different variants have diverse deposition pathways. Recently, research on histone variants is not only a new hotspot in epigenetics, but also a new annotation of "histone code". In addition, histone exchange reveals new changing mechanism of DNA-histone interaction.

  14. Electron microscopic visualization of the RecA protein-mediated pairing and branch migration phases of DNA strand exchange

    DEFF Research Database (Denmark)

    Register, JC; Christiansen, Gunna; Griffith, J


    The RecA protein of Escherichia coli will drive the pairing and exchange of strands between homologous DNA molecules in a reaction stimulated by single-stranded binding protein. Here, reactions utilizing three homologous DNA pairs which can undergo both paranemic and plectonemic joining were exam...

  15. Luminescent CuInS2 quantum dots by partial cation exchange in Cu2- xS nanocrystals

    NARCIS (Netherlands)

    Van Der Stam, Ward; Berends, Anne C.; Rabouw, Freddy T.; Willhammar, Tom; Ke, Xiaoxing; Meeldijk, Johannes D.; Bals, Sara; De Mello Donega, Celso


    Here, we show successful partial cation exchange reactions in Cu2-xS nanocrystals (NCs) yielding luminescent CuInS2 (CIS) NCs. Our approach of mild reaction conditions ensures slow Cu extraction rates, which results in a balance with the slow In incorporation rate. With this method, we obtain CIS

  16. Excited State Atom-Ion Charge-Exchange (United States)

    Li, Ming; Makrides, Constantinos; Petrov, Alexander; Kotochigova, Svetlana


    We theoretically investigate the exothermic charge-exchange reaction between an excited atom and a ground-state positive ion. In particular, we focus on MOT-excited Ca*(4s4p 1P) atoms colliding with ground-state Yb+ ions, which are under active study by the experimental group of E. Hudson at UCLA. Collisions between an excited atom and an ion are guided by two major contributions to the long-range interaction potentials, the induction C4 /R4 and charge-quadrupole C3 /R3 potentials, and their coupling by the electron-exchange interaction. Our model of these forces leads to close-coupling equations for multiple reaction channels. We find several avoided crossings between the potentials that couple to the nearby asymptotic limits of Yb*+Ca+, some of which can possibly provide large charge exchange rate coefficients above 10-10 cm3 / s. We acknowledge support from the US Army Research Office, MURI Grants W911NF-14-1-0378 and the US National Science Foundation, Grant PHY-1619788.

  17. Design criteria for extraction with chemical reaction and liquid membrane permeation (United States)

    Bart, H. J.; Bauer, A.; Lorbach, D.; Marr, R.


    The design criteria for heterogeneous chemical reactions in liquid/liquid systems formally correspond to those of classical physical extraction. More complex models are presented which describe the material exchange at the individual droplets in an extraction with chemical reaction and in liquid membrane permeation.

  18. Reactions to Attitudinal Deviancy. (United States)

    Levine, John M.; Allen, Vernon L.

    This paper presents a critical review of empirical and theoretical treatments of group reaction to attitudinal deviancy. Inspired by Festinger's (1950) ideas on resolution of attitudinal discrepancies in groups, Schachter (1951) conducted an experiment that has greatly influenced subsequent research and theory concerning reaction to attitudinal…


    African Journals Online (AJOL)

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    Chemists, educators and students are entitled to their mental constructs about reaction mechanism in the classroom. What pedagogical implications have these knowledge claims for teaching and learning reaction mechanisms in organic chemistry? This is the main interest of the paper. Thus three questions were critically ...

  20. Hydrogen evolution reaction catalyst (United States)

    Subbaraman, Ram; Stamenkovic, Vojislav; Markovic, Nenad; Tripkovic, Dusan


    Systems and methods for a hydrogen evolution reaction catalyst are provided. Electrode material includes a plurality of clusters. The electrode exhibits bifunctionality with respect to the hydrogen evolution reaction. The electrode with clusters exhibits improved performance with respect to the intrinsic material of the electrode absent the clusters.