Sample records for h-d exchange mass

  1. Rapid Screening for Potential Epitopes Reactive with a Polycolonal Antibody by Solution-Phase H/D Exchange Monitored by FT-ICR Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Zhang, Qian; Noble, Kyle A.; Mao, Yuan; Young, Nicolas L.; Sathe, Shridhar K.; Roux, Kenneth H.; Marshall, Alan G.

    2013-07-01

    The potential epitopes of a recombinant food allergen protein, cashew Ana o 2, reactive to polyclonal antibodies, were mapped by solution-phase amide backbone H/D exchange (HDX) coupled with Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Ana o 2 polyclonal antibodies were purified in the serum from a goat immunized with cashew nut extract. Antibodies were incubated with recombinant Ana o 2 (rAna o 2) to form antigen:polyclonal antibody (Ag:pAb) complexes. Complexed and uncomplexed (free) rAna o 2 were then subjected to HDX-MS analysis. Four regions protected from H/D exchange upon pAb binding are identified as potential epitopes and mapped onto a homologous model.

  2. Acetone and Water on TiO₂(110): H/D Exchange

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

    Henderson, Michael A.

    2005-04-12

    Isotopic H/D exchange between coadsorbed acetone and water on the TiO?(110) surface was examined using temperature programmed desorption (TPD) as a function of coverage and two surface pretreatments (oxidation and reduction). Coadsorbed acetone and water interact repulsively on reduced TiO?(110) based on results from the companion paper to this study, with water exerting a greater influence in destabilizing acetone and acetone having only a nominal influence on water. Despite the repulsive interaction between these coadsorbates, about 0.02 ML of a 1 ML d6-acetone on the reduced surface exhibits H/D exchange with coadsorbed water, with the exchange occurring exclusively in themore » high temperature region of the d?-acetone TPD spectrum at {approx}340 K. The effect was confirmed with combinations of d?-acetone and D?O. The extent of exchange decreased on the reduced surface with water coverages above {approx}0.3 ML due to the ability of water to displace coadsorbed acetone from first layer sites to the multilayer. In contrast, the extent of exchange increased by a factor of 3 when the surface was pre-oxidized prior to coadsorption. In this case, there was no evidence for the negative influence of high water coverages on the extent of H/D exchange. Comparison of the TPD spectra from the exchange products (either d?- or d?-acetone depending on the coadsorption pairing) suggests that, in addition to the 340 K exchange process seen on the reduced surface, a second exchange process was observed on the oxidized surface at {approx}390 K. In both cases (oxidized and reduced), desorption of the H/D exchange products appeared to be reaction limited and to involve the influence of OH/OD groups (or water formed during recombinative desorption of OH/OD groups) instead of molecularly adsorbed water. The 340 K exchange process is assigned to reaction at step sites and the 390 K exchange process is attributed to the influence of oxygen adatoms deposited during surface oxidation

  3. Kinetics of hydrogen isotope exchange in β-phase Pd-H-D

    DOE PAGES

    Luo, Weifang; Cowgill, Donald F.

    2015-07-22

    Hydrogen isotope gas exchange within palladium powders is examined using a batch-type reactor coupled to a residual gas analyzer (RGA). Furthermore, the exchange rates in both directions (H 2 + PdD and D 2 + PdH) are measured in the temperature range 178–323 K for the samples with different particle sizes. The results show this batch-type exchange is closely approximated as a first-order kinetic process with a rate directly proportional to the surface area of the powder particles. An exchange rate constant of 1.40 ± 0.24 μmol H 2/atm cm 2 s is found for H 2 + PdD atmore » 298 K, 1.4 times higher than that for D 2 + PdH, with an activation energy of 25.0 ± 3.2 kJ/mol H for both exchange directions. Finally, a comparison of exchange measurement techniques shows these coefficients, and the fundamental exchange probabilities are in good agreement with those obtained by NMR and flow techniques.« less

  4. Hydrophobic Peptides Affect Binding of Calmodulin and Ca2+ as Explored by H/D Amide Exchange and Mass Spectrometry

    PubMed Central

    Sperry, Justin B.; Huang, Richard Y-C.; Zhu, Mei M.; Rempel, Don L.; Gross, Michael L.

    2010-01-01

    Calmodulin (CaM), a ubiquitous intracellular sensor protein, binds Ca2+ and interacts with various targets as part of signal transduction. Using hydrogen/deuterium exchange (H/DX) and a high resolution PLIMSTEX (Protein-Ligand Interactions by Mass Spectrometry, Titration, and H/D Exchange) protocol, we examined five different states of calmodulin: calcium-free, calcium-loaded, and three states of calcium-loaded in the presence of either melittin, mastoparan, or skeletal myosin light-chain kinase (MLCK). When CaM binds Ca2+, the extent of HDX decreased, consistent with the protein becoming stabilized upon binding. Furthermore, Ca2+-saturated calmodulin exhibits increased protection when bound to the peptides, forming high affinity complexes. The protocol reveals significant changes in EF hands 1, 3, and 4 with saturating levels of Ca2+. Titration of the protein using PLIMSTEX provides the binding affinity of Ca2+ to calmodulin within previously reported values. The affinities of calmodulin to Ca2+ increase by factors of 300 and 1000 in the presence of melittin and mastoparan, respectively. A modified PLIMSTEX protocol whereby the protein is digested to component peptides gives a region-specific titration. The titration data taken in this way show a decrease in the root mean square fit of the residuals, indicating a better fit of the data. The global H/D exchange results and those obtained in a region-specific way provide new insight into the Ca2+-binding properties of this well-studied protein. PMID:21765646

  5. D/H Exchange Reactions in Salts Extracted from LEW 85320

    NASA Astrophysics Data System (ADS)

    Socki, R. A.; Romanek, C. S.; Gibson, E. K., Jr.

    1993-07-01

    ). Mass balance calculations reveal that absorption of the spiked water is stoichiometric with respect to the formation of CaSO4.2H2O, while within limits of sampling error no net change of weight was observed for the nesquehonite. Assuming that the change in deltaDnesq. is due entirely to exchange (i.e., no absorption), mass balance constraints dictate that less than 5 wt% of water exchanged. These data suggest that nesquehonite retains its original deltaD composition even under conditions of relatively high temperature and humidity. Hydrogen isotope data of water extracted from three generations of nesquehonite on LEW85320 are plotted as a function of the theoretical delta18O composition of water in equilibrium with the carbonate at 0 degrees C (where delta18Onesq. is derived by phosphoric acid digestion of the carbonate, assuming a calcite-CO2 fractionation factor of 1.01012). Our data plot very near the meteoric water line indicating formation from slightly enriched Antarctic meltwater. Water extracted from generations II (,99), salts consisting mostly of hydromagnesite (Mg5(CO3)4(OH)2.4H2O) (Gooding, 1993, personal communication), and III (,102), with mineralogy as yet unknown, is enriched in D (deltaD = -55 and -75 permil, respectively) and plot above the meteoric water line. Both generations precipitated in the Houston curatorial facility. Data suggest either that hydrogen isotopes have exchanged at least partially with local (i.e., Houston) water, or that the exchange reactions differ between structural sites within or among the various generations of efflorescent salts. Hydrogen isotopes extracted from hydrous weathering products can reveal information about the environment of crystal growth. However, hydrogen isotope exchange systematics could be complicated if water within the crystal structure of the mineral is located in multiple sites. Furthermore, these results could have profound implications for curation and long-term storage strategies in curatorial

  6. Hydrogen/deuterium exchange in mass spectrometry.

    PubMed

    Kostyukevich, Yury; Acter, Thamina; Zherebker, Alexander; Ahmed, Arif; Kim, Sunghwan; Nikolaev, Eugene

    2018-03-30

    The isotopic exchange approach is in use since the first observation of such reactions in 1933 by Lewis. This approach allows the investigation of the pathways of chemical and biochemical reactions, determination of structure, composition, and conformation of molecules. Mass spectrometry has now become one of the most important analytical tools for the monitoring of the isotopic exchange reactions. Investigation of conformational dynamics of proteins, quantitative measurements, obtaining chemical, and structural information about individual compounds of the complex natural mixtures are mainly based on the use of isotope exchange in combination with high resolution mass spectrometry. The most important reaction is the Hydrogen/Deuterium exchange, which is mainly performed in the solution. Recently we have developed the approach allowing performing of the Hydrogen/Deuterium reaction on-line directly in the ionization source under atmospheric pressure. Such approach simplifies the sample preparation and can accelerate the exchange reaction so that certain hydrogens that are considered as non-labile will also participate in the exchange. The use of in-ionization source H/D exchange in modern mass spectrometry for structural elucidation of molecules serves as the basic theme in this review. We will focus on the mechanisms of the isotopic exchange reactions and on the application of in-ESI, in-APCI, and in-APPI source Hydrogen/Deuterium exchange for the investigation of petroleum, natural organic matter, oligosaccharides, and proteins including protein-protein complexes. The simple scenario for adaptation of H/D exchange reactions into mass spectrometric method is also highlighted along with a couple of examples collected from previous studies. © 2018 Wiley Periodicals, Inc.

  7. Slow histidine H/D exchange protocol for thermodynamic analysis of protein folding and stability using mass spectrometry.

    PubMed

    Tran, Duc T; Banerjee, Sambuddha; Alayash, Abdu I; Crumbliss, Alvin L; Fitzgerald, Michael C

    2012-02-07

    Described here is a mass spectrometry-based protocol to study the thermodynamic stability of proteins and protein-ligand complexes using the chemical denaturant dependence of the slow H/D exchange reaction of the imidazole C(2) proton in histidine side chains. The protocol is developed using several model protein systems including: ribonuclease (Rnase) A, myoglobin, bovine carbonic anhydrase (BCA) II, hemoglobin (Hb), and the hemoglobin-haptoglobin (Hb-Hp) protein complex. Folding free energies consistent with those previously determined by other more conventional techniques were obtained for the two-state folding proteins, Rnase A and myoglobin. The protocol successfully detected a previously observed partially unfolded intermediate stabilized in the BCA II folding/unfolding reaction, and it could be used to generate a K(d) value of 0.24 nM for the Hb-Hp complex. The compatibility of the protocol with conventional mass spectrometry-based proteomic sample preparation and analysis methods was also demonstrated in an experiment in which the protocol was used to detect the binding of zinc to superoxide dismutase in the yeast cell lysate sample. The yeast cell sample analyses also helped define the scope of the technique, which requires the presence of globally protected histidine residues in a protein's three-dimensional structure for successful application. © 2011 American Chemical Society

  8. Isotopic exchange processes in cold plasmas of H2/D2 mixtures.

    PubMed

    Jiménez-Redondo, Miguel; Carrasco, Esther; Herrero, Víctor J; Tanarro, Isabel

    2011-05-28

    Isotope exchange in low pressure cold plasmas of H(2)/D(2) mixtures has been investigated by means of mass spectrometric measurements of neutrals and ions, and kinetic model calculations. The measurements, which include also electron temperatures and densities, were performed in a stainless steel hollow cathode reactor for three discharge pressures: 1, 2 and 8 Pa, and for mixture compositions ranging from 100% H(2) to 100% D(2). The data are analyzed in the light of the model calculations, which are in good global agreement with the experiments. Isotope selective effects are found both in the surface recombination and in the gas-phase ionic chemistry. The dissociation of the fuel gas molecules is followed by wall recycling, which regenerates H(2) and D(2) and produces HD. Atomic recombination at the wall is found to proceed through an Eley-Rideal mechanism, with a preference for reaction of the adsorbed atoms with gas phase D atoms. The best fit probabilities for Eley-Rideal abstraction with H and D are: γ(ER H) = 1.5 × 10(-3), γ(ER D) = 2.0 × 10(-3). Concerning ions, at 1 Pa the diatomic species H(2)(+), D(2)(+) and HD(+), formed directly by electron impact, prevail in the distributions, and at 8 Pa, the triatomic ions H(3)(+), H(2)D(+), HD(2)(+) and D(3)(+), produced primarily in reactions of diatomic ions with molecules, dominate the plasma composition. In this higher pressure regime, the formation of the mixed ions H(2)D(+) and HD(2)(+) is favoured in comparison with that of H(3)(+) and D(3)(+), as expected on statistical grounds. The model results predict a very small preference, undetectable within the precision of the measurements, for the generation of triatomic ions with a higher degree of deuteration, which is probably a residual influence at room temperature of the marked zero point energy effects (ZPE), relevant for deuterium fractionation in interstellar space. In contrast, ZPE effects are found to be decisive for the observed distribution of

  9. Arene-mercury complexes stabilized by gallium chloride: relative rates of H/D and arene exchange.

    PubMed

    Branch, Catherine S; Barron, Andrew R

    2002-11-27

    We have previously proposed that the Hg(arene)(2)(GaCl(4))(2) catalyzed H/D exchange reaction of C(6)D(6) with arenes occurs via an electrophilic aromatic substitution reaction in which the coordinated arene protonates the C(6)D(6). To investigate this mechanism, the kinetics of the Hg(C(6)H(5)Me)(2)(GaCl(4))(2) catalyzed H/D exchange reaction of C(6)D(6) with naphthalene has been studied. Separate second-order rate constants were determined for the 1- and 2-positions on naphthalene; that is, the initial rate of H/D exchange = k(1i)[Hg][C-H(1)] + k(2i)[Hg][C-H(2)]. The ratio of k(1i)/k(2i) ranges from 11 to 2.5 over the temperature range studied, commensurate with the proposed electrophilic aromatic substitution reaction. Observation of the reactions over an extended time period shows that the rates change with time, until they again reach a new and constant second-order kinetics regime. The overall form of the rate equation is unchanged: final rate = k(1f)[Hg][C-H(1)] + k(2f)[Hg][C-H(2)]. This change in the H/D exchange is accompanied by ligand exchange between Hg(C(6)D(6))(2)(GaCl(4))(2) and naphthalene to give Hg(C(10)H(8))(2)(GaCl(4))(2,) that has been characterized by (13)C CPMAS NMR and UV-visible spectroscopy. The activation parameters for the ligand exchange may be determined and are indicative of a dissociative reaction and are consistent with our previously calculated bond dissociation for Hg(C(6)H(6))(2)(AlCl(4))(2). The initial Hg(arene)(2)(GaCl(4))(2) catalyzed reaction of naphthalene with C(6)D(6) involves the deuteration of naphthalene by coordinated C(6)D(6); however, as ligand exchange progresses, the pathway for H/D exchange changes to where the protonation of C(6)D(6) by coordinated naphthalene dominates. The site selectivity for the H/D exchange is initially due to the electrophilic aromatic substitution of naphthalene. As ligand exchange occurs, this selectivity is controlled by the activation of the naphthalene C-H bonds by mercury.

  10. The use of spin desalting columns in DMSO-quenched H/D-exchange NMR experiments

    PubMed Central

    Chandak, Mahesh S; Nakamura, Takashi; Takenaka, Toshio; Chaudhuri, Tapan K; Yagi-Utsumi, Maho; Chen, Jin; Kato, Koichi; Kuwajima, Kunihiro

    2013-01-01

    Dimethylsulfoxide (DMSO)-quenched hydrogen/deuterium (H/D)-exchange is a powerful method to characterize the H/D-exchange behaviors of proteins and protein assemblies, and it is potentially useful for investigating non-protected fast-exchanging amide protons in the unfolded state. However, the method has not been used for studies on fully unfolded proteins in a concentrated denaturant or protein solutions at high salt concentrations. In all of the current DMSO-quenched H/D-exchange studies of proteins so far reported, lyophilization was used to remove D2O from the protein solution, and the lyophilized protein was dissolved in the DMSO solution to quench the H/D exchange reactions and to measure the amide proton signals by two-dimensional nuclear magnetic resonance (2D NMR) spectra. The denaturants or salts remaining after lyophilization thus prevent the measurement of good NMR spectra. In this article, we report that the use of spin desalting columns is a very effective alternative to lyophilization for the medium exchange from the D2O buffer to the DMSO solution. We show that the medium exchange by a spin desalting column takes only about 10 min in contrast to an overnight length of time required for lyophilization, and that the use of spin desalting columns has made it possible to monitor the H/D-exchange behavior of a fully unfolded protein in a concentrated denaturant. We report the results of unfolded ubiquitin in 6.0M guanidinium chloride. PMID:23339068

  11. Minimizing Carry-Over in an Online Pepsin Digestion System used for the H/D Exchange Mass Spectrometric Analysis of an IgG1 Monoclonal Antibody

    NASA Astrophysics Data System (ADS)

    Majumdar, Ranajoy; Manikwar, Prakash; Hickey, John M.; Arora, Jayant; Middaugh, C. Russell; Volkin, David B.; Weis, David D.

    2012-12-01

    Chromatographic carry-over can severely distort measurements of amide H/D exchange in proteins analyzed by LC/MS. In this work, we explored the origin of carry-over in the online digestion of an IgG1 monoclonal antibody using an immobilized pepsin column under quenched H/D exchange conditions (pH 2.5, 0 °C). From a consensus list of 169 different peptides consistently detected during digestion of this large, ~150 kDa protein, approximately 30 % of the peptic peptides exhibited carry-over. The majority of carry-over originates from the online digestion. Carry-over can be substantially decreased by washing the online digestion flow-path and pepsin column with two wash cocktails: [acetonitrile (5 %)/ isopropanol (5 %)/ acetic acid (20 %) in water] and [2 M guanidine hydrochloride in 100 mM phosphate buffer pH 2.5]. Extended use of this two-step washing procedure does not adversely affect the specificity or activity of the immobilized pepsin column. The results suggest that although the mechanism of carry-over appears to be chemical in nature, and not hydrodynamic, carry-over cannot be attributed to a single factor such as mass, abundance, pI, or hydrophobicity of the peptides.

  12. Isotope exchange in reactions between D2O and size-selected ionic water clusters containing pyridine, H+ (pyridine)m(H2O)n.

    PubMed

    Ryding, Mauritz Johan; Zatula, Alexey S; Andersson, Patrik Urban; Uggerud, Einar

    2011-01-28

    Pyridine containing water clusters, H(+)(pyridine)(m)(H(2)O)(n), have been studied both experimentally by a quadrupole time-of-flight mass spectrometer and by quantum chemical calculations. In the experiments, H(+)(pyridine)(m)(H(2)O)(n) with m = 1-4 and n = 0-80 are observed. For the cluster distributions observed, there are no magic numbers, neither in the abundance spectra, nor in the evaporation spectra from size selected clusters. Experiments with size-selected clusters H(+)(pyridine)(m)(H(2)O)(n), with m = 0-3, reacting with D(2)O at a center-of-mass energy of 0.1 eV were also performed. The cross-sections for H/D isotope exchange depend mainly on the number of water molecules in the cluster and not on the number of pyridine molecules. Clusters having only one pyridine molecule undergo D(2)O/H(2)O ligand exchange, while H(+)(pyridine)(m)(H(2)O)(n), with m = 2, 3, exhibit significant H/D scrambling. These results are rationalized by quantum chemical calculations (B3LYP and MP2) for H(+)(pyridine)(1)(H(2)O)(n) and H(+)(pyridine)(2)(H(2)O)(n), with n = 1-6. In clusters containing one pyridine, the water molecules form an interconnected network of hydrogen bonds associated with the pyridinium ion via a single hydrogen bond. For clusters containing two pyridines, the two pyridine molecules are completely separated by the water molecules, with each pyridine being positioned diametrically opposite within the cluster. In agreement with experimental observations, these calculations suggest a "see-saw mechanism" for pendular proton transfer between the two pyridines in H(+)(pyridine)(2)(H(2)O)(n) clusters.

  13. Minimizing back exchange in the hydrogen exchange-mass spectrometry experiment.

    PubMed

    Walters, Benjamin T; Ricciuti, Alec; Mayne, Leland; Englander, S Walter

    2012-12-01

    The addition of mass spectrometry (MS) analysis to the hydrogen exchange (HX) proteolytic fragmentation experiment extends powerful HX methodology to the study of large biologically important proteins. A persistent problem is the degradation of HX information due to back exchange of deuterium label during the fragmentation-separation process needed to prepare samples for MS measurement. This paper reports a systematic analysis of the factors that influence back exchange (solution pH, ionic strength, desolvation temperature, LC column interaction, flow rates, system volume). The many peptides exhibit a range of back exchange due to intrinsic amino acid HX rate differences. Accordingly, large back exchange leads to large variability in D-recovery from one residue to another as well as one peptide to another that cannot be corrected for by reference to any single peptide-level measurement. The usual effort to limit back exchange by limiting LC time provides little gain. Shortening the LC elution gradient by 3-fold only reduced back exchange by ~2%, while sacrificing S/N and peptide count. An unexpected dependence of back exchange on ionic strength as well as pH suggests a strategy in which solution conditions are changed during sample preparation. Higher salt should be used in the first stage of sample preparation (proteolysis and trapping) and lower salt (<20 mM) and pH in the second stage before electrospray injection. Adjustment of these and other factors together with recent advances in peptide fragment detection yields hundreds of peptide fragments with D-label recovery of 90% ± 5%.

  14. Minimizing Back Exchange in the Hydrogen Exchange-Mass Spectrometry Experiment

    NASA Astrophysics Data System (ADS)

    Walters, Benjamin T.; Ricciuti, Alec; Mayne, Leland; Englander, S. Walter

    2012-12-01

    The addition of mass spectrometry (MS) analysis to the hydrogen exchange (HX) proteolytic fragmentation experiment extends powerful HX methodology to the study of large biologically important proteins. A persistent problem is the degradation of HX information due to back exchange of deuterium label during the fragmentation-separation process needed to prepare samples for MS measurement. This paper reports a systematic analysis of the factors that influence back exchange (solution pH, ionic strength, desolvation temperature, LC column interaction, flow rates, system volume). The many peptides exhibit a range of back exchange due to intrinsic amino acid HX rate differences. Accordingly, large back exchange leads to large variability in D-recovery from one residue to another as well as one peptide to another that cannot be corrected for by reference to any single peptide-level measurement. The usual effort to limit back exchange by limiting LC time provides little gain. Shortening the LC elution gradient by 3-fold only reduced back exchange by ~2 %, while sacrificing S/N and peptide count. An unexpected dependence of back exchange on ionic strength as well as pH suggests a strategy in which solution conditions are changed during sample preparation. Higher salt should be used in the first stage of sample preparation (proteolysis and trapping) and lower salt (<20 mM) and pH in the second stage before electrospray injection. Adjustment of these and other factors together with recent advances in peptide fragment detection yields hundreds of peptide fragments with D-label recovery of 90 % ± 5 %.

  15. Conformations of cationized linear oligosaccharides revealed by FTMS combined with in-ESI H/D exchange.

    PubMed

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

    2015-10-01

    Previously (Kostyukevich et al. Anal Chem 2014, 86, 2595), we have reported that oligosaccharides anions are produced in the electrospray in two different conformations, which differ by the rate of gas phase hydrogen/deuterium (H/D) exchange reaction. In the present paper, we apply the in-electrospray ionization (ESI) source H/D exchange approach for the investigation of the oligosaccharides cations formed by attaching of metal ions (Na, K) to the molecule. It was observed that the formation of different conformers can be manipulated by varying the temperature of the desolvating capillary of the ESI interphase. Separation of the conformers was performed using gas phase H/D approach. Because the conformers have different rates of the H/D exchange reaction, the deuterium distribution spectrum becomes bimodal. It was found that the conformation corresponding to the slow H/D exchange rate dominates in the spectrum when the capillary temperature is low (~200 °C), and the conformation corresponding to the fast H/D exchange rate dominates at high (~400 °C) temperatures. In the intermediate temperature region, two conformers are present simultaneously. It was also observed that large oligosaccharide requires higher temperature for the formation of another conformer. It was found that the presence of the conformers considerably depends on the solvent used for ESI and the pH. We have compared these results with the previously performed in-ESI source H/D exchange experiments with peptides and proteins. Copyright © 2015 John Wiley & Sons, Ltd.

  16. Seven perspectives on GPCR H/D-exchange proteomics methods

    PubMed Central

    Zhang, Xi

    2017-01-01

    Recent research shows surging interest to visualize human G protein-coupled receptor (GPCR) dynamic structures using the bottom-up H/D-exchange (HDX) proteomics technology. This opinion article clarifies critical technical nuances and logical thinking behind the GPCR HDX proteomics method, to help scientists overcome cross-discipline pitfalls, and understand and reproduce the protocol at high quality. The 2010 89% HDX structural coverage of GPCR was achieved with both structural and analytical rigor. This article emphasizes systematically considering membrane protein structure stability and compatibility with chromatography and mass spectrometry (MS) throughout the pipeline, including the effects of metal ions, zero-detergent shock, and freeze-thaws on HDX result rigor. This article proposes to view bottom-up HDX as two steps to guide choices of detergent buffers and chromatography settings: (I) protein HDX labeling in native buffers, and (II) peptide-centric analysis of HDX labels, which applies (a) bottom-up MS/MS to construct peptide matrix and (b) HDX MS to locate and quantify H/D labels. The detergent-low-TCEP digestion method demystified the challenge of HDX-grade GPCR digestion. GPCR HDX proteomics is a structural approach, thus its choice of experimental conditions should let structure lead and digestion follow, not the opposite. PMID:28529698

  17. Valence-bond study of the /H2, D2/ exchange reaction mechanism.

    NASA Technical Reports Server (NTRS)

    Freihaut, B.; Raff, L. M.

    1973-01-01

    The exchange reaction of H2 with D2 to form 2 HD is important in that it is fundamentally the simplest four-body exchange reaction and should therefore represent a model system on which various theories of reactions dynamics might be tested. A number of theoretical and experimental investigations carried out on this system are reviewed. It is concluded that a Y yields T yields Y mechanism for the (H2, D2) exchange is not a low energy pathway that would make theory compatible with the shock-tube experiments of Bauer and Ossa (1966) and of Burcat and Lifshits (1967).

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

    PubMed

    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

    2015-07-07

    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.

  19. Probing the Gaseous Structure of a β-Hairpin Peptide with H/D Exchange and Electron Capture Dissociation.

    PubMed

    Straus, Rita N; Jockusch, Rebecca A

    2017-02-01

    An improved understanding of the extent to which native protein structure is retained upon transfer to the gas phase promises to enhance biological mass spectrometry, potentially streamlining workflows and providing fundamental insights into hydration effects. Here, we investigate the gaseous conformation of a model β-hairpin peptide using gas-phase hydrogen-deuterium (H/D) exchange with subsequent electron capture dissociation (ECD). Global gas-phase H/D exchange levels, and residue-specific exchange levels derived from ECD data, are compared among the wild type 16-residue peptide GB1p and several variants. High protection from H/D exchange observed for GB1p, but not for a truncated version, is consistent with the retention of secondary structure of GB1p in the gas phase or its refolding into some other compact structure. Four alanine mutants that destabilize the hairpin in solution show levels of protection similar to that of GB1p, suggesting collapse or (re)folding of these peptides upon transfer to the gas phase. These results offer a starting point from which to understand how a key secondary structural element, the β-hairpin, is affected by transfer to the gas phase. This work also demonstrates the utility of a much-needed addition to the tool set that is currently available for the investigation of the gaseous conformation of biomolecules, which can be employed in the future to better characterize gaseous proteins and protein complexes. Graphical Abstract ᅟ.

  20. Probing the Gaseous Structure of a β-Hairpin Peptide with H/D Exchange and Electron Capture Dissociation

    NASA Astrophysics Data System (ADS)

    Straus, Rita N.; Jockusch, Rebecca A.

    2017-02-01

    An improved understanding of the extent to which native protein structure is retained upon transfer to the gas phase promises to enhance biological mass spectrometry, potentially streamlining workflows and providing fundamental insights into hydration effects. Here, we investigate the gaseous conformation of a model β-hairpin peptide using gas-phase hydrogen-deuterium (H/D) exchange with subsequent electron capture dissociation (ECD). Global gas-phase H/D exchange levels, and residue-specific exchange levels derived from ECD data, are compared among the wild type 16-residue peptide GB1p and several variants. High protection from H/D exchange observed for GB1p, but not for a truncated version, is consistent with the retention of secondary structure of GB1p in the gas phase or its refolding into some other compact structure. Four alanine mutants that destabilize the hairpin in solution show levels of protection similar to that of GB1p, suggesting collapse or (re)folding of these peptides upon transfer to the gas phase. These results offer a starting point from which to understand how a key secondary structural element, the β-hairpin, is affected by transfer to the gas phase. This work also demonstrates the utility of a much-needed addition to the tool set that is currently available for the investigation of the gaseous conformation of biomolecules, which can be employed in the future to better characterize gaseous proteins and protein complexes.

  1. Hydrogen/deuterium (H/D) exchange of gelatinized starch studied by two-dimensional (2D) near-infrared (NIR) correlation spectroscopy

    NASA Astrophysics Data System (ADS)

    Shinzawa, Hideyuki; Mizukado, Junji

    2018-05-01

    Hydrogen/deuterium (H/D) exchange of gelatinized starch was probed by in-situ near-infrared (NIR) monitoring coupled with two-dimensional (2D) correlation spectroscopy. Gelatinized starch undergoes spontaneous H/D exchange in D2O. During the substitution, the exchange rate essentially becomes different depending on solvent accessibility of various parts of the molecule. Thus, by analyzing the change in the NIR feature observed during the substitution, it becomes possible to sort out local structure and dynamics of the system. 2D correlation analysis of the time-dependent NIR spectra reveals the presence of different local structure of the starch, each having different solvent accessibility. For example, during the H/D exchange, the D2O is first absorbed by starch molecules especially around the surface area between the starch and water, where the water molecules are weakly interacted with the starch molecules. This absorption is quickly followed by the development of HDO species. Further absorption of the D2O results in the penetration of the molecules inside the starch and eventually develops the relatively strong interaction between the HDO and starch molecules because of the presence of dominant starch molecules.

  2. Dynamics and unsteady morphologies at ice interfaces driven by D2O–H2O exchange

    PubMed Central

    Holmes-Cerfon, Miranda; Kohn, Robert V.

    2017-01-01

    The growth dynamics of D2O ice in liquid H2O in a microfluidic device were investigated between the melting points of D2O ice (3.8 °C) and H2O ice (0 °C). As the temperature was decreased at rates between 0.002 °C/s and 0.1 °C/s, the ice front advanced but retreated immediately upon cessation of cooling, regardless of the temperature. This is a consequence of the competition between diffusion of H2O into the D2O ice, which favors melting of the interface, and the driving force for growth supplied by cooling. Raman microscopy tracked H/D exchange across the solid H2O–solid D2O interface, with diffusion coefficients consistent with transport of intact H2O molecules at the D2O ice interface. At fixed temperatures below 3 °C, the D2O ice front melted continuously, but at temperatures near 0 °C a scalloped interface morphology appeared with convex and concave sections that cycled between growth and retreat. This behavior, not observed for D2O ice in contact with D2O liquid or H2O ice in contact with H2O liquid, reflects a complex set of cooperative phenomena, including H/D exchange across the solid–liquid interface, latent heat exchange, local thermal gradients, and the Gibbs–Thomson effect on the melting points of the convex and concave features. PMID:29042511

  3. Online Simultaneous Hydrogen/Deuterium Exchange of Multitarget Gas-Phase Molecules by Electrospray Ionization Mass Spectrometry Coupled with Gas Chromatography.

    PubMed

    Jeong, Eun Sook; Cha, Eunju; Cha, Sangwon; Kim, Sunghwan; Oh, Han Bin; Kwon, Oh-Seung; Lee, Jaeick

    2017-11-21

    In this study, a hydrogen/deuterium (H/D) exchange method using gas chromatography-electrospray ionization/mass spectrometry (GC-ESI/MS) was first investigated as a novel tool for online H/D exchange of multitarget analytes. The GC and ESI source were combined with a homemade heated column transfer line. GC-ESI/MS-based H/D exchange occurs in an atmospheric pressure ion source as a result of reacting the gas-phase analyte eluted from GC with charged droplets of deuterium oxide infused as the ESI spray solvent. The consumption of the deuterated solvent at a flow rate of 2 μL min -1 was more economical than that in online H/D exchange methods reported to date. In-ESI-source H/D exchange by GC-ESI/MS was applied to 11 stimulants with secondary amino or hydroxyl groups. After H/D exchange, the spectra of the stimulants showed unexchanged, partially exchanged, and fully exchanged ions showing various degrees of exchange. The relative abundances corrected for naturally occurring isotopes of the fully exchanged ions of stimulants, except for etamivan, were in the range 24.3-85.5%. Methylephedrine and cyclazodone showed low H/D exchange efficiency under acidic, neutral, and basic spray solvent conditions and nonexchange for etamivan with an acidic phenolic OH group. The in-ESI-source H/D exchange efficiency by GC-ESI/MS was sufficient to determine the number of hydrogen by elucidation of fragmentation from the spectrum. Therefore, this online H/D exchange technique using GC-ESI/MS has potential as an alternative method for simultaneous H/D exchange of multitarget analytes.

  4. Impurity profiling of liothyronine sodium by means of reversed phase HPLC, high resolution mass spectrometry, on-line H/D exchange and UV/Vis absorption.

    PubMed

    Ruggenthaler, M; Grass, J; Schuh, W; Huber, C G; Reischl, R J

    2017-09-05

    For the first time, a comprehensive investigation of the impurity profile of the synthetic thyroid API (active pharmaceutical ingredient) liothyronine sodium (LT 3 Na) was performed by using reversed phase HPLC and advanced structural elucidation techniques including high resolution tandem mass spectrometry (HRMS/MS) and on-line hydrogen-deuterium (H/D) exchange. Overall, 39 compounds were characterized and 25 of these related substances were previously unknown to literature. The impurity classification system recently developed for the closely related API levothyroxine sodium (LT 4 Na) could be applied to the newly characterized liothyronine sodium impurities resulting in a wholistic thyroid API impurity classification system. Furthermore, the mass-spectrometric CID-fragmentation of specific related substances was discussed and rationalized by detailed fragmentation pathways. Moreover, the UV/Vis absorption characteristics of the API and selected impurities were investigated to corroborate chemical structure assignments derived from MS data. Copyright © 2017 Elsevier B.V. All rights reserved.

  5. Extratropical Stratosphere-Troposphere Mass Exchange

    NASA Technical Reports Server (NTRS)

    Schoeberl, Mark R.

    2004-01-01

    Understanding the exchange of gases between the stratosphere and the troposphere is important for determining how pollutants enter the stratosphere and how they leave. This study does a global analysis of that the exchange of mass between the stratosphere and the troposphere. While the exchange of mass is not the same as the exchange of constituents, you can t get the constituent exchange right if you have the mass exchange wrong. Thus this kind of calculation is an important test for models which also compute trace gas transport. In this study I computed the mass exchange for two assimilated data sets and a GCM. The models all agree that amount of mass descending from the stratosphere to the troposphere in the Northern Hemisphere extra tropics is approx. 10(exp 10) kg/s averaged over a year. The value for the Southern Hemisphere by about a factor of two. ( 10(exp 10) kg of air is the amount of air in 100 km x 100 km area with a depth of 100 m - roughly the size of the D.C. metro area to a depth of 300 feet.) Most people have the idea that most of the mass enters the stratosphere through the tropics. But this study shows that almost 5 times more mass enters the stratosphere through the extra-tropics. This mass, however, is quickly recycled out again. Thus the lower most stratosphere is a mixture of upper stratospheric air and tropospheric air. This is an important result for understanding the chemistry of the lower stratosphere.

  6. Analytical Description of the H/D Exchange Kinetic of Macromolecule.

    PubMed

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

    2018-04-17

    We present the accurate analytical solution obtained for the system of rate equations describing the isotope exchange process for molecules containing an arbitrary number of equivalent labile atoms. The exact solution was obtained using Mathematica 7.0 software, and this solution has the form of the time-dependent Gaussian distribution. For the case when forward exchange considerably overlaps the back exchange, it is possible to estimate the activation energy of the reaction by obtaining a temperature dependence of the reaction degree. Using a previously developed approach for performing H/D exchange directly in the ESI source, we have estimated the activation energies for ions with different functional groups and they were found to be in a range 0.04-0.3 eV. Since the value of the activation energy depends on the type of functional group, the developed approach can have potential analytical applications for determining types of functional groups in complex mixtures, such as petroleum, humic substances, bio-oil, and so on.

  7. Site-Specific Hydrogen Isotope Composition of Propane: Mass spectrometric methods, equilibrium temperature dependence, and kinetics of exchange

    NASA Astrophysics Data System (ADS)

    Xie, H.; Ponton, C.; Kitchen, N.; Lloyd, M. K.; Lawson, M.; Formolo, M. J.; Eiler, J. M.

    2016-12-01

    Intramolecular isotope ordering can constrain temperatures of synthesis, mechanisms of formation, and/or source substrates of organic compounds. Here we explore site-specific hydrogen isotope variations of propane. Statistical thermodynamic models predict that at equilibrium methylene hydrogen (-CH2-) in propane will be 10's of per mil higher in D/H ratio than methyl hydrogen (-CH3) at geologically relevant temperatures, and that this difference is highly temperature dependent ( 0.5-1 ‰/°C). Chemical-kinetic controls on site-specific D/H in propane could constrain the mechanisms, conditions and extents of propane synthesis or destruction. We have developed a method for measuring the difference in D/H ratio between methylene and methyl hydrogen in propane by gas source mass spectrometry. The data were measured using the Thermo Fisher Double Focusing Sector high resolution mass spectrometer (DFS), and involve comparison of the D/H ratios of molecular ion (C3H8+) and the ethyl fragmental ion (C2H5+). We demonstrate the accuracy and precision of this method through analysis of D-labeled and independently analyzed propanes. In the exchange experiments, propane was heated (100-200 oC) either alone or in the presence of D-enriched water (δD=1,1419 ‰ SMOW), with or without one of several potentially catalytic substrates for hours to weeks. Propane was found to exchange hydrogen with water vigorously at 200 °C in the presence of metal catalysts. In the presence of Ni catalyst, methylene hydrogen exchanges 2.5 times faster than methyl hydrogen. Hydrogen exchange in the presence of Pd catalyst is more effective and can equilibrate hydrogen isotope distribution on propane on the order of 7 days. Isotopic exchange in the presence of natural materials have also been tested, but is only measurable in the methylene group at 200 °C. High catalytic activity of Pd permits attainment of a bracketed, time-invariant equilibrium state that we use to calibrate the site

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

    NASA Astrophysics Data System (ADS)

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

    2012-04-01

    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.

  9. Empirical Correction for Differences in Chemical Exchange Rates in Hydrogen Exchange-Mass Spectrometry Measurements.

    PubMed

    Toth, Ronald T; Mills, Brittney J; Joshi, Sangeeta B; Esfandiary, Reza; Bishop, Steven M; Middaugh, C Russell; Volkin, David B; Weis, David D

    2017-09-05

    A barrier to the use of hydrogen exchange-mass spectrometry (HX-MS) in many contexts, especially analytical characterization of various protein therapeutic candidates, is that differences in temperature, pH, ionic strength, buffering agent, or other additives can alter chemical exchange rates, making HX data gathered under differing solution conditions difficult to compare. Here, we present data demonstrating that HX chemical exchange rates can be substantially altered not only by the well-established variables of temperature and pH but also by additives including arginine, guanidine, methionine, and thiocyanate. To compensate for these additive effects, we have developed an empirical method to correct the hydrogen-exchange data for these differences. First, differences in chemical exchange rates are measured by use of an unstructured reporter peptide, YPI. An empirical chemical exchange correction factor, determined by use of the HX data from the reporter peptide, is then applied to the HX measurements obtained from a protein of interest under different solution conditions. We demonstrate that the correction is experimentally sound through simulation and in a proof-of-concept experiment using unstructured peptides under slow-exchange conditions (pD 4.5 at ambient temperature). To illustrate its utility, we applied the correction to HX-MS excipient screening data collected for a pharmaceutically relevant IgG4 mAb being characterized to determine the effects of different formulations on backbone dynamics.

  10. Application of Atmospheric Pressure Photoionization H/D-exchange Mass Spectrometry for Speciation of Sulfur-containing Compounds.

    PubMed

    Acter, Thamina; Kim, Donghwi; Ahmed, Arif; Ha, Ji-Hyoung; Kim, Sunghwan

    2017-08-01

    Herein we report the observation of atmospheric pressure in-source hydrogen-deuterium exchange (HDX) of thiol group for the first time. The HDX for thiol group was optimized for positive atmospheric pressure photoionization (APPI) mass spectrometry (MS). The optimized HDX-MS was applied for 31 model compounds (thiols, thiophenes, and sulfides) to demonstrate that exchanged peaks were observed only for thiols. The optimized method has been successfully applied to the isolated fractions of sulfur-rich oil samples. The exchange of one and two thiol hydrogens with deuterium was observed in the thiol fraction; no HDX was observed in the other fractions. Thus, the results presented in this study demonstrate that the HDX-MS method using APPI ionization source can be effective for speciation of sulfur compounds. This method has the potential to be used to access corrosion problems caused by thiol-containing compounds. Graphical Abstract ᅟ.

  11. High resolution main-ion charge exchange spectroscopy in the DIII-D H-mode pedestal.

    PubMed

    Grierson, B A; Burrell, K H; Chrystal, C; Groebner, R J; Haskey, S R; Kaplan, D H

    2016-11-01

    A new high spatial resolution main-ion (deuterium) charge-exchange spectroscopy system covering the tokamak boundary region has been installed on the DIII-D tokamak. Sixteen new edge main-ion charge-exchange recombination sightlines have been combined with nineteen impurity sightlines in a tangentially viewing geometry on the DIII-D midplane with an interleaving design that achieves 8 mm inter-channel radial resolution for detailed profiles of main-ion temperature, velocity, charge-exchange emission, and neutral beam emission. At the plasma boundary, we find a strong enhancement of the main-ion toroidal velocity that exceeds the impurity velocity by a factor of two. The unique combination of experimentally measured main-ion and impurity profiles provides a powerful quasi-neutrality constraint for reconstruction of tokamak H-mode pedestals.

  12. High resolution main-ion charge exchange spectroscopy in the DIII-D H-mode pedestal

    DOE PAGES

    Grierson, B. A.; Burrell, K. H.; Chrystal, C.; ...

    2016-09-12

    A new high spatial resolution main-ion (deuterium) charge-exchange spectroscopy system covering the tokamak boundary region has been installed on the DIII-D tokamak. Sixteen new edge main-ion charge-exchange recombination sightlines have been combined with nineteen impurity sightlines in a tangentially viewing geometry on the DIII-D midplane with an interleaving design that achieves 8 mm inter-channel radial resolution for detailed profiles of main-ion temperature, velocity, charge-exchange emission, and neutral beam emission. At the plasma boundary, we find a strong enhancement of the main-ion toroidal velocity that exceeds the impurity velocity by a factor of two. Furthermore, the unique combination of experimentally measuredmore » main-ion and impurity profiles provides a powerful quasi-neutrality constraint for reconstruction of tokamak H-mode pedestals.« less

  13. D/H ratios and hydrogen exchangeability of type-II kerogens with increasing thermal maturity

    USGS Publications Warehouse

    Lis, G.P.; Schimmelmann, A.; Mastalerz, Maria

    2006-01-01

    Stable isotope ratios of non-exchangeable hydrogen (??Dn) and of carbon were measured in type-II kerogens from two suites of Late Devonian to Early Mississippian black shale, one from the New Albany Shale (Illinois Basin) and the other from the Exshaw Formation (Alberta Basin). The largely marine-derived organic matter had similar original stable isotope ratios, but today the suites of kerogens express gradients in thermal maturity that have altered their chemical and isotopic compositions. In both suites, ??D n values increase with maturation up to a vitrinite reflectance of Ro 1.5%, then level out. Increasing ??Dn values suggest isotopic exchange of organic hydrogen with water-derived deuterium and/or preferential loss of 1H-enriched chemical moieties from kerogen during maturation. The resulting changes in ??Dn values are altering the original hydrogen isotopic paleoenvironmental signal in kerogen, albeit in a systematic fashion. The specific D/H response of each kerogen suite through maturation correlates with H/C elemental ratio and can therefore be corrected to yield paleoenvironmentally relevant information for a calibrated system. With increasing thermal maturity, the abundance of hydrogen in the kerogen that is isotopically exchangeable with water hydrogen (expressed as Hex, in % of total hydrogen) first decreases to reach a minimum at Ro ??? 0.8-1.1%, followed by a substantial increase at higher thermal maturity. ?? 2005 Elsevier Ltd. All rights reserved.

  14. Efficient catalytic decomposition of formic acid for the selective generation of H2 and H/D exchange with a water-soluble rhodium complex in aqueous solution.

    PubMed

    Fukuzumi, Shunichi; Kobayashi, Takeshi; Suenobu, Tomoyoshi

    2008-01-01

    Formic acid (HCOOH) decomposes efficiently to afford H2 and CO2 selectively in the presence of a catalytic amount of a water-soluble rhodium aqua complex, [Rh(III)(Cp*)(bpy)(H2O)]2+ (Cp*=pentamethylcyclopentadienyl, bpy=2,2'-bipyridine) in aqueous solution at 298 K. No CO was produced in this catalytic decomposition of HCOOH. The decomposition rate reached a maximum value at pH 3.8. No deterioration of the catalyst was observed during the catalytic decomposition of HCOOH, and the catalytic activity remained the same for the repeated addition of HCOOH. The rhodium-hydride complex was detected as the catalytic active species that undergoes efficient H/D exchange with water. When the catalytic decomposition of HCOOH was performed in D2O, D2 was produced selectively. Such an efficient H/D exchange and the observation of a deuterium kinetic isotope effect in the catalytic decomposition of DCOOH in H2O provide valuable mechanistic insight into this efficient and selective decomposition process.

  15. Regulation of Phenylalanine Hydroxylase: Conformational Changes Upon Phenylalanine Binding Detected by H/D Exchange and Mass Spectrometry†

    PubMed Central

    Li, Jun; Dangott, Lawrence J.; Fitzpatrick, Paul F.

    2010-01-01

    Phenylalanine acts as an allosteric activator of the tetrahydropterin-dependent enzyme phenylalanine hydroxylase. Hydrogen/deuterium exchange monitored by mass spectrometry has been used to gain insight into local conformational changes accompanying activation of rat phenylalanine hydroxylase by phenylalanine. Peptides in the regulatory and catalytic domains that lie in the interface between these two domains show large increases in the extent of deuterium incorporation from solvent in the presence of phenylalanine. In contrast, the effects of phenylalanine on the exchange kinetics of a mutant enzyme lacking the regulatory domain are limited to peptides surrounding the binding site for the amino acid substrate. These results support a model in which the N-terminus of the protein acts as an inhibitory peptide, with phenylalanine binding causing a conformational change in the regulatory domain that alters the interaction between the catalytic and regulatory domains. PMID:20307070

  16. On-tissue Direct Monitoring of Global Hydrogen/Deuterium Exchange by MALDI Mass Spectrometry: Tissue Deuterium Exchange Mass Spectrometry (TDXMS)*

    PubMed Central

    Quanico, Jusal; Franck, Julien

    2016-01-01

    Hydrogen/deuterium exchange mass spectrometric (H/DXMS) methods for protein structural analysis are conventionally performed in solution. We present Tissue Deuterium Exchange Mass Spectrometry (TDXMS), a method to directly monitor deuterium uptake on tissue, as a means to better approximate the deuterium exchange behavior of proteins in their native microenvironment. Using this method, a difference in deuterium uptake behavior was observed when the same proteins were monitored in solution and on tissue. The higher maximum deuterium uptake at equilibrium for all proteins analyzed in solution suggests a more open conformation in the absence of interacting partners normally observed on tissue. We also demonstrate a difference in the deuterium uptake behavior of a few proteins across different morphological regions of the same tissue section. Modifications of the total number of hydrogens exchanged, as well as the kinetics of exchange, were both observed. These results provide information on the implication of protein interactions with partners as well as on the conformational changes related to these interactions, and illustrate the importance of examining protein deuterium exchange behavior in the presence of its specific microenvironment directly at the level of tissues. PMID:27512083

  17. D/H fractionation in the H2-H2O system at supercritical water conditions: Compositional and hydrogen bonding effects

    NASA Astrophysics Data System (ADS)

    Foustoukos, Dionysis I.; Mysen, Bjorn O.

    2012-06-01

    A series of experiments has been conducted in the H2-D2-D2O-H2O-Ti-TiO2 system at temperatures ranging from 300 to 800 °C and pressures between ∼0.3 and 1.3 GPa in a hydrothermal diamond anvil cell, utilizing Raman spectroscopy as a quantitative tool to explore the relative distribution of hydrogen and deuterium isotopologues of the H2 and H2O in supercritical fluids. In detail, H2O-D2O solutions (1:1) were reacted with Ti metal (3-9 h) in the diamond cell, leading to formation of H2, D2, HD, and HDO species through Ti oxidation and H-D isotope exchange reactions. Experimental results obtained in situ and at ambient conditions on quenched samples indicate significant differences from the theoretical estimates of the equilibrium thermodynamic properties of the H-D exchange reactions. In fact, the estimated enthalpy for the H2(aq)-D2(aq) disproportionation reaction (ΔHrxn) is about -3.4 kcal/mol, which differs greatly from the +0.16 kcal/mol predicted for the exchange reaction in the gas phase by statistical mechanics models. The exothermic behavior of the exchange reaction implies enhanced stability of H2 and D2 relative to HD. Accordingly, the significant energy difference of the internal H2(aq)-D2(aq)-HD(aq) equilibrium translates to strong differences of the fractionation effects between the H2O-H2 and D2O-D2 isotope exchange relationships. The D/H fractionation factors between H2O-H2(aq) and D2O-D2(aq) differ by 365‰ in the 600-800 °C temperature range, and are indicative of the greater effect of D2O contribution to the δD isotopic composition of supercritical fluids. The negative ΔHrxn values for the H2(aq)-D2(aq)-HD(aq) equilibrium and the apparent decrease of the equilibrium constant with increasing temperature might be because of differences of the Henry’s law constant between the H- and D-bearing species dissolved in supercritical aqueous solutions. Such effects may be attributed to the stronger hydrogen bonding in the O-H⋯O relative to the

  18. Solution and Gas-Phase H/D Exchange of Protein-Small-Molecule Complexes: Cex and Its Inhibitors

    NASA Astrophysics Data System (ADS)

    Kang, Yang; Terrier, Peran; Ding, Chuanfan; Douglas, D. J.

    2012-01-01

    The properties of noncovalent complexes of the enzyme exo-1,4-β-D-glycanase ("Cex") with three aza-sugar inhibitors, deoxynojirimycin (X2DNJ), isofagomine lactam (X2IL), and isofagomine (X2IF), have been studied with solution and gas-phase hydrogen deuterium exchange (H/Dx) and measurements of collision cross sections of gas-phase ions. In solution, complexes have lower H/Dx levels than free Cex because binding the inhibitors blocks some sites from H/Dx and reduces fluctuations of the protein. In mass spectra of complexes, abundant Cex ions are seen, which mostly are formed by dissociation of complexes in the ion sampling interface. Both complex ions and Cex ions formed from a solution containing complexes have lower cross sections than Cex ions from a solution of Cex alone. This suggests the Cex ions formed by dissociation "remember" their solution conformations. For a given charge, ions of the complexes have greater gas-phase H/Dx levels than ions of Cex. Unlike cross sections, H/Dx levels of the complexes do not correlate with the relative gas-phase binding strengths measured by MS/MS. Cex ions from solutions with or without inhibitors, which have different cross sections, show the same H/Dx level after 15 s, indicating the ions may fold or unfold on the seconds time scale of the H/Dx experiment. Thus, cross sections show that complexes have more compact conformations than free protein ions on the time scale of ca. 1 ms. The gas-phase H/Dx measurements show that at least some complexes retain different conformations from the Cex ions on a time scale of seconds.

  19. Highly efficient D2 generation by dehydrogenation of formic acid in D2O through H+/D+ exchange on an iridium catalyst: application to the synthesis of deuterated compounds by transfer deuterogenation.

    PubMed

    Wang, Wan-Hui; Hull, Jonathan F; Muckerman, James T; Fujita, Etsuko; Hirose, Takuji; Himeda, Yuichiro

    2012-07-23

    Deuterated compounds have received increasing attention in both academia and industrial fields. However, preparations of these compounds are limited for both economic and practical reasons. Herein, convenient generation of deuterium gas (D(2)) and the preparation of deuterated compounds on a laboratory scale are demonstrated by using a half-sandwich iridium complex with 4,4'-dihydroxy-2,2'-bipyridine. The "umpolung" (i.e., reversal of polarity) of a hydrogen atom of water was achieved in consecutive reactions, that is, a cationic H(+)/D(+) exchange reaction and anionic hydride or deuteride transfer, under mild conditions. Selective D(2) evolution (purity up to 89 %) was achieved by using HCO(2)H as an electron source and D(2)O as a deuterium source; a rhodium analogue provided HD gas (98 %) under similar conditions. Furthermore, pressurized D(2) (98 %) without CO gas was generated by using DCO(2)D in D(2)O in a glass autoclave. Transfer deuterogenation of ketones gave α-deuterated alcohols with almost quantitative yields and high deuterium content by using HCO(2)H in D(2)O. Mechanistic studies show that the H(+)/D(+) exchange reaction in the iridium hydride complex was much faster than β-elimination and hydride (deuteride) transfer. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    PubMed Central

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

    2015-01-01

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

  1. Na+/H+ exchange activity in the plasma membrane of Arabidopsis.

    PubMed

    Qiu, Quan-Sheng; Barkla, Bronwyn J; Vera-Estrella, Rosario; Zhu, Jian-Kang; Schumaker, Karen S

    2003-06-01

    In plants, Na+/H+ exchangers in the plasma membrane are critical for growth in high levels of salt, removing toxic Na+ from the cytoplasm by transport out of the cell. The molecular identity of a plasma membrane Na+/H+ exchanger in Arabidopsis (SOS1) has recently been determined. In this study, immunological analysis provided evidence that SOS1 localizes to the plasma membrane of leaves and roots. To characterize the transport activity of this protein, purified plasma membrane vesicles were isolated from leaves of Arabidopsis. Na+/H+ exchange activity, monitored as the ability of Na to dissipate an established pH gradient, was absent in plants grown without salt. However, exchange activity was induced when plants were grown in 250 mm NaCl and increased with prolonged salt exposure up to 8 d. H+-coupled exchange was specific for Na, because chloride salts of other monovalent cations did not dissipate the pH gradient. Na+/H+ exchange activity was dependent on Na (substrate) concentration, and kinetic analysis indicated that the affinity (apparent Km) of the transporter for Na+ is 22.8 mm. Data from two experimental approaches supports electroneutral exchange (one Na+ exchanged for one proton): (a) no change in membrane potential was measured during the exchange reaction, and (b) Na+/H+ exchange was unaffected by the presence or absence of a membrane potential. Results from this research provide a framework for future studies into the regulation of the plant plasma membrane Na+/H+ exchanger and its relative contribution to the maintenance of cellular Na+ homeostasis during plant growth in salt.

  2. Quasielastic neutrino charged-current scattering off 12C: Effects of the meson exchange currents and large nucleon axial mass

    NASA Astrophysics Data System (ADS)

    Butkevich, A. V.; Luchuk, S. V.

    2018-04-01

    The quasielastic scattering of muon neutrino and electrons on a carbon target are analyzed using the relativistic distorted-wave impulse approximation (RDWIA). We also evaluate the contribution of the two-particle and two-hole meson exchange current (2 p -2 h MEC) to electroweak response functions. The nuclear model dependence of the (anti)neutrino cross sections is studied within the RDWIA+MEC approach and RDWIA model with the large nucleon axial mass. It is shown that the results for the squared momentum transfer distribution d σ /d Q2 and for invariant mass of the final hadronic system distribution d σ /d W obtained within these models are substantially different.

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

    PubMed

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

    2016-04-01

    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. Graphical Abstract ᅟ.

  4. Formation of metal-nicotianamine complexes as affected by pH, ligand exchange with citrate and metal exchange. A study by electrospray ionization time-of-flight mass spectrometry.

    PubMed

    Rellán-Alvarez, Rubén; Abadía, Javier; Alvarez-Fernández, Ana

    2008-05-01

    Nicotianamine (NA) is considered as a key element in plant metal homeostasis. This non-proteinogenic amino acid has an optimal structure for chelation of metal ions, with six functional groups that allow octahedral coordination. The ability to chelate metals by NA is largely dependent on the pK of the resulting complex and the pH of the solution, with most metals being chelated at neutral or basic pH values. In silico calculations using pKa and pK values have predicted the occurrence of metal-NA complexes in plant fluids, but the use of soft ionization techniques (e.g. electrospray), together with high-resolution mass spectrometers (e.g. time-of-flight mass detector), can offer direct and metal-specific information on the speciation of NA in solution. We have used direct infusion electrospray ionization mass spectrometry (time-of-flight) ESI-MS(TOF) to study the complexation of Mn, Fe(II), Fe(III), Ni, Cu by NA. The pH dependence of the metal-NA complexes in ESI-MS was compared to that predicted in silico. Possible exchange reactions that may occur between Fe-NA and other metal micronutrients as Zn and Cu, as well as between Fe-NA and citrate, another possible Fe ligand candidate in plants, were studied at pH 5.5 and 7.5, values typical of the plant xylem and phloem saps. Metal-NA complexes were generally observed in the ESI-MS experiments at a pH value approximately 1-2 units lower than that predicted in silico, and this difference could be only partially explained by the estimated error, approximately 0.3 pH units, associated with measuring pH in organic solvent-containing solutions. Iron-NA complexes are less likely to participate in ligand- and metal-exchange reactions at pH 7.5 than at pH 5.5. Results support that NA may be the ligand chelating Fe at pH values usually found in phloem sap, whereas in the xylem sap NA is not likely to be involved in Fe transport, conversely to what occurs with other metals such as Cu and Ni. Some considerations that need to be

  5. ATP Dependence of Na+/H+ Exchange

    PubMed Central

    Demaurex, Nicolas; Romanek, Robert R.; Orlowski, John; Grinstein, Sergio

    1997-01-01

    We studied the ATP dependence of NHE-1, the ubiquitous isoform of the Na+/H+ antiporter, using the whole-cell configuration of the patch-clamp technique to apply nucleotides intracellularly while measuring cytosolic pH (pHi) by microfluorimetry. Na+/H+ exchange activity was measured as the Na+-driven pHi recovery from an acid load, which was imposed via the patch pipette. In Chinese hamster ovary (CHO) fibroblasts stably transfected with NHE-1, omission of ATP from the pipette solution inhibited Na+/H+ exchange. Conversely, ATP perfusion restored exchange activity in cells that had been metabolically depleted by 2-deoxy-d-glucose and oligomycin. In cells dialyzed in the presence of ATP, no “run-down” was observed even after extended periods, suggesting that the nucleotide is the only diffusible factor required for optimal NHE-1 activity. Half-maximal activation of the antiporter was obtained at ∼5 mM Mg-ATP. Submillimolar concentrations failed to sustain Na+/H+ exchange even when an ATP regenerating system was included in the pipette solution. High ATP concentrations are also known to be required for the optimal function of other cation exchangers. In the case of the Na/Ca2+ exchanger, this requirement has been attributed to an aminophospholipid translocase, or “flippase.” The involvement of this enzyme in Na+/H+ exchange was examined using fluorescent phosphatidylserine, which is actively translocated by the flippase. ATP depletion decreased the transmembrane uptake of NBD-labeled phosphatidylserine (NBD-PS), indicating that the flippase was inhibited. Diamide, an agent reported to block the flippase, was as potent as ATP depletion in reducing NBD-PS uptake. However, diamide had no effect on Na+/H+ exchange, implying that the effect of ATP is not mediated by changes in lipid distribution across the plasma membrane. K-ATP and ATPγS were as efficient as Mg-ATP in sustaining NHE-1 activity, while AMP-PNP and AMP-PCP only partially substituted for ATP. In

  6. Frequency Comb Assisted IR Measurements of H_3^+, H_2D^+ and D_2H^+ Transitions

    NASA Astrophysics Data System (ADS)

    Jusko, Pavol; Asvany, Oskar; Schlemmer, Stephan

    2016-06-01

    We present recent measurements of the fundamental transitions of H_3^+, H_2D^+ and D_2H^+ in a 4 K 22-pole trap by action spectroscopic techniques. Either Laser Induced Inhibition of Cluster Growth (He attachment at T≈4 K), endothermic reaction of H_3^+ with O_2, or deuterium exchange has been used as measurement scheme. We used a 3 μm optical parametric oscillator coupled to a frequency comb in order to achieve accuracy generally below 1 MHz. Five transitions of H_3^+, eleven of H_2D^+ and ten of D_2H^+ were recorder in our spectral range. We compare our H_3^+ results with two previous frequency comb assisted works. Moreover, accurate determination of the frequency allows us to predict pure rotational transitions for H_2D^+ and D_2H^+ in the THz range. P. Jusko, C. Konietzko, S. Schlemmer, O. Asvany, J. Mol. Spec. 319 (2016) 55 O. Asvany, S. Brünken, L. Kluge, S. Schlemmer, Appl. Phys. B 114 (2014) 203 O. Asvany, J. Krieg, S. Schlemmer, Rev. Sci. Instr. 83 (2012) 093110 J.N. Hodges, A.J. Perry, P.A. Jenkins, B.M. Siller, B.J. McCall, J. Chem. Phys. 139 (2013) 164201 H.-C. Chen, C.-Y. Hsiao, J.-L. Peng, T. Amano, J.-T. Shy, Phys. Rev. Lett. 109 (2012) 263002

  7. Na+/H+ Exchange Activity in the Plasma Membrane of Arabidopsis1

    PubMed Central

    Qiu, Quan-Sheng; Barkla, Bronwyn J.; Vera-Estrella, Rosario; Zhu, Jian-Kang; Schumaker, Karen S.

    2003-01-01

    In plants, Na+/H+ exchangers in the plasma membrane are critical for growth in high levels of salt, removing toxic Na+ from the cytoplasm by transport out of the cell. The molecular identity of a plasma membrane Na+/H+ exchanger in Arabidopsis (SOS1) has recently been determined. In this study, immunological analysis provided evidence that SOS1 localizes to the plasma membrane of leaves and roots. To characterize the transport activity of this protein, purified plasma membrane vesicles were isolated from leaves of Arabidopsis. Na+/H+ exchange activity, monitored as the ability of Na to dissipate an established pH gradient, was absent in plants grown without salt. However, exchange activity was induced when plants were grown in 250 mm NaCl and increased with prolonged salt exposure up to 8 d. H+-coupled exchange was specific for Na, because chloride salts of other monovalent cations did not dissipate the pH gradient. Na+/H+ exchange activity was dependent on Na (substrate) concentration, and kinetic analysis indicated that the affinity (apparent Km) of the transporter for Na+ is 22.8 mm. Data from two experimental approaches supports electroneutral exchange (one Na+ exchanged for one proton): (a) no change in membrane potential was measured during the exchange reaction, and (b) Na+/H+ exchange was unaffected by the presence or absence of a membrane potential. Results from this research provide a framework for future studies into the regulation of the plant plasma membrane Na+/H+ exchanger and its relative contribution to the maintenance of cellular Na+ homeostasis during plant growth in salt. PMID:12805632

  8. Probing peptide fragment ion structures by combining sustained off-resonance collision-induced dissociation and gas-phase H/D exchange (SORI-HDX) in Fourier transform ion-cyclotron resonance (FT-ICR) instruments.

    PubMed

    Somogyi, Arpád

    2008-12-01

    The usefulness of gas-phase H/D exchange is demonstrated to probe heterogeneous fragment and parent ion populations. Singly and multiply protonated peptides/proteins were fragmented by using sustained off-resonance irradiation collision-induced dissociation (SORI-CID). The fragments and the surviving precursor ions then all undergo H/D exchange in the gas-phase with either D(2)O or CD(3)OD under the same experimental conditions. Usually, 10 to 60 s of reaction time is adequate to monitor characteristic differences in the H/D exchange kinetic rates. These differences are then correlated to isomeric ion structures. The SORI-HDX method can be used to rapidly test fragment ion structures and provides useful insights into peptide fragmentation mechanisms.

  9. SAIDE: A Semi-Automated Interface for Hydrogen/Deuterium Exchange Mass Spectrometry.

    PubMed

    Villar, Maria T; Miller, Danny E; Fenton, Aron W; Artigues, Antonio

    2010-01-01

    Deuterium/hydrogen exchange in combination with mass spectrometry (DH MS) is a sensitive technique for detection of changes in protein conformation and dynamics. Since temperature, pH and timing control are the key elements for reliable and efficient measurement of hydrogen/deuterium content in proteins and peptides, we have developed a small, semiautomatic interface for deuterium exchange that interfaces the HPLC pumps with a mass spectrometer. This interface is relatively inexpensive to build, and provides efficient temperature and timing control in all stages of enzyme digestion, HPLC separation and mass analysis of the resulting peptides. We have tested this system with a series of standard tryptic peptides reconstituted in a solvent containing increasing concentration of deuterium. Our results demonstrate the use of this interface results in minimal loss of deuterium due to back exchange during HPLC desalting and separation. For peptides reconstituted in a buffer containing 100% deuterium, and assuming that all amide linkages have exchanged hydrogen with deuterium, the maximum loss of deuterium content is only 17% of the label, indicating the loss of only one deuterium molecule per peptide.

  10. SAIDE: A Semi-Automated Interface for Hydrogen/Deuterium Exchange Mass Spectrometry

    PubMed Central

    Villar, Maria T.; Miller, Danny E.; Fenton, Aron W.; Artigues, Antonio

    2011-01-01

    Deuterium/hydrogen exchange in combination with mass spectrometry (DH MS) is a sensitive technique for detection of changes in protein conformation and dynamics. Since temperature, pH and timing control are the key elements for reliable and efficient measurement of hydrogen/deuterium content in proteins and peptides, we have developed a small, semiautomatic interface for deuterium exchange that interfaces the HPLC pumps with a mass spectrometer. This interface is relatively inexpensive to build, and provides efficient temperature and timing control in all stages of enzyme digestion, HPLC separation and mass analysis of the resulting peptides. We have tested this system with a series of standard tryptic peptides reconstituted in a solvent containing increasing concentration of deuterium. Our results demonstrate the use of this interface results in minimal loss of deuterium due to back exchange during HPLC desalting and separation. For peptides reconstituted in a buffer containing 100% deuterium, and assuming that all amide linkages have exchanged hydrogen with deuterium, the maximum loss of deuterium content is only 17% of the label, indicating the loss of only one deuterium molecule per peptide. PMID:25309638

  11. Oligonucleotide gas-phase hydrogen/deuterium exchange with D2S in the collision cell of a quadrupole-Fourier transform ion cyclotron resonance mass spectrometer.

    PubMed

    Mo, Jingjie; Håkansson, Kristina

    2007-10-15

    We have implemented gas-phase hydrogen/deuterium exchange (HDX) experiments in the external collision cell of a hybrid quadrupole-Fourier transform ion cyclotron resonance mass spectrometer. In this configuration, multiply charged oligonucleotide anions undergo significant exchange with D(2)S at reaction intervals ranging from 0.11 to 60.1 s. For DNA homohexamers, relative exchange rates were dC(6) approximately dA(6) > dG(6) > dT(6), correlating with the gas-phase acidities of nucleobases (C > A > T > G), except for guanine. Our results are consistent with a relay mechanism in which D(2)S interacts with both a backbone phosphate group and a neutral nucleobase through hydrogen bonding. We propose that the faster exchange of polyguanosine compared to polythymidine is due to the larger size of guanine and the orientation of its labile hydrogens, which may result in gas-phase conformations more favorable for forming complexes with D(2)S. Similar trends were observed for RNA homohexamers, although their HDX rates were faster than for DNA, suggesting they can also exchange via another relay process involving the 2'-hydroxyl group. HDX of DNA duplexes further supports the involvement of nucleobase hydrogens because duplexes exchanged slower than their corresponding single strands, presumably due to the intermolecular hydrogen bonds between nucleobases. This work constitutes the first investigation of the mechanisms of oligonucleotide gas-phase HDX. Our results on duplexes show promise for application of this strategy to the characterization of structured nucleic acids.

  12. Hydrogen–Deuterium Exchange and Mass Spectrometry Reveal the pH-Dependent Conformational Changes of Diphtheria Toxin T Domain

    PubMed Central

    2015-01-01

    The translocation (T) domain of diphtheria toxin plays a critical role in moving the catalytic domain across the endosomal membrane. Translocation/insertion is triggered by a decrease in pH in the endosome where conformational changes of T domain occur through several kinetic intermediates to yield a final trans-membrane form. High-resolution structural studies are only applicable to the static T-domain structure at physiological pH, and studies of the T-domain translocation pathway are hindered by the simultaneous presence of multiple conformations. Here, we report the application of hydrogen–deuterium exchange mass spectrometry (HDX-MS) for the study of the pH-dependent conformational changes of the T domain in solution. Effects of pH on intrinsic HDX rates were deconvolved by converting the on-exchange times at low pH into times under our “standard condition” (pH 7.5). pH-Dependent HDX kinetic analysis of T domain clearly reveals the conformational transition from the native state (W-state) to a membrane-competent state (W+-state). The initial transition occurs at pH 6 and includes the destabilization of N-terminal helices accompanied by the separation between N- and C-terminal segments. The structural rearrangements accompanying the formation of the membrane-competent state expose a hydrophobic hairpin (TH8–9) to solvent, prepare it to insert into the membrane. At pH 5.5, the transition is complete, and the protein further unfolds, resulting in the exposure of its C-terminal hydrophobic TH8–9, leading to subsequent aggregation in the absence of membranes. This solution-based study complements high resolution crystal structures and provides a detailed understanding of the pH-dependent structural rearrangement and acid-induced oligomerization of T domain. PMID:25290210

  13. Hydrogen-deuterium exchange and mass spectrometry reveal the pH-dependent conformational changes of diphtheria toxin T domain.

    PubMed

    Li, Jing; Rodnin, Mykola V; Ladokhin, Alexey S; Gross, Michael L

    2014-11-04

    The translocation (T) domain of diphtheria toxin plays a critical role in moving the catalytic domain across the endosomal membrane. Translocation/insertion is triggered by a decrease in pH in the endosome where conformational changes of T domain occur through several kinetic intermediates to yield a final trans-membrane form. High-resolution structural studies are only applicable to the static T-domain structure at physiological pH, and studies of the T-domain translocation pathway are hindered by the simultaneous presence of multiple conformations. Here, we report the application of hydrogen-deuterium exchange mass spectrometry (HDX-MS) for the study of the pH-dependent conformational changes of the T domain in solution. Effects of pH on intrinsic HDX rates were deconvolved by converting the on-exchange times at low pH into times under our "standard condition" (pH 7.5). pH-Dependent HDX kinetic analysis of T domain clearly reveals the conformational transition from the native state (W-state) to a membrane-competent state (W(+)-state). The initial transition occurs at pH 6 and includes the destabilization of N-terminal helices accompanied by the separation between N- and C-terminal segments. The structural rearrangements accompanying the formation of the membrane-competent state expose a hydrophobic hairpin (TH8-9) to solvent, prepare it to insert into the membrane. At pH 5.5, the transition is complete, and the protein further unfolds, resulting in the exposure of its C-terminal hydrophobic TH8-9, leading to subsequent aggregation in the absence of membranes. This solution-based study complements high resolution crystal structures and provides a detailed understanding of the pH-dependent structural rearrangement and acid-induced oligomerization of T domain.

  14. Local dynamics measured by hydrogen/deuterium exchange and mass spectrometry of creatine kinase digested by two proteases.

    PubMed

    Mazon, Hortense; Marcillat, Olivier; Forest, Eric; Vial, Christian

    2005-12-01

    Hydrogen/deuterium exchange coupled to mass spectrometry has been used to investigate the structure and dynamics of native dimeric cytosolic muscle creatine kinase. The protein was incubated in D2O for various time. After H/D exchange and rapid quenching of the reaction, the partially deuterated protein was cleaved in parallel by two different proteases (pepsin or type XIII protease from Aspergillus saitoi) to increase the sequence coverage and spatial resolution of deuterium incorporation. The resulting peptides were analyzed by liquid chromatography coupled to mass spectrometry. In comparison with the 3D structure of MM-CK, the analysis of the two independent proteolysis deuteration patterns allowed us to get new insights into CK local dynamics as compared to a previous study using pepsin [Mazon et al. Protein Science 13 (2004) 476-486]. In particular, we obtained more information on the kinetics and extent of deuterium exchange in the N- and C-terminal extremities represented by the 1-22 and 362-380 pepsin peptides. Indeed, we observed a very different behaviour of the 1-12 and 13-22 type XIII protease peptides, and similarly for the 362-373 and 374-380 peptides. Moreover, comparison of the deuteration patterns of type XIII protease segments of the large 90-126 pepsin peptide led us to identify a small relatively dynamic region (108-114).

  15. Requirements for functional models of the iron hydrogenase active site: D2/H2O exchange activity in ((mu-SMe)(mu-pdt)[Fe(CO)2(PMe3)]2+)[BF4-].

    PubMed

    Georgakaki, Irene P; Miller, Matthew L; Darensbourg, Marcetta Y

    2003-04-21

    Hydrogen uptake in hydrogenase enzymes can be assayed by H/D exchange reactivity in H(2)/D(2)O or H(2)/D(2)/H(2)O mixtures. Diiron(I) complexes that serve as structural models for the active site of iron hydrogenase are not active in such isotope scrambling but serve as precursors to Fe(II)Fe(II) complexes that are functional models of [Fe]H(2)ase. Using the same experimental protocol as used previously for ((mu-H)(mu-pdt)[Fe(CO)(2)(PMe(3))](2)(+)), 1-H(+) (Zhao et al. J. Am. Chem. Soc. 2001, 123, 9710), we now report the results of studies of ((mu-SMe)(mu-pdt)[Fe(CO)(2)(PMe(3))](2)(+)), 1-SMe(+), toward H/D exchange. The 1-SMe(+) complex can take up H(2) and catalyze the H/D exchange reaction in D(2)/H(2)O mixtures under photolytic, CO-loss conditions. Unlike 1-H(+), it does not catalyze H(2)/D(2) scrambling under anhydrous conditions. The molecular structure of 1-SMe(+) involves an elongated Fe.Fe separation, 3.11 A, relative to 2.58 A in 1-H(+). It is proposed that the strong SMe(-) bridging ligand results in catalytic activity localized on a single Fe(II) center, a scenario that is also a prominent possibility for the enzyme active site. The single requirement is an open site on Fe(II) available for binding of D(2) (or H(2)), followed by deprotonation by the external base H(2)O (or D(2)O).

  16. Pyrite-H2S/SO4 S isotope exchange at hydrothermal conditions: An experimental study at 300°C and 500 bars

    NASA Astrophysics Data System (ADS)

    Syverson, D. D.; Ono, S.; Seyfried, W. E., Jr.

    2017-12-01

    The rate of exchange and multiple S isotope fractionation between pyrite and dissolved H2S and SO4 was determined at 300°C and 500 bars at physiochemical conditions indicative of natural MOR hydrothermal systems by using the flexible gold cell reactor system [1]. A 34S enriched solution was designed to track reaction progress and to not significantly perturb mass dependent relationships between 33S and 36S, allowing for observations of natural mass dependent fractionation between pyrite and dissolved species during dissolution and recrystallization. The experimental data are compared with previously determined experimental constraints of S isotope exchange between fluid species [2] and with Fe and S isotope experiments conducted at higher temperature and where pyrite was precipitated rapidly from solution at 300 and 350°C and 500 bars [3, 4]. Briefly, the 34S isotope data indicate that the rate of exchange between pyrite and dissolved aqueous species is sluggish, where insignificant exchange occurred after the course of 4000 hours at 300°C, approximately 4%. Furthermore, the 33,36S mineral-fluid data indicate that upon pyrite dissolution, the light isotopes are preferentially removed into solution and incorporated as H2S and SO4-. These data are consistent with natural observations of pyrite-dissolved S disequilibrium and provide important insight towards mineral reactivity and retentiveness of recording mineral formation conditions. [1] Seyfried Jr., W.E., Janecky, D.R. & Berndt, M.E. 1987 Rocking autoclaves for hydrothermal experiments: II. The flexible reaction-cell system. Hydrothermal Experimental Techniques 216-239. [2] Ohmoto, H. & Lasaga, A.C. 1982 Kinetics of reactions between aqueous sulfates and sulfides in hydrothermal systems. Geochimica et Cosmochimica Acta 46, 1727-1745. [3] Syverson, D.D., Borrok, D.M. & Seyfried Jr., W.E. 2013 Experimental determination of equilibrium Fe isotopic fractionation between pyrite and dissolved Fe under hydrothermal

  17. Heat and mass exchanger

    DOEpatents

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

    2007-09-18

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

  18. Heat and mass exchanger

    DOEpatents

    Lowenstein, Andrew [Princeton, NJ; Sibilia, Marc J [Princeton, NJ; Miller, Jeffrey A [Hopewell, NJ; Tonon, Thomas [Princeton, NJ

    2011-06-28

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

  19. Analytical aspects of hydrogen exchange mass spectrometry

    PubMed Central

    Engen, John R.; Wales, Thomas E.

    2016-01-01

    The analytical aspects of measuring hydrogen exchange by mass spectrometry are reviewed. The nature of analytical selectivity in hydrogen exchange is described followed by review of the analytical tools required to accomplish fragmentation, separation, and the mass spectrometry measurements under restrictive exchange quench conditions. In contrast to analytical quantitation that relies on measurements of peak intensity or area, quantitation in hydrogen exchange mass spectrometry depends on measuring a mass change with respect to an undeuterated or deuterated control, resulting in a value between zero and the maximum amount of deuterium that could be incorporated. Reliable quantitation is a function of experimental fidelity and to achieve high measurement reproducibility, a large number of experimental variables must be controlled during sample preparation and analysis. The method also reports on important qualitative aspects of the sample, including conformational heterogeneity and population dynamics. PMID:26048552

  20. Mars D/H: Implications for Volatile Evolution and Climate History

    NASA Astrophysics Data System (ADS)

    Jakosky, B. M.; Leshin, L.

    2001-05-01

    The lighter isotope of H in the martian atmosphere escapes more readily to space than does the heavier D, so that loss to space leaves the atmosphere enriched in D. The observed enrichment in D/H thus is an indicator of the degree of loss. As the H comes primarily from water, it informs the discussion of volatile and climate history. In order to understand the meaning of the enrichment, we need to understand (i) the initial D/H incorporated into the planet at its origin, (ii) the history of outgassing of water to the surface, (iii) atmospheric chemistry and dynamics that results in supply of the upper atmosphere with D and H from H2O in the bulk atmosphere, (iv) current loss rates to space, and (v) the present-day atmospheric D/H ratio. In addition, the D/H ratio can be affected by the exchange of water between the atmosphere and non-atmospheric reservoirs, including the polar caps, the regolith, and the crust, both by diffusion and driven by groundwater circulation (perhaps in hydrothermal systems). There is convincing evidence for the existence of each of these non-atmospheric reservoirs, but only limited information on the history of exchange. The system appears to be sufficiently complex that any attempt to describe it as a two- or three-component system is doomed to failure. Despite this, there are some conclusions for which a compelling case can be made: (i) Enrichment of D/H requires loss of substantial quantities of H to space, with water providing the source. (ii) Improvements in our understanding of the initial and present-day D/H, and the photodissociation of water and supply to the upper atmosphere have changed the quantitative interpretation from a decade ago; as a result, the time-integrated enrichment factor is substantially less than had been previously thought, and the resulting fraction of water lost is less. Roughly 2/3 of the exchangeable water must have been lost. (iii) The unknown time-dependent exchange of water with the polar caps and the

  1. Theory of proximity-induced exchange coupling in graphene on hBN/(Co, Ni)

    NASA Astrophysics Data System (ADS)

    Zollner, Klaus; Gmitra, Martin; Frank, Tobias; Fabian, Jaroslav

    2016-10-01

    Graphene, being essentially a surface, can borrow some properties of an insulating substrate (such as exchange or spin-orbit couplings) while still preserving a great degree of autonomy of its electronic structure. Such derived properties are commonly labeled as proximity. Here we perform systematic first-principles calculations of the proximity exchange coupling, induced by cobalt (Co) and nickel (Ni) in graphene, via a few (up to three) layers of hexagonal boron nitride (hBN). We find that the induced spin splitting of the graphene bands is of the order of 10 meV for a monolayer of hBN, decreasing in magnitude but alternating in sign by adding each new insulating layer. We find that the proximity exchange can be giant if there is a resonant d level of the transition metal close to the Dirac point. Our calculations suggest that this effect could be present in Co heterostructures, in which a d level strongly hybridizes with the valence-band orbitals of graphene. Since this hybridization is spin dependent, the proximity spin splitting is unusually large, about 10 meV even for two layers of hBN. An external electric field can change the offset of the graphene and transition-metal orbitals and can lead to a reversal of the sign of the exchange parameter. This we predict to happen for the case of two monolayers of hBN, enabling electrical control of proximity spin polarization (but also spin injection) in graphene/hBN/Co structures. Nickel-based heterostructures show weaker proximity effects than cobalt heterostructures. We introduce two phenomenological models to describe the first-principles data. The minimal model comprises the graphene (effective) pz orbitals and can be used to study transport in graphene with proximity exchange, while the pz-d model also includes hybridization with d orbitals, which is important to capture the giant proximity exchange. Crucial to both models is the pseudospin-dependent exchange coupling, needed to describe the different spin

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

    PubMed

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

    2011-10-30

    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.

  3. Identification of regions of rabbit muscle pyruvate kinase important for allosteric regulation by phenylalanine, detected by H/D exchange mass spectrometry†

    PubMed Central

    Prasannan, Charulata B.; Villar, Maria T.; Artigues, Antonio; Fenton, Aron W.

    2013-01-01

    Mass spectrometry has been used to determine the number of exchangeable backbone amide protons and the associated rate constants that are altered when rabbit muscle pyruvate kinase (rM1-PYK) binds either the allosteric inhibitor (phenylalanine) or a non-allosteric analogue of the inhibitor. Alanine is used as the non-allosteric analogue since it binds competitively with phenylalanine, but elicits a negligible allosteric inhibition, i.e. a negligible reduction of the affinity of rM1-PYK for the substrate, phosphoenolpyruvate (PEP). This experimental design is expected to distinguish changes in the protein caused by effector binding (i.e. those changes common upon the addition of alanine vs. phenylalanine) from changes associated with allosteric regulation (i.e. those elicited by the addition of phenylalanine binding, but not alanine binding). High quality peptic fragments covering 98% of the protein were identified. Changes in both the number of exchangeable protons per peptide and in the rate constant associated with exchange highlight regions of the protein with allosteric roles. The set of allosterically relevant peptides identified by this technique include residues previously identified by mutagenesis to have roles in the allosteric regulation by phenylalanine. PMID:23418858

  4. Quantum-tunneling isotope-exchange reaction H2+D-→HD +H-

    NASA Astrophysics Data System (ADS)

    Yuen, Chi Hong; Ayouz, Mehdi; Endres, Eric S.; Lakhamanskaya, Olga; Wester, Roland; Kokoouline, Viatcheslav

    2018-02-01

    The tunneling reaction H2+D-→HD +H- was studied in a recent experimental work at low temperatures (10, 19, and 23 K) by Endres et al. [Phys. Rev. A 95, 022706 (2017), 10.1103/PhysRevA.95.022706]. An upper limit of the rate coefficient was found to be about 10-18cm3 /s. In the present study, reaction probabilities are determined using the ABC program developed by Skouteris et al. [Comput. Phys. Commun. 133, 128 (2000), 10.1016/S0010-4655(00)00167-3]. The probabilities for ortho-H2 and para-H2 in their ground rovibrational states are obtained numerically at collision energies above 50 meV with the total angular momentum J =0 -15 and extrapolated below 50 meV using a WKB approach. Thermally averaged rate coefficients for ortho- and para-H2 are obtained; the largest one, for ortho-H2, is about 3.1 ×10-20cm3 /s, which agrees with the experimental results.

  5. Iridium-catalysed ortho-H/D and -H/T exchange under basic conditions: C-H activation of unprotected tetrazoles.

    PubMed

    Kerr, William J; Lindsay, David M; Reid, Marc; Atzrodt, Jens; Derdau, Volker; Rojahn, Patrick; Weck, Remo

    2016-05-10

    The first examples of selective ortho-directed C-H activation with unprotected 2-aryltetrazoles are described. A new base-assisted protocol for iridium(i) hydrogen isotope exchange catalysis allows access to ortho-deuterated and tritiated tetrazoles, including the tetrazole-containing pharmaceutical, Valsartan. Preliminary mechanistic studies are also presented.

  6. Time-resolved pulsed hydrogen/deuterium exchange mass spectrometry probes gaseous proteins structural kinetics.

    PubMed

    Rajabi, Khadijeh

    2015-01-01

    A pulsed hydrogen/deuterium exchange (HDX) method has been developed for rapid monitoring of the exchange kinetics of protein ions with D2O a few milliseconds after electrospray ionization (ESI). The stepwise gradual evolution of HDX of multiply charged protein ions was monitored using the pulsed HDX mass spectrometry technique. Upon introducing a very short pulse of D2O (in the μs to ms time scale) into the linear ion trap (LIT) of a time-of-flight (TOF) mass spectrometer, bimodal distributions were detected for the ions of cytochrome c and ubiquitin. Mechanistic details of HDX reactions for ubiquitin and cytochrome c in the gas phase were uncovered and the structural transitions were followed by analyzing the kinetics of HDX.

  7. D/H isotopic fractionation effects in the H2-H2O system: An in-situ experimental study at supercritical water conditions

    NASA Astrophysics Data System (ADS)

    Foustoukos, D.; Mysen, B. O.

    2011-12-01

    Understanding the effect of temperature on the relative distribution of volatiles in supercritical aqueous solutions is important to constrain elemental and isotopic partitioning/fractionation effects in systems applicable to planetary interiors where the temperature-pressure conditions are often beyond existing experimental or theoretical datasets. For example, very little exists for the fundamental equilibria between H2, D2 and HD (H2 + D2 = 2HD), which, in turn, constrains the internal D/H isotope exchange and the evolution of HD in H2-containing systems such as H2-CH4 and H2-H2O. Theoretical calculations considering the partition functions of the molecules predict that with temperature increase, the equilibrium constant of this reaction approximates values that correspond to the stochastic distribution of species. These calculations consider pure harmonic vibrational frequencies, which, however, do not apply to the diatomic molecule of hydrogen, especially because anharmonic oscillations are anticipated to become stronger at high temperatures. Published experimental data have been limited to conditions lower than 468°C with large uncertainties at elevated temperatures. To address the lack of experimental data, a series of hydrothermal diamond anvil experiments has been conducted utilizing vibrational spectroscopy as a novel quantitative method to explore the relative distribution of H- and D-bearing volatiles in the H2-D2-D2O-H2O-Ti-TiO2 system. The fundamentals of this methodology are based on the distinct Raman frequency shift resulting from deuterium substitution in the H-H and O-H bonds. In detail, H2O-D2O solutions (1:1) were reacted with Ti metal (for 3-9hrs) at 600-800°C and pressures of 0.5-1 GPa, leading to formation of H2, D2, HD and HDO species through Ti oxidation and H-D isotope exchange reactions. Experimental results obtained in-situ and in the quenched gas phase, indicate a significant deviation from the theoretical estimate of the equilibrium

  8. Hydrogen isotope exchanges between water and methanol in interstellar ices

    NASA Astrophysics Data System (ADS)

    Faure, A.; Faure, M.; Theulé, P.; Quirico, E.; Schmitt, B.

    2015-12-01

    The deuterium fractionation of gas-phase molecules in hot cores is believed to reflect the composition of interstellar ices. The deuteration of methanol is a major puzzle, however, because the isotopologue ratio [CH2DOH]/[CH3OD], which is predicted to be equal to 3 by standard grain chemistry models, is much larger (~20) in low-mass hot corinos and significantly lower (~1) in high-mass hot cores. This dichotomy in methanol deuteration between low-mass and massive protostars is currently not understood. In this study, we report a simplified rate equation model of the deuterium chemistry occurring in the icy mantles of interstellar grains. We apply this model to the chemistry of hot corinos and hot cores, with IRAS 16293-2422 and the Orion KL Compact Ridge as prototypes, respectively. The chemistry is based on a statistical initial deuteration at low temperature followed by a warm-up phase during which thermal hydrogen/deuterium (H/D) exchanges occur between water and methanol. The exchange kinetics is incorporated using laboratory data. The [CH2DOH]/[CH3OD] ratio is found to scale inversely with the D/H ratio of water, owing to the H/D exchange equilibrium between the hydroxyl (-OH) functional groups of methanol and water. Our model is able to reproduce the observed [CH2DOH]/[CH3OD] ratios provided that the primitive fractionation of water ice [HDO]/[H2O] is ~2% in IRAS 16293-2422 and ~0.6% in Orion KL. We conclude that the molecular D/H ratios measured in hot cores may not be representative of the original mantles because molecules with exchangeable deuterium atoms can equilibrate with water ice during the warm-up phase.

  9. Quantification of genetically modified soya using strong anion exchange chromatography and time-of-flight mass spectrometry.

    PubMed

    Chang, Po-Chih; Reddy, P Muralidhar; Ho, Yen-Peng

    2014-09-01

    Stable-isotope dimethyl labeling was applied to the quantification of genetically modified (GM) soya. The herbicide-resistant gene-related protein 5-enolpyruvylshikimate-3-phosphate synthase (CP4 EPSPS) was labeled using a dimethyl labeling reagent, formaldehyde-H2 or -D2. The identification and quantification of CP4 EPSPS was performed using matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS). The CP4 EPSPS protein was separated from high abundance proteins using strong anion exchange chromatography and sodium dodecyl sulfate-polyacrylamide gel electrophoresis. Then, the tryptic peptides from the samples and reference were labeled with formaldehyde-H2 and formaldehyde-D2, respectively. The two labeled pools were mixed and analyzed using MALDI-MS. The data showed a good correlation between the peak ratio of the H- and D-labeled peptides and the GM soya percentages at 0.5, 1, 3, and 5 %, with R (2) of 0.99. The labeling reagents are readily available. The labeling experiments and the detection procedures are simple. The approach is useful for the quantification of GM soya at a level as low as 0.5 %.

  10. High Capacity Na+/H+ Exchange Activity in Mineralizing Osteoblasts

    PubMed Central

    Liu, Li; Schlesinger, Paul H.; Slack, Nicole M.; Friedman, Peter A.; Blair, Harry C.

    2015-01-01

    Osteoblasts synthesize bone in polarized groups of cells sealed by tight junctions. Large amounts of acid are produced as bone mineral is precipitated. We addressed the mechanism by which cells manage this acid load by measuring intracellular pH (pHi) in non-transformed osteoblasts in response to weak acid or bicarbonate loading. Basal pHi in mineralizing osteoblasts was ∼7.3 and decreased by ∼ 1.4 units upon replacing extracellular Na+ with N-methyl-d-glucamine. Loading with 40 mM acetic or propionic acids, in normal extracellular Na+, caused only mild cytosolic acidification. In contrast, in Na+-free solutions, weak acids reduced pHi dramatically. After Na+ reintroduction, pHi recovered rapidly, in keeping with Na+/H+exchanger (NHE) activity. Sodium-dependent pHi recovery from weak acid loading was inhibited by amiloride with the Ki consistent with NHEs. NHE1 and NHE6 were expressed strongly, and expression was upregulated highly, by mineralization, in human osteoblasts. Antibody labeling of mouse bone showed NHE1 on basolateral surfaces of all osteoblasts. NHE6 occurred on basolateral surfaces of osteoblasts mainly in areas of mineralization. Conversely, elevated HCO3- alkalinized osteoblasts, and pH recovered in medium containing CI-, with or without Na+, in keeping with Na+-independent CI-/HCO3- exchange. The exchanger AE2 also occurred on the basolateral surface of osteoblasts, consistent with CI-/HCO3- exchange for elimination of metabolic carbonate. Overexpression of NHE6 or knockdown of NHE1 in MG63 human osteosarcoma cells confirmed roles of NHE1 and NHE6 in maintaining pHi. We conclude that in mineralizing osteoblasts, slightly basic basal pHi is maintained, and external acid load is dissipated, by high-capacity Na+/H+ exchange via NHE1 and NHE6. PMID:21413028

  11. Microchannel laminated mass exchanger and method of making

    DOEpatents

    Martin, Peter M [Kennewick, WA; Bennett, Wendy D [Kennewick, WA; Matson, Dean W [Kennewick, WA; Stewart, Donald C [Richland, WA; Drost, Monte K [Pasco, WA; Wegeng, Robert S [Richland, WA; Perez, Joseph M [Richland, WA; Feng, Xiangdong [West Richland, WA; Liu, Jun [West Richland, WA

    2003-03-18

    The present invention is a microchannel mass exchanger having a first plurality of inner thin sheets and a second plurality of outer thin sheets. The inner thin sheets each have a solid margin around a circumference, the solid margin defining a slot through the inner thin sheet thickness. The outer thin sheets each have at least two header holes on opposite ends and when sandwiching an inner thin sheet. The outer thin sheets further have a mass exchange medium. The assembly forms a closed flow channel assembly wherein fluid enters through one of the header holes into the slot and exits through another of the header holes after contacting the mass exchange medium.

  12. Microchannel laminated mass exchanger and method of making

    DOEpatents

    Martin, Peter M.; Bennett, Wendy D.; Matson, Dean W.; Stewart, Donald C.; Drost, Monte K.; Wegeng, Robert S.; Perez, Joseph M.; Feng, Xiangdong; Liu, Jun

    2000-01-01

    The present invention is a microchannel mass exchanger having a first plurality of inner thin sheets and a second plurality of outer thin sheets. The inner thin sheets each have a solid margin around a circumference, the solid margin defining a slot through the inner thin sheet thickness. The outer thin sheets each have at least two header holes on opposite ends and when sandwiching an inner thin sheet. The outer thin sheets further have a mass exchange medium. The assembly forms a closed flow channel assembly wherein fluid enters through one of the header holes into the slot and exits through another of the header holes after contacting the mass exchange medium.

  13. Microchannel laminated mass exchanger and method of making

    DOEpatents

    Martin, Peter M [Kennewick, WA; Bennett, Wendy D [Kennewick, WA; Matson, Dean W [Kennewick, WA; Stewart, Donald C [Richland, WA; Drost, Monte K [Pasco, WA; Wegeng, Robert S [Richland, WA; Perez, Joseph M [Richland, WA; Feng, Xiangdong [West Richland, WA; Liu, Jun [West Richland, WA

    2002-03-05

    The present invention is a microchannel mass exchanger having a first plurality of inner thin sheets and a second plurality of outer thin sheets. The inner thin sheets each have a solid margin around a circumference, the solid margin defining a slot through the inner thin sheet thickness. The outer thin sheets each have at least two header holes on opposite ends and when sandwiching an inner thin sheet. The outer thin sheets further have a mass exchange medium. The assembly forms a closed flow channel assembly wherein fluid enters through one of the header holes into the slot and exits through another of the header holes after contacting the mass exchange medium.

  14. Water D/H Ratio In Low-Mass Protostars

    NASA Astrophysics Data System (ADS)

    Persson, Magnus V.; Jørgensen, Jes K.; van Dishoeck, Ewine F.; Harsono, Daniel

    2013-07-01

    Water is an important molecule for our life on Earth, but its way from formation on the surfaces of dust grains to planets and the accompanying chemical processing are not well understood. Through evaporation in the warm inner regions of protostars, water brings complex organics and other species previously locked up in the ice into the gas phase. The water deuterium fractionation (HDO/H2O abundance ratio) has traditionally been used to infer the amount of water that was brought to the Earth by comets. Deducing this ratio in the warm gas of deeply-embedded low-mass protostars allows to extend the discussion of the origin of Earth's water to earlier evolutionary stages. This poster present high-angular resolution, ground based interferometric observations of both HDO and H2(18)O water isotopologues toward several Class~0 low-mass protostars. The emission is compact, and stems from the inner few 100 AU in all sources. The derived amount of deuterium fractionation in water, obtained assuming LTE and optically thin emission, is the same within the uncertainties in all sources and shows only small enhancements compared with Earth's oceans and solar system's comets.

  15. D/H in Water Evolved from Martian Rocks in Gale Crater

    NASA Astrophysics Data System (ADS)

    Mahaffy, P. R.; Franz, H. B.; Atreya, S. K.; Webster, C. R.

    2017-12-01

    The Sample Analysis at Mars (SAM) instrument suite with its Quadrupole Mass Spectrometer (QMS) and Tunable Laser Spectrometer (TSL) measures isotopes such as δ34S in SO2 [1], δ37Cl in HCl [2], δ15N in N2 or NO [3], δ13C in CH4 [4], δ13C and δ18O in CO2 [5-6], δD in H2O [7], and a variety of noble gas isotopes [8-9]. Fractionation of isotopes of H, C, O, N, Ar, and Xe indicates a substantial loss of atmosphere to space. For xenon this may have occurred early in the history of Mars by hydrodynamic escape [10] or spread over time for C, O, N, and Ar [11]. Nevertheless, the detailed history of atmospheric loss and the predictions of the climate when the Gale crater was a lake are still not well constrained. Isotopes from light elements that are presently measured in the atmosphere but that were also locked into minerals in rocks more than 3 billion years ago are of particular interest as they may provide additional constraints on the history of atmospheric loss. These include 15N/14N presently measured in atmospheric N2 [3] but also in nitrogen released from ancient nitrates as NO [12] and D/H in atmospheric water [13] and in water or hydroxyl locked into minerals and released in the SAM evolved gas analysis (EGA) experiments [7]. D/H in water can be measured by both the TSL and the QMS. Typically the D/H decreases over the course of the EGA temperature ramp, since gas that has exchanged with the current atmosphere is released at lower temperatures. Less easily exchanged gas reflecting the D/H ratio in the water of formation of a mineral, such as that from the dehydroxylation of a phylosillicate, is released at higher temperatures. We will examine some of the D/H measurements made on drilled and powdered rocks and the trends in the variation of the D/H ratio with release temperature. We will compare these ratios with the D/H in atmospheric water and discuss possible consequences for loss of D/H over time. References: [1] Franz et al., in press. [2] Farley et al

  16. Charge exchange collisions of slow C6 + with atomic and molecular H

    NASA Astrophysics Data System (ADS)

    Saha, Bidhan C.; Guevara, Nicolais L.; Sabin, John R.; Deumens, Erik; Öhrn, Yngve

    2016-04-01

    Charge exchange in collisions of C6+ ions with H and H2 is investigated theoretically at projectile energies 0.1 < E < 10 keV/amu, using electron nuclear dynamics (END) - a semi-classical approximation which not only includes electron translation factors for avoiding spurious couplings but also employs full dynamical trajectories to treat nuclear motions. Both the total and partial cross sections are reported for the collision of C6+ ions with atomic and molecular hydrogen. A comparison with other theoretical and experimental results shows, in general good agreement except at very low energy, considered here. For H2, the one- and two-electron charge exchange cross sections are calculated and compared with other theoretical and experimental results. Small but non-negligible isotope effects are found at the lowest energy studied in the charge transfer of C6+ with H. In low energy region, it is observed that H2 has larger isotope effects than H atom due to the polarizability effect which is larger than the mass effect.

  17. Two-step ion-exchange chromatographic purification combined with reversed-phase chromatography to isolate C-peptide for mass spectrometric analysis.

    PubMed

    Kabytaev, Kuanysh; Durairaj, Anita; Shin, Dmitriy; Rohlfing, Curt L; Connolly, Shawn; Little, Randie R; Stoyanov, Alexander V

    2016-02-01

    A liquid chromatography with mass spectrometry on-line platform that includes the orthogonal techniques of ion exchange and reversed phase chromatography is applied for C-peptide analysis. Additional improvement is achieved by the subsequent application of cation- and anion-exchange purification steps that allow for isolating components that have their isoelectric points in a narrow pH range before final reversed-phase mass spectrometry analysis. The utility of this approach for isolating fractions in the desired "pI window" for profiling complex mixtures is discussed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. General Formalism of Mass Scaling Approach for Replica-Exchange Molecular Dynamics and its Application

    NASA Astrophysics Data System (ADS)

    Nagai, Tetsuro

    2017-01-01

    Replica-exchange molecular dynamics (REMD) has demonstrated its efficiency by combining trajectories of a wide range of temperatures. As an extension of the method, the author formalizes the mass-manipulating replica-exchange molecular dynamics (MMREMD) method that allows for arbitrary mass scaling with respect to temperature and individual particles. The formalism enables the versatile application of mass-scaling approaches to the REMD method. The key change introduced in the novel formalism is the generalized rules for the velocity and momentum scaling after accepted replica-exchange attempts. As an application of this general formalism, the refinement of the viscosity-REMD (V-REMD) method [P. H. Nguyen, J. Chem. Phys. 132, 144109 (2010)] is presented. Numerical results are provided using a pilot system, demonstrating easier and more optimized applicability of the new version of V-REMD as well as the importance of adherence to the generalized velocity scaling rules. With the new formalism, more sound and efficient simulations will be performed.

  19. A Mass Computation Model for Lightweight Brayton Cycle Regenerator Heat Exchangers

    NASA Technical Reports Server (NTRS)

    Juhasz, Albert J.

    2010-01-01

    Based on a theoretical analysis of convective heat transfer across large internal surface areas, this paper discusses the design implications for generating lightweight gas-gas heat exchanger designs by packaging such areas into compact three-dimensional shapes. Allowances are made for hot and cold inlet and outlet headers for assembly of completed regenerator (or recuperator) heat exchanger units into closed cycle gas turbine flow ducting. Surface area and resulting volume and mass requirements are computed for a range of heat exchanger effectiveness values and internal heat transfer coefficients. Benefit cost curves show the effect of increasing heat exchanger effectiveness on Brayton cycle thermodynamic efficiency on the plus side, while also illustrating the cost in heat exchanger required surface area, volume, and mass requirements as effectiveness is increased. The equations derived for counterflow and crossflow configurations show that as effectiveness values approach unity, or 100 percent, the required surface area, and hence heat exchanger volume and mass tend toward infinity, since the implication is that heat is transferred at a zero temperature difference. To verify the dimensional accuracy of the regenerator mass computational procedure, calculation of a regenerator specific mass, that is, heat exchanger weight per unit working fluid mass flow, is performed in both English and SI units. Identical numerical values for the specific mass parameter, whether expressed in lb/(lb/sec) or kg/(kg/sec), show the dimensional consistency of overall results.

  20. A Mass Computation Model for Lightweight Brayton Cycle Regenerator Heat Exchangers

    NASA Technical Reports Server (NTRS)

    Juhasz, Albert J.

    2010-01-01

    Based on a theoretical analysis of convective heat transfer across large internal surface areas, this paper discusses the design implications for generating lightweight gas-gas heat exchanger designs by packaging such areas into compact three-dimensional shapes. Allowances are made for hot and cold inlet and outlet headers for assembly of completed regenerator (or recuperator) heat exchanger units into closed cycle gas turbine flow ducting. Surface area and resulting volume and mass requirements are computed for a range of heat exchanger effectiveness values and internal heat transfer coefficients. Benefit cost curves show the effect of increasing heat exchanger effectiveness on Brayton cycle thermodynamic efficiency on the plus side, while also illustrating the cost in heat exchanger required surface area, volume, and mass requirements as effectiveness is increased. The equations derived for counterflow and crossflow configurations show that as effectiveness values approach unity, or 100 percent, the required surface area, and hence heat exchanger volume and mass tend toward infinity, since the implication is that heat is transferred at a zero temperature difference. To verify the dimensional accuracy of the regenerator mass computational procedure, calculation of a regenerator specific mass, that is, heat exchanger weight per unit working fluid mass flow, is performed in both English and SI units. Identical numerical values for the specific mass parameter, whether expressed in lb/(lb/sec) or kg/ (kg/sec), show the dimensional consistency of overall results.

  1. Hydrophilic Strong Anion Exchange (hSAX) Chromatography for Highly Orthogonal Peptide Separation of Complex Proteomes

    PubMed Central

    2013-01-01

    Due to its compatibility and orthogonality to reversed phase (RP) liquid chromatography (LC) separation, ion exchange chromatography, and mainly strong cation exchange (SCX), has often been the first choice in multidimensional LC experiments in proteomics. Here, we have tested the ability of three strong anion exchanger (SAX) columns differing in their hydrophobicity to fractionate RAW264.7 macrophage cell lysate. IonPac AS24, a strong anion exchange material with ultralow hydrophobicity, demonstrated to be superior to other materials by fractionation and separation of tryptic peptides from both a mixture of 6 proteins as well as mouse cell lysate. The chromatography displayed very high orthogonality and high robustness depending on the hydrophilicity of column chemistry, which we termed hydrophilic strong anion exchange (hSAX). Mass spectrometry analysis of 34 SAX fractions from RAW264.7 macrophage cell lysate digest resulted in an identification of 9469 unique proteins and 126318 distinct peptides in one week of instrument time. Moreover, when compared to an optimized high pH/low pH RP separation approach, the method presented here raised the identification of proteins and peptides by 10 and 28%, respectively. This novel hSAX approach provides robust, reproducible, and highly orthogonal separation of complex protein digest samples for deep coverage proteome analysis. PMID:23294059

  2. Ion-exchange equilibrium of N-acetyl-D-neuraminic acid on a strong anionic exchanger.

    PubMed

    Wu, Jinglan; Ke, Xu; Zhang, Xudong; Zhuang, Wei; Zhou, Jingwei; Ying, Hanjie

    2015-09-15

    N-acetyl-D-neuraminic acid (Neu5Ac) is a high value-added product widely applied in the food industry. A suitable equilibrium model is required for purification of Neu5Ac based on ion-exchange chromatography. Hence, the equilibrium uptake of Neu5Ac on a strong anion exchanger, AD-1 was investigated experimentally and theoretically. The uptake of Neu5Ac by the hydroxyl form of the resin occurred primarily by a stoichiometric exchange of Neu5Ac(-) and OH(-). The experimental data showed that the selectivity coefficient for the exchange of Neu5Ac(-) with OH(-) was a non-constant quantity. Subsequently, the Saunders' model, which took into account the dissociation reactions of Neu5Ac and the condition of electroneutrality, was used to correlate the Neu5Ac sorption isotherms at various solution pHs and Neu5Ac concentrations. The model provided an excellent fit to the binary exchange data for Cl(-)/OH(-) and Neu5Ac(-)/OH(-), and an approximate prediction of equilibrium in the ternary system Cl(-)/Neu5Ac(-)/OH(-). This basic information combined with the general mass transfer model could lay the foundation for the prediction of dynamic behavior of fixed bed separation process afterwards. Copyright © 2015 Elsevier Ltd. All rights reserved.

  3. Hydrogen/deuterium exchange mass spectrometry with top-down electron capture dissociation for characterizing structural transitions of a 17 kDa protein.

    PubMed

    Pan, Jingxi; Han, Jun; Borchers, Christoph H; Konermann, Lars

    2009-09-09

    Amide H/D exchange (HDX) mass spectrometry (MS) is widely used for protein structural studies. Traditionally, this technique involves protein labeling in D(2)O, followed by acid quenching, proteolytic digestion, and analysis of peptide deuteration levels by HPLC/MS. There is great interest in the development of alternative HDX approaches involving the top-down fragmentation of electrosprayed protein ions, instead of relying on enzymatic cleavage and solution-phase separations. A number of recent studies have demonstrated that electron capture dissociation (ECD) results in fragmentation of gaseous protein ions with little or no H/D scrambling. However, the successful application of this approach for in-depth protein conformational studies has not yet been demonstrated. The current work uses horse myoglobin as a model system for assessing the suitability of HDX-MS with top-down ECD for experiments of this kind. It is found that ECD can pinpoint the locations of protected amides with an average resolution of less than two residues for this 17 kDa protein. Native holo-myoglobin (hMb) shows considerable protection from exchange in all of its helices, whereas loops are extensively deuterated. Fraying is observable at some helix termini. Removal of the prosthetic heme group from hMb produces apo-myoglobin (aMb). Both hMb and aMb share virtually the same HDX protection pattern in helices A-E, whereas helix F is unfolded in aMb. In addition, destabilization is evident for some residues close to the beginning of helix G, the end of helix H, and the C-terminus of the protein. The structural changes reported herein are largely consistent with earlier NMR data for sperm whale myoglobin, although small differences between the two systems are evident. Our findings demonstrate that the level of structural information obtainable with top-down ECD for small to medium-sized proteins considerably surpasses that of traditional HDX-MS experiments, while at the same time greatly reducing

  4. Isotopic ratios D/H and 15N/14N in giant planets

    NASA Astrophysics Data System (ADS)

    Marboeuf, Ulysse; Thiabaud, Amaury; Alibert, Yann; Benz, Willy

    2018-04-01

    The determination of isotopic ratios in planets is important since it allows us to investigate the origins and initial composition of materials. The present work aims to determine the possible range of values for isotopic ratios D/H and 15N/14N in giant planets. The main objective is to provide valuable theoretical assumptions on the isotopic composition of giant planets, their internal structure, and the main reservoirs of species. We use models of ice formation and planet formation that compute the composition of ices and gas accreted in the core and the envelope of planets. Assuming a single initial value for isotopic ratios in volatile species, and disruption of planetesimals in the envelope of gaseous planets, we obtain a wide variety of D/H and 15N/14N ratios in low-mass planets (≤100 Mearth) due to the migration pathway of planets, the accretion time of gas species whose relative abundance evolves with time, and isotope exchanges among species. If giant planets with mass greater than 100 Mearth have solar isotopic ratios such as Jupiter and Saturn due to their higher envelope mass, Neptune-type planets present values ranging between one and three times the solar value. It seems therefore difficult to use isotopic ratios in the envelope of these planets to get information about their formation in the disc. For giant planets, the ratios allow us to constrain the mass fraction of volatile species in the envelope needed to reproduce the observational data by assuming initial values for isotopic ratios in volatile species.

  5. Hydrogen Exchange Mass Spectrometry

    PubMed Central

    Mayne, Leland

    2018-01-01

    Hydrogen exchange (HX) methods can reveal much about the structure, energetics, and dynamics of proteins. The addition of mass spectrometry (MS) to an earlier fragmentation-separation HX analysis now extends HX studies to larger proteins at high structural resolution and can provide information not available before. This chapter discusses experimental aspects of HX labeling, especially with respect to the use of MS and the analysis of MS data. PMID:26791986

  6. The Relationship between TOC and pH with Exchangeable Heavy Metal Levels in Lithuanian Podzols

    NASA Astrophysics Data System (ADS)

    Khaledian, Yones; Pereira, Paulo; Brevik, Eric C.; Pundyte, Neringa; Paliulis, Dainius

    2017-04-01

    Heavy metals can have a negative impact on public and environmental health. The objective of this study was to investigate the relationship between total organic carbon (TOC) and pH with exchangeable heavy metals (Pb, Cd, Cu and Zn) in order to predict exchangeable heavy metal content in soils sampled near Panevėžys and Kaunas, Lithuania. Principal component regression (PCR) and nonlinear regression methods were tested to find the statistical relationship between TOC and pH with heavy metals. The results of PCR [R2 = 0.68, RMSE = 0.07] and non-linear regression [R2 = 0.74, RMSE= 0.065] (pH with TOC and exchangeable parameters) were statistically significant. However, this was not observed in the relationships of pH and TOC separately with exchangeable heavy metals. The results indicated that pH had a higher correlation with exchangeable heavy metals (non-linear regression [R2 = 0.72, RMSE= 0.066]) than TOC with heavy metals [R2 = 0.30, RMSE= 0.004]. It can be concluded that even though there was a strong relationship between TOC and pH with exchangeable metals, the metal mobility (exchangeable metals) can be explained by pH better than TOC in this study. Finally, manipulating soil pH could likely be productive to assess and control heavy metals when financial and time limitations exist (Khaledian et al. 2016). Reference(s) Khaledian Y, Pereira P, Brevik E.C, Pundyte N, Paliulis D. 2016. The Influence of Organic Carbon and pH on Heavy Metals, Potassium, and Magnesium Levels in Lithuanian Podzols. Land Degradation and Development. DOI: 10.1002/ldr.2638

  7. Measurement of deuterium density profiles in the H-mode steep gradient region using charge exchange recombination spectroscopy on DIII-D

    DOE PAGES

    Haskey, S. R.; Grierson, B. A.; Burrell, K. H.; ...

    2016-09-26

    Recent completion of a thirty two channel main-ion (deuterium) charge exchange recombination spectroscopy (CER) diagnostic on the DIII-D tokamak enables detailed comparisons between impurity and main-ion temperature, density, and toroidal rotation. In a H-mode DIII-D discharge, these new measurement capabilities are used to provide the deuterium density profile, demonstrate the importance of profile alignment between Thomson scattering and CER diagnostics, and aid in determining the electron temperature at the separatrix. Sixteen sightlines cover the core of the plasma and another sixteen are densely packed towards the plasma edge, providing high resolution measurements across the pedestal and steep gradient region inmore » H-mode plasmas. Extracting useful physical quantities such as deuterium density is challenging due to multiple photoemission processes. Finally, these challenges are overcome using a detailed fitting model and by forward modeling the photoemission using the FIDASIM code, which implements a comprehensive collisional radiative model. Published by AIP Publishing.« less

  8. Measurement of deuterium density profiles in the H-mode steep gradient region using charge exchange recombination spectroscopy on DIII-D.

    PubMed

    Haskey, S R; Grierson, B A; Burrell, K H; Chrystal, C; Groebner, R J; Kaplan, D H; Pablant, N A; Stagner, L

    2016-11-01

    Recent completion of a thirty two channel main-ion (deuterium) charge exchange recombination spectroscopy (CER) diagnostic on the DIII-D tokamak [J. L. Luxon, Nucl. Fusion 42, 614 (2002)] enables detailed comparisons between impurity and main-ion temperature, density, and toroidal rotation. In a H-mode DIII-D discharge, these new measurement capabilities are used to provide the deuterium density profile, demonstrate the importance of profile alignment between Thomson scattering and CER diagnostics, and aid in determining the electron temperature at the separatrix. Sixteen sightlines cover the core of the plasma and another sixteen are densely packed towards the plasma edge, providing high resolution measurements across the pedestal and steep gradient region in H-mode plasmas. Extracting useful physical quantities such as deuterium density is challenging due to multiple photoemission processes. These challenges are overcome using a detailed fitting model and by forward modeling the photoemission using the FIDASIM code, which implements a comprehensive collisional radiative model.

  9. Measurement of deuterium density profiles in the H-mode steep gradient region using charge exchange recombination spectroscopy on DIII-D

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

    Haskey, S. R.; Grierson, B. A.; Burrell, K. H.

    Recent completion of a thirty two channel main-ion (deuterium) charge exchange recombination spectroscopy (CER) diagnostic on the DIII-D tokamak enables detailed comparisons between impurity and main-ion temperature, density, and toroidal rotation. In a H-mode DIII-D discharge, these new measurement capabilities are used to provide the deuterium density profile, demonstrate the importance of profile alignment between Thomson scattering and CER diagnostics, and aid in determining the electron temperature at the separatrix. Sixteen sightlines cover the core of the plasma and another sixteen are densely packed towards the plasma edge, providing high resolution measurements across the pedestal and steep gradient region inmore » H-mode plasmas. Extracting useful physical quantities such as deuterium density is challenging due to multiple photoemission processes. Finally, these challenges are overcome using a detailed fitting model and by forward modeling the photoemission using the FIDASIM code, which implements a comprehensive collisional radiative model. Published by AIP Publishing.« less

  10. Measurement of deuterium density profiles in the H-mode steep gradient region using charge exchange recombination spectroscopy on DIII-D

    NASA Astrophysics Data System (ADS)

    Haskey, S. R.; Grierson, B. A.; Burrell, K. H.; Chrystal, C.; Groebner, R. J.; Kaplan, D. H.; Pablant, N. A.; Stagner, L.

    2016-11-01

    Recent completion of a thirty two channel main-ion (deuterium) charge exchange recombination spectroscopy (CER) diagnostic on the DIII-D tokamak [J. L. Luxon, Nucl. Fusion 42, 614 (2002)] enables detailed comparisons between impurity and main-ion temperature, density, and toroidal rotation. In a H-mode DIII-D discharge, these new measurement capabilities are used to provide the deuterium density profile, demonstrate the importance of profile alignment between Thomson scattering and CER diagnostics, and aid in determining the electron temperature at the separatrix. Sixteen sightlines cover the core of the plasma and another sixteen are densely packed towards the plasma edge, providing high resolution measurements across the pedestal and steep gradient region in H-mode plasmas. Extracting useful physical quantities such as deuterium density is challenging due to multiple photoemission processes. These challenges are overcome using a detailed fitting model and by forward modeling the photoemission using the FIDASIM code, which implements a comprehensive collisional radiative model.

  11. Advanced Heat/Mass Exchanger Technology for Geothermal and Solar Renewable Energy Systems

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

    Greiner, Miles; Childress, Amy; Hiibel, Sage

    2014-12-16

    Northern Nevada has abundant geothermal and solar energy resources, and these renewable energy sources provide an ample opportunity to produce economically viable power. Heat/mass exchangers are essential components to any energy conversion system. Improvements in the heat/mass exchange process will lead to smaller, less costly (more efficient) systems. There is an emerging heat transfer technology, based on micro/nano/molecular-scale surface science that can be applied to heat/mass exchanger design. The objective is to develop and characterize unique coating materials, surface configurations and membranes capable of accommodating a 10-fold increase in heat/mass exchanger performance via phase change processes (boiling, condensation, etc.) andmore » single phase convective heat/mass transfer.« less

  12. D/H diffusion in serpentine

    NASA Astrophysics Data System (ADS)

    Pilorgé, Hélène; Reynard, Bruno; Remusat, Laurent; Le Floch, Sylvie; Montagnac, Gilles; Cardon, Hervé

    2017-04-01

    different typical grain sizes. They lie below 130˚ C for carbonaceous chondrites, indicating that D/H isotopic exchange may have persisted down to very low temperatures on their parent bodies. D/H isotopic composition may be associated with grain size heterogeneities in carbonaceous chondrites due to protracted alteration of fine-grained material with the lowest closure temperatures (ca 50˚ C).

  13. D/H diffusion in serpentine

    NASA Astrophysics Data System (ADS)

    Pilorgé, Hélène; Reynard, Bruno; Remusat, Laurent; Le Floch, Sylvie; Montagnac, Gilles; Cardon, Hervé

    2017-08-01

    carbonaceous chondrites, indicating that D/H isotopic exchange may have persisted down to very low temperatures in their parent bodies. Local D/H isotopic compositions may be associated with grain size heterogeneities in carbonaceous chondrites due to protracted alteration of fine-grained material with the lowest closure temperatures (ca 80 °C).

  14. HDX Workbench: Software for the Analysis of H/D Exchange MS Data

    NASA Astrophysics Data System (ADS)

    Pascal, Bruce D.; Willis, Scooter; Lauer, Janelle L.; Landgraf, Rachelle R.; West, Graham M.; Marciano, David; Novick, Scott; Goswami, Devrishi; Chalmers, Michael J.; Griffin, Patrick R.

    2012-09-01

    Hydrogen/deuterium exchange mass spectrometry (HDX-MS) is an established method for the interrogation of protein conformation and dynamics. While the data analysis challenge of HDX-MS has been addressed by a number of software packages, new computational tools are needed to keep pace with the improved methods and throughput of this technique. To address these needs, we report an integrated desktop program titled HDX Workbench, which facilitates automation, management, visualization, and statistical cross-comparison of large HDX data sets. Using the software, validated data analysis can be achieved at the rate of generation. The application is available at the project home page http://hdx.florida.scripps.edu.

  15. CFD analysis of the plate heat exchanger - Mathematical modelling of mass and heat transfer in serial connection with tubular heat exchanger

    NASA Astrophysics Data System (ADS)

    Bojko, Marian; Kocich, Radim

    2016-06-01

    Application of numerical simulations based on the CFD calculation when the mass and heat transfer between the fluid flows is essential component of thermal calculation. In this article the mathematical model of the heat exchanger is defined, which is subsequently applied to the plate heat exchanger, which is connected in series with the other heat exchanger (tubular heat exchanger). The present contribution deals with the possibility to use the waste heat of the flue gas produced by small micro turbine. Inlet boundary conditions to the mathematical model of the plate heat exchanger are obtained from the results of numerical simulation of the tubular heat exchanger. Required parameters such for example inlet temperature was evaluated from temperature field, which was subsequently imported to the inlet boundary condition to the simulation of plate heat exchanger. From the results of 3D numerical simulations are evaluated basic flow variables including the evaluation of dimensionless parameters such as Colburn j-factor and friction ft factor. Numerical simulation is realized by software ANSYS Fluent15.0.

  16. Halo mass dependence of H I and O VI absorption: evidence for differential kinematics

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

    Mathes, Nigel L.; Churchill, Christopher W.; Nielsen, Nikole M.

    2014-09-10

    We studied a sample of 14 galaxies (0.1 < z < 0.7) using HST/WFPC2 imaging and high-resolution HST/COS or HST/STIS quasar spectroscopy of Lyα, Lyβ, and O VI λλ1031, 1037 absorption. The galaxies, having 10.8 ≤ log (M {sub h}/M {sub ☉}) ≤ 12.2, lie within D = 300 kpc of quasar sightlines, probing out to D/R {sub vir} = 3. When the full range of M {sub h} and D/R {sub vir} of the sample are examined, ∼40% of the H I absorbing clouds can be inferred to be escaping their host halo. The fraction of bound clouds decreasesmore » as D/R {sub vir} increases such that the escaping fraction is ∼15% for D/R {sub vir} < 1, ∼45% for 1 ≤ D/R {sub vir} < 2, and ∼90% for 2 ≤ D/R {sub vir} < 3. Adopting the median mass log M {sub h}/M {sub ☉} = 11.5 to divide the sample into 'higher' and 'lower' mass galaxies, we find a mass dependency for the hot circumgalactic medium kinematics. To our survey limits, O VI absorption is found in only ∼40% of the H I clouds in and around lower mass halos as compared to ∼85% around higher mass halos. For D/R {sub vir} < 1, lower mass halos have an escape fraction of ∼65%, whereas higher mass halos have an escape fraction of ∼5%. For 1 ≤ D/R {sub vir} < 2, the escape fractions are ∼55% and ∼35% for lower mass and higher mass halos, respectively. For 2 ≤ D/R {sub vir} < 3, the escape fraction for lower mass halos is ∼90%. We show that it is highly likely that the absorbing clouds reside within 4R {sub vir} of their host galaxies and that the kinematics are dominated by outflows. Our finding of 'differential kinematics' is consistent with the scenario of 'differential wind recycling' proposed by Oppenheimer et al. We discuss the implications for galaxy evolution, the stellar to halo mass function, and the mass-metallicity relationship of galaxies.« less

  17. The D/H ratio in water from Halley

    NASA Technical Reports Server (NTRS)

    Eberhardt, P.; Dolder, U.; Schulte, W.; Krankowsky, D.; Laemmerzahl, P.; Hoffman, J. H.; Hodges, R. R.; Berthelier, J. J.; Illiano, J. M.

    1986-01-01

    The neutral gas mass spectrometer on Giotto made neutral and ion composition measurements with a high mass resolution. Evaluation of the ion data within the contact surface gives a D/H ratio in water from Halley between 0.00006 and 0.00048. While this ratio is definitely not compatible with the D/H in molecular hydrogen of the protosolar nebula or the Jovian and Saturnian atmospheres, it is in the range observed for hydrogen in solar system objects which acquired their hydrogen as part of volatile molecules, e.g., as ices.

  18. Combining H/D exchange mass spectroscopy and computational docking reveals extended DNA-binding surface on uracil-DNA glycosylase

    PubMed Central

    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.

    2012-01-01

    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

  19. Rotational Energy as Mass in H3 + and Lower Limits on the Atomic Masses of D and 3He

    NASA Astrophysics Data System (ADS)

    Smith, J. A.; Hamzeloui, S.; Fink, D. J.; Myers, E. G.

    2018-04-01

    We have made precise measurements of the cyclotron frequency ratios H3 +/HD+ and H3 +/ 3He+ and observe that different H3+ ions result in different cyclotron frequency ratios. We interpret these differences as due to the molecular rotational energy of H3 + changing its inertial mass. We also confirm that certain high J , K rotational levels of H3+ have mean lifetimes exceeding several weeks. From measurements with the lightest H3+ ion we obtain lower limits on the atomic masses of deuterium and helium-3 with respect to the proton.

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

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

    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.

  1. Direct and Quantitative Characterization of Dynamic Ligand Exchange between Coordination-Driven Self-Assembled Supramolecular Polygons

    PubMed Central

    Zheng, Yao-Rong; Stang, Peter J.

    2009-01-01

    The direct observation of dynamic ligand exchange beween Pt-N coordination-driven self-assembled supramolecular polygons (triangles and rectangles) has been achieved using stable isotope labeling (1H/2D) of the pyridyl donors and electrospray ionization mass spectrometry (ESI-MS) together with NMR spectroscopy. Both the thermodynamic and kinetic aspects of such exchange processes have been established based on quantitative mass spectral results. Further investigation showed that the exchange is highly dependent on experimental conditions such as temperature, solvent, and the counter anions. PMID:19243144

  2. Direct and quantitative characterization of dynamic ligand exchange between coordination-driven self-assembled supramolecular polygons.

    PubMed

    Zheng, Yao-Rong; Stang, Peter J

    2009-03-18

    The direct observation of dynamic ligand exchange between Pt-N coordination-driven self-assembled supramolecular polygons (triangles and rectangles) has been achieved using stable (1)H/(2)D isotope labeling of the pyridyl donors and electrospray ionization mass spectrometry combined with NMR spectroscopy. Both the thermodynamic and kinetic aspects of such exchange processes have been established on the basis of quantitative mass spectral results. Further investigation has shown that the exchange is highly dependent on experimental conditions such as temperature, solvent, and the counteranions.

  3. Exchangeable hydrogen explains the pH of spodosol Oa horizons

    USGS Publications Warehouse

    Ross, D.S.; David, M.B.; Lawrence, G.B.; Bartlett, R.J.

    1996-01-01

    The chemistry of extremely acid Oa horizons does not conform to traditional pH, Al, and base saturation relationships. Results from two separate studies of northeastern U.S. forested soils were used to investigate relationships between pH in water or dilute salt solutions and other soil characteristics. In Oa horizons with pH below 4, soil pH in dilute CaCl2 solution was correlated with exchangeable H+ measured either by titration (r = -0.88, P = 0.0001, n = 142) or by electrode (r = -0.89, P = 0.0001, n = 45). Exchangeable H+ expressed as a percentage of the cation-exchange capacity (CEC) was linear with pH and showed similar slopes for data from both studies. For all samples, pHw = 4.21 - 1.80 x H+/CEC (R2 = 0.69, n = 194). The reciprocal of the H+/CEC ratio is base saturation with Al added to the bases. Because of the low pH, exchangeable Al does not appear to behave as an acid. Exchangeable H+ remains an operationally defined quantity because of the difficulty in separating exchange and hydrolysis reactions. In a variety of neutral-salt extractants, concentration of H+ were correlated with 0.1 M BaCl2-exchangeable H+ (r > 0.91, P = 0.0001, n = 26) regardless of the strength of the extract. Nine successive extractions with 0.33 mM CaCl2 removed more H+ than was removed by single batch extractions with either 1 M KCl or 0.1 M BaCl2 (average H+ of 70, 43, and 49 mmol kg-1, respectively for 26 samples). The data showed little difference in the chemical behavior of Oa horizons from a variety of geographical sites and vegetation types.

  4. Enhanced picture of protein-folding intermediates using organic solvents in H/D exchange and quench-flow experiments

    PubMed Central

    Nishimura, Chiaki; Dyson, H. Jane; Wright, Peter E.

    2005-01-01

    Hydrogen/deuterium exchange followed by trapping of the labeled species in the aprotic solvent DMSO has been used to elucidate structure in both the burst-phase molten globule-folding intermediate of apomyoglobin and in an equilibrium intermediate that models the kinetic intermediate. Precise estimates can be made of exchange times in an interrupted exchange-out experiment at pH 4 followed by analysis in DMSO solution, giving extensive sequence-specific information about the structure of the equilibrium intermediate. In addition, the use of DMSO as a solvent for NMR measurements after quench-flow pH-pulse labeling experiments gives a greatly increased data set for the elucidation of the kinetic folding pathway. Interestingly, differences are observed in some regions of apomyoglobin between the equilibrium and kinetic intermediates. These differences are quantitative rather than qualitative; that is, the overall patterns of labeling and secondary structure formation remain similar between the two species. However, local differences are observed, which probably reflect the difference in the solution conditions for the equilibrium experiment (pH 4) vs. the kinetic experiment (pH 6) and the change in the status of the stabilizing hydrogen bond between the side chains of His-24 and His-119. PMID:15769860

  5. The mechanism for water exchange in [UO(2)(H(2)O)(5)](2+) and [UO(2)(oxalate)(2)(H(2)O)](2-), as studied by quantum chemical methods.

    PubMed

    Vallet, V; Wahlgren, U; Schimmelpfennig, B; Szabó, Z; Grenthe, I

    2001-12-05

    The mechanisms for the exchange of water between [UO(2)(H(2)O)(5)](2+), [UO(2)(oxalate)(2)(H(2)O)](2)(-)(,) and water solvent along dissociative (D), associative (A) and interchange (I) pathways have been investigated with quantum chemical methods. The choice of exchange mechanism is based on the computed activation energy and the geometry of the identified transition states and intermediates. These quantities were calculated both in the gas phase and with a polarizable continuum model for the solvent. There is a significant and predictable difference between the activation energy of the gas phase and solvent models: the energy barrier for the D-mechanism increases in the solvent as compared to the gas phase, while it decreases for the A- and I-mechanisms. The calculated activation energy, Delta U(++), for the water exchange in [UO(2)(H(2)O)(5)](2+) is 74, 19, and 21 kJ/mol, respectively, for the D-, A-, and I-mechanisms in the solvent, as compared to the experimental value Delta H(++) = 26 +/- 1 kJ/mol. This indicates that the D-mechanism for this system can be ruled out. The energy barrier between the intermediates and the transition states is small, indicating a lifetime for the intermediate approximately 10(-10) s, making it very difficult to distinguish between the A- and I-mechanisms experimentally. There is no direct experimental information on the rate and mechanism of water exchange in [UO(2)(oxalate)(2)(H(2)O)](2-) containing two bidentate oxalate ions. The activation energy and the geometry of transition states and intermediates along the D-, A-, and I-pathways were calculated both in the gas phase and in a water solvent model, using a single-point MP2 calculation with the gas phase geometry. The activation energy, Delta U(++), in the solvent for the D-, A-, and I-mechanisms is 56, 12, and 53 kJ/mol, respectively. This indicates that the water exchange follows an associative reaction mechanism. The geometry of the A- and I-transition states for both [UO

  6. The vibration-rotation-tunneling levels of N2-H2O and N2-D2O.

    PubMed

    Wang, Xiao-Gang; Carrington, Tucker

    2015-07-14

    In this paper, we report vibration-rotation-tunneling levels of the van der Waals clusters N2-H2O and N2-D2O computed from an ab initio potential energy surface. The only dynamical approximation is that the monomers are rigid. We use a symmetry adapted Lanczos algorithm and an uncoupled product basis set. The pattern of the cluster's levels is complicated by splittings caused by H-H exchange tunneling (larger splitting) and N-N exchange tunneling (smaller splitting). An interesting result that emerges from our calculation is that whereas in N2-H2O, the symmetric H-H tunnelling state is below the anti-symmetric H-H tunnelling state for both K = 0 and K = 1, the order is reversed in N2-D2O for K = 1. The only experimental splitting measurements are the D-D exchange tunneling splittings reported by Zhu et al. [J. Chem. Phys. 139, 214309 (2013)] for N2-D2O in the v2 = 1 region of D2O. Due to the inverted order of the split levels, they measure the sum of the K = 0 and K = 1 tunneling splittings, which is in excellent agreement with our calculated result. Other splittings we predict, in particular those of N2-H2O, may guide future experiments.

  7. The vibration-rotation-tunneling levels of N2-H2O and N2-D2O

    NASA Astrophysics Data System (ADS)

    Wang, Xiao-Gang; Carrington, Tucker

    2015-07-01

    In this paper, we report vibration-rotation-tunneling levels of the van der Waals clusters N2-H2O and N2-D2O computed from an ab initio potential energy surface. The only dynamical approximation is that the monomers are rigid. We use a symmetry adapted Lanczos algorithm and an uncoupled product basis set. The pattern of the cluster's levels is complicated by splittings caused by H-H exchange tunneling (larger splitting) and N-N exchange tunneling (smaller splitting). An interesting result that emerges from our calculation is that whereas in N2-H2O, the symmetric H-H tunnelling state is below the anti-symmetric H-H tunnelling state for both K = 0 and K = 1, the order is reversed in N2-D2O for K = 1. The only experimental splitting measurements are the D-D exchange tunneling splittings reported by Zhu et al. [J. Chem. Phys. 139, 214309 (2013)] for N2-D2O in the v2 = 1 region of D2O. Due to the inverted order of the split levels, they measure the sum of the K = 0 and K = 1 tunneling splittings, which is in excellent agreement with our calculated result. Other splittings we predict, in particular those of N2-H2O, may guide future experiments.

  8. D-Tagatose, a stereoisomer of D-fructose, increases hydrogen production in humans without affecting 24-hour energy expenditure or respiratory exchange ratio.

    PubMed

    Buemann, B; Toubro, S; Astrup, A

    1998-09-01

    In growth studies on rats, the ketohexose D-tagatose has been shown to contribute no net metabolizable energy, and a pronounced thermic effect of the sugar has been suggested to account for the absence of energy. In a double-blind and balanced cross-over design, we measured 24-h energy expenditure in eight normal weight humans in a respiration chamber during the consumption of 30 g D-tagatose or 30 g sucrose/d. Metabolic measurements were performed before and after a 2-wk adaptation period with a 30-g daily intake of the test sugar. Total 24-h energy expenditure and hour-by-hour profile were unaffected by the test sugar. The nonprotein respiratory exchange ratio (RERnp) was similar during consumption of D-tagatose and sucrose. However, the effect on RERnp due to CO2 produced by fermentation of D-tagatose could not be quantified in this study. A significant increase in 24-h H2 production (35%) during D-tagatose administration suggests a substantial malabsorption of the sugar. We found no effects of the 2-wk adaptation period on the measured gas exchange variables. Significantly lower fasting plasma insulin and triglyceride concentrations were observed during D-tagatose administration compared with the sucrose period. No effects of D-tagatose on body weight and composition were seen, but the perception of fullness 2.5 h after the sugar load was greater with D-tagatose. In conclusion, this study does not suggest a pronounced thermic effect of D-tagatose, and other mechanisms seem to be required to explain its lack of net energy.

  9. Resonant charge exchange for H-H+ in Debye plasmas

    NASA Astrophysics Data System (ADS)

    Laricchiuta, Annarita; Colonna, Gianpiero; Capitelli, Mario; Kosarim, Alexander; Smirnov, Boris M.

    2017-11-01

    The dynamics of resonant charge exchange in proton-hydrogen collisions embedded in plasma is investigated in the framework of the asymptotic approach, modified to account for the effect of Debye-Hückel screening in particle interactions. The cross sections exhibit a marked dependence on the Debye length in regimes of severe plasma confinement. Processes involving excited states H( n)-H+ are also discussed.

  10. Development of a pair of differential H/D isotope-coded derivatization reagents d(0)/d(3)-4-(1-methyl-1H-phenanthro[9,10-d]imidazol-2-yl)phenlamine and its application for determination of aldehydes in selected aquatic products by liquid chromatography-tandem mass spectrometry.

    PubMed

    Sun, Zhiwei; Wang, Xiaoxiang; Cai, Yiping; Fu, Junqing; You, Jinmao

    2014-03-01

    A new pair of derivatization reagents, d0-4-(1-methyl-1H-phenanthro[9,10-d]imidazol-2-yl)phenlamine (d0-MPIA) and d3-4-(1-methyl-1H-phenanthro[9,10-d]imidazol-2-yl)phenlamine (d3-MPIA) have been designed and synthesized. It was successfully used to label aliphatic aldehydes and the aldehyde derivatives were analyzed by high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). The new isotope-coded reagents could easily label aldehydes under acidic conditions in the presence of NaCNBH3. The target derivatives exhibited intense [M+H](+) and regular product ions with electrospray ionization source in positive mode. The d0/d3-MPIA-aldehydes were monitored by the transitions of [M+H](+)→m/z 322 and [M+H](+)→m/z 165, and the obtained detection limits were in the range of 0.18-15.9 pg/mL at signal to noise ratio of 3. The global isotope internal standard technology was employed for quantification analysis with d3-MPIA-aldehyde as internal standard for corresponding d0-MPIA-aldehyde. Excellent linear responses for relative quantification were observed in the range of 1/10-10/1 with coefficients >0.998. The developed method has been applied to the quantification of aliphatic aldehydes in selected aquatic products with RSD<3.6% and recoveries >85.2%. © 2013 Elsevier B.V. All rights reserved.

  11. NMR structural studies of the ionizing radiation adduct 7-hydro-8-oxodeoxyguanosine (8-oxo-7H-dG) opposite deoxyadenosine in a DNA duplex. 8-oxo-7H-dG(syn)ter dot dA(anti) alignment at lesion site

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

    Kouchakdjian, M.; Patel, D.J.; Bodepudi, V.

    1991-02-05

    Proton NMR studies are reported on the complementary d(C1-C2-A3-C4-T5-A6-oxo-G7-T8-C9-A10-C11-C12){center dot}d(G13-G14-T15-G16-A17-A18-T19-A20-G21-T22-G23-G24) dodecanucleotide duplex (designated 8-oxo-7H-dG{center dot}dA 12-mer), which contains a centrally located 7-hydro-8-oxodeoxyguanosine (8-oxo-7H-dG) residue, a group commonly found in DNA that has been exposed to ionizing radiation or oxidizing free radicals. From the NMR spectra it can be deduced that this moiety exists as two tautomers, or gives rise to two DNA conformations, that are in equilibrium and that exchange slowly. The present study focuses on the major component of the equilibrium that originates in the 6,8-dioxo tautomer of 8-oxo-7H-dG. The authors have assigned the exchangeable NH1, NH7, and NH{submore » 2}-2 base protons located on the Watson-Crick and Hoogsteen edges of 8-oxo-7H-dG7 in the 8-oxo-7H-dG{center dot}dA 12-mer duplex, using an analysis of one- and two-dimensional nuclear Overhauser enhancement (NOE) data in H{sub 2}O solution. They were able to detect a set of intra- and interstrand NOEs between protons (exchangeable and nonexchangeable) on adjacent residues in the d(A6-oxo-G7-T8){center dot}d(A17-A18-T19) trinucleotide segment centered about the lesion site that establishes stacking of the oxo-dG7(syn){center dot}dA(anti) pair between stable Watson-Crick dA6{center dot}dT19 and dT8{center dot}A17 base pairs with minimal perturbation of the helix. The structural studies demonstrate that 8-oxo-7H-dG(syn){center dot}dA(anti) forms a stable pair in the interior of the helix, providing a basis for the observed incorporation of dA opposite 8-oxo-7H-dG when readthrough occurs past this oxidized nucleoside base.« less

  12. 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.

    PubMed

    Mistarz, Ulrik H; Brown, Jeffery M; Haselmann, Kim F; Rand, Kasper D

    2014-12-02

    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 inside a mass spectrometer immediately after ESI (gas-phase HDX-MS) and show utility for studying the primary and higher-order structure of peptides and proteins. HDX was achieved by passing N2-gas through a container filled with aqueous deuterated ammonia reagent (ND3/D2O) and admitting the saturated 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/D2O as HDX reagent indicate that labeling is facilitated exclusively through gaseous ND3, yielding similar results to the infusion of purified ND3-gas, while circumventing the complications associated with the use of hazardous purified gases. Comparison of the solution-phase- and gas-phase deuterium uptake of Leu-Enkephalin and Glu-Fibrinopeptide B, confirmed that this gas-phase HDX-MS approach allows for labeling of sites (heteroatom-bound non-amide hydrogens located on side-chains, N-terminus and C-terminus) not accessed by classical solution-phase HDX-MS. The simple setup is compatible 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 separation or electron transfer dissociation, thus enabling multiple orthogonal analyses of the structural properties of peptides and proteins in a single automated LC-MS workflow.

  13. D/H isotope ratios of kerogen, bitumen, oil, and water in hydrous pyrolysis of source rocks containing kerogen types I, II, IIS, and III

    USGS Publications Warehouse

    Schimmelmann, A.; Lewan, M.D.; Wintsch, R.P.

    1999-01-01

    Immature source rock chips containing different types of kerogen (I, II, IIS, III) were artificially matured in isotopically distinct waters by hydrous pyrolysis and by pyrolysis in supercritical water. Converging isotopic trends of inorganic (water) and organic (kerogen, bitumen, oil) hydrogen with increasing time and temperature document that water-derived hydrogen is added to or exchanged with organic hydrogen, or both, during chemical reactions that take place during thermal maturation. Isotopic mass-balance calculations show that, depending on temperature (310-381??C), time (12-144 h), and source rock type, between ca. 45 and 79% of carbon-bound hydrogen in kerogen is derived from water. Estimates for bitumen and oil range slightly lower, with oil-hydrogen being least affected by water-derived hydrogen. Comparative hydrous pyrolyses of immature source rocks at 330??C for 72 h show that hydrogen in kerogen, bitumen, and expelled oil/wax ranks from most to least isotopically influenced by water-derived hydrogen in the order IIS > II ~ III > I. Pyrolysis of source rock containing type II kerogen in supercritical water at 381 ??C for 12 h yields isotopic results that are similar to those from hydrous pyrolysis at 350??C for 72 h, or 330??C for 144 h. Bulk hydrogen in kerogen contains several percent of isotopically labile hydrogen that exchanges fast and reversibly with hydrogen in water vapor at 115??C. The isotopic equilibration of labile hydrogen in kerogen with isotopic standard water vapors significantly reduces the analytical uncertainty of D/H ratios when compared with simple D/H determination of bulk hydrogen in kerogen. If extrapolation of our results from hydrous pyrolysis is permitted to natural thermal maturation at lower temperatures, we suggest that organic D/H ratios of fossil fuels in contact with formation waters are typically altered during chemical reactions, but that D/H ratios of generated hydrocarbons are subsequently little or not affected

  14. Effect of azathioprine on Na(+)/H(+) exchanger activity in dendritic cells.

    PubMed

    Bhandaru, Madhuri; Pasham, Venkanna; Yang, Wenting; Bobbala, Diwakar; Rotte, Anand; Lang, Florian

    2012-01-01

    Azathioprine is a powerful immunosuppressive drug, which is partially effective by interfering with the maturation and function of dendritic cells (DCs), antigen-presenting cells linking innate and adaptive immunity. DCs are stimulated by bacterial lipopolysaccharides (LPS), which trigger the formation of reactive oxygen species (ROS), paralleled by activation of the Na(+)/H(+) exchanger. The carrier is involved in the regulation of cytosolic pH, cell volume and migration. The present study explored whether azathioprine influences Na(+)/H(+) exchanger activity in DCs. DCs were isolated from murine bone marrow, cytosolic pH (pH(i)) was estimated utilizing 2',7'-bis-(2-carboxyethyl)-5-(and-6)-carboxyfluorescein (BCECF-AM) fluorescence, Na(+)/H(+) exchanger activity from the Na(+)-dependent realkalinization following an ammonium pulse, cell volume from forward scatter in FACS analysis, ROS production from 2',7'-dichlorodihydrofluorescein diacetate (DCFDA) fluorescence, TNFα release utilizing ELISA, and migration utilizing transwell migration assays. Exposure of DCs to lipopolysaccharide (LPS, 1 μg/ml) led to a transient increase of Na(+)/H(+) exchanger activity, an effect paralleled by ROS formation, increased cell volume, TNFα production and stimulated migration. Azathioprine (10 μM) did not significantly alter the Na(+)/H(+) exchanger activity, cell volume and ROS formation prior to LPS exposure but significantly blunted the LPS-induced stimulation of Na(+)/H(+) exchanger activity, ROS formation, cell swelling, TNFα production and cell migration. In conclusion, azathioprine interferes with the activation of dendritic cell Na(+)/H(+) exchanger by bacterial lipopolysaccharides, an effect likely participating in the anti-inflammatory action of the drug. Copyright © 2012 S. Karger AG, Basel.

  15. Effect of magnetic exchange, double exchange, vibronic coupling, and asymmetry on magnetic properties in d2-d3 mixed-valence dimers

    NASA Astrophysics Data System (ADS)

    Yang, Xiaohua; Hu, Haiquan; Chen, Zhida

    The effect of magnetic exchange, double exchange, vibronic coupling, and asymmetry on magnetic properties of d2-d3 systems is discussed. The temperature-dependent magnetic moment was calculated with the semiclassical adiabatic approach. The results show that the vibronic coupling from the out-of-phase breathing vibration on the metal sites (Piepho, Krausz, and Schatz [PKS] model) and the vibronic coupling from the stretching vibration between the metal sites (P model) favor the localization and delocalization of the "extra" electron in mixed-valence dimers, respectively. The magnetic properties are determined by the interplay among magnetic exchange, double exchange, and vibronic coupling. The results obtained by analyzing d2-d3 systems can be generalized to other full delocalized dinuclear mixed valence systems with a unique transferable electron.

  16. Design and Validation of In-Source Atmospheric Pressure Photoionization Hydrogen/Deuterium Exchange Mass Spectrometry with Continuous Feeding of D2O.

    PubMed

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

    2018-01-01

    In this study, continuous in-source hydrogen/deuterium exchange (HDX) atmospheric pressure photoionization (APPI) mass spectrometry (MS) with continuous feeding of D 2 O was developed and validated. D 2 O 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 D 2 O 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. Graphical abstract ᅟ.

  17. Design and Validation of In-Source Atmospheric Pressure Photoionization Hydrogen/Deuterium Exchange Mass Spectrometry with Continuous Feeding of D2O

    NASA Astrophysics Data System (ADS)

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

    2018-01-01

    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.

  18. Gas phase 1H NMR studies and kinetic modeling of dihydrogen isotope equilibration catalyzed by Ru-nanoparticles under normal conditions: dissociative vs. associative exchange.

    PubMed

    Limbach, Hans-Heinrich; Pery, Tal; Rothermel, Niels; Chaudret, Bruno; Gutmann, Torsten; Buntkowsky, Gerd

    2018-04-25

    The equilibration of H2, HD and D2 between the gas phase and surface hydrides of solid organic-ligand-stabilized Ru metal nanoparticles has been studied by gas phase 1H NMR spectroscopy using closed NMR tubes as batch reactors at room temperature and 800 mbar. When two different nanoparticle systems, Ru/PVP (PVP ≡ polyvinylpyrrolidone) and Ru/HDA (HDA ≡ hexadecylamine) were exposed to D2 gas, only the release of HD from the hydride containing surface could be detected in the initial stages of the reaction, but no H2. In the case of Ru/HDA also the reverse experiment was performed where surface deuterated nanoparticles were exposed to H2. In that case, the conversion of H2 into gaseous HD was detected. In order to analyze the experimental kinetic and spectroscopic data, we explored two different mechanisms taking into account potential kinetic and equilibrium H/D isotope effects. Firstly, we explored the dissociative exchange mechanism consisting of dissociative adsorption of dihydrogen, fast hydride surface diffusion and associative desorption of dihydrogen. It is shown that if D2 is the reaction partner, only H2 will be released in the beginning of the reaction, and HD only in later reaction stages. The second mechanism, dubbed here associative exchange consists of the binding of dihydrogen to Ru surface atoms, followed by a H-transfer to or by H-exchange with an adjacent hydride site, and finally of the associative desorption of dihydrogen. In that case, in the exchange with D2, only HD will be released in the beginning of the reaction. Our experimental results are not compatible with the dissociative exchange but can be explained in terms of the associative exchange. Whereas the former will dominate at low temperatures and pressures, the latter will prevail around room temperature and normal pressures where transition metal nanoparticles are generally used as reaction catalysts.

  19. Tunneling chemical reactions D +H2→DH+H and D +DH→D2+H in solid D2-H2 and HD -H2 mixtures: An electron-spin-resonance study

    NASA Astrophysics Data System (ADS)

    Kumada, Takayuki

    2006-03-01

    Tunneling chemical reactions D +H2→DH+H and D +DH→D2+H in solid HD -H2 and D2-H2 mixtures were studied in the temperature range between 4 and 8K. These reactions were initiated by UV photolysis of DI molecules doped in these solids for 30s and followed by measuring the time course of electron-spin-resonance (ESR) intensities of D and H atoms. ESR intensity of D atoms produced by the photolysis decreases but that of H atoms increases with time. Time course of the D and H intensities has the fast and slow processes. The fast process, which finishes within ˜300s after the photolysis, is assigned to the reaction of D atom with one of its nearest-neighboring H2 molecules, D(H2)n(HD)12-n→H(H2)n-1(HD)13-n or D(H2)n(D2)12-n→H(HD )(H2)n-1(D2)12-n for 12⩾n⩾1. Rate constant for the D +H2 reaction between neighboring D atom-H2 molecule pair is determined to be (7.5±0.7)×10-3s-1 in solid HD -H2 and (1.3±0.3)×10-2s-1 in D2-H2 at 4.1K, which is very close to that calculated based on the theory of chemical reaction in gas phase by Hancock et al. [J. Chem. Phys. 91, 3492 (1989)] and Takayanagi and Sato [J. Chem. Phys. 92, 2862 (1990)]. This rate constant was found to be independent of temperature up to 7K within experimental error of ±30%. The slow process is assigned to the reaction of D atom produced in a cage fully surrounded by HD or D2 molecules, D(HD)12 or D(D2)12. This D atom undergoes the D +DH reaction with one of its nearest-neighboring HD molecules in solid HD -H2 or diffuses to the neighbor of H2 molecules to allow the D +H2 reaction in solid HD -H2 and D2-H2. The former is the main channel in solid HD -H2 below 6K where D atoms diffuse very slowly, whereas the latter dominates over the former above 6K. Rate for the reactions in the slow process is independent of temperature below 6K but increases with the increase in temperature above 6K. We found that the increase is due to the increase in hopping rate of D atoms to the neighbor of H2 molecules. Rate

  20. Hydrogen exchange equilibria in thiols.

    PubMed

    Hofstetter, Dustin; Thalmann, Basil; Nauser, Thomas; Koppenol, Willem H

    2012-09-17

    Cysteine, cysteinyl-glycine, glutathione, phenylalanyl-cysteinyl-glycine, and histidyl-cysteinyl-glycine were dissolved in acidic and neutral D(2)O in the presence of the radical generator 2,2'-azobis(2-methylpropionamidine) dihydrochloride and radical mediator compounds (benzyl alcohol and 2-propanol). An exchange of H-atoms by D-atoms took place in these peptides due to intramolecular H-abstraction equilibria. NMR measurements allow one to follow the extent of H-D exchanges and to identify the sites where these exchanges take place. Significant exchanges occur in acidic media in GSH at positions Glu-β and Glu-γ, in Phe-Cys-Gly at positions Phe ortho, Phe-β, Cys-α, Cys-β, and Gly-α, and in His-Cys-Gly at positions His H1, His H2, His β, Cys β, and Gly α. In neutral media, exchanges occur in Cys-Gly at position Cys β and in GSH at position Cys α. Phe-Cys-Gly and His-Cys-Gly were not examined in neutral media. Sites participating in the radical exchange equilibria are highly dependent on structure and pH; the availability of electron density in the form of lone pairs appears to increase the extent of exchange. Interestingly, and unexpectedly, 2D NMR experiments show that GSH rearranges itself in acidic solution: the signals shift, but their patterns do not change. The formation of a thiolactone from Gly and Cys residues matches the changes observed.

  1. Scalable 3D bicontinuous fluid networks: polymer heat exchangers toward artificial organs.

    PubMed

    Roper, Christopher S; Schubert, Randall C; Maloney, Kevin J; Page, David; Ro, Christopher J; Yang, Sophia S; Jacobsen, Alan J

    2015-04-17

    A scalable method for fabricating architected materials well-suited for heat and mass exchange is presented. These materials exhibit unprecedented combinations of small hydraulic diameters (13.0-0.09 mm) and large hydraulic-diameter-to-thickness ratios (5.0-30,100). This process expands the range of material architectures achievable starting from photopolymer waveguide lattices or additive manufacturing. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Hydrogen Exchange and Mass Spectrometry: A Historical Perspective

    PubMed Central

    Englander, S. Walter

    2012-01-01

    Protein molecules naturally emit streams of information-rich signals in the language of hydrogen exchange concerning the intimate details of their stability, dynamics, function, changes therein, and effects thereon, all resolved to the level of their individual amino acids. The effort to measure protein hydrogen exchange behavior, understand the underlying chemistry and structural physics of hydrogen exchange processes, and use this information to learn about protein properties and function has continued for 50 years. Recent work uses mass spectrometric analysis together with an earlier proteolytic fragmentation method to extend the hydrogen exchange capability to large biologically interesting proteins. This article briefly reviews the advances that have led us to this point and the understanding that has so far been achieved. PMID:16876429

  3. Isotopic exchange during derivatization of platelet activating factor for gas chromatography-mass spectrometry

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

    Haroldsen, P.E.; Gaskell, S.J.; Weintraub, S.T.

    1991-04-01

    One approach to the quantitative analysis of platelet activating factor (PAF, 1-O-alkyl-2-acetyl-sn-glycerol-3-phosphocholine; also referred to as AGEPC, alkyl glyceryl ether phosphocholine) is hydrolytic removal of the phosphocholine group and conversion to an electron-capturing derivative for gas chromatography-negative ion mass spectrometry. (2H3)Acetyl-AGEPC has been commonly employed as an internal standard. When 1-hexadecyl-2-(2H3)acetyl glycerol (obtained by enzymatic hydrolysis of (2H3)-C16:0 AGEPC) is treated with pentafluorobenzoyl chloride at 120 degrees C, the resulting 3-pentafluorobenzoate derivative shows extensive loss of the deuterium label. This exchange is evidently acid-catalyzed since derivatization of 1-hexadecyl-2-acetyl glycerol under the same conditions in the presence of a trace ofmore » 2HCl results in the incorporation of up to three deuterium atoms. Isotope exchange can be avoided if the reaction is carried out at low temperature in the presence of base. Direct derivatization of (2H3)-C16:0 AGEPC by treatment with pentafluorobenzoyl chloride or heptafluorobutyric anhydride also results in loss of the deuterium label. The use of (13C2)-C16:0 AGEPC as an internal standard is recommended for rigorous quantitative analysis.« less

  4. Transport of H2S and HS− across the human red blood cell membrane: rapid H2S diffusion and AE1-mediated Cl−/HS− exchange

    PubMed Central

    2013-01-01

    The rates of H2S and HS− transport across the human erythrocyte membrane were estimated by measuring rates of dissipation of pH gradients in media containing 250 μM H2S/HS−. Net acid efflux is caused by H2S/HS− acting analogously to CO2/HCO3− in the Jacobs-Stewart cycle. The steps are as follows: 1) H2S efflux through the lipid bilayer and/or a gas channel, 2) extracellular H2S deprotonation, 3) HS− influx in exchange for Cl−, catalyzed by the anion exchange protein AE1, and 4) intracellular HS− protonation. Net acid transport by the Cl−/HS−/H2S cycle is more efficient than by the Cl−/HCO3−/CO2 cycle because of the rapid H2S-HS− interconversion in cells and medium. The rates of acid transport were analyzed by solving the mass flow equations for the cycle to produce estimates of the HS− and H2S transport rates. The data indicate that HS− is a very good substrate for AE1; the Cl−/HS− exchange rate is about one-third as rapid as Cl−/HCO3− exchange. The H2S permeability coefficient must also be high (>10−2 cm/s, half time <0.003 s) to account for the pH equilibration data. The results imply that H2S and HS− enter erythrocytes very rapidly in the microcirculation of H2S-producing tissues, thereby acting as a sink for H2S and lowering the local extracellular concentration, and the fact that HS− is a substrate for a Cl−/HCO3− exchanger indicates that some effects of exogenous H2S/HS− may not result from a regulatory role of H2S but, rather, from net acid flux by H2S and HS− transport in a Jacobs-Stewart cycle. PMID:23864610

  5. Transport of H2S and HS(-) across the human red blood cell membrane: rapid H2S diffusion and AE1-mediated Cl(-)/HS(-) exchange.

    PubMed

    Jennings, Michael L

    2013-11-01

    The rates of H2S and HS(-) transport across the human erythrocyte membrane were estimated by measuring rates of dissipation of pH gradients in media containing 250 μM H2S/HS(-). Net acid efflux is caused by H2S/HS(-) acting analogously to CO2/HCO3(-) in the Jacobs-Stewart cycle. The steps are as follows: 1) H2S efflux through the lipid bilayer and/or a gas channel, 2) extracellular H2S deprotonation, 3) HS(-) influx in exchange for Cl(-), catalyzed by the anion exchange protein AE1, and 4) intracellular HS(-) protonation. Net acid transport by the Cl(-)/HS(-)/H2S cycle is more efficient than by the Cl(-)/HCO3(-)/CO2 cycle because of the rapid H2S-HS(-) interconversion in cells and medium. The rates of acid transport were analyzed by solving the mass flow equations for the cycle to produce estimates of the HS(-) and H2S transport rates. The data indicate that HS(-) is a very good substrate for AE1; the Cl(-)/HS(-) exchange rate is about one-third as rapid as Cl(-)/HCO3(-) exchange. The H2S permeability coefficient must also be high (>10(-2) cm/s, half time <0.003 s) to account for the pH equilibration data. The results imply that H2S and HS(-) enter erythrocytes very rapidly in the microcirculation of H2S-producing tissues, thereby acting as a sink for H2S and lowering the local extracellular concentration, and the fact that HS(-) is a substrate for a Cl(-)/HCO3(-) exchanger indicates that some effects of exogenous H2S/HS(-) may not result from a regulatory role of H2S but, rather, from net acid flux by H2S and HS(-) transport in a Jacobs-Stewart cycle.

  6. The atom-molecule reaction D plus H2 yields HD plus H studied by molecular beams

    NASA Technical Reports Server (NTRS)

    Geddes, J.; Krause, H. F.; Fite, W. L.

    1972-01-01

    Collisions between deuterium atoms and hydrogen molecules were studied in a modulated crossed beam experiment. The relative signal intensity and the signal phase for the product HD from reactive collisions permitted determination of both the angular distribution and HD mean velocity as a function of angle. From these a relative differential reactive scattering cross section in center-of-mass coordinates was deduced. The experiment indicates that reactively formed HD which has little or no internal excitation departs from the collision anisotropically, with maximum amplitude 180 deg from the direction of the incident D beam in center-of-mass coordinates, which shows that the D-H-H reacting configuration is short-lived compared to its rotation time. Non reactive scattering of D by H2 was used to assign absolute values to the differential reactive scattering cross sections.

  7. Hydromechanics and heat and mass exchange in weightlessness (Russian book): Table of contents

    NASA Technical Reports Server (NTRS)

    Avduyevskiy, V. S.; Poleshayev, V. I.

    1983-01-01

    The table of contents is given for a book on hydromechanics and heat and mass exchange in weightlessness. The book covers such subjects as hydromechanics, convection and heat and mass exchange, and technological experiments and complicated systems.

  8. Kinetics of hydrogen/deuterium exchanges in cometary ices

    NASA Astrophysics Data System (ADS)

    Faure, Mathilde; Quirico, Eric; Faure, Alexandre; Schmitt, Bernard; Theulé, Patrice; Marboeuf, Ulysse

    2015-11-01

    The D/H composition of volatile molecules composing cometary ices brings key constraints on the origin of comets, on the extent of their presolar heritage, as well as on the origin of atmospheres and hydrospheres of terrestrial planets. Nevertheless, the D/H composition may have been modified to various extents in the nucleus when a comet approaches the Sun and experiences deep physical and chemical modifications in its subsurface. We question here the evolution of the D/H ratio of organic species by proton exchanges with water ice. We experimentally studied the kinetics of D/H exchanges on the ice mixtures H2O:CD3OD, H2O:CD3ND2 and D2O:HCN. Our results show that fast exchanges occur on the -OH and -NH2 chemical groups, which are processed through hydrogen bonds exchanges with water and by the molecular mobility triggered by structural changes, such as glass transition or crystallization. D/H exchanges kinetic is best described by a second-order kinetic law with activation energies of 4300 ± 900 K and 3300 ± 100 K for H2O:CD3OD and H2O:CD3ND2 ice mixtures, respectively. The corresponding pre-exponential factors ln(A(s-1)) are 25 ± 7 and 20 ± 1, respectively. No exchange was observed in the case of HCN trapped in D2O ice. These results strongly suggest that upon thermal heating (1) -OH and -NH2 chemical groups of any organic molecules loose their primordial D/H composition and equilibrate with water ice, (2) HCN does not experience proton transfer and keeps a primordial D/H composition and (3) C-H chemical groups are not isotopically modified.

  9. Application of linear pH gradients for the modeling of ion exchange chromatography: Separation of monoclonal antibody monomer from aggregates.

    PubMed

    Kluters, Simon; Wittkopp, Felix; Jöhnck, Matthias; Frech, Christian

    2016-02-01

    The mobile phase pH is a key parameter of every ion exchange chromatography process. However, mechanistic insights into the pH influence on the ion exchange chromatography equilibrium are rare. This work describes a mechanistic model capturing salt and pH influence in ion exchange chromatography. The pH dependence of the characteristic protein charge and the equilibrium constant is introduced to the steric mass action model based on a protein net charge model considering the number of amino acids interacting with the stationary phase. This allows the description of the adsorption equilibrium of the chromatographed proteins as a function of pH. The model parameters were determined for a monoclonal antibody monomer, dimer, and a higher aggregated species based on a manageable set of pH gradient experiments. Without further modification of the model parameters the transfer to salt gradient elution at fixed pH is demonstrated. A lumped rate model was used to predict the separation of the monoclonal antibody monomer/aggregate mixture in pH gradient elution and for a pH step elution procedure-also at increased protein loadings up to 48 g/L packed resin. The presented model combines both salt and pH influence and may be useful for the development and deeper understanding of an ion exchange chromatography separation. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. NMR resonance splitting of urea in stretched hydrogels: proton exchange and (1)H/(2)H isotopologues.

    PubMed

    Kuchel, Philip W; Naumann, Christoph; Chapman, Bogdan E; Shishmarev, Dmitry; Håkansson, Pär; Bacskay, George; Hush, Noel S

    2014-10-01

    Urea at ∼12 M in concentrated gelatin gel, that was stretched, gave (1)H and (2)H NMR spectral splitting patterns that varied in a predictable way with changes in the relative proportions of (1)H2O and (2)H2O in the medium. This required consideration of the combinatorics of the two amide groups in urea that have a total of four protonation/deuteration sites giving rise to 16 different isotopologues, if all the atoms were separately identifiable. The rate constant that characterized the exchange of the protons with water was estimated by back-transformation analysis of 2D-EXSY spectra. There was no (1)H NMR spectral evidence that the chiral gelatin medium had caused in-equivalence in the protons bonded to each amide nitrogen atom. The spectral splitting patterns in (1)H and (2)H NMR spectra were accounted for by intra-molecular scalar and dipolar interactions, and quadrupolar interactions with the electric field gradients of the gelatin matrix, respectively. Copyright © 2014 Elsevier Inc. All rights reserved.

  11. An investigation of one- versus two-dimensional semiclassical transition state theory for H atom abstraction and exchange reactions.

    PubMed

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

    2016-02-28

    We investigate which terms in Reduced-Dimensionality Semiclassical Transition State Theory (RD SCTST) contribute most significantly in rate constant calculations of hydrogen extraction and exchange reactions of hydrocarbons. We also investigate the importance of deep tunneling corrections to the theory. In addition, we introduce a novel formulation of the theory in Jacobi coordinates. For the reactions of H atoms with methane, ethane, and cyclopropane, we find that a one-dimensional (1-D) version of the theory without deep tunneling corrections compares well with 2-D SCTST results and accurate quantum scattering results. For the "heavy-light-heavy" H atom exchange reaction between CH3 and CH4, deep tunneling corrections are needed to yield 1-D results that compare well with 2-D results. The finding that accurate rate constants can be obtained from derivatives of the potential along only one dimension further validates RD SCTST as a computationally efficient yet accurate rate constant theory.

  12. Characterization of D-maltose as a T2 -exchange contrast agent for dynamic contrast-enhanced MRI.

    PubMed

    Goldenberg, Joshua M; Pagel, Mark D; Cárdenas-Rodríguez, Julio

    2018-09-01

    We sought to investigate the potential of D-maltose, D-sorbitol, and D-mannitol as T 2 exchange magnetic resonance imaging (MRI) contrast agents. We also sought to compare the in vivo pharmacokinetics of D-maltose with D-glucose with dynamic contrast enhancement (DCE) MRI. T 1 and T 2 relaxation time constants of the saccharides were measured using eight pH values and nine concentrations. The effect of echo spacing in a multiecho acquisition sequence used for the T 2 measurement was evaluated for all samples. Finally, performances of D-maltose and D-glucose during T 2 -weighted DCE-MRI were compared in vivo. Estimated T 2 relaxivities (r 2 ) of D-glucose and D-maltose were highly and nonlinearly dependent on pH and echo spacing, reaching their maximum at pH = 7.0 (∼0.08 mM -1 s -1 ). The r 2 values of D-sorbitol and D-mannitol were estimated to be ∼0.02 mM -1 s -1 and were invariant to pH and echo spacing for pH ≤7.0. The change in T 2 in tumor and muscle tissues remained constant after administration of D-maltose, whereas the change in T 2 decreased in tumor and muscle after administration of D-glucose. Therefore, D-maltose has a longer time window for T 2 -weighted DCE-MRI in tumors. We have demonstrated that D-maltose can be used as a T 2 exchange MRI contrast agent. The larger, sustained T 2 -weighted contrast from D-maltose relative to D-glucose has practical advantages for tumor diagnoses during T 2 -weighted DCE-MRI. Magn Reson Med 80:1158-1164, 2018. © 2018 International Society for Magnetic Resonance in Medicine. © 2018 International Society for Magnetic Resonance in Medicine.

  13. A new route of oxygen isotope exchange in the solid phase: demonstration in CuSO4.5H2O.

    PubMed

    Danon, Albert; Saig, Avraham; Finkelstein, Yacov; Koresh, Jacob E

    2005-11-10

    Temperature-programmed desorption mass spectrometry (TPD-MS) measurements on [(18)O]water-enriched copper sulfate pentahydrate (CuSO(4).5H(2)(18)O) reveal an unambiguous occurrence of efficient oxygen isotope exchange between the water of crystallization and the sulfate in its CuSO(4) solid phase. To the best of our knowledge, the occurrence of such an exchange was never observed in a solid phase. The exchange process was observed during the stepwise dehydration (50-300 degrees C) of the compound. Specifically, the exchange promptly occurs somewhere between 160 and 250 degrees C; however, the exact temperature could not be resolved conclusively. It is shown that only the fifth, sulfate-associated, anionic H(2)O molecule participates in the exchange process and that the exchange seems to occur in a preferable fashion with, at the most, one oxygen atom in SO(4). Such an exchange, occurring below 250 degrees C, questions the common conviction of unfeasible oxygen exchange under geothermic conditions. This new oxygen exchange phenomenon is not exclusive to copper sulfate but is unambiguously observed also in other sulfate- and nitrate-containing minerals.

  14. Advantages of isotopic depletion of proteins for hydrogen/deuterium exchange experiments monitored by mass spectrometry.

    PubMed

    Bou-Assaf, George M; Chamoun, Jean E; Emmett, Mark R; Fajer, Piotr G; Marshall, Alan G

    2010-04-15

    Solution-phase hydrogen/deuterium exchange (HDX) monitored by mass spectrometry is an excellent tool to study protein-protein interactions and conformational changes in biological systems, especially when traditional methods such as X-ray crystallography or nuclear magnetic resonance are not feasible. Peak overlap among the dozens of proteolytic fragments (including those from autolysis of the protease) can be severe, due to high protein molecular weight(s) and the broad isotopic distributions due to multiple deuterations of many peptides. In addition, different subunits of a protein complex can yield isomeric proteolytic fragments. Here, we show that depletion of (13)C and/or (15)N for one or more protein subunits of a complex can greatly simplify the mass spectra, increase the signal-to-noise ratio of the depleted fragment ions, and remove ambiguity in assignment of the m/z values to the correct isomeric peptides. Specifically, it becomes possible to monitor the exchange progress for two isobaric fragments originating from two or more different subunits within the complex, without having to resort to tandem mass spectrometry techniques that can lead to deuterium scrambling in the gas phase. Finally, because the isotopic distribution for a small to medium-size peptide is essentially just the monoisotopic species ((12)C(c)(1)H(h)(14)N(n)(16)O(o)(32)S(s)), it is not necessary to deconvolve the natural abundance distribution for each partially deuterated peptide during HDX data reduction.

  15. Regulation of intracellular pH in LLC-PK1 cells by Na+/H+ exchange.

    PubMed

    Montrose, M H; Murer, H

    1986-01-01

    Suspensions of LLC-PK1 cells (a continuous epitheliod cell line with renal characteristics) are examined for mechanisms of intracellular pH regulation using the fluorescent probe BCECF. Initial experiments determine suitable calibration procedures for use of the BCECF fluorescent signal. They also determine that the cell suspension contains cells which (after 4 hr in suspension) have Na+ and K+ gradients comparable to those of cells in monolayer culture. The steady-state intracellular pH (7.05 +/- 0.01, n = 5) of cells which have recovered in (pH 7.4) Na+-containing medium is not affected over several minutes by addition of 100 microM amiloride or removal of extracellular Na+ (Na+o less than 1 mM). In contrast, when the cells recover from an acid load (caused by NH4 preincubation and removal), the recovery is largely Na+ dependent and is sensitive to 100 microM amiloride. These results suggest that with resting pH near neutrality, both Na+o/H+i and Na+i/H+o exchange reactions are functionally inactive (compared to cellular buffering capacity). In contrast, Na+o/H+i exchange is activated by an increased cellular acid load. This activation may be observed directly either as a stimulation of net H+ efflux or net Na+ influx with decreasing intracellular pH. The extrapolation of this latter data suggests a "set point" of Na+/H+ exchange of approximately pH 7.0, consistent with the observed resting intracellular pH of approximately 7.05.

  16. Isotopic exchange of carbon-bound hydrogen over geologic timescales

    NASA Astrophysics Data System (ADS)

    Sessions, Alex L.; Sylva, Sean P.; Summons, Roger E.; Hayes, John M.

    2004-04-01

    The increasing popularity of compound-specific hydrogen isotope (D/H) analyses for investigating sedimentary organic matter raises numerous questions about the exchange of carbon-bound hydrogen over geologic timescales. Important questions include the rates of isotopic exchange, methods for diagnosing exchange in ancient samples, and the isotopic consequences of that exchange. This article provides a review of relevant literature data along with new data from several pilot studies to investigate such issues. Published experimental estimates of exchange rates between organic hydrogen and water indicate that at warm temperatures (50-100°C) exchange likely occurs on timescales of 104 to 108 yr. Incubation experiments using organic compounds and D-enriched water, combined with compound-specific D/H analyses, provide a new and highly sensitive method for measuring exchange at low temperatures. Comparison of δD values for isoprenoid and n-alkyl carbon skeletons in sedimentary organic matter provides no evidence for exchange in young (<1 Ma), cool sediments, but strong evidence for exchange in ancient (>350 Ma) rocks. Specific rates of exchange are probably influenced by the nature and abundance of organic matter, pore-water chemistry, the presence of catalytic mineral surfaces, and perhaps even enzymatic activity. Estimates of equilibrium fractionation factors between organic H and water indicate that typical lipids will be depleted in D relative to water by ∼75 to 140‰ at equilibrium (30°C). Thus large differences in δD between organic molecules and water cannot be unambiguously interpreted as evidence against hydrogen exchange. A better approach may be to use changes in stereochemistry as a proxy for hydrogen exchange. For example, estimated rates of H exchange in pristane are similar to predicted rates for stereochemical inversion in steranes and hopanes. The isotopic consequences of this exchange remain in question. Incubations of cholestene with D2O indicate

  17. Back-exchange: a novel approach to quantifying oxygen diffusion and surface exchange in ambient atmospheres.

    PubMed

    Cooper, Samuel J; Niania, Mathew; Hoffmann, Franca; Kilner, John A

    2017-05-17

    A novel two-step Isotopic Exchange (IE) technique has been developed to investigate the influence of oxygen containing components of ambient air (such as H 2 O and CO 2 ) on the effective surface exchange coefficient (k*) of a common mixed ionic electronic conductor material. The two step 'back-exchange' technique was used to introduce a tracer diffusion profile, which was subsequently measured using Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS). The isotopic fraction of oxygen in a dense sample as a function of distance from the surface, before and after the second exchange step, could then be used to determine the surface exchange coefficient in each atmosphere. A new analytical solution was found to the diffusion equation in a semi-infinite domain with a variable surface exchange boundary, for the special case where D* and k* are constant for all exchange steps. This solution validated the results of a numerical, Crank-Nicolson type finite-difference simulation, which was used to extract the parameters from the experimental data. When modelling electrodes, D* and k* are important input parameters, which significantly impact performance. In this study La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ (LSCF6428) was investigated and it was found that the rate of exchange was increased by around 250% in ambient air compared to high purity oxygen at the same pO 2 . The three experiments performed in this study were used to validate the back-exchange approach and show its utility.

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

    PubMed

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

    2017-02-05

    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.

  19. H3PO4 imbibed polyacrylamide-graft-chitosan frameworks for high-temperature proton exchange membranes

    NASA Astrophysics Data System (ADS)

    Yuan, Shuangshuang; Tang, Qunwei; He, Benlin; Chen, Haiyan; Li, Qinghua; Ma, Chunqing; Jin, Suyue; Liu, Zhichao

    2014-03-01

    Proton exchange membrane (PEM), transferring protons from anode to cathode, is a key component in a PEM fuel cell. In the current work, a new class of PEMs are synthesized benefiting from the imbibition behavior of three-dimensional (3D) polyacrylamide-graft-chitosan (PAAm-graft-chitosan) frameworks to H3PO4 aqueous solution. Interconnected 3D framework of PAAm-graft-chitosan provides tremendous space for holding proton-conducting H3PO4. The highest anhydrous proton conductivity of 0.13 S cm-1 at 165 °C is obtained. A fuel cell using a thick membrane as a PEM showed a peak power density of 405 mW cm-2 with O2 and H2 as the oxidant and fuel, respectively. Results indicate that the interconnected 3D framework provides superhighway for proton conduction. The valued merits on anhydrous proton conductivity, huge H3PO4 loading, and easy synthesis promise the new membranes to be good alternatives as high-temperature PEMs.

  20. Dynamical Effects on the Escape of H and D: Martian Water Reservoirs

    NASA Technical Reports Server (NTRS)

    Hartle, Richard E.; Einaudi, Franco (Technical Monitor)

    2002-01-01

    The evolution of water on Mars is dependent on the loss rates of H and D from its atmosphere, where the dominant loss mechanism for these constituents is Jeans escape. Throughout time, preferential escape of H over D has produced a deuterium rich atmosphere with a D/H ratio 5.2 times that of terrestrial water. Motion in the atmosphere of Mars is shown to change the Jeans escape rates of H and D in two important ways: (1) Atmospheric wind and rotation at the exobase increase the escape fluxes of H and D above the corresponding Jeans fluxes. (2) The percentage increase in escape flux due to motion is greatest for D. Recently, several models have been used to estimate the magnitudes of current and ancient crustal water reservoirs on Mars that freely exchange with its atmosphere. Differences in the reservoir sizes are influenced by differences in the composition at the exobase, thermal history of the atmosphere and the D/H ratio of earlier epochs as inferred from meteorites. When motion enhanced Jeans escape is applied to each of these models, it is shown in every case that factors (1) and (2) above lead to current and ancient crustal water reservoirs that are larger than those obtained without motion.

  1. Formation Location of Enceladus and Comets from D/H Measurements

    NASA Astrophysics Data System (ADS)

    Petit, J.-M.; Mousis, O.; Kavelaars, J. J.

    2012-04-01

    The building blocks of Enceladus could have formed in Saturn's subnebula, thus bearing no connection with planetesimals condensed in Saturn's feeding zone. We have shown that the D/H ratio in H2O in Saturn's sub-nebula reaches the protosolar value in about 1,000 yr, well before ice forms again at Enceladus' location (several 10,000 yr). However, the D/H ratio measured by the Ion and Neutral Mass Spectrometer aboard the Cassini spacecraft in Saturn's satellite Enceladus is remarkably similar to the values observed in the nearly-isotropic comets. Hence the building blocks of Enceladus formed in the solar nebula. Nearly-isotropic comets originate from the Oort cloud. Delivery of material into the Oort cloud reservoir is controlled by Uranus-Neptune scattering. The D/H ratio in comets is therefore representative of that of the location of Uranus-Neptune at the time of formation of the Oort cloud. Since D/H strongly depends on heliocentric distance in the solar nebula, the similarity of D/H ratios links the primordial source region of the nearly-isotropic comets with the formation location of Enceladus. This precludes these comets from having formed beyond ~15 AU from the Sun. which in turn implies that Uranus and Neptune were originally closer to Saturn's location during the feeding of the Oort cloud, likely in the 12-15 AU region. Such a configuration is consistent with the Nice model of evolution of the outer Solar System. 103P/Hartley 2 being D-poor compared to these bodies questions the current models. A fraction of ecliptic comets could have formed at closer distances from the Sun than assumed here and has been ejected outward and then display a low R/H ratio. However, they would only represent a small fraction of all ecliptic comets. The high level of deuteration predicted in ecliptic comets from the description of the isotopic exchange between H2 and H2O in the gas phase of the disk is based on classical models of the solar nebula (the alpha-turbulent model) in

  2. Total body skeletal muscle mass: estimation by creatine (methyl-d3) dilution in humans

    PubMed Central

    Walker, Ann C.; O'Connor-Semmes, Robin L.; Leonard, Michael S.; Miller, Ram R.; Stimpson, Stephen A.; Turner, Scott M.; Ravussin, Eric; Cefalu, William T.; Hellerstein, Marc K.; Evans, William J.

    2014-01-01

    Current methods for clinical estimation of total body skeletal muscle mass have significant limitations. We tested the hypothesis that creatine (methyl-d3) dilution (D3-creatine) measured by enrichment of urine D3-creatinine reveals total body creatine pool size, providing an accurate estimate of total body skeletal muscle mass. Healthy subjects with different muscle masses [n = 35: 20 men (19–30 yr, 70–84 yr), 15 postmenopausal women (51–62 yr, 70–84 yr)] were housed for 5 days. Optimal tracer dose was explored with single oral doses of 30, 60, or 100 mg D3-creatine given on day 1. Serial plasma samples were collected for D3-creatine pharmacokinetics. All urine was collected through day 5. Creatine and creatinine (deuterated and unlabeled) were measured by liquid chromatography mass spectrometry. Total body creatine pool size and muscle mass were calculated from D3-creatinine enrichment in urine. Muscle mass was also measured by magnetic resonance imaging (MRI), dual-energy x-ray absorptiometry (DXA), and traditional 24-h urine creatinine. D3-creatine was rapidly absorbed and cleared with variable urinary excretion. Isotopic steady-state of D3-creatinine enrichment in the urine was achieved by 30.7 ± 11.2 h. Mean steady-state enrichment in urine provided muscle mass estimates that correlated well with MRI estimates for all subjects (r = 0.868, P < 0.0001), with less bias compared with lean body mass assessment by DXA, which overestimated muscle mass compared with MRI. The dilution of an oral D3-creatine dose determined by urine D3-creatinine enrichment provides an estimate of total body muscle mass strongly correlated with estimates from serial MRI with less bias than total lean body mass assessment by DXA. PMID:24764133

  3. Total body skeletal muscle mass: estimation by creatine (methyl-d3) dilution in humans.

    PubMed

    Clark, Richard V; Walker, Ann C; O'Connor-Semmes, Robin L; Leonard, Michael S; Miller, Ram R; Stimpson, Stephen A; Turner, Scott M; Ravussin, Eric; Cefalu, William T; Hellerstein, Marc K; Evans, William J

    2014-06-15

    Current methods for clinical estimation of total body skeletal muscle mass have significant limitations. We tested the hypothesis that creatine (methyl-d3) dilution (D3-creatine) measured by enrichment of urine D3-creatinine reveals total body creatine pool size, providing an accurate estimate of total body skeletal muscle mass. Healthy subjects with different muscle masses [n = 35: 20 men (19-30 yr, 70-84 yr), 15 postmenopausal women (51-62 yr, 70-84 yr)] were housed for 5 days. Optimal tracer dose was explored with single oral doses of 30, 60, or 100 mg D3-creatine given on day 1. Serial plasma samples were collected for D3-creatine pharmacokinetics. All urine was collected through day 5. Creatine and creatinine (deuterated and unlabeled) were measured by liquid chromatography mass spectrometry. Total body creatine pool size and muscle mass were calculated from D3-creatinine enrichment in urine. Muscle mass was also measured by magnetic resonance imaging (MRI), dual-energy x-ray absorptiometry (DXA), and traditional 24-h urine creatinine. D3-creatine was rapidly absorbed and cleared with variable urinary excretion. Isotopic steady-state of D3-creatinine enrichment in the urine was achieved by 30.7 ± 11.2 h. Mean steady-state enrichment in urine provided muscle mass estimates that correlated well with MRI estimates for all subjects (r = 0.868, P < 0.0001), with less bias compared with lean body mass assessment by DXA, which overestimated muscle mass compared with MRI. The dilution of an oral D3-creatine dose determined by urine D3-creatinine enrichment provides an estimate of total body muscle mass strongly correlated with estimates from serial MRI with less bias than total lean body mass assessment by DXA. Copyright © 2014 the American Physiological Society.

  4. Implications for Extraterrestrial Hydrocarbon Chemistry: Analysis of Ethylene (C2H4) and D4-Ethylene (C2D4) Ices Exposed to Ionizing Radiation via Combined Infrared Spectroscopy and Reflectron Time-of-flight Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Abplanalp, Matthew J.; Kaiser, Ralf I.

    2017-02-01

    The processing of the hydrocarbon ice, ethylene (C2H4/C2D4), via energetic electrons, thus simulating the processes in the track of galactic cosmic-ray particles, was carried out in an ultrahigh vacuum apparatus. The chemical evolution of the ices was monitored online and in situ utilizing Fourier transform infrared spectroscopy (FTIR) and during temperature programmed desorption, via a quadrupole mass spectrometer utilizing electron impact ionization (EI-QMS) and a reflectron time-of-flight mass spectrometer utilizing a photoionization source (PI-ReTOF-MS). Several previous in situ studies of ethylene ice irradiation using FTIR were substantiated with the detection of six products: [CH4 (CD4)], acetylene [C2H2 (C2D2)], the ethyl radical [C2H5 (C2D5)], ethane [C2H6 (C2D6)], 1-butene [C4H8 (C4D8)], and n-butane [C4H10 (C4D10)]. Contrary to previous gas phase studies, the PI-ReTOF-MS detected several groups of hydrocarbon with varying degrees of saturation: C n H2n+2 (n = 4-10), C n H2n (n = 2-12, 14, 16), C n H2n-2 (n = 3-12, 14, 16), C n H2n-4 (n = 4-12, 14, 16), C n H2n-6 (n = 4-10, 12), C n H2n-8 (n = 6-10), and C n H2n-10 (n = 6-10). Multiple laboratory studies have shown the facile production of ethylene from methane, which is a known ice constituent in the interstellar medium. Various astrophysically interesting molecules can be associated with the groups detected here, such as allene/methylacetylene (C3H4) or 1, 3-butadiene (C4H6) and its isomers, which have been shown to lead to polycyclic aromatic hydrocarbons. Finally, several hydrocarbon groups detected here are unique to ethylene ice versus ethane ice and may provide understanding of how complex hydrocarbons form in astrophysical environments.

  5. The Area between Exchange Curves as a Measure of Conformational Differences in Hydrogen-Deuterium Exchange Mass Spectrometry Studies

    PubMed Central

    Mazur, Sharlyn J.; Weber, Daniel P.

    2018-01-01

    Hydrogen-deuterium exchange mass spectrometry (HDX-MS) provides information about protein conformational mobility under native conditions. The area between exchange curves, Abec, 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, Abec 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. PMID:28236290

  6. Restoration of normal pH triggers ischemia-reperfusion injury in lung by Na+/H+ exchange activation.

    PubMed

    Moore, T M; Khimenko, P L; Taylor, A E

    1995-10-01

    The effects of acidotic extracellular pH and Na+/H+ exchange inhibition on ischemia-reperfusion (I/R)-induced microvascular injury were studied in the isolated, buffer-perfused rat lung. When lungs were subjected to 45 min of ischemia followed by 30 min of reperfusion, the capillary filtration coefficient (Kfc) increased significantly, resulting in a change in Kfc (delta Kfc) of 0.360 +/- 0.09 ml.min-1.cmH2O-1.100 g-1. Addition of hydrochloric acid to the perfusate before ischemia at a concentration sufficient to reduce perfusate pH from 7.38 +/- 0.03 to 7.09 +/- 0.04 completely prevented the increase in Kfc associated with I/R (delta Kfc = 0.014 +/- 0.034 ml.min-1.cmH2O-1.100 g-1). Addition of a Na+/H+ exchange inhibitor, 5-(N,N-dimethyl)-amiloride, to the perfusate either before ischemia or at reperfusion also prevented the I/R-induced permeability increase (delta Kfc = 0.01 +/- 0.02 and -0.001 +/- 0.02 ml.min-1.cmH2O-1.100 g-1, respectively). We conclude that restoration of flow at physiological pH to the postischemic lung activates the Na+/H+ exchange system, which may represent the "triggering mechanism" responsible for initiating reperfusion-induced microvascular injury.

  7. Cation Exchange in Dynamic 3D Porous Magnets: Improvement of the Physical Properties.

    PubMed

    Grancha, Thais; Acosta, Alvaro; Cano, Joan; Ferrando-Soria, Jesús; Seoane, Beatriz; Gascon, Jorge; Pasán, Jorge; Armentano, Donatella; Pardo, Emilio

    2015-11-16

    We report two novel three-dimensional porous coordination polymers (PCPs) of formulas Li4{Mn4[Cu2(Me3mpba)2]3}·68H2O (2) and K4{Mn4[Cu2(Me3mpba)2]3}·69H2O (3) obtained-via alkali cation exchange in a single-crystal to single-crystal process-from the earlier reported anionic manganese(II)-copper(II) PCP of formula Na4{Mn4[Cu2(Me3mpba)2]3}·60H2O (1) [Me3mpba(4-) = N,N'-2,4,6-trimethyl-1,3-phenylenebis(oxamate)]. This postsynthetic process succeeds where the direct synthesis in solution from the corresponding building blocks fails and affords significantly more robust PCPs with enhanced magnetic properties [long-range 3D magnetic ordering temperatures for the dehydrated phases (1'-3') of 2.0 (1'), 12.0 (2'), and 20.0 K (3')]. Changes in the adsorptive properties upon postsynthetic exchange suggest that the nature, electrostatic properties, mobility, and location of the cations within the framework are crucial for the enhanced structural stability. Overall, these results further confirm the potential of postsynthetic methods (including cation exchange) to obtain PCPs with novel or enhanced physical properties while maintaining unaltered their open-framework structures.

  8. The NIH 3D Print Exchange: A Public Resource for Bioscientific and Biomedical 3D Prints.

    PubMed

    Coakley, Meghan F; Hurt, Darrell E; Weber, Nick; Mtingwa, Makazi; Fincher, Erin C; Alekseyev, Vsevelod; Chen, David T; Yun, Alvin; Gizaw, Metasebia; Swan, Jeremy; Yoo, Terry S; Huyen, Yentram

    2014-09-01

    The National Institutes of Health (NIH) has launched the NIH 3D Print Exchange, an online portal for discovering and creating bioscientifically relevant 3D models suitable for 3D printing, to provide both researchers and educators with a trusted source to discover accurate and informative models. There are a number of online resources for 3D prints, but there is a paucity of scientific models, and the expertise required to generate and validate such models remains a barrier. The NIH 3D Print Exchange fills this gap by providing novel, web-based tools that empower users with the ability to create ready-to-print 3D files from molecular structure data, microscopy image stacks, and computed tomography scan data. The NIH 3D Print Exchange facilitates open data sharing in a community-driven environment, and also includes various interactive features, as well as information and tutorials on 3D modeling software. As the first government-sponsored website dedicated to 3D printing, the NIH 3D Print Exchange is an important step forward to bringing 3D printing to the mainstream for scientific research and education.

  9. Tunneling chemical reactions D+H{sub 2}{yields}DH+H and D+DH{yields}D{sub 2}+H in solid D{sub 2}-H{sub 2} and HD-H{sub 2} mixtures: An electron-spin-resonance study

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

    Kumada, Takayuki

    2006-03-07

    Tunneling chemical reactions D+H{sub 2}{yields}DH+H and D+DH{yields}D{sub 2}+H in solid HD-H{sub 2} and D{sub 2}-H{sub 2} mixtures were studied in the temperature range between 4 and 8 K. These reactions were initiated by UV photolysis of DI molecules doped in these solids for 30 s and followed by measuring the time course of electron-spin-resonance (ESR) intensities of D and H atoms. ESR intensity of D atoms produced by the photolysis decreases but that of H atoms increases with time. Time course of the D and H intensities has the fast and slow processes. The fast process, which finishes within {approx}300more » s after the photolysis, is assigned to the reaction of D atom with one of its nearest-neighboring H{sub 2} molecules, D(H{sub 2}){sub n}(HD){sub 12-n}{yields}H(H{sub 2}){sub n-1}(HD){sub 13-n} or D(H{sub 2}){sub n}(D{sub 2}){sub 12-n}{yields}H(HD)(H{sub 2}){sub n-1}(D{sub 2}){sub 12-n} for 12{>=}n{>=}1. Rate constant for the D+H{sub 2} reaction between neighboring D atom-H{sub 2} molecule pair is determined to be (7.5{+-}0.7)x10{sup -3} s{sup -1} in solid HD-H{sub 2} and (1.3{+-}0.3)x10{sup -2} s{sup -1} in D{sub 2}-H{sub 2} at 4.1 K, which is very close to that calculated based on the theory of chemical reaction in gas phase by Hancock et al. [J. Chem. Phys. 91, 3492 (1989)] and Takayanagi and Sato [J. Chem. Phys. 92, 2862 (1990)]. This rate constant was found to be independent of temperature up to 7 K within experimental error of {+-}30%. The slow process is assigned to the reaction of D atom produced in a cage fully surrounded by HD or D{sub 2} molecules, D(HD){sub 12} or D(D{sub 2}){sub 12}. This D atom undergoes the D+DH reaction with one of its nearest-neighboring HD molecules in solid HD-H{sub 2} or diffuses to the neighbor of H{sub 2} molecules to allow the D+H{sub 2} reaction in solid HD-H{sub 2} and D{sub 2}-H{sub 2}. The former is the main channel in solid HD-H{sub 2} below 6 K where D atoms diffuse very slowly, whereas the latter dominates

  10. Online hydrogen/deuterium exchange performed in the ion mobility cell of a hybrid mass spectrometer.

    PubMed

    Nagy, Kornél; Redeuil, Karine; Rezzi, Serge

    2009-11-15

    The present paper describes the performance of online, gas-phase hydrogen/deuterium exchange implemented in the ion mobility cell of a quadrupole time-of-flight mass spectrometer. Deuterium oxide and deuterated methanol were utilized to create deuterated vapor that is introduced into the ion mobility region of the mass spectrometer. Hydrogen/deuterium exchange occurs spontaneously in the milliseconds time frame without the need of switching the instrument into ion mobility mode. The exchange was studied in case of low molecular weight molecules and proteins. The observed number of exchanged hydrogens was equal to the number of theoretically exchangeable hydrogens for all low molecular weight compounds. This method needs only minimal instrumental modifications, is simple, cheap, environment friendly, compatible with ultraperformance liquid chromatography, and can be implemented on commercially available instruments. It does not compromise choice of liquid chromatographic solvents and accurate mass or parallel-fragmentation (MS(E)) methods. The performance of this method was compared to that of conventional alternatives where the deuterated solvent is introduced into the cone gas of the instrument. Although the degree of exchange was similar between the two methods, the "cone gas method" requires 10 times higher deuterated solvent volumes (50 muL/min) and offers reduced sensitivity in the tandem mass spectrometry (MS/MS) mode. The presented method is suggested as a standard future element of mass spectrometers to aid online structural characterization of unknowns and to study conformational changes of proteins with hydrogen/deuterium exchange.

  11. Metabolism of D-[1-3H]glucose, D-[2-3H]glucose, D-[5-3H]glucose, D-[6-3H]glucose and D-[U-14C]glucose by rat and human erythrocytes incubated in the presence of H2O or D2O.

    PubMed

    Conget, I; Malaisse, W J

    1995-02-01

    The present study investigates whether heavy water affects the efficiency of 3HOH production from D-[1-3H]glucose, D-[2-3H]glucose, D-[5-3H]glucose and D-[6-3H]glucose relative to the total generation of tritiated metabolites produced by either rat or human erythrocytes. The relative 3HOH yield was close to 95% with D-[5-3H]glucose, 72% with D-[2-3H]glucose, 22-32% with D-[1-3H]glucose, and only 12% with D-[6-3H]glucose. In the latter case, the comparison of the specific radioactivity of intracellular and extracellular acidic metabolites, expressed relative to that of 14C-labelled metabolites produced from D-[U-14C]glucose, indicated that the generation of 3HOH from D-[6-3H]glucose occurs at distal metabolic steps, such as the partial reversion of the pyruvate kinase reaction or the interconversion of pyruvate and L-alanine in the reaction catalysed by glutamate-pyruvate transaminase. As a rule, the substitution of H2O by D2O only caused minor to negligible changes in the relative 3HOH yield. This implies that the unexpectedly high deuteration of 13C-labelled D-glucose metabolites recently documented in erythrocytes exposed to D2O cannot be attributed to any major interference of heavy water with factors regulating both the deuteration and detritiation efficiency, such as the enzyme-to-enzyme tunnelling of specific glycolytic intermediates.

  12. Quantum dynamics of the Mu+H2(HD,D2) and H+MuH(MuD) reactions

    NASA Astrophysics Data System (ADS)

    Tsuda, Ken-ichiro; Moribayashi, Kengo; Nakamura, Hiroki

    1995-10-01

    Quantum mechanically accurate calculations are carried out for the following reactions involving muonium atom (Mu) using the hyperspherical coordinate approach: Mu+H2→MuH+H, Mu+D2→MuD+D, Mu+HD→MuH(MuD)+D(H), H+MuH→MuH+H, and H+MuD ↔MuH+D. The initial vibrational state is restricted to the ground state (vi=0) and the collision energies considered are up to ˜1.2 eV. The various aspects of the dynamics, such as the isotope effects, the initial rotational state (ji) dependence, and the final rotational state (jf) distribution are analyzed for a wide range of ji and jf. Some of the isotope effects can be interpreted in terms of the variations in reaction barrier and endothermicity. The following two intriguing features are also found: (1) strong enhancement of reaction by initial rotational excitation, and (2) oscillation of integral cross section as a function of collision energy in the case of the Mu-transfer reactions.

  13. Analysis of Protein Conformation and Dynamics by Hydrogen/Deuterium Exchange MS

    PubMed Central

    Engen, John R.

    2009-01-01

    synopsis Recent technological advances hydrogen exchange MS have led to improvements in the technique’s ability to analyze the shape and movements of proteins. John Engen of Northeastern University gives a much needed update on the field. The cover, created by Engen, shows proteins “swimming” in an H2O/D2O solution with a sample mass spectrum in the background. PMID:19788312

  14. Structure of [M + H - H(2)O](+) from protonated tetraglycine revealed by tandem mass spectrometry and IRMPD spectroscopy.

    PubMed

    Bythell, Benjamin J; Dain, Ryan P; Curtice, Stephanie S; Oomens, Jos; Steill, Jeffrey D; Groenewold, Gary S; Paizs, Béla; Van Stipdonk, Michael J

    2010-04-22

    Multiple-stage tandem mass spectrometry and collision-induced dissociation were used to investigate loss of H(2)O or CH(3)OH from protonated versions of GGGX (where X = G, A, and V), GGGGG, and the methyl esters of these peptides. In addition, wavelength-selective infrared multiple photon dissociation was used to characterize the [M + H - H(2)O](+) product derived from protonated GGGG and the major MS(3) fragment, [M + H - H(2)O - 29](+) of this peak. Consistent with the earlier work [ Ballard , K. D. ; Gaskell , S. J. J. Am. Soc. Mass Spectrom. 1993 , 4 , 477 - 481 ; Reid , G. E. ; Simpson , R. J. ; O'Hair , R. A. J. Int. J. Mass Spectrom. 1999 , 190/191 , 209 -230 ], CID experiments show that [M + H - H(2)O](+) is the dominant peak generated from both protonated GGGG and protonated GGGG-OMe. This strongly suggests that the loss of the H(2)O molecule occurs from a position other than the C-terminal free acid and that the product does not correspond to formation of the b(4) ion. Subsequent CID of [M + H - H(2)O](+) supports this proposal by resulting in a major product that is 29 mass units less than the precursor ion. This is consistent with loss of HN horizontal lineCH(2) rather than loss of carbon monoxide (28 mass units), which is characteristic of oxazolone-type b(n) ions. Comparison between experimental and theoretical infrared spectra for a group of possible structures confirms that the [M + H - H(2)O](+) peak is not a substituted oxazolone but instead suggests formation of an ion that features a five-membered ring along the peptide backbone, close to the amino terminus. Additionally, transition structure calculations and comparison of theoretical and experimental spectra of the [M + H - H(2)O - 29](+) peak also support this proposal.

  15. H(+)/solute-induced intracellular acidification leads to selective activation of apical Na(+)/H(+) exchange in human intestinal epithelial cells.

    PubMed

    Thwaites, D T; Ford, D; Glanville, M; Simmons, N L

    1999-09-01

    The intestinal absorption of many nutrients and drug molecules is mediated by ion-driven transport mechanisms in the intestinal enterocyte plasma membrane. Clearly, the establishment and maintenance of the driving forces - transepithelial ion gradients - are vital for maximum nutrient absorption. The purpose of this study was to determine the nature of intracellular pH (pH(i)) regulation in response to H(+)-coupled transport at the apical membrane of human intestinal epithelial Caco-2 cells. Using isoform-specific primers, mRNA transcripts of the Na(+)/H(+) exchangers NHE1, NHE2, and NHE3 were detected by RT-PCR, and identities were confirmed by sequencing. The functional profile of Na(+)/H(+) exchange was determined by a combination of pH(i), (22)Na(+) influx, and EIPA inhibition experiments. Functional NHE1 and NHE3 activities were identified at the basolateral and apical membranes, respectively. H(+)/solute-induced acidification (using glycylsarcosine or beta-alanine) led to Na(+)-dependent, EIPA-inhibitable pH(i) recovery or EIPA-inhibitable (22)Na(+) influx at the apical membrane only. Selective activation of apical (but not basolateral) Na(+)/H(+) exchange by H(+)/solute cotransport demonstrates that coordinated activity of H(+)/solute symport with apical Na(+)/H(+) exchange optimizes the efficient absorption of nutrients and Na(+), while maintaining pH(i) and the ion gradients involved in driving transport.

  16. CO2 and O2 Gas Exchange in an Experimental Model of the Btlss with Plant Wastes and Human Wastes Included in the Mass Exchange

    NASA Astrophysics Data System (ADS)

    Ushakova, Sofya; Tikhomirov, Alexander A.; Velichko, Vladimir; Tikhomirova, Natalia; Trifonov, Sergey V.

    2016-07-01

    Mass exchange processes in the new experimental model of the biotechnical life support system (BTLSS) constructed at the Institute of Biophysics SB RAS have a higher degree of closure than in the previous BTLSS, and, thus, the technologies employed in the new system are more complex. Therefore, before closing the loops of mass exchange processes for several months, the new model of the BTLSS was run to match the technologies employed to cultivate plants and the methods used to involve inedible plant parts and human wastes into the mass exchange with the CO2 absorption rate and the amount of the resulting O2. The plant compartment included vegetables grown on the soil-like substrate (SLS) (chufa, beet, carrot, radish, and lettuce), plants hydroponically grown on expanded clay aggregate (wheat, soybean, watercress), and plants grown in aquaculture (common glasswort and watercress). Nutrient solutions for hydroponically grown plants were prepared by using products of physicochemical mineralization of human wastes. Growing the plants in aquaculture enabled maintaining NaCl concentration in the irrigation solution for hydroponically grown plants at a level safe for the plants. Inedible plant biomass was added to the SLS. Three cycles of closing the system were run, which lasted 7, 7, and 10 days. The comparison of the amount of CO2 fed into the system over 24 h (simulating human respiration) and the amount of CO2 daily exhaled by a 70-kg middle-aged human showed that between 1% and 4% of the daily emissions of CO2 were assimilated in the system, and about 3% of the average human daily O2 requirement accumulated in the system. Plant productivity was between 4 and 4.7% of the human daily vegetable requirement, or between 3 and 3.5% of the total human daily food requirement. Thus, testing of the BTLSS showed a match between the technologies employed to arrange mass exchange processes. This study was supported by the grant of the Russian Science Foundation (Project No. 14-14-00599).

  17. Membrane device and process for mass exchange, separation, and filtration

    DOEpatents

    Liu, Wei; Canfield, Nathan L.

    2016-11-15

    A membrane device and processes for fabrication and for using are disclosed. The membrane device may include a number of porous metal membranes that provide a high membrane surface area per unit volume. The membrane device provides various operation modes that enhance throughput and selectivity for mass exchange, mass transfer, separation, and/or filtration applications between feed flow streams and permeate flow streams.

  18. New lessons from the H I size-mass relation of galaxies

    NASA Astrophysics Data System (ADS)

    Wang, Jing; Koribalski, Bärbel S.; Serra, Paolo; van der Hulst, Thijs; Roychowdhury, Sambit; Kamphuis, Peter; Chengalur, Jayaram N.

    2016-08-01

    We revisit the H I size-mass (D_{H I}-MH I) relation of galaxies with a sample of more than 500 nearby galaxies covering over five orders of magnitude in H I mass and more than 10 B-band magnitudes. The relation is remarkably tight with a scatter σ ˜ 0.06 dex, or 14 per cent. The scatter does not change as a function of galaxy luminosity, H I richness or morphological type. The relation is linked to the fact that dwarf and spiral galaxies have a homogeneous radial profile of H I surface density in the outer regions when the radius is normalized by DH I. The early-type disc galaxies typically have shallower H I radial profiles, indicating a different gas accretion history. We argue that the process of atomic-to-molecular gas conversion or star formation cannot explain the tightness of the DH I-MH I relation. This simple relation puts strong constraints on simulation models for galaxy formation.

  19. Mixed-bed ion exchange chromatography employing a salt-free pH gradient for improved sensitivity and compatibility in MudPIT.

    PubMed

    Mommen, Geert P M; Meiring, Hugo D; Heck, Albert J R; de Jong, Ad P J M

    2013-07-16

    In proteomics, comprehensive analysis of peptides mixtures necessitates multiple dimensions of separation prior to mass spectrometry analysis to reduce sample complexity and increase the dynamic range of analysis. The main goal of this work was to improve the performance of (online) multidimensional protein identification technology (MudPIT) in terms of sensitivity, compatibility and recovery. The method employs weak anion and strong cation mixed-bed ion exchange chromatography (ACE) in the first separation dimension and reversed phase chromatography (RP) in the second separation dimension (Motoyama et.al. Anal. Chem 2007, 79, 3623-34.). We demonstrated that the chromatographic behavior of peptides in ACE chromatography depends on both the WAX/SCX mixing ratio as the ionic strength of the mobile phase system. This property allowed us to replace the conventional salt gradient by a (discontinuous) salt-free, pH gradient. First dimensional separation of peptides was accomplished with mixtures of aqueous formic acid and dimethylsulfoxide with increasing concentrations. The overall performance of this mobile phase system was found comparable to ammonium acetate buffers in application to ACE chromatography, but clearly outperformed strong cation exchange for use in first dimensional peptide separation. The dramatically improved compatibility between (salt-free) ion exchange chromatography and reversed phase chromatography-mass spectrometry allowed us to downscale the dimensions of the RP analytical column down to 25 μm i.d. for an additional 2- to 3-fold improvement in performance compared to current technology. The achieved levels of sensitivity, orthogonality, and compatibility demonstrates the potential of salt-free ACE MudPIT for the ultrasensitive, multidimensional analysis of very modest amounts of sample material.

  20. Quantifying hydrogen-deuterium exchange of meteoritic dicarboxylic acids during aqueous extraction

    NASA Astrophysics Data System (ADS)

    Fuller, M.; Huang, Y.

    2003-03-01

    Hydrogen isotope ratios of organic compounds in carbonaceous chondrites provide critical information about their origins and evolutionary history. However, because many of these compounds are obtained by aqueous extraction, the degree of hydrogen-deuterium (H/D) exchange that occurs during the process needs to be quantitatively evaluated. This study uses compound- specific hydrogen isotopic analysis to quantify the H/D exchange during aqueous extraction. Three common meteoritic dicarboxylic acids (succinic, glutaric, and 2-methyl glutaric acids) were refluxed under conditions simulating the extraction process. Changes in D values of the dicarboxylic acids were measured following the reflux experiments. A pseudo-first order rate law was used to model the H/D exchange rates which were then used to calculate the isotope exchange resulting from aqueous extraction. The degree of H/D exchange varies as a result of differences in molecular structure, the alkalinity of the extraction solution and presence/absence of meteorite powder. However, our model indicates that succinic, glutaric, and 2-methyl glutaric acids with a D of 1800 would experience isotope changes of 38, 10, and 6, respectively during the extraction process. Therefore, the overall change in D values of the dicarboxylic acids during the aqueous extraction process is negligible. We also demonstrate that H/D exchange occurs on the chiral -carbon in 2-methyl glutaric acid. The results suggest that the racemic mixture of 2-methyl glutaric acid in the Tagish Lake meteorite could result from post-synthesis aqueous alteration. The approach employed in this study can also be used to quantify H/D exchange for other important meteoritic compounds such as amino acids.

  1. Deuterium enrichment of polycyclic aromatic hydrocarbons by photochemically induced exchange with deuterium-rich cosmic ices

    NASA Technical Reports Server (NTRS)

    Sandford, S. A.; Bernstein, M. P.; Allamandola, L. J.; Gillette, J. S.; Zare, R. N.

    2000-01-01

    The polycyclic aromatic hydrocarbon (PAH) coronene (C24H12) frozen in D2O ice in a ratio of less than 1 part in 500 rapidly exchanges its hydrogen atoms with the deuterium in the ice at interstellar temperatures and pressures when exposed to ultraviolet radiation. Exchange occurs via three different chemical processes: D atom addition, D atom exchange at oxidized edge sites, and D atom exchange at aromatic edge sites. Observed exchange rates for coronene (C24H12)-D2O and d12-coronene (C24D12)-H2O isotopic substitution experiments show that PAHs in interstellar ices could easily attain the D/H levels observed in meteorites. These results may have important consequences for the abundance of deuterium observed in aromatic materials in the interstellar medium and in meteorites. These exchange mechanisms produce deuteration in characteristic molecular locations on the PAHs that may distinguish them from previously postulated processes for D enrichment of PAHs.

  2. Levothyroxine sodium revisited: A wholistic structural elucidation approach of new impurities via HPLC-HRMS/MS, on-line H/D exchange, NMR spectroscopy and chemical synthesis.

    PubMed

    Ruggenthaler, M; Grass, J; Schuh, W; Huber, C G; Reischl, R J

    2017-02-20

    The structural elucidation of unknown pharmaceutical impurities plays an important role in the quality control of newly developed and well-established active pharmaceutical ingredients (APIs). The United States Pharmacopeia (USP) monograph for the API Levothyroxine Sodium, a synthetic thyroid hormone, features two high pressure liquid chromatography (HPLC) methods using UV-VIS absorption detection to determine organic impurities in the drug substance. The impurity profile of the first USP method ("Procedure 1") has already been extensively studied, however for the second method ("Procedure 2"), which exhibits a significantly different impurity profile, no wholistic structural elucidation of impurities has been performed yet. Applying minor modifications to the chromatographic parameters of USP "Procedure 2" and using various comprehensive structural elucidation methods such as high resolution tandem mass spectrometry with on-line hydrogen-deuterium (H/D) exchange or two-dimensional nuclear magnetic resonance spectroscopy (NMR) we gained new insights about the complex impurity profile of the synthetic thyroid hormone. This resulted in the characterization of 24 compounds previously unknown to literature and the introduction of two new classes of Levothyroxine Sodium impurities. Five novel compounds were unambiguously identified via isolation or synthesis of reference substances and subsequent NMR spectroscopic investigation. Additionally, Collision-Induced Dissociation (CID)-type fragmentation of identified major impurities as well as neutral loss fragmentation patterns of many characterized impurities were discussed. Copyright © 2016 Elsevier B.V. All rights reserved.

  3. Calcineurin homologous protein as an essential cofactor for Na+/H+ exchangers.

    PubMed

    Pang, T; Su, X; Wakabayashi, S; Shigekawa, M

    2001-05-18

    The Na+/H+ exchangers (NHEs) comprise a family of transporters that catalyze cell functions such as regulation of the pH and volume of a cell and epithelial absorption of Na+ and bicarbonate. Ubiquitous calcineurin B homologous protein (CHP or p22) is co-localized and co-immunoprecipitated with expressed NHE1, NHE2, or NHE3 independently of its myristoylation and Ca2+ binding, and its binding site was identified as the juxtamembrane region within the carboxyl-terminal cytoplasmic domain of exchangers. CHP binding-defective mutations of NHE1-3 or CHP depletion by injection of the competitive CHP-binding region of NHE1 into Xenopus oocytes resulted in a dramatic reduction (>90%) in the Na+/H+ exchange activity. The data suggest that CHP serves as an essential cofactor, which supports the physiological activity of NHE family members.

  4. The 6dF Galaxy Survey: dependence of halo occupation on stellar mass

    NASA Astrophysics Data System (ADS)

    Beutler, Florian; Blake, Chris; Colless, Matthew; Jones, D. Heath; Staveley-Smith, Lister; Campbell, Lachlan; Parker, Quentin; Saunders, Will; Watson, Fred

    2013-03-01

    In this paper we study the stellar mass dependence of galaxy clustering in the 6dF Galaxy Survey (6dFGS). The near-infrared selection of 6dFGS allows more reliable stellar mass estimates compared to optical bands used in other galaxy surveys. Using the halo occupation distribution model, we investigate the trend of dark matter halo mass and satellite fraction with stellar mass by measuring the projected correlation function, wp(rp). We find that the typical halo mass (M1) as well as the satellite power-law index (α) increases with stellar mass. This indicates (1) that galaxies with higher stellar mass sit in more massive dark matter haloes and (2) that these more massive dark matter haloes accumulate satellites faster with growing mass compared to haloes occupied by low stellar mass galaxies. Furthermore, we find a relation between M1 and the minimum dark matter halo mass (Mmin) of M1 ≈ 22 Mmin, in agreement with similar findings for Sloan Digital Sky Survey galaxies. The satellite fraction of 6dFGS galaxies declines with increasing stellar mass from 21 per cent at Mstellar = 2.6 × 1010 h-2 M⊙ to 12 per cent at Mstellar = 5.4 × 1010 h-2 M⊙ indicating that high stellar mass galaxies are more likely to be central galaxies. We compare our results to two different semi-analytic models derived from the Millennium Simulation, finding some disagreement. Our results can be used for placing new constraints on semi-analytic models in the future, particularly the behaviour of luminous red satellites. Finally, we compare our results to studies of halo occupation using galaxy-galaxy weak lensing. We find good overall agreement, representing a valuable cross-check for these two different tools of studying the matter distribution in the Universe.

  5. The mechanisms of brush border Na+/H+ exchanger activation by corticosteroids.

    PubMed

    Zallocchi, Marisa; Igarreta, Pilar; Calvo, Juan Carlos; Reboucas, Nancy Amaral; Damasco, María Christina

    2003-02-01

    Previously we showed that corticosterone and aldosterone increased proton fluxes in proximal tubule, by micropuncture and stationary microperfusion. Since the Na+/H+ exchanger is responsible for the main proximal proton secretion, we have now evaluated the effects aldosterone on Na+/H+ exchange activity in brush border vesicles. In order to evaluate the mechanism of action of glucocorticoids and mineralocorticoids, we studied the comparative effects of corticosterone and aldosterone on the abundance of NHE3 and NHE2 isoforms. We isolated renal brush border vesicles from rats by differential centrifugation in sham-operated, adrenalectomized, and adrenalectomized-aldosterone treated (ADX + aldosterone) animals. We measured the kinetics of H+ transport in response to increasing concentrations of Sodium Gluconate by fluorimetry using acridine orange. For Na+/H+ exchanger abundance we used Western blot analysis of brush border proteins in the above groups and in adrenalectomized-corticosterone treated rats. The Vmax in adrenalectomized animals was 22,162+/-1828 fluorescence units/min; in sham animals, 37,020+/-2722; and in ADX + aldosterone, 42,344+/-3044 (p<0.01 adrenalectomized vs others). No differences in Km were observed. Adrenalectomy decreased NHE3 abundance over Sham by 32% without modifying NHE2. Corticosterone-replacement enhanced NHE3 abundance by 76% and failed to increase NHE2. Aldosterone enhanced NHE2 abundance by 75% and did not increase NHE3. Mineralocorticoids enhance Na+/H+ exchange activity by increasing NHE2 abundance; glucocorticoids, by increasing NHE3 abundance.

  6. Intracellular acidification-induced alkali metal cation/H+ exchange in human neutrophils

    PubMed Central

    1987-01-01

    Pretreatment of isolated human neutrophils (resting pHi congruent to 7.25 at pHo 7.40) with 30 mM NH4Cl for 30 min leads to an intracellular acidification (pHi congruen to 6.60) when the NH4Cl prepulse is removed. Thereafter, in 140 mM Na+ medium, pHi recovers exponentially with time (initial rate, approximately 0.12 pH/min) to reach the normal resting pHi by approximately 20 min, a process that is accomplished mainly, if not exclusively, though an exchange of internal H+ for external Na+. This Na+/H+ countertransport is stimulated by external Na+ (Km congruent to 21 mM) and by external Li+ (Km congruent to 14 mM), though the maximal transport rate for Na+ is about twice that for Li+. Both Na+ and Li+ compete as substrates for the same translocation sites on the exchange carrier. Other alkali metal cations, such as K+, Rb+, or Cs+, do not promote pHi recovery, owing to an apparent lack of affinity for the carrier. The exchange system is unaffected by ouabain or furosemide, but can be competitively inhibited by the diuretic amiloride (Ki congruent to 8 microM). The influx of Na+ or Li+ is accompanied by an equivalent counter-reflux of H+, indicating a 1:1 stoichiometry for the exchange reaction, a finding consistent with the lack of voltage sensitivity (i.e., electroneutrality) of pHi recovery. These studies indicate that the predominant mechanism in human neutrophils for pHi regulation after intracellular acidification is an amiloride-sensitive alkali metal cation/H+ exchange that shares a number of important features with similar recovery processes in a variety of other mammalian cell types. PMID:3694176

  7. An extension of ASM2d including pH calculation.

    PubMed

    Serralta, J; Ferrer, J; Borrás, L; Seco, A

    2004-11-01

    This paper presents an extension of the Activated Sludge Model No. 2d (ASM2d) including a chemical model able to calculate the pH value in biological processes. The developed chemical model incorporates the complete set of chemical species affecting the pH value to ASM2d describing non-equilibrium biochemical processes. It considers the system formed by one aqueous phase, in which biochemical processes take place, and one gaseous phase, and is based on the assumptions of instantaneous chemical equilibrium under liquid phase and kinetically governed mass transport between the liquid and gas phase. The ASM2d enlargement comprises the addition of every component affecting the pH value and an ion-balance for the calculation of the pH value and the dissociation species. The significant pH variations observed in a sequencing batch reactor operated for enhanced biological phosphorus removal were used to verify the capability of the extended model for predicting the dynamics of pH jointly with concentrations of acetic acid and phosphate. A pH inhibition function for polyphosphate accumulating bacteria has also been included in the model to simulate the behaviour observed. Experimental data obtained in four different experiments (with different sludge retention time and influent phosphorus concentrations) were accurately reproduced.

  8. Spin-lock imaging of exogenous exchange-based contrast agents to assess tissue pH.

    PubMed

    Zu, Zhongliang; Li, Hua; Jiang, Xiaoyu; Gore, John C

    2018-01-01

    Some X-ray contrast agents contain exchangeable protons that give rise to exchange-based effects on MRI, including chemical exchange saturation transfer (CEST). However, CEST has poor specificity to explicit exchange parameters. Spin-lock sequences at high field are also sensitive to chemical exchange. Here, we evaluate whether spin-locking techniques can detect the contrast agent iohexol in vivo after intravenous administration, and their potential for measuring changes in tissue pH. Two metrics of contrast based on R 1ρ , the spin lattice relaxation rate in the rotating frame, were derived from the behavior of R 1ρ at different locking fields. Solutions containing iohexol at different concentrations and pH were used to evaluate the ability of the two metrics to quantify exchange effects. Images were also acquired from rat brains bearing tumors before and after intravenous injections of iohexol to evaluate the potential of spin-lock techniques for detecting the agent and pH variations. The two metrics were found to depend separately on either agent concentration or pH. Spin-lock imaging may therefore provide specific quantification of iohexol concentration and the iohexol-water exchange rate, which reports on pH. Spin-lock techniques may be used to assess the dynamics of intravenous contrast agents and detect extracellular acidification. Magn Reson Med 79:298-305, 2018. © 2017 International Society for Magnetic Resonance in Medicine. © 2017 International Society for Magnetic Resonance in Medicine.

  9. Measurement of the D^{*}(2010)^{+}-D^{+} Mass Difference.

    PubMed

    Lees, J P; Poireau, V; Tisserand, V; Grauges, E; Palano, A; Eigen, G; Brown, D N; Kolomensky, Yu G; Fritsch, M; Koch, H; Schroeder, T; Hearty, C; Mattison, T S; McKenna, J A; So, R Y; Blinov, V E; Buzykaev, A R; Druzhinin, V P; Golubev, V B; Kravchenko, E A; Onuchin, A P; Serednyakov, S I; Skovpen, Yu I; Solodov, E P; Todyshev, K Yu; Lankford, A J; Gary, J W; Long, O; Eisner, A M; Lockman, W S; Panduro Vazquez, W; Chao, D S; Cheng, C H; Echenard, B; Flood, K T; Hitlin, D G; Kim, J; Miyashita, T S; Ongmongkolkul, P; Porter, F C; Röhrken, M; Huard, Z; Meadows, B T; Pushpawela, B G; Sokoloff, M D; Smith, J G; Wagner, S R; Bernard, D; Verderi, M; Bettoni, D; Bozzi, C; Calabrese, R; Cibinetto, G; Fioravanti, E; Garzia, I; Luppi, E; Santoro, V; Calcaterra, A; de Sangro, R; Finocchiaro, G; Martellotti, S; Patteri, P; Peruzzi, I M; Piccolo, M; Rotondo, M; Zallo, A; Passaggio, S; Patrignani, C; Lacker, H M; Bhuyan, B; Mallik, U; Chen, C; Cochran, J; Prell, S; Ahmed, H; Gritsan, A V; Arnaud, N; Davier, M; Le Diberder, F; Lutz, A M; Wormser, G; Lange, D J; Wright, D M; Coleman, J P; Gabathuler, E; Hutchcroft, D E; Payne, D J; Touramanis, C; Bevan, A J; Di Lodovico, F; Sacco, R; Cowan, G; Banerjee, Sw; Brown, D N; Davis, C L; Denig, A G; Gradl, W; Griessinger, K; Hafner, A; Schubert, K R; Barlow, R J; Lafferty, G D; Cenci, R; Jawahery, A; Roberts, D A; Cowan, R; Robertson, S H; Dey, B; Neri, N; Palombo, F; Cheaib, R; Cremaldi, L; Godang, R; Summers, D J; Taras, P; De Nardo, G; Sciacca, C; Raven, G; Jessop, C P; LoSecco, J M; Honscheid, K; Kass, R; Gaz, A; Margoni, M; Posocco, M; Simi, G; Simonetto, F; Stroili, R; Akar, S; Ben-Haim, E; Bomben, M; Bonneaud, G R; Calderini, G; Chauveau, J; Marchiori, G; Ocariz, J; Biasini, M; Manoni, E; Rossi, A; Batignani, G; Bettarini, S; Carpinelli, M; Casarosa, G; Chrzaszcz, M; Forti, F; Giorgi, M A; Lusiani, A; Oberhof, B; Paoloni, E; Rama, M; Rizzo, G; Walsh, J J; Smith, A J S; Anulli, F; Faccini, R; Ferrarotto, F; Ferroni, F; Pilloni, A; Piredda, G; Bünger, C; Dittrich, S; Grünberg, O; Heß, M; Leddig, T; Voß, C; Waldi, R; Adye, T; Wilson, F F; Emery, S; Vasseur, G; Aston, D; Cartaro, C; Convery, M R; Dorfan, J; Dunwoodie, W; Ebert, M; Field, R C; Fulsom, B G; Graham, M T; Hast, C; Innes, W R; Kim, P; Leith, D W G S; Luitz, S; MacFarlane, D B; Muller, D R; Neal, H; Ratcliff, B N; Roodman, A; Sullivan, M K; Va'vra, J; Wisniewski, W J; Purohit, M V; Wilson, J R; Randle-Conde, A; Sekula, S J; Bellis, M; Burchat, P R; Puccio, E M T; Alam, M S; Ernst, J A; Gorodeisky, R; Guttman, N; Peimer, D R; Soffer, A; Spanier, S M; Ritchie, J L; Schwitters, R F; Izen, J M; Lou, X C; Bianchi, F; De Mori, F; Filippi, A; Gamba, D; Lanceri, L; Vitale, L; Martinez-Vidal, F; Oyanguren, A; Albert, J; Beaulieu, A; Bernlochner, F U; King, G J; Kowalewski, R; Lueck, T; Nugent, I M; Roney, J M; Sobie, R J; Tasneem, N; Gershon, T J; Harrison, P F; Latham, T E; Prepost, R; Wu, S L; Sun, L

    2017-11-17

    We measure the mass difference, Δm_{+}, between the D^{*}(2010)^{+} and the D^{+} using the decay chain D^{*}(2010)^{+}→D^{+}π^{0} with D^{+}→K^{-}π^{+}π^{+}. The data were recorded with the BABAR detector at center-of-mass energies at and near the ϒ(4S) resonance, and correspond to an integrated luminosity of approximately 468  fb^{-1}. We measure Δm_{+}=(140 601.0±6.8[stat]±12.9[syst])  keV. We combine this result with a previous BABAR measurement of Δm_{0}≡m(D^{*}(2010)^{+})-m(D^{0}) to obtain Δm_{D}=m(D^{+})-m(D^{0})=(4824.9±6.8[stat]±12.9[syst])  keV. These results are compatible with and approximately five times more precise than the Particle Data Group averages.

  10. Measurement of the D * ( 2010 ) + - D + Mass Difference

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

    Lees, J. P.; Poireau, V.; Tisserand, V.

    Here, we measure the mass difference, Δm +, between the D* (2010) + and the D + using the decay chain D* (2010) + → D + π 0 with D + → K - π + π +. The data were recorded with the BABAR detector at center-of-mass energies at and near the Υ(4S) resonance, and correspond to an integrated luminosity of approximately 468 fb -1. We measure Δm + = (140 601.0 ± 6.8 [stat] ± 12.9 [syst] ) keV . We combine this result with a previous BABAR measurement of Δm 0 ≡ m(D* (2010) +) -more » m (D 0) to obtain Δm D = m (D +) - m (D 0) = ( 4824.9 ± 6.8 [stat] ± 12.9 [syst]) keV . These results are compatible with and approximately five times more precise than the Particle Data Group averages.« less

  11. Measurement of the D * ( 2010 ) + - D + Mass Difference

    DOE PAGES

    Lees, J. P.; Poireau, V.; Tisserand, V.; ...

    2017-11-14

    Here, we measure the mass difference, Δm +, between the D* (2010) + and the D + using the decay chain D* (2010) + → D + π 0 with D + → K - π + π +. The data were recorded with the BABAR detector at center-of-mass energies at and near the Υ(4S) resonance, and correspond to an integrated luminosity of approximately 468 fb -1. We measure Δm + = (140 601.0 ± 6.8 [stat] ± 12.9 [syst] ) keV . We combine this result with a previous BABAR measurement of Δm 0 ≡ m(D* (2010) +) -more » m (D 0) to obtain Δm D = m (D +) - m (D 0) = ( 4824.9 ± 6.8 [stat] ± 12.9 [syst]) keV . These results are compatible with and approximately five times more precise than the Particle Data Group averages.« less

  12. P39-T Analysis of Oligosaccharides by Capillary-Scale High-Performance Anion-Exchange Chromatography with Pulsed Amperometric Detection (CHPAEC-PAD) and On-Line Electrospray-Ionization Ion-Trap Mass Spectrometry (CHPAEC-ITMS)

    PubMed Central

    Bruggink, C.; Koeleman, C.; Barreto, V.; Lui, Y.; Pohl, C.; Ingendoh, A.; Wuhrer, M.; Hokke, C.; Deelder, A.

    2007-01-01

    High-pH anion-exchange chromatography with pulsed amperometric detection (HPAEC-PAD) is an established technique for selective separation and analysis of underivatized carbohydrates. The miniaturization of chromatographic techniques by means of capillary columns, and on-line coupling to mass spectrometry are critical to the further development of glycan analysis methods that are compatible with the current requirements in clinical settings. A system has been developed based on the Dionex BioLC equipped with a microbore gradient pump with PEEK flow splitter, a FAMOS micro autosampler, a modified electrochemical cell for on-line capillary PAD, and a capillary column (380 μm i.d.) packed with a new type of anion-exchange resin. This system operates with sensitivity in the low femtomol range. In addition, an on-line capillary desalter has been developed to allow direct coupling to the Bruker Esquire 3000 ion-trap mass spectrometer with electrospray ionization interface (ESI-IT-MS). Both systems have been evaluated using oligosaccharide standards as well as urine samples exhibiting various lysosomal oligosaccharide storage diseases. Initial data indicate that the robust and selective anion-exchange system, in combination with ESI-IT-MS for structure confirmation and analysis, provides a powerful platform that complements existing nano/capillary LC-MS methods for analytical determination of oligosaccharides in biological matrices.

  13. Isotopic Exchange in Porous and Dense Magnesium Borohydride.

    PubMed

    Zavorotynska, Olena; Deledda, Stefano; Li, Guanqiao; Matsuo, Motoaki; Orimo, Shin-ichi; Hauback, Bjørn C

    2015-09-01

    Magnesium borohydride (Mg(BH4)2) is one of the most promising complex hydrides presently studied for energy-related applications. Many of its properties depend on the stability of the BH4(-) anion. The BH4(-) stability was investigated with respect to H→D exchange. In situ Raman measurements on high-surface-area porous Mg(BH4 )2 in 0.3 MPa D2 have shown that the isotopic exchange at appreciable rates occurs already at 373 K. This is the lowest exchange temperature observed in stable borohydrides. Gas-solid isotopic exchange follows the BH4(-) +D˙ →BH3D(-) +H˙ mechanism at least at the initial reaction steps. Ex situ deuteration of porous Mg(BH4)2 and its dense-phase polymorph indicates that the intrinsic porosity of the hydride is the key behind the high isotopic exchange rates. It implies that the solid-state H(D) diffusion is considerably slower than the gas-solid H→D exchange reaction at the surface and it is a rate-limiting steps for hydrogen desorption and absorption in Mg(BH4)2. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Isotopic exchange in mineral-fluid systems. IV. The crystal chemical controls on oxygen isotope exchange rates in carbonate-H 2O and layer silicate-H 2O systems

    NASA Astrophysics Data System (ADS)

    Cole, David R.

    2000-03-01

    Oxygen isotope exchange between minerals and water in systems far from chemical equilibrium is controlled largely by surface reactions such as dissolution-precipitation. In many cases, this behavior can be modeled adequately by a simple pseudo-first order rate model that accounts for changes in surface area of the solid. Previous modeling of high temperature isotope exchange data for carbonates, sulfates, and silicates indicated that within a given mineral group there appears to be a systematic relationship between rate and mineral chemistry. We tested this idea by conducting oxygen isotope exchange experiments in the systems, carbonate-H 2O and layer silicate-H 2O at 300 and 350°C, respectively. Witherite (BaCO 3), strontianite (SrCO 3) and calcite (CaCO 3) were reacted with pure H 2O for different lengths of time (271-1390 h) at 300°C and 100 bars. The layer silicates, chlorite, biotite and muscovite were reacted with H 2O for durations ranging from 132 to 3282 h at 350°C and 250 bars. A detailed survey of grain sizes and grain habits using scanning electron microscopy (SEM) indicated that grain regrowth occurred in all experiments to varying extents. Changes in the mean grain diameters were particularly significant in experiments involving withertite, strontianite and biotite. The variations in the extent of oxygen isotope exchange were measured as a function of time, and fit to a pseudo-first order rate model that accounted for the change in surface area of the solid during reaction. The isotopic rates (ln r) for the carbonate-H 2O system are -20.75 ± 0.44, -18.95 ± 0.62 and -18.51 ± 0.48 mol O m -2 s -1 for calcite, strontianite and witherite, respectively. The oxygen isotope exchange rates for layer silicate-H 2O systems are -23.99 ± 0.89, -23.14 ± 0.74 and -22.40 ± 0.66 mol O m -2 s -1 for muscovite, biotite and chlorite, respectively. The rates for the carbonate-H 2O systems increase in order from calcite to strontianite to witherite. This order

  15. Mass of the H Dibaryon

    NASA Astrophysics Data System (ADS)

    Shanahan, P. E.; Thomas, A. W.; Young, R. D.

    2011-08-01

    Recent lattice QCD calculations have reported evidence for the existence of a bound state with strangeness -2 and baryon number 2 at quark masses somewhat higher than the physical values. By developing a description of the dependence of this binding energy on the up, down and strange quark masses that allows a controlled chiral extrapolation, we explore the hypothesis that this state is to be identified with the H dibaryon. Taking as input the recent results of the HAL and NPLQCD Collaborations, we show that the H dibaryon is likely to be unbound by 13±14MeV at the physical point.

  16. Equilibrium and kinetic folding of rabbit muscle triosephosphate isomerase by hydrogen exchange mass spectrometry.

    PubMed

    Pan, Hai; Raza, Ashraf S; Smith, David L

    2004-03-05

    Unfolding and refolding of rabbit muscle triosephosphate isomerase (TIM), a model for (betaalpha)8-barrel proteins, has been studied by amide hydrogen exchange/mass spectrometry. Unfolding was studied by destabilizing the protein in guanidine hydrochloride (GdHCl) or urea, pulse-labeling with 2H2O and analyzing the intact protein by HPLC electrospray ionization mass spectrometry. Bimodal isotope patterns were found in the mass spectra of the labeled protein, indicating two-state unfolding behavior. Refolding experiments were performed by diluting solutions of TIM unfolded in GdHCl or urea and pulse-labeling with 2H2O at different times. Mass spectra of the intact protein labeled after one to two minutes had three envelopes of isotope peaks, indicating population of an intermediate. Kinetic modeling indicates that the stability of the folding intermediate in water is only 1.5 kcal/mol. Failure to detect the intermediate in the unfolding experiments was attributed to its low stability and the high concentrations of denaturant required for unfolding experiments. The folding status of each segment of the polypeptide backbone was determined from the deuterium levels found in peptic fragments of the labeled protein. Analysis of these spectra showed that the C-terminal half folds to form the intermediate, which then forms native TIM with folding of the N-terminal half. These results show that TIM folding fits the (4+4) model for folding of (betaalpha)8-barrel proteins. Results of a double-jump experiment indicate that proline isomerization does not contribute to the rate-limiting step in the folding of TIM.

  17. NMR detection of pH-dependent histidine-water proton exchange reveals the conduction mechanism of a transmembrane proton channel.

    PubMed

    Hu, Fanghao; Schmidt-Rohr, Klaus; Hong, Mei

    2012-02-29

    The acid-activated proton channel formed by the influenza M2 protein is important for the life cycle of the virus. A single histidine, His37, in the M2 transmembrane domain (M2TM) is responsible for pH activation and proton selectivity of the channel. Recent studies suggested three models for how His37 mediates proton transport: a shuttle mechanism involving His37 protonation and deprotonation, a H-bonded imidazole-imidazolium dimer model, and a transporter model involving large protein conformational changes in synchrony with proton conduction. Using magic-angle-spinning (MAS) solid-state NMR spectroscopy, we examined the proton exchange and backbone conformational dynamics of M2TM in a virus-envelope-mimetic membrane. At physiological temperature and pH, (15)N NMR spectra show fast exchange of the imidazole (15)N between protonated and unprotonated states. To quantify the proton exchange rates, we measured the (15)N T(2) relaxation times and simulated them for chemical-shift exchange and fluctuating N-H dipolar fields under (1)H decoupling and MAS. The exchange rate is 4.5 × 10(5) s(-1) for Nδ1 and 1.0 × 10(5) s(-1) for Nε2, which are approximately synchronized with the recently reported imidazole reorientation. Binding of the antiviral drug amantadine suppressed both proton exchange and ring motion, thus interfering with the proton transfer mechanism. By measuring the relative concentrations of neutral and cationic His as a function of pH, we determined the four pK(a) values of the His37 tetrad in the viral membrane. Fitting the proton current curve using the charge-state populations from these pK(a)'s, we obtained the relative conductance of the five charge states, which showed that the +3 channel has the highest time-averaged unitary conductance. At physiologically relevant pH, 2D correlation spectra indicated that the neutral and cationic histidines do not have close contacts, ruling out the H-bonded dimer model. Moreover, a narrowly distributed nonideal

  18. H/D exchange mass spectrometry and statistical coupling analysis reveal a role for allostery in a ferredoxin-dependent bifurcating transhydrogenase catalytic cycle.

    PubMed

    Berry, Luke; Poudel, Saroj; Tokmina-Lukaszewska, Monika; Colman, Daniel R; Nguyen, Diep M N; Schut, Gerrit J; Adams, Michael W W; Peters, John W; Boyd, Eric S; Bothner, Brian

    2018-01-01

    Recent investigations into ferredoxin-dependent transhydrogenases, a class of enzymes responsible for electron transport, have highlighted the biological importance of flavin-based electron bifurcation (FBEB). FBEB generates biomolecules with very low reduction potential by coupling the oxidation of an electron donor with intermediate potential to the reduction of high and low potential molecules. Bifurcating systems can generate biomolecules with very low reduction potentials, such as reduced ferredoxin (Fd), from species such as NADPH. Metabolic systems that use bifurcation are more efficient and confer a competitive advantage for the organisms that harbor them. Structural models are now available for two NADH-dependent ferredoxin-NADP + oxidoreductase (Nfn) complexes. These models, together with spectroscopic studies, have provided considerable insight into the catalytic process of FBEB. However, much about the mechanism and regulation of these multi-subunit proteins remains unclear. Using hydrogen/deuterium exchange mass spectrometry (HDX-MS) and statistical coupling analysis (SCA), we identified specific pathways of communication within the model FBEB system, Nfn from Pyrococus furiosus, under conditions at each step of the catalytic cycle. HDX-MS revealed evidence for allosteric coupling across protein subunits upon nucleotide and ferredoxin binding. SCA uncovered a network of co-evolving residues that can provide connectivity across the complex. Together, the HDX-MS and SCA data show that protein allostery occurs across the ensemble of iron‑sulfur cofactors and ligand binding sites using specific pathways that connect domains allowing them to function as dynamically coordinated units. Copyright © 2017 Elsevier B.V. All rights reserved.

  19. EDGE2D-EIRENE modelling of near SOL E r: possible impact on the H-mode power threshold

    NASA Astrophysics Data System (ADS)

    Chankin, A. V.; Delabie, E.; Corrigan, G.; Harting, D.; Maggi, C. F.; Meyer, H.; Contributors, JET

    2017-04-01

    Recent EDGE2D-EIRENE simulations of JET plasmas showed a significant difference between radial electric field (E r) profiles across the separatrix in two divertor configurations, with the outer strike point on the horizontal target (HT) and vertical target (VT) (Chankin et al 2016 Nucl. Mater. Energy, doi: 10.1016/j.nme.2016.10.004). Under conditions (input power, plasma density) where the HT plasma went into the H-mode, a large positive E r spike in the near scrape-off layer (SOL) was seen in the code output, leading to a very large E × B shear across the separatrix over a narrow region of a fraction of a cm width. No such E r feature was obtained in the code solution for the VT configuration, where the H-mode power threshold was found to be twice as high as in the HT configuration. It was hypothesised that the large E × B shear across the separatrix in the HT configuration could be responsible for the turbulence suppression leading to an earlier (at lower input power) L-H transition compared to the VT configuration. In the present work these ideas are extended to cover some other experimental observations on the H-mode power threshold variation with parameters which typically are not included in the multi-machine H-mode power threshold scalings, namely: ion mass dependence (isotope H-D-T exchange), dependence on the ion ∇B drift direction, and dependence on the wall material composition (ITER-like wall versus carbon wall in JET). In all these cases EDGE2D-EIRENE modelling shows larger positive E r spikes in the near SOL under conditions where the H-mode power threshold is lower, at least in the HT configuration.

  20. D/H Ratios in Lipids as a Tool to Elucidate Microbial Metabolism

    NASA Astrophysics Data System (ADS)

    Wijker, Reto S.; Sessions, Alex L.

    2016-04-01

    Large D/H fractionations have been observed in the lipids and growth water of most organisms studied today. These fractionations have generally been assumed to be constant across most biota because they originate solely from isotope effects imposed by the highly conserved lipid biosynthetic pathway. Recent data is illustrating this conclusion as incomplete. Lipids from field and laboratory samples exhibit huge variations in D/H fractionation. In environmental samples, lipids vary in δD by up to 300 ‰ and in laboratory cultures the documented variation is up to 500 ‰ within the same organism. Remarkably, the isotope fractionation appears to be correlated with the type of metabolism employed by the host organism. However, the underlying biochemical mechanisms leading to these isotopic variations are not yet fully understood. Because the largest proportion of H-bound C in fatty acids is derived directly from NADPH during biosynthesis, the original hypothesis was that large differences in the isotopic composition of NADPH, generated by different central metabolic pathways, were the primary source of D/H variation in lipids. However, recent observations indicate that this cannot be the whole story and lead us to the conclusion that additional processes must affect the isotope composition of NADPH. These processes may include the isotopic exchange of NADPH with water as well as fractionation of NADPH by transhydrogenases, interconverting NADH to NADPH by exhibiting large isotope effects. In this project, our objective is to ascertain whether D/H fractionation and these biochemical processes are correlated. We investigate correlations between cellular NADPH/NADP+ as well as NADH/NAD+ pool sizes and the D/H fractionation in a set of different microorganisms and will present the trends here. Our results will contribute to a more comprehensive understanding of the basic biological regulations over D/H fractionation and potentially enables their use as tracers and

  1. Identification of the Dimer Exchange Interface of the Bacterial DNA Damage Response Protein UmuD.

    PubMed

    Murison, David A; Timson, Rebecca C; Koleva, Bilyana N; Ordazzo, Michael; Beuning, Penny J

    2017-09-12

    The Escherichia coli SOS response, an induced DNA damage response pathway, confers survival on bacterial cells by providing accurate repair mechanisms as well as the potentially mutagenic pathway translesion synthesis (TLS). The umuD gene products are upregulated after DNA damage and play roles in both nonmutagenic and mutagenic aspects of the SOS response. Full-length UmuD is expressed as a homodimer of 139-amino-acid subunits, which eventually cleaves its N-terminal 24 amino acids to form UmuD'. The cleavage product UmuD' and UmuC form the Y-family polymerase DNA Pol V (UmuD' 2 C) capable of performing TLS. UmuD and UmuD' exist as homodimers, but their subunits can readily exchange to form UmuDD' heterodimers preferentially. Heterodimer formation is an essential step in the degradation pathway of UmuD'. The recognition sequence for ClpXP protease is located within the first 24 amino acids of full-length UmuD, and the partner of full-length UmuD, whether UmuD or UmuD', is degraded by ClpXP. To better understand the mechanism by which UmuD subunits exchange, we measured the kinetics of exchange of a number of fluorescently labeled single-cysteine UmuD variants as detected by Förster resonance energy transfer. Labeling sites near the dimer interface correlate with increased rates of exchange, indicating that weakening the dimer interface facilitates exchange, whereas labeling sites on the exterior decrease the rate of exchange. In most but not all cases, homodimer and heterodimer exchange exhibit similar rates, indicating that somewhat different molecular surfaces mediate homodimer exchange and heterodimer formation.

  2. Expression of Na(+)/H(+) exchanger isoforms 1, 2, 3, and 4 in bovine endometrium and the influence of uterine pH at time of fixed-time AI of pregnancy success.

    PubMed

    Bolzenius, Jennifer K; Cushman, Robert A; Perry, George A

    2016-08-01

    Cows that exhibit estrus prior to fixed-time AI had increased sperm transport to the site of fertilization, and improved embryo quality on d 6 after insemination. Sperm transport is influenced by uterine pH, and research has reported that uterine pH decreased at onset of estrus, but must return to normal prior to ovulation. Therefore, the objectives of these studies were to investigate a possible mechanism for the regulation of uterine pH around the onset of estrus, and to determine if uterine pH at time of fixed-time AI influenced pregnancy success. In experiment 1, Angus-cross beef cows (n=40 and 28 in rep. 1 and 2, respectively) were synchronized with the PG 6-day CIDR protocol (PGF2α on d -9, GnRH and insertion of a CIDR on d -6, and PGF2α and CIDR removal on d 0). Cows were blocked by follicle size at time of CIDR removal, and uterine biopsies were collected at 0, 12, 24, 36, 48, 60 (Rep. 1), 72, 84, or 96h (Rep2) after CIDR removal, and total cellular RNA was extracted from all biopsies. Estrus was monitored by the HeatWatch Estrous Detection System. In experiment 2, 223 postpartum beef cows in 2 herds were synchronized with a fixed-time AI protocol (herd 1: n=97; CO-Synch plus CIDR protocol; herd 2: n=126; Co-synch protocol). Uterine pH was determined at time of AI (n=80 and 63 for herd 1 and 2, respectively), and estrus was monitored by visual estrus detection with the aid of an ESTROTECT estrous detection patches, and pregnancy was determined by transrectal ultrasonography. In experiment 1, there was a significant (P<0.01), quadratic relationship in expression of Na(+)/H(+) exchanger isoforms 1, 2, and 3 among animals that exhibited estrus, with expression greatest at time of CIDR removal, decreasing to the onset of estrus, and then increasing again following the onset of estrus. Among cows that did not exhibit estrus, the preceding relationship did not exist (P>0.46). In experiment 2, cows that had initiated estrus prior to fixed-time AI had decreased

  3. Computational methods and challenges in hydrogen/deuterium exchange mass spectrometry.

    PubMed

    Claesen, Jürgen; Burzykowski, Tomasz

    2017-09-01

    Hydrogen/Deuterium exchange (HDX) has been applied, since the 1930s, as an analytical tool to study the structure and dynamics of (small) biomolecules. The popularity of using HDX to study proteins increased drastically in the last two decades due to the successful combination with mass spectrometry (MS). Together with this growth in popularity, several technological advances have been made, such as improved quenching and fragmentation. As a consequence of these experimental improvements and the increased use of protein-HDXMS, large amounts of complex data are generated, which require appropriate analysis. Computational analysis of HDXMS requires several steps. A typical workflow for proteins consists of identification of (non-)deuterated peptides or fragments of the protein under study (local analysis), or identification of the deuterated protein as a whole (global analysis); determination of the deuteration level; estimation of the protection extent or exchange rates of the labile backbone amide hydrogen atoms; and a statistically sound interpretation of the estimated protection extent or exchange rates. Several algorithms, specifically designed for HDX analysis, have been proposed. They range from procedures that focus on one specific step in the analysis of HDX data to complete HDX workflow analysis tools. In this review, we provide an overview of the computational methods and discuss outstanding challenges. © 2016 Wiley Periodicals, Inc. Mass Spec Rev 36:649-667, 2017. © 2016 Wiley Periodicals, Inc.

  4. Development to term of sheep embryos reconstructed after inner cell mass/trophoblast exchange.

    PubMed

    Loi, Pasqualino; Galli, Cesare; Lazzari, Giovanna; Matsukawa, Kazutsugu; Fulka, Josef; Goeritz, Frank; Hildebrandt, Thomas B

    2018-04-13

    Here we report in vitro and term development of sheep embryos after the inner cell mass (ICM) from one set of sheep blastocysts were injected into the trophoblast vesicles of another set. We also observed successful in vitro development of chimeric blastocysts made from sheep trophoblast vesicles injected with bovine ICM. First, we dissected ICMs from 35 sheep blastocysts using a stainless steel microblade and injected them into 29 re-expanded sheep trophoblastic vesicles. Of the 25 successfully micromanipulated trophoblastic vesicles, 15 (51.7%) re-expanded normally and showed proper ICM integration. The seven most well reconstructed embryos were transferred for development to term. Three ewes receiving manipulated blastocysts were pregnant at day 45 (42.8%), and all delivered normal offspring (singletons, two females and one male, average weight: 3.54 ± 0.358 kg). Next, we monitored in vitro development of sheep trophoblasts injected with bovine ICMs. Of 17 injected trophoblastic vesicles, 10 (58.8%) re-expanded after 4 h in culture, and four (40%) exhibited integrated bovine ICM. Our results indicate that ICM/trophoblast exchange is feasible, allowing full term development with satisfactory lambing rate. Therefore, ICM exchange is a promising approach for endangered species conservation.

  5. 2D Hexagonal Boron Nitride (2D-hBN) Explored for the Electrochemical Sensing of Dopamine.

    PubMed

    Khan, Aamar F; Brownson, Dale A C; Randviir, Edward P; Smith, Graham C; Banks, Craig E

    2016-10-04

    Crystalline 2D hexagonal boron nitride (2D-hBN) nanosheets are explored as a potential electrocatalyst toward the electroanalytical sensing of dopamine (DA). The 2D-hBN nanosheets are electrically wired via a drop-casting modification process onto a range of commercially available carbon supporting electrodes, including glassy carbon (GC), boron-doped diamond (BDD), and screen-printed graphitic electrodes (SPEs). 2D-hBN has not previously been explored toward the electrochemical detection/electrochemical sensing of DA. We critically evaluate the potential electrocatalytic performance of 2D-hBN modified electrodes, the effect of supporting carbon electrode platforms, and the effect of "mass coverage" (which is commonly neglected in the 2D material literature) toward the detection of DA. The response of 2D-hBN modified electrodes is found to be largely dependent upon the interaction between 2D-hBN and the underlying supporting electrode material. For example, in the case of SPEs, modification with 2D-hBN (324 ng) improves the electrochemical response, decreasing the electrochemical oxidation potential of DA by ∼90 mV compared to an unmodified SPE. Conversely, modification of a GC electrode with 2D-hBN (324 ng) resulted in an increased oxidation potential of DA by ∼80 mV when compared to the unmodified electrode. We explore the underlying mechanisms of the aforementioned examples and infer that electrode surface interactions and roughness factors are critical considerations. 2D-hBN is utilized toward the sensing of DA in the presence of the common interferents ascorbic acid (AA) and uric acid (UA). 2D-hBN is found to be an effective electrocatalyst in the simultaneous detection of DA and UA at both pH 5.0 and 7.4. The peak separations/resolution between DA and UA increases by ∼70 and 50 mV (at pH 5.0 and 7.4, respectively, when utilizing 108 ng of 2D-hBN) compared to unmodified SPEs, with a particularly favorable response evident in pH 5.0, giving rise to a

  6. Nepenthesin from monkey cups for hydrogen/deuterium exchange mass spectrometry.

    PubMed

    Rey, Martial; Yang, Menglin; Burns, Kyle M; Yu, Yaping; Lees-Miller, Susan P; Schriemer, David C

    2013-02-01

    Studies of protein dynamics, structure and interactions using hydrogen/deuterium exchange mass spectrometry (HDX-MS) have sharply increased over the past 5-10 years. The predominant technology requires fast digestion at pH 2-3 to retain deuterium label. Pepsin is used almost exclusively, but it provides relatively low efficiency under the constraints of the experiment, and a selectivity profile that renders poor coverage of intrinsically disordered regions. In this study we present nepenthesin-containing secretions of the pitcher plant Nepenthes, commonly called monkey cups, for use in HDX-MS. We show that nepenthesin is at least 1400-fold more efficient than pepsin under HDX-competent conditions, with a selectivity profile that mimics pepsin in part, but also includes efficient cleavage C-terminal to "forbidden" residues K, R, H, and P. High efficiency permits a solution-based analysis with no detectable autolysis, avoiding the complication of immobilized enzyme reactors. Relaxed selectivity promotes high coverage of disordered regions and the ability to "tune" the mass map for regions of interest. Nepenthesin-enriched secretions were applied to an analysis of protein complexes in the nonhomologous end-joining DNA repair pathway. The analysis of XRCC4 binding to the BRCT domains of Ligase IV points to secondary interactions between the disordered C-terminal tail of XRCC4 and remote regions of the BRCT domains, which could only be identified with a nepenthesin-based workflow. HDX data suggest that stalk-binding to XRCC4 primes a BRCT conformation in these remote regions to support tail interaction, an event which may be phosphoregulated. We conclude that nepenthesin is an effective alternative to pepsin for all HDX-MS applications, and especially for the analysis of structural transitions among intrinsically disordered proteins and their binding partners.

  7. Evaluation of Hydrogen Isotope Exchange Methodology on Adsorbents for Tritium Removal

    DOE PAGES

    Morgan, Gregg A.; Xiao, S. Xin

    2015-03-06

    The Savannah River National Laboratory has demonstrated a potential process that can be used to remove tritium from tritiated water using Pt-catalyzed molecular sieves. The process is an elemental isotope exchange process in which H 2 (when flowed through the molecular sieves) will exchange with the adsorbed water, D 2O, leaving H 2O adsorbed on the molecular sieves. Various formulations of catalyzed molecular sieve material were prepared using two different techniques, Pt-implantation and Pt-ion exchange. This technology has been demonstrated for a protium (H) and deuterium (D) system, but can also be used for the removal of tritium from contaminatedmore » water (T 2O, HTO, and DTO) using D 2 (or H 2)« less

  8. The direct exchange mechanism of induced spin polarization of low-dimensional π-conjugated carbon- and h-BN fragments at LSMO(001) MnO-terminated interfaces

    NASA Astrophysics Data System (ADS)

    Kuklin, Artem V.; Kuzubov, Alexander A.; Kovaleva, Evgenia A.; Lee, Hyosun; Sorokin, Pavel B.; Sakai, Seiji; Entani, Shiro; Naramoto, Hiroshi; Avramov, Paul

    2017-10-01

    Induced spin polarization of π-conjugated carbon and h-BN low dimensional fragments at the interfaces formed by deposition of pentacene molecule and narrow zigzag graphene and h-BN nanoribbons on MnO2-terminated LSMO(001) thin film was studied using GGA PBE+U PAW D3-corrected approach. Induced spin polarization of π-conjugated low-dimensional fragments is caused by direct exchange with Mn ions of LSMO(001) MnO-derived surface. Due to direct exchange, the pentacene molecule changes its diamagnetic narrow-band gap semiconducting nature to the ferromagnetic semiconducting state with 0.15 eV energy shift between spin-up and spin-down valence bands and total magnetic moment of 0.11 μB. Direct exchange converts graphene nanoribbon to 100% spin-polarized half-metal with large amplitude of spin-up electronic density at the Fermi level. The direct exchange narrows the h-BN nanoribbon band gap from 4.04 to 1.72 eV in spin-up channel and converts the h-BN ribbon semiconducting diamagnetic nature to a semiconducting magnetic one. The electronic structure calculations demonstrate a possibility to control the spin properties of low-dimensional π-conjugated carbon and h-BN fragments by direct exchange with MnO-derived LSMO(001) surface for spin-related applications.

  9. Impact of D2O/H2O Solvent Exchange on the Emission of HgTe and CdTe Quantum Dots: Polaron and Energy Transfer Effects.

    PubMed

    Wen, Qiannan; Kershaw, Stephen V; Kalytchuk, Sergii; Zhovtiuk, Olga; Reckmeier, Claas; Vasilevskiy, Mikhail I; Rogach, Andrey L

    2016-04-26

    We have studied light emission kinetics and analyzed carrier recombination channels in HgTe quantum dots that were initially grown in H2O. When the solvent is replaced by D2O, the nonradiative recombination rate changes highlight the role of the vibrational degrees of freedom in the medium surrounding the dots, including both solvent and ligands. The contributing energy loss mechanisms have been evaluated by developing quantitative models for the nonradiative recombination via (i) polaron states formed by strong coupling of ligand vibration modes to a surface trap state (nonresonant channel) and (ii) resonant energy transfer to vibration modes in the solvent. We conclude that channel (i) is more important than (ii) for HgTe dots in either solution. When some of these modes are removed from the relevant spectral range by the H2O to D2O replacement, the polaron effect becomes weaker and the nonradiative lifetime increases. Comparisons with CdTe quantum dots (QDs) served as a reference where the resonant energy loss (ii) a priori was not a factor, also confirmed by our experiments. The solvent exchange (H2O to D2O), however, is found to slightly increase the overall quantum yield of CdTe samples, probably by increasing the fraction of bright dots in the ensemble. The fundamental study reported here can serve as the foundation for the design and optimization principles of narrow bandgap quantum dots aimed at applications in long wavelength colloidal materials for infrared light emitting diodes and photodetectors.

  10. GUM 48d: AN EVOLVED H II REGION WITH ONGOING STAR FORMATION

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

    Karr, J. L.; Ohashi, N.; Manoj, P.

    2009-05-20

    High-mass star formation and the evolution of H II regions have a substantial impact on the morphology and star formation history of molecular clouds. The H II region Gum 48d, located in the Centaurus Arm at a distance of 3.5 kpc, is an old, well evolved H II region whose ionizing stars have moved off the main sequence. As such, it represents a phase in the evolution of H II regions that is less well studied than the earlier, more energetic, main-sequence phase. In this paper, we use multiwavelength archive data from a variety of sources to perform a detailedmore » study of this interesting region. Morphologically, Gum 48d displays a ring-like faint H II region associated with diffuse emission from the associated photodissociation region, and is formed from part of a large, massive molecular cloud complex. There is extensive ongoing star formation in the region, at scales ranging from low to high mass, which is consistent with triggered star formation scenarios. We investigate the dynamical history and evolution of this region, and conclude that the original H II region was once larger and more energetic than the faint region currently seen. The proposed history of this molecular cloud complex is one of multiple, linked generations of star formation, over a period of 10 Myr. Gum 48d differs significantly in morphology and star formation from the other H II regions in the molecular cloud; these differences are likely the result of the advanced age of the region, and its different evolutionary status.« less

  11. Modeling approaches to describe H2O and CO2 exchange in mare ecosystems

    NASA Astrophysics Data System (ADS)

    Olchev, A.; Novenko, E.; Volkova, E.

    2012-04-01

    The modern climatic conditions is strongly influenced by both internal variability of climatic system, and various external natural and anthropogenic factors (IPCC 2007). Significant increase of concentration of greenhouse gases in the atmosphere and especially the growth of atmospheric CO2 due to human activity are considered as the main factors that are responsible for global warming and climate changes. A significant part of anthropogenic CO2 is absorbed from the atmosphere by land biota and especially by vegetation cover. However, it is still not completely clear what is the role of different land ecosystems and especially forests and mares in global cycles of H2O and CO2 and what is a sensitivity of these ecosystems to climate changes. Within the frameworks of this study the spatial and temporal variability of H2O and CO2 fluxes in different types of mare ecosystems of the forest-steppe zone in European part of Russia was described using modeling approaches and results of field measurements. For this modeling and experimental study the mare ecosystems of Tula region were selected. The Tula region is located mostly in the forest-steppe zone and it is unique area for such studies because almost all existed types of mare ecosystems of Northern Eurasia distinguished by a geomorphological position, water and mineral supply can be found there. Most mares in Tula region have a relatively small size and surrounded by very heterogeneous forests that make not possible an application of the classical measuring and modeling approaches e.g. an eddy covariance technique or one-dimensional H2O and CO2 exchange models for flux estimation in such sites. In our study to describe the radiation, sensible heat, H2O and CO2 exchange between such heterogeneous mare ecosystems and the atmosphere a three-dimensional model Forbog-3D and one-dimensional Mixfor-SVAT were applied. The main concept used in the Forbog-3D and Mixfor-SVAT models is an aggregated description of physical and

  12. Improved edge charge exchange recombination spectroscopy in DIII-D

    NASA Astrophysics Data System (ADS)

    Chrystal, C.; Burrell, K. H.; Grierson, B. A.; Haskey, S. R.; Groebner, R. J.; Kaplan, D. H.; Briesemeister, A.

    2016-11-01

    The charge exchange recombination spectroscopy diagnostic on the DIII-D tokamak has been upgraded with the addition of more high radial resolution view chords near the edge of the plasma (r/a > 0.8). The additional views are diagnosed with the same number of spectrometers by placing fiber optics side-by-side at the spectrometer entrance with a precise separation that avoids wavelength shifted crosstalk without the use of bandpass filters. The new views improve measurement of edge impurity parameters in steep gradient, H-mode plasmas with many different shapes. The number of edge view chords with 8 mm radial separation has increased from 16 to 38. New fused silica fibers have improved light throughput and clarify the observation of non-Gaussian spectra that suggest the ion distribution function can be non-Maxwellian in low collisionality plasmas.

  13. Improved edge charge exchange recombination spectroscopy in DIII-D.

    PubMed

    Chrystal, C; Burrell, K H; Grierson, B A; Haskey, S R; Groebner, R J; Kaplan, D H; Briesemeister, A

    2016-11-01

    The charge exchange recombination spectroscopy diagnostic on the DIII-D tokamak has been upgraded with the addition of more high radial resolution view chords near the edge of the plasma (r/a > 0.8). The additional views are diagnosed with the same number of spectrometers by placing fiber optics side-by-side at the spectrometer entrance with a precise separation that avoids wavelength shifted crosstalk without the use of bandpass filters. The new views improve measurement of edge impurity parameters in steep gradient, H-mode plasmas with many different shapes. The number of edge view chords with 8 mm radial separation has increased from 16 to 38. New fused silica fibers have improved light throughput and clarify the observation of non-Gaussian spectra that suggest the ion distribution function can be non-Maxwellian in low collisionality plasmas.

  14. Evaluation of hydrogen isotope exchange methodology on adsorbents for tritium removal

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

    Morgan, G.A.; Xin Xiao, S.

    2015-03-15

    The Savannah River National Laboratory has demonstrated a potential process that can be used to remove tritium from tritiated water using Pt-catalyzed molecular sieves. The process is an elemental isotope exchange process in which H{sub 2} (when flowed through the molecular sieves) will exchange with the adsorbed water, D{sub 2}O, leaving H{sub 2}O adsorbed on the molecular sieves. Various formulations of catalyzed molecular sieve material were prepared using two different techniques, Pt-implantation and Pt-ion exchange. This technology has been demonstrated for a protium (H) and deuterium (D) system, but can also be used for the removal of tritium from contaminatedmore » water (T{sub 2}O, HTO, and DTO) using D{sub 2} (or H{sub 2}). (authors)« less

  15. Implications for Extraterrestrial Hydrocarbon Chemistry: Analysis of Ethylene (C{sub 2}H{sub 4}) and D4-Ethylene (C{sub 2}D{sub 4}) Ices Exposed to Ionizing Radiation via Combined Infrared Spectroscopy and Reflectron Time-of-flight Mass Spectrometry

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

    Abplanalp, Matthew J.; Kaiser, Ralf I., E-mail: ra

    The processing of the hydrocarbon ice, ethylene (C{sub 2}H{sub 4}/C{sub 2}D{sub 4}), via energetic electrons, thus simulating the processes in the track of galactic cosmic-ray particles, was carried out in an ultrahigh vacuum apparatus. The chemical evolution of the ices was monitored online and in situ utilizing Fourier transform infrared spectroscopy (FTIR) and during temperature programmed desorption, via a quadrupole mass spectrometer utilizing electron impact ionization (EI-QMS) and a reflectron time-of-flight mass spectrometer utilizing a photoionization source (PI-ReTOF-MS). Several previous in situ studies of ethylene ice irradiation using FTIR were substantiated with the detection of six products: [CH{sub 4} (CD{submore » 4})], acetylene [C{sub 2}H{sub 2} (C{sub 2}D{sub 2})], the ethyl radical [C{sub 2}H{sub 5} (C{sub 2}D{sub 5})], ethane [C{sub 2}H{sub 6} (C{sub 2}D{sub 6})], 1-butene [C{sub 4}H{sub 8} (C{sub 4}D{sub 8})], and n -butane [C{sub 4}H{sub 10} (C{sub 4}D{sub 10})]. Contrary to previous gas phase studies, the PI-ReTOF-MS detected several groups of hydrocarbon with varying degrees of saturation: C{sub n}H{sub 2n+2} (n = 4–10), C{sub n}H{sub 2n} ( n = 2–12, 14, 16), C{sub n}H{sub 2n−2} ( n = 3–12, 14, 16), C{sub n}H{sub 2n−4} (n = 4–12, 14, 16), C{sub n}H{sub 2n−6} (n = 4–10, 12), C{sub n}H{sub 2n−8} ( n = 6–10), and C{sub n}H{sub 2n−10} ( n = 6–10). Multiple laboratory studies have shown the facile production of ethylene from methane, which is a known ice constituent in the interstellar medium. Various astrophysically interesting molecules can be associated with the groups detected here, such as allene/methylacetylene (C{sub 3}H{sub 4}) or 1, 3-butadiene (C{sub 4}H{sub 6}) and its isomers, which have been shown to lead to polycyclic aromatic hydrocarbons. Finally, several hydrocarbon groups detected here are unique to ethylene ice versus ethane ice and may provide understanding of how complex hydrocarbons form in

  16. Total-body creatine pool size and skeletal muscle mass determination by creatine-(methyl-D3) dilution in rats.

    PubMed

    Stimpson, Stephen A; Turner, Scott M; Clifton, Lisa G; Poole, James C; Mohammed, Hussein A; Shearer, Todd W; Waitt, Greg M; Hagerty, Laura L; Remlinger, Katja S; Hellerstein, Marc K; Evans, William J

    2012-06-01

    There is currently no direct, facile method to determine total-body skeletal muscle mass for the diagnosis and treatment of skeletal muscle wasting conditions such as sarcopenia, cachexia, and disuse. We tested in rats the hypothesis that the enrichment of creatinine-(methyl-d(3)) (D(3)-creatinine) in urine after a defined oral tracer dose of D(3)-creatine can be used to determine creatine pool size and skeletal muscle mass. We determined 1) an oral tracer dose of D(3)-creatine that was completely bioavailable with minimal urinary spillage and sufficient enrichment in the body creatine pool for detection of D(3)-creatine in muscle and D(3)-creatinine in urine, and 2) the time to isotopic steady state. We used cross-sectional studies to compare total creatine pool size determined by the D(3)-creatine dilution method to lean body mass determined by independent methods. The tracer dose of D(3)-creatine (<1 mg/rat) was >99% bioavailable with 0.2-1.2% urinary spillage. Isotopic steady state was achieved within 24-48 h. Creatine pool size calculated from urinary D(3)-creatinine enrichment at 72 h significantly increased with muscle accrual in rat growth, significantly decreased with dexamethasone-induced skeletal muscle atrophy, was correlated with lean body mass (r = 0.9590; P < 0.0001), and corresponded to predicted total muscle mass. Total-body creatine pool size and skeletal muscle mass can thus be accurately and precisely determined by an orally delivered dose of D(3)-creatine followed by the measurement of D(3)-creatinine enrichment in a single urine sample and is promising as a noninvasive tool for the clinical determination of skeletal muscle mass.

  17. Reversible formation of intermediates during H/sub 3/O/sup +/-catalyzed hydrolysis of amides. Observation of substantial /sup 18/O exchange accompanying the hydrolysis of acetanilide and N-cyclohexylacetamide

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

    Slebocka-Tilk, H.; Brown, R.S.; Olekszyk, J.

    1987-07-22

    Careful mass spectrometric analysis of the /sup 18/O content of approx. 50% enriched acetanilide (2) and N-cyclohexylacetamide (3) recovered from acidic media during the course of hydrolysis reveals that both species suffer /sup 18/O loss. The percent of /sup 18/O exchange per t/sub 1/2/ of hydrolysis increases as (H/sub 3/O/sup +/) decreases. For 2 at 72/sup 0/C the amount of exchange increases from 0.5 +/- 0.5% (per t/sub 1/2/) in 1 M HCl to 9.4 +/- 0.5% in glycine buffer, (H/sub 3/O/sup +/) = 0.003 M. For 3 at 100/sup 0/C the exchange is 1.05 +/- 0.3% (per t/sub 1/2/)more » at 1 M HCl and 9.0 +/- 0.4% in 0.01 M HCl. When these data are used to compute k/sub ex/ (the exchange rate constant), it shows a first-order dependence on (H/sub 3/O/sup +/) followed by a plateau at high (H/sub 3/O/sup +/) for both 2 and 3.« less

  18. Geometric phase effects in ultracold collisions of H/D with rotationally excited HD

    NASA Astrophysics Data System (ADS)

    Kendrick, Brian K.; Croft, James F. E.; Hazra, Jisha; Balakrishnan, N.

    2017-04-01

    Quantum reactive scattering calculations for the H/D + HD(v = 4 , j = 1 , 2) -> H/D + HD(v', j') and H + H2(v = 4 , j = 1 , 2) -> H + H2(v', j') exchange reactions are presented for the ground electronic state of H3. A numerically exact three-dimensional time-independent scattering method based on hyperspherical coordinates is used to compute rotationally resolved reaction cross sections and non-thermal rate coefficients for collision energies between 1 μK and 100 K . The geometric (Berry) phase associated with the D3h conical intersection in H3 is included using a U(1) vector (gauge) potential approach. It is shown that the geometric phase leads to a significant (up to three orders of magnitude) enhancement or suppression of the ultracold reaction rate coefficients depending upon whether the interference between the reaction pathways encircling the conical intersection is constructive or destructive. The nature of the interference is governed by a newly discovered mechanism which leads to an effective quantization of the ultracold scattering phase shifts. Interesting behavior due to rotational excitation of the HD and H2 is observed which might be exploited by experimentalists to control the reaction outcome. This work was supported in part by NSF Grant PHY-1505557 (N.B.) and ARO MURI Grant No. W911NF-12-1-0476 (N.B.), and DOE LDRD Grant No. 20170221ER (B.K.).

  19. Fast, accurate 2D-MR relaxation exchange spectroscopy (REXSY): Beyond compressed sensing

    PubMed Central

    Bai, Ruiliang; Benjamini, Dan; Cheng, Jian; Basser, Peter J.

    2016-01-01

    Previously, we showed that compressive or compressed sensing (CS) can be used to reduce significantly the data required to obtain 2D-NMR relaxation and diffusion spectra when they are sparse or well localized. In some cases, an order of magnitude fewer uniformly sampled data were required to reconstruct 2D-MR spectra of comparable quality. Nonetheless, this acceleration may still not be sufficient to make 2D-MR spectroscopy practicable for many important applications, such as studying time-varying exchange processes in swelling gels or drying paints, in living tissue in response to various biological or biochemical challenges, and particularly for in vivo MRI applications. A recently introduced framework, marginal distributions constrained optimization (MADCO), tremendously accelerates such 2D acquisitions by using a priori obtained 1D marginal distribution as powerful constraints when 2D spectra are reconstructed. Here we exploit one important intrinsic property of the 2D-MR relaxation exchange spectra: the fact that the 1D marginal distributions of each 2D-MR relaxation exchange spectrum in both dimensions are equal and can be rapidly estimated from a single Carr–Purcell–Meiboom–Gill (CPMG) or inversion recovery prepared CPMG measurement. We extend the MADCO framework by further proposing to use the 1D marginal distributions to inform the subsequent 2D data-sampling scheme, concentrating measurements where spectral peaks are present and reducing them where they are not. In this way we achieve compression or acceleration that is an order of magnitude greater than that in our previous CS method while providing data in reconstructed 2D-MR spectral maps of comparable quality, demonstrated using several simulated and real 2D T2 – T2 experimental data. This method, which can be called “informed compressed sensing,” is extendable to other 2D- and even ND-MR exchange spectroscopy. PMID:27782473

  20. D/H Ratios in Lipids as a Tool to Elucidate Microbial Metabolism

    NASA Astrophysics Data System (ADS)

    Wijker, R. S.; Sessions, A. L.

    2015-12-01

    Large D/H fractionations have been observed in the lipids and growth water of most organisms studied today. These fractionations have generally been assumed to be constant across most biota because they originate solely from isotope effects imposed by the highly conserved lipid biosynthetic pathway. Recent data is illustrating this conclusion as incomplete. Lipids from field and laboratory samples exhibit huge variations in D/H fractionation. In environmental samples, lipids vary in δD by up to 300 ‰ and in laboratory cultures the documented variation is up to 500 ‰ within the same organism. Remarkably, the isotope fractionation appears to be correlated with the type of metabolism employed by the host organism. However, the underlying biochemical mechanisms leading to these isotopic variations are not yet fully understood. Because the largest proportion of H-bound C in fatty acids is derived directly from NADPH during biosynthesis, the original hypothesis was that large differences in the isotopic composition of NADPH, generated by different central metabolic pathways, were the primary source of D/H variation in lipids. However, recent observations indicate that this cannot be the whole story and lead us to the conclusion that additional processes must affect the isotope composition of NADPH. These processes may include the isotopic exchange of NADPH with water as well as fractionation of NADPH by transhydrogenases, interconverting NADH to NADPH by exhibiting large isotope effects. In this project, our objective is to ascertain whether D/H fractionation and these biochemical processes are correlated. We investigate correlations between cellular NADPH/NADP+ as well as NADH/NAD+ pool sizes and the D/H fractionation in a set of different microorganisms and will present the first trends here. Our results will contribute to a more comprehensive understanding of the basic biological regulations over D/H fractionation and potentially enables their use as tracers and

  1. Systematic generation of buffer systems for pH gradient ion exchange chromatography and their application.

    PubMed

    Kröner, Frieder; Hubbuch, Jürgen

    2013-04-12

    pH gradient protein separations are widely used techniques in the field of protein analytics, of which isoelectric focusing is the most well known application. The chromatographic variant, based on the formation of pH gradients in ion exchange columns is only rarely applied due to the difficulties to form controllable, linear pH gradients over a broad pH range. This work describes a method for the systematic generation of buffer compositions with linear titration curves, resulting in well controllable pH gradients. To generate buffer compositions with linear titration curves an in silico method was successfully developed. With this tool, buffer compositions for pH gradient ion exchange chromatography with pH ranges spanning up to 7.5 pH units were established and successfully validated. Subsequently, the buffer systems were used to characterize the elution behavior of 22 different model proteins in cation and anion exchange pH gradient chromatography. The results of both chromatographic modes as well as isoelectric focusing were compared to describe differences in between the methods. Copyright © 2013 Elsevier B.V. All rights reserved.

  2. Fourier Transfrom Ion Cyclotron Resonance Mass Spectrometry at High Magnetic Field

    NASA Astrophysics Data System (ADS)

    Marshall, Alan G.

    1998-03-01

    At high magnetic field (9.4 tesla at NHMFL), Fourier transform ion cyclotron resonance mass spectrometry performance improves dramatically: mass resolving power, axialization efficiency, and scan speed (each proportional to B), maximum ion mass, dynamic range, ion trapping period, kinetic energy, and electron self-cooling rate for sympathetic cooling (each proportional to B^2), and ion coalescence tendency (proportional 1/B^2). These advantages may apply singly (e.g., unit mass resolution for proteins of >100,000 Da), or compound (e.g., 10-fold improvement in S/N ratio for 9.4 T vs. 6 T at the same resolving power). Examples range from direct determination of molecular formulas of diesel fuel components by accurate mass measurement (=B10.1 ppm) to protein structure and dynamics probed by H/D exchange. This work was supported by N.S.F. (CHE-93-22824; CHE-94-13008), N.I.H. (GM-31683), Florida State University, and the National High Magnetic Field Laboratory in Tallahassee, FL.

  3. Sulfate-chloride exchange by lobster hepatopancreas is regulated by pH-sensitive modifier sites

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

    Cattey, M.A.; Ahearn, G.A.; Gerencser, G.A.

    1991-03-15

    {sup 35}SO{sub 4}{sup 2{minus}} uptake by Atlantic lobster (Homarus americanus) hepatopancreatic epithelial brush border membrane vesicles (BBMV) was stimulated by internal Cl{sup {minus}}, but not internal HCO{sub 3}{sup {minus}}, or external Na{sup +}. Sulfate-chloride exchange was stimulated by inside positive, and inhibited by inside negative, trans-membrane K diffusion potentials. {sup 35}SO{sub 4}{sup 2{minus}}-Cl{sup {minus}} exchange was strongly inhibited by 4,4{prime} diisothiocyanostilbene-2,2{prime}-disulfonic acid (DIDS), 4-acetamido-4{prime}-isotheocynaostilbene-2,2{prime}-disulfonic acid, (SITS), and thiosulfate. Chloride, bicarbonate, furosamide, and bumetanide slightly, yet significantly, cis-inhibited {sup 35}SO{sub 4}{sup 2{minus}}-Cl{sup {minus}} exchange. Altering bilateral pH from 8.0 to 5.4 stimulated {sup 35}SO{sub 4}{sup 2{minus}}-Cl{sup {minus}} exchange when vesicles weremore » loaded with Cl{sup {minus}}, but reduced bilateral pH alone or the presence of pH gradients did not affect {sup 35}SO{sub 4}{sup 2{minus}} transport in the absence of internal Cl{sup {minus}}. {sup 36}Cl uptake into SO{sub 4}{sup 2{minus}}-loaded BBMV was stimulated by an internal negative membrane potential and inhibited when the interior was electrically positive. A model is proposed which suggests that SO{sub 4}{sup 2{minus}}-Cl{sup {minus}} exchange is regulated by internal and external pH-sensitive modifier sites on the anion antiporter and by coupling to the electrogenic 2 Na{sup +}/1 H{sup +} antiporter and by coupling to the electrogenic 2 Na{sup +}/1 H{sup +} antiporter on the same membrane.« less

  4. Normal and anomalous nuclear spin-lattice relaxation at high temperatures in Sc-H(D), Y-H, and Lu-H solid solutions

    NASA Astrophysics Data System (ADS)

    Barnes, R. G.; Han, J.-W.; Torgeson, D. R.; Baker, D. B.; Conradi, M. S.; Norberg, R. E.

    1995-02-01

    We report the results of measurements of the proton (1H) spin-lattice relaxation rate R1 at high temperatures (to ~1400 K) in the hcp (α) solid-solution phases of the Sc-H, Y-H, and Lu-H systems, and of R1(45Sc) in Sc-H and Sc-D solid solutions. The latter measurements show unambiguous evidence of an anomalous increase at ~1000 K, whereas R1(1H) shows no such increase at any temperature. This behavior of R1(1H) contrasts with that in the bcc V-H, etc., solid solutions where anomalous relaxation occurs below ~1000 K, and in all investigated metal dihydride phases, MH2-x. The anomalous R1(1H) behavior in α-VHx, α-NbHx, etc., may be understood in terms of fast spin relaxation in the H2 gas in equilibrium with the solid, mediated by fast gas-solid exchange of hydrogen. However, in the present systems, α-ScHx, α-YHx, etc., the H2 gas pressure in equilibrium with the hcp systems is extremely low, resulting in negligible H2 concentration in the gas phase, and consequently a negligible contribution to R1(1H). In contrast, some of the present measurements indicate that the R1(45Sc) anomaly does result from the hydrogen content of the metal, but the mechanism remains unexplained.

  5. Development to term of sheep embryos reconstructed after inner cell mass/trophoblast exchange

    PubMed Central

    LOI, Pasqualino; GALLI, Cesare; LAZZARI, Giovanna; MATSUKAWA, Kazutsugu; FULKA, Josef; GOERITZ, Frank; HILDEBRANDT, Thomas B.

    2018-01-01

    Here we report in vitro and term development of sheep embryos after the inner cell mass (ICM) from one set of sheep blastocysts were injected into the trophoblast vesicles of another set. We also observed successful in vitro development of chimeric blastocysts made from sheep trophoblast vesicles injected with bovine ICM. First, we dissected ICMs from 35 sheep blastocysts using a stainless steel microblade and injected them into 29 re-expanded sheep trophoblastic vesicles. Of the 25 successfully micromanipulated trophoblastic vesicles, 15 (51.7%) re-expanded normally and showed proper ICM integration. The seven most well reconstructed embryos were transferred for development to term. Three ewes receiving manipulated blastocysts were pregnant at day 45 (42.8%), and all delivered normal offspring (singletons, two females and one male, average weight: 3.54 ± 0.358 kg). Next, we monitored in vitro development of sheep trophoblasts injected with bovine ICMs. Of 17 injected trophoblastic vesicles, 10 (58.8%) re-expanded after 4 h in culture, and four (40%) exhibited integrated bovine ICM. Our results indicate that ICM/trophoblast exchange is feasible, allowing full term development with satisfactory lambing rate. Therefore, ICM exchange is a promising approach for endangered species conservation. PMID:29445070

  6. Improvements to in-line desalting of oligosaccharides separated by high-pH anion exchange chromatography with pulsed amperometric detection.

    PubMed

    Thayer, J R; Rohrer, J S; Avdalovic, N; Gearing, R P

    1998-02-15

    High-pH anion exchange chromatography with pulsed amperometric detection (HPAEC/PAD) (1) is routinely used to separate neutral and charged oligosaccharides differing by branch, linkage, and positional isomerism. Oligosaccharides are eluted in 0.1 M NaOH with gradients of sodium acetate (up to 0.25 M). Analyses of HPAEC/PAD-purified oligosaccharides generally require neutralization and removal of eluent salts. To facilitate the process, we designed and produced a cation-exchange system to remove sodium ions (Na+) from the eluent after oligosaccharide detection [the Carbohydrate Membrane Desalter (CMD), with a volatile regenerant]. Exchange of >99.5% of eluent Na+ for hydronium ions (H3O+) within the CMD generates dilute acetic acid (removable by vacuum evaporation). The exchange process desalts up to 0.35 M Na+ at 1.0 ml/min. Oligosaccharides collected after on-line desalting, evaporated and resuspended in their original volume of deionized water contained < or = 350 muM residual Na+ when the eluting sodium concentration was 300 mM. This represents a desalting efficiency of >99.8%. Recovery of neutral and sialylated oligosaccharides under these conditions ranged from 75 to 100%. With the CMD system and postcollection evaporation, HPAEC/PAD can purify oligosaccharides ready for further characterization. As a proof test, oligosaccharides from a human monoclonal antibody were separated by HPAEC/PAD, desalted with the CMD system, dried, and analyzed by matrix-assisted laser desorption-ionization, time-of-flight mass spectrometry. Copyright 1998 Academic Press.

  7. HIghMass—High H I Mass, H I-rich Galaxies at z ˜ 0: Combined H I and H2 Observations

    NASA Astrophysics Data System (ADS)

    Hallenbeck, Gregory; Huang, Shan; Spekkens, Kristine; Haynes, Martha P.; Giovanelli, Riccardo; Adams, Elizabeth A. K.; Brinchmann, Jarle; Carpenter, John; Chengalur, Jayaram; Hunt, Leslie K.; Masters, Karen L.; Saintonge, Amélie

    2016-12-01

    We present resolved {{H}} {{I}} and CO observations of three galaxies from the HIghMass sample, a sample of {{H}} {{I}}-massive ({M}{{H}{{I}}}\\gt {10}10 {M}⊙ ), gas-rich ({M}{{H}{{I}}} in the top 5% for their M *) galaxies identified in the ALFALFA survey. Despite their high gas fractions, these are not low-surface-brightness galaxies and have typical specific star formation rates (SFR/{M}* ) for their stellar masses. The three galaxies have normal SFRs for their {{{H}}}2 masses, but unusually short star formation efficiency scale lengths, indicating that the star formation bottleneck in these galaxies is in the conversion of {{H}} {{I}} to {{{H}}}2, not in converting {{{H}}}2 to stars. In addition, their dark matter spin parameters (λ) are above average, but not exceptionally high, suggesting that their star formation has been suppressed over cosmic time but is now becoming active, in agreement with prior Hα observations.

  8. Ortho-para-H2 conversion by hydrogen exchange: comparison of theory and experiment.

    PubMed

    Lique, François; Honvault, Pascal; Faure, Alexandre

    2012-10-21

    We report fully-quantum time-independent calculations of cross sections and rate coefficients for the collisional (de)excitation of H(2) by H. Our calculations are based on the H(3) global potential energy surface of Mielke et al. [J. Chem. Phys. 116, 4142 (2002)]. The reactive hydrogen exchange channels are taken into account. We show that the ortho-para and para-ortho conversion of H(2) are significant processes at temperatures above ~300 K and for the last process we provide the first comparison with available experimental rate coefficients between 300 and 444 K. The good agreement between theory and experiment is a new illustration of our detailed understanding of the simplest chemical reaction. The importance of the ortho-para-H(2) conversion by hydrogen exchange in astrophysics is discussed.

  9. Energy exchange dynamics across L–H transitions in NSTX

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

    Diallo, A.; Banerjee, S.; Zweben, S. J.

    Here, we studied the energy exchange dynamics across the low-to-high-confinement (L–H) transition in NSTX discharges using the gas-puff imaging (GPI) diagnostic. The investigation focused on the energy exchange between flows and turbulence to help clarify the mechanism of the L–H transition. We applied this study to three types of heating schemes, including a total of 17 shots from the NSTX 2010 campaign run. Results show that the edge fluctuation characteristics (fluctuation levels, radial and poloidal correlation lengths) measured using GPI do not vary just prior to the H-mode transition, but change after the transition. Using a velocimetry approach (orthogonal-dynamics programming), velocity fields of amore » $$24\\times 30$$ cm GPI view during the L–H transition were obtained with good spatial (~1 cm) and temporal (~2.5 μs) resolutions. Analysis using these velocity fields shows that the production term is systematically negative just prior to the L–H transition, indicating a transfer from mean flows to turbulence, which is inconsistent with the predator–prey paradigm. Moreover, the inferred absolute value of the production term is two orders of magnitude too small to explain the observed rapid L–H transition. These discrepancies are further reinforced by consideration of the ratio between the kinetic energy in the mean flow to the thermal free energy, which is estimated to be much less than 1, suggesting again that the turbulence depletion mechanism may not play an important role in the transition to the H-mode. Although the Reynolds work therefore appears to be too small to directly deplete the turbulent free energy reservoir, order-of-magnitude analysis shows that the Reynolds stress may still make a non-negligible contribution to the observed poloidal flows.« less

  10. Energy exchange dynamics across L-H transitions in NSTX

    NASA Astrophysics Data System (ADS)

    Diallo, A.; Banerjee, S.; Zweben, S. J.; Stoltzfus-Dueck, T.

    2017-06-01

    We studied the energy exchange dynamics across the low-to-high-confinement (L-H) transition in NSTX discharges using the gas-puff imaging (GPI) diagnostic. The investigation focused on the energy exchange between flows and turbulence to help clarify the mechanism of the L-H transition. We applied this study to three types of heating schemes, including a total of 17 shots from the NSTX 2010 campaign run. Results show that the edge fluctuation characteristics (fluctuation levels, radial and poloidal correlation lengths) measured using GPI do not vary just prior to the H-mode transition, but change after the transition. Using a velocimetry approach (orthogonal-dynamics programming), velocity fields of a 24× 30 cm GPI view during the L-H transition were obtained with good spatial (˜1 cm) and temporal (˜2.5 μs) resolutions. Analysis using these velocity fields shows that the production term is systematically negative just prior to the L-H transition, indicating a transfer from mean flows to turbulence, which is inconsistent with the predator-prey paradigm. Moreover, the inferred absolute value of the production term is two orders of magnitude too small to explain the observed rapid L-H transition. These discrepancies are further reinforced by consideration of the ratio between the kinetic energy in the mean flow to the thermal free energy, which is estimated to be much less than 1, suggesting again that the turbulence depletion mechanism may not play an important role in the transition to the H-mode. Although the Reynolds work therefore appears to be too small to directly deplete the turbulent free energy reservoir, order-of-magnitude analysis shows that the Reynolds stress may still make a non-negligible contribution to the observed poloidal flows.

  11. Energy exchange dynamics across L–H transitions in NSTX

    DOE PAGES

    Diallo, A.; Banerjee, S.; Zweben, S. J.; ...

    2017-05-10

    Here, we studied the energy exchange dynamics across the low-to-high-confinement (L–H) transition in NSTX discharges using the gas-puff imaging (GPI) diagnostic. The investigation focused on the energy exchange between flows and turbulence to help clarify the mechanism of the L–H transition. We applied this study to three types of heating schemes, including a total of 17 shots from the NSTX 2010 campaign run. Results show that the edge fluctuation characteristics (fluctuation levels, radial and poloidal correlation lengths) measured using GPI do not vary just prior to the H-mode transition, but change after the transition. Using a velocimetry approach (orthogonal-dynamics programming), velocity fields of amore » $$24\\times 30$$ cm GPI view during the L–H transition were obtained with good spatial (~1 cm) and temporal (~2.5 μs) resolutions. Analysis using these velocity fields shows that the production term is systematically negative just prior to the L–H transition, indicating a transfer from mean flows to turbulence, which is inconsistent with the predator–prey paradigm. Moreover, the inferred absolute value of the production term is two orders of magnitude too small to explain the observed rapid L–H transition. These discrepancies are further reinforced by consideration of the ratio between the kinetic energy in the mean flow to the thermal free energy, which is estimated to be much less than 1, suggesting again that the turbulence depletion mechanism may not play an important role in the transition to the H-mode. Although the Reynolds work therefore appears to be too small to directly deplete the turbulent free energy reservoir, order-of-magnitude analysis shows that the Reynolds stress may still make a non-negligible contribution to the observed poloidal flows.« less

  12. Dynamic mass exchange in doubly degenerate binaries. I - 0.9 and 1.2 solar mass stars

    NASA Technical Reports Server (NTRS)

    Benz, W.; Cameron, A. G. W.; Press, W. H.; Bowers, R. L.

    1990-01-01

    The dynamic mass exchange process in doubly degenerate binaries was investigated using a three-dimensional numerical simulation of the evolution of a doubly degenerate binary system in which the primary is a 1.2-solar-mass white dwarf and the Roche lobe filling secondary is a 0.9-solar-mass dwarf. The results show that, in a little more than two orbital periods, the secondary is completely destroyed and transformed into a thick disk orbiting about the primary. Since only a very small fraction of the mass (0.0063 solar mass) escapes the system, the evolution of the binary results in the formation of a massive object. This object is composed of three parts, the initial white dwarf primary, a very hot pressure-supported spherical envelope, and a rotationally supported outer disk. The evolution of the system can be understood in terms of a simple analytical model where it is shown that the angular momentum carried by the mass during the transfer and stored in the disk determines the evolution of the system.

  13. Improved edge charge exchange recombination spectroscopy in DIII-D

    DOE PAGES

    Chrystal, Colin; Burrell, K. H.; Grierson, Brian A.; ...

    2016-08-02

    The charge exchange recombination spectroscopy diagnostic on the DIII-D tokamak has been upgraded with the addition of more high radial resolution view chords near the edge of the plasma ( r/a > 0.8). The additional views are diagnosed with the same number of spectrometers by placing fiber optics side-by-side at the spectrometer entrance with a precise separation that avoids wavelength shifted crosstalk without the use of bandpass filters. The new views improve measurement of edge impurity parameters in steep gradient, H-mode plasmas with many different shapes. The number of edge view chords with 8 mm radial separation has increased frommore » 16 to 38.As a result, new fused silica fibers have improved light throughput and clarify the observation of non-Gaussian spectra that suggest the ion distribution function can be non-Maxwellian in low collisionality plasmas.« less

  14. Core-mass nonadiabatic corrections to molecules: H2, H2+, and isotopologues.

    PubMed

    Diniz, Leonardo G; Alijah, Alexander; Mohallem, José Rachid

    2012-10-28

    For high-precision calculations of rovibrational states of light molecules, it is essential to include non-adiabatic corrections. In the absence of crossings of potential energy surfaces, they can be incorporated in a single surface picture through coordinate-dependent vibrational and rotational reduced masses. We present a compact method for their evaluation and relate in particular the vibrational mass to a well defined nuclear core mass derived from a Mulliken analysis of the electronic density. For the rotational mass we propose a simple, but very effective parametrization. The use of these masses in the nuclear Schrödinger equation yields numerical data for the corrections of a much higher quality than can be obtained with optimized constant masses, typically better than 0.1 cm(-1). We demonstrate the method for H(2), H(2)(+), and singly deuterated isotopologues. Isotopic asymmetry does not present any particular difficulty. Generalization to polyatomic molecules is straightforward.

  15. U/Th dating by SHRIMP RG ion-microprobe mass spectrometry using single ion-exchange beads

    NASA Astrophysics Data System (ADS)

    Bischoff, James L.; Wooden, Joe; Murphy, Fred; Williams, Ross W.

    2005-04-01

    We present a new analytical method for U-series isotopes using the SHRIMP RG (Sensitive High mass Resolution Ion MicroProbe) mass spectrometer that utilizes the preconcentration of the U-series isotopes from a sample onto a single ion-exchange bead. Ion-microprobe mass spectrometry is capable of producing Th ionization efficiencies in excess of 2%. Analytical precision is typically better than alpha spectroscopy, but not as good as thermal ionization mass spectroscopy (TIMS) and inductively coupled plasma multicollector mass spectrometry (ICP-MS). Like TIMS and ICP-MS the method allows analysis of small samples sizes, but also adds the advantage of rapidity of analysis. A major advantage of ion-microprobe analysis is that U and Th isotopes are analyzed in the same bead, simplifying the process of chemical separation. Analytical time on the instrument is ˜60 min per sample, and a single instrument-loading can accommodate 15-20 samples to be analyzed in a 24-h day. An additional advantage is that the method allows multiple reanalyses of the same bead and that samples can be archived for reanalysis at a later time. Because the ion beam excavates a pit only a few μm deep, the mount can later be repolished and reanalyzed numerous times. The method described of preconcentrating a low concentration sample onto a small conductive substrate to allow ion-microprobe mass spectrometry is potentially applicable to many other systems.

  16. U/Th dating by SHRIMP RG ion-microprobe mass spectrometry using single ion-exchange beads

    USGS Publications Warehouse

    Bischoff, J.L.; Wooden, J.; Murphy, F.; Williams, Ross W.

    2005-01-01

    We present a new analytical method for U-series isotopes using the SHRIMP RG (Sensitive High mass Resolution Ion MicroProbe) mass spectrometer that utilizes the preconcentration of the U-series isotopes from a sample onto a single ion-exchange bead. Ion-microprobe mass spectrometry is capable of producing Th ionization efficiencies in excess of 2%. Analytical precision is typically better than alpha spectroscopy, but not as good as thermal ionization mass spectroscopy (TIMS) and inductively coupled plasma multicollector mass spectrometry (ICP-MS). Like TIMS and ICP-MS the method allows analysis of small samples sizes, but also adds the advantage of rapidity of analysis. A major advantage of ion-microprobe analysis is that U and Th isotopes are analyzed in the same bead, simplifying the process of chemical separation. Analytical time on the instrument is ???60 min per sample, and a single instrument-loading can accommodate 15-20 samples to be analyzed in a 24-h day. An additional advantage is that the method allows multiple reanalyses of the same bead and that samples can be archived for reanalysis at a later time. Because the ion beam excavates a pit only a few ??m deep, the mount can later be repolished and reanalyzed numerous times. The method described of preconcentrating a low concentration sample onto a small conductive substrate to allow ion-microprobe mass spectrometry is potentially applicable to many other systems. Copyright ?? 2005 Elsevier Ltd.

  17. Simulating contaminant attenuation, double-porosity exchange, and water age in aquifers using MOC3D

    USGS Publications Warehouse

    Goode, Daniel J.

    1999-01-01

    MOC3D is a general-purpose computer model developed by the U.S. Geological Survey (USGS) for simulation of three-dimensional solute transport in ground water (Konikow and others, 1996). The model is an update to the widely used USGS two-dimensional solute-transport model (MOC) and is implemented as an optional “package” for the ground-water flow model MODFLOW (Harbaugh and McDonald, 1996). Directly coupling the time-tested MOC transport algorithms with the widely used MODFLOW program makes MOC3D a powerful tool for simulation of solute transport in ground water in many hydrogeologic settings. The model simulates transport processes that include:Advection - Transport of dissolved solutes at the same rate as the average ground-water flow velocity.Diffusion - Spreading of solute from areas of high concentration to areas of low concentration, caused by “random” molecular motionDispersion - Diffusion-like spreading of solute that is caused primarily by spatial variability in aquifer properties, which results in spatial variability in transport velocity.Retardation - Reduction in the apparent solute velocity, compared to the ground-water velocity, caused by linear equilibrium sorption on aquifer materials.Decay - Disappearance of solute caused by reactions such as radioactive decay or biodegradation that are proportional to concentration.Growth - Creation (or disappearance) of solute mass caused by reactions that proceed independent of the solute concentration, such as some cases of biodegradationDouble-porosity exchange - rate-limited exchange of solute mass between mobile and immobile zones; for example, between fractures and the rock matrix.

  18. Improving respiration measurements with gas exchange analyzers.

    PubMed

    Montero, R; Ribas-Carbó, M; Del Saz, N F; El Aou-Ouad, H; Berry, J A; Flexas, J; Bota, J

    2016-12-01

    Dark respiration measurements with open-flow gas exchange analyzers are often questioned for their low accuracy as their low values often reach the precision limit of the instrument. Respiration was measured in five species, two hypostomatous (Vitis Vinifera L. and Acanthus mollis) and three amphistomatous, one with similar amount of stomata in both sides (Eucalyptus citriodora) and two with different stomata density (Brassica oleracea and Vicia faba). CO 2 differential (ΔCO 2 ) increased two-fold with no change in apparent R d , when the two leaves with higher stomatal density faced outside. These results showed a clear effect of the position of stomata on ΔCO 2 . Therefore, it can be concluded that leaf position is important to guarantee the improvement of respiration measurements increasing ΔCO 2 without affecting the respiration results by leaf or mass units. This method will help to increase the accuracy of leaf respiration measurements using gas exchange analyzers. Copyright © 2016 Elsevier GmbH. All rights reserved.

  19. Modelling non-adiabatic effects in H_3^+: Solution of the rovibrational Schrödinger equation with motion-dependent masses and mass surfaces

    NASA Astrophysics Data System (ADS)

    Mátyus, Edit; Szidarovszky, Tamás; Császár, Attila G.

    2014-10-01

    Introducing different rotational and vibrational masses in the nuclear-motion Hamiltonian is a simple phenomenological way to model rovibrational non-adiabaticity. It is shown on the example of the molecular ion H_3^+, for which a global adiabatic potential energy surface accurate to better than 0.1 cm-1 exists [M. Pavanello, L. Adamowicz, A. Alijah, N. F. Zobov, I. I. Mizus, O. L. Polyansky, J. Tennyson, T. Szidarovszky, A. G. Császár, M. Berg et al., Phys. Rev. Lett. 108, 023002 (2012)], that the motion-dependent mass concept yields much more accurate rovibrational energy levels but, unusually, the results are dependent upon the choice of the embedding of the molecule-fixed frame. Correct degeneracies and an improved agreement with experimental data are obtained if an Eckart embedding corresponding to a reference structure of D3h point-group symmetry is employed. The vibrational mass of the proton in H_3^+ is optimized by minimizing the root-mean-square (rms) deviation between the computed and recent high-accuracy experimental transitions. The best vibrational mass obtained is larger than the nuclear mass of the proton by approximately one third of an electron mass, m^(v)_opt,p=m_nuc,p+0.31224 m_e. This optimized vibrational mass, along with a nuclear rotational mass, reduces the rms deviation of the experimental and computed rovibrational transitions by an order of magnitude. Finally, it is shown that an extension of the algorithm allowing the use of motion-dependent masses can deal with coordinate-dependent mass surfaces in the rovibrational Hamiltonian, as well.

  20. Interaction Between Cytochrome c and the Hapten 2,4-Dinitro-fluorobenzene by Electrospray Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Wu, Bo; Chu, Yan-qiu; Dai, Zhao-yun; Ding, Chuan-fan

    2008-06-01

    Allergic contact dermatitis is a delayed hypersensitivity reaction, which results from skin exposure to low molecular weight chemicals such as haptens. To clarify the pathogenic mechanism, electrospray ionization mass spectrometry (ESI-MS) and hydrogen/deuterium (H/D) exchange, as well as UV spectroscopy, were applied to determine the interaction between the model protein cytochrome c (cyt c) and the hapten 2,4-dinitro-fluorobenzene (DNFB). The ESI-MS results demonstrate that the conformation of cyt c can change from native folded state into partially unfolded state with the increase of DNFB. The equilibrium state H/D exchange followed by ESI-MS further confirms the above results. UV spectroscopy indicates that the strong-field coordination between iron of heme (prosthetic group) and His18 or Met80 of cyt c is not obviously affected by the hapten.

  1. Ternary recombination of H3+, H2D+, HD2+, and D3+ with electrons in He/Ar/H2/D2 gas mixtures

    NASA Astrophysics Data System (ADS)

    Kalosi, Abel; Dohnal, Petr; Plasil, Radek; Johnsen, Rainer; Glosik, Juraj

    2016-09-01

    The temperature dependence of the ternary recombination rate coefficients of H2D+ and HD2+ ions has been studied in the temperature range of 80-150 K at pressures from 500 to 1700 Pa in a stationary afterglow apparatus equipped with a cavity ring-down spectrometer. Neutral gas mixtures consisting of He/Ar/H2/D2 (with typical number densities 1017 /1014 /1014 /1014 cm-3) were employed to produce the desired ionic species and their fractional abundances were monitored as a function of helium pressure and the [D2]/[H2] ratio of the neutral gas. In addition, the translational and the rotational temperature and the ortho to para ratio were monitored for both H2D+ and HD2+ ions. A fairly strong pressure dependence of the effective recombination rate coefficient was observed for both ion species, leading to ternary recombination rate coefficients close to those previously found for (helium assisted) ternary recombination of H3+ and D3+. Work supported by: Czech Science Foundation projects GACR 14-14649P, GACR 15-15077S, GACR P209/12/0233, and by Charles University in Prague Project Nr. GAUK 692214.

  2. Cast and 3D printed ion exchange membranes for monolithic microbial fuel cell fabrication

    NASA Astrophysics Data System (ADS)

    Philamore, Hemma; Rossiter, Jonathan; Walters, Peter; Winfield, Jonathan; Ieropoulos, Ioannis

    2015-09-01

    We present novel solutions to a key challenge in microbial fuel cell (MFC) technology; greater power density through increased relative surface area of the ion exchange membrane that separates the anode and cathode electrodes. The first use of a 3D printed polymer and a cast latex membrane are compared to a conventionally used cation exchange membrane. These new techniques significantly expand the geometric versatility available to ion exchange membranes in MFCs, which may be instrumental in answering challenges in the design of MFCs including miniaturisation, cost and ease of fabrication. Under electrical load conditions selected for optimal power transfer, peak power production (mean 10 batch feeds) was 11.39 μW (CEM), 10.51 μW (latex) and 0.92 μW (Tangoplus). Change in conductivity and pH of anolyte were correlated with MFC power production. Digital and environmental scanning electron microscopy show structural changes to and biological precipitation on membrane materials following long term use in an MFC. The cost of the novel membranes was lower than the conventional CEM. The efficacy of two novel membranes for ion exchange indicates that further characterisation of these materials and their fabrication techniques, shows great potential to significantly increase the range and type of MFCs that can be produced.

  3. MARVEL analysis of the rotational-vibrational states of the molecular ions H2D+ and D2H+.

    PubMed

    Furtenbacher, Tibor; Szidarovszky, Tamás; Fábri, Csaba; Császár, Attila G

    2013-07-07

    Critically evaluated rotational-vibrational line positions and energy levels, with associated critically reviewed labels and uncertainties, are reported for two deuterated isotopologues of the H3(+) molecular ion: H2D(+) and D2H(+). The procedure MARVEL, standing for Measured Active Rotational-Vibrational Energy Levels, is used to determine the validated levels and lines and their self-consistent uncertainties based on the experimentally available information. The spectral ranges covered for the isotopologues H2D(+) and D2H(+) are 5.2-7105.5 and 23.0-6581.1 cm(-1), respectively. The MARVEL energy levels of the ortho and para forms of the ions are checked against ones determined from accurate variational nuclear motion computations employing the best available adiabatic ab initio potential energy surfaces of these isotopologues. The number of critically evaluated, validated and recommended experimental (levels, lines) are (109, 185) and (104, 136) for H2D(+) and D2H(+), respectively. The lists of assigned MARVEL lines and levels and variational levels obtained for H2D(+) and D2H(+) as part of this study are deposited in the ESI to this paper.

  4. Gas-Phase Hydrogen-Deuterium Exchange Labeling of Select Peptide Ion Conformer Types: a Per-Residue Kinetics Analysis.

    PubMed

    Khakinejad, Mahdiar; Kondalaji, Samaneh Ghassabi; Tafreshian, Amirmahdi; Valentine, Stephen J

    2015-07-01

    The per-residue, gas-phase hydrogen deuterium exchange (HDX) kinetics for individual amino acid residues on selected ion conformer types of the model peptide KKDDDDDIIKIIK have been examined using ion mobility spectrometry (IMS) and HDX-tandem mass spectrometry (MS/MS) techniques. The [M + 4H](4+) ions exhibit two major conformer types with collision cross sections of 418 Å(2) and 446 Å(2); the [M + 3H](3+) ions also yield two different conformer types having collision cross sections of 340 Å(2) and 367 Å(2). Kinetics plots of HDX for individual amino acid residues reveal fast- and slow-exchanging hydrogens. The contributions of each amino acid residue to the overall conformer type rate constant have been estimated. For this peptide, N- and C-terminal K residues exhibit the greatest contributions for all ion conformer types. Interior D and I residues show decreased contributions. Several charge state trends are observed. On average, the D residues of the [M + 3H](3+) ions show faster HDX rate contributions compared with [M + 4H](4+) ions. In contrast the interior I8 and I9 residues show increased accessibility to exchange for the more elongated [M + 4H](4+) ion conformer type. The contribution of each residue to the overall uptake rate showed a good correlation with a residue hydrogen accessibility score model calculated using a distance from charge site and initial incorporation site for nominal structures obtained from molecular dynamic simulations (MDS).

  5. Comparative Study of Exchange-Correlation Functional and Potential for Evaluating Thermoelectric Transport Properties in d0 Perovskite Oxides

    NASA Astrophysics Data System (ADS)

    Ohkubo, Isao; Mori, Takao

    2017-07-01

    The influence of two different types of exchange-correlation functional/potential, namely, the generalized gradient approximation Perdew-Burke-Ernzerhof (GGA-PBE) functional and the modified Becke-Johnson (mBJ) potential, on the thermoelectric transport properties of d0 perovskite oxides (SrTiO3 and KTaO3) was investigated. The reduction of band dispersion induced by the mBJ scheme allows the improved prediction of band gap values by thelocal density approximation (LDA) and GGA, which increases the resolution of the increases in the density of states (DOS), carrier concentration, and effective mass near the conduction band edge. A comparison of the experimental effective mass values of d0 perovskite oxides shows that the effective mass values provided by the mBJ potential are similar to those provided by the GGA-PBE functional. Comparative analysis of the data obtained from Boltzmann theory calculations using the electronic structures determined with the GGA-PBE functional and the mBJ potential shows a difference in the transport coefficients owing to the increases in the DOS, carrier concentration, and effective mass induced by the mBJ scheme.

  6. Influence of substrate structure on turnover of the organic cation/H+ exchanger of the renal luminal membrane.

    PubMed

    Wright, S H; Wunz, T M

    1998-08-01

    We examined the influence of organic cation (OC) structure on the rate of turnover of the OC/H+ exchanger in rabbit renal brush-border membrane vesicles (BBMV). The rate of efflux of [14C]tetraethylammonium ([14C]TEA) from BBMV, measured in the presence of an inwardly directed chemical gradient for test agent, provided an indirect measure of activity of the OC/H+(OC) exchanger. The trans-stimulation of [14C]TEA efflux from BBMV was a saturable function of increasing extravesicular concentration of both unlabeled TEA and tetramethylammonium (TMA), with an apparent Michaelis constant (Kt) for the interaction of these compounds with the OC/H+(OC) exchanger of 25 microM and 1 mM, respectively. The effect on [14C]TEA efflux of saturating extravesicular concentrations of a series of n-tetraalkylammonium compounds was examined. Whereas the short-chain compounds TMA and TEA markedly stimulated [14C]TEA efflux (by 830% and 690%, respectively), the long-chain compounds tetrapropylammonium and tetrabutylammonium were less effective, increasing efflux by only 40% and 120%, respectively. When the exchanger was saturated with tetrapentylammonium, mediated efflux of [14C]TEA was reduced. Increasing alkyl chain length was also correlated with an increase in the inhibitory effect (as measured by the apparent inhibition constant, Ki, or the IC50 value) that these compounds had against transport of [14C]TEA by the OC/H+(OC) exchanger; i.e., there was a correlation between decreasing IC50 and decreasing turnover of the OC/H+(OC) exchanger. This same correlation was observed for a broader set of test agents of diverse molecular structure, including a series of n-tetraalkylammonium and -phosphonium compounds and the OCs, choline, N1-methyl nicotinamide, 1-methyl-4-phenylpyridinium, and amiloride. Because high affinity of substrates for the OC/H+(OC) exchanger is correlated with increasing substrate hydrophobicity, we conclude that the interaction of hydrophobic OCs with the renal OC/H

  7. The ALFALFA H I mass function: a dichotomy in the low-mass slope and a locally suppressed `knee' mass

    NASA Astrophysics Data System (ADS)

    Jones, Michael G.; Haynes, Martha P.; Giovanelli, Riccardo; Moorman, Crystal

    2018-06-01

    We present the most precise measurement of the z = 0 H I mass function (HIMF) to date based on the final catalogue of the ALFALFA (Arecibo Legacy Fast ALFA) blind H I survey of the nearby Universe. The Schechter function fit has a `knee' mass log (M_{*} h2_{70}/M_{⊙}) = 9.94 ± 0.01 ± 0.05, a low-mass slope parameter α = -1.25 ± 0.02 ± 0.1, and a normalization φ _{*} = (4.5 ± 0.2 ± 0.8) × 10^{-3} h3_{70} Mpc^{-3 dex^{-1}}, with both random and systematic uncertainties as quoted. Together these give an estimate of the H I content of the z = 0 Universe as Ω _{H I} = (3.9 ± 0.1 ± 0.6) × 10^{-4} h^{-1}_{70} (corrected for H I self-absorption). Our analysis of the uncertainties indicates that the `knee' mass is a cosmologically fair measurement of the z = 0 value, with its largest uncertainty originating from the absolute flux calibration, but that the low-mass slope is only representative of the local Universe. We also explore large-scale trends in α and M* across the ALFALFA volume. Unlike with the 40 per cent sample, there is now sufficient coverage in both of the survey fields to make an independent determination of the HIMF in each. We find a large discrepancy in the low-mass slope (Δα = 0.14 ± 0.03) between the two regions, and argue that this is likely caused by the presence of a deep void in one field and the Virgo cluster in the other. Furthermore, we find that the value of the `knee' mass within the Local Volume appears to be suppressed by 0.18 ± 0.04 dex compared to the global ALFALFA value, which explains the lower value measured by the shallower H I Parkes All Sky Survey (HIPASS). We discuss possible explanations and interpretations of these results and how they can be expanded on with future surveys.

  8. Theory of the Protein Equilibrium Population Snapshot by H/D Exchange Electrospray Ionization Mass Spectrometry (PEPS-HDX-ESI-MS) Method used to obtain Protein Folding Energies/Rates and Selected Supporting Experimental Evidence.

    PubMed

    Liyanage, Rohana; Devarapalli, Nagarjuna; Pyland, Derek B; Puckett, Latisha M; Phan, N H; Starch, Joel A; Okimoto, Mark R; Gidden, Jennifer; Stites, Wesley E; Lay, Jackson O

    2012-12-15

    Protein equilibrium snapshot by hydrogen/deuterium exchange electrospray ionization mass spectrometry (PEPS-HDX-ESI-MS or PEPS) is a method recently introduced for estimating protein folding energies and rates. Herein we describe the basis for this method using both theory and new experiments. Benchmark experiments were conducted using ubiquitin because of the availability of reference data for folding and unfolding rates from NMR studies. A second set of experiments was also conducted to illustrate the surprising resilience of the PEPS to changes in HDX time, using staphylococcal nuclease and time frames ranging from a few seconds to several minutes. Theory suggests that PEPS experiments should be conducted at relatively high denaturant concentrations, where the protein folding/unfolding rates are slow with respect to HDX and the life times of both the closed and open states are long enough to be sampled experimentally. Upon deliberate denaturation, changes in folding/unfolding are correlated with associated changes in the ESI-MS signal upon fast HDX. When experiments are done quickly, typically within a few seconds, ESI-MS signals, corresponding to the equilibrium population of the native (closed) and denatured (open) states can both be detected. The interior of folded proteins remains largely un-exchanged. Amongst MS methods, the simultaneous detection of both states in the spectrum is unique to PEPS and provides a "snapshot" of these populations. The associated ion intensities are used to estimate the protein folding equilibrium constant (or the free energy change, ΔG). Linear extrapolation method (LEM) plots of derived ΔG values for each denaturant concentration can then be used to calculate ΔG in the absence of denaturant, ΔG(H(2)O). In accordance with the requirement for detection of signals for both the folded and unfolded states, this theoretical framework predicts that PEPS experiments work best at the middle of the denaturation curve where natured

  9. 17 CFR 249.328T - Form 17-H, Risk assessment report for brokers and dealers pursuant to section 17(h) of the...

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 17 Commodity and Securities Exchanges 3 2010-04-01 2010-04-01 false Form 17-H, Risk assessment report for brokers and dealers pursuant to section 17(h) of the Securities Exchange Act of 1934 and rules... Under Sections 13 and 15(d) of the Securities Exchange Act of 1934 § 249.328T Form 17-H, Risk assessment...

  10. Roles of pH and the Na+/H+ exchanger NHE1 in cancer: From cell biology and animal models to an emerging translational perspective?

    PubMed

    Stock, Christian; Pedersen, Stine Falsig

    2017-04-01

    Acidosis is characteristic of the solid tumor microenvironment. Tumor cells, because they are highly proliferative and anabolic, have greatly elevated metabolic acid production. To sustain a normal cytosolic pH homeostasis they therefore need to either extrude excess protons or to neutralize them by importing HCO 3 - , in both cases causing extracellular acidification in the poorly perfused tissue microenvironment. The Na + /H + exchanger isoform 1 (NHE1) is a ubiquitously expressed acid-extruding membrane transport protein, and upregulation of its expression and/or activity is commonly correlated with tumor malignancy. The present review discusses current evidence on how altered pH homeostasis, and in particular NHE1, contributes to tumor cell motility, invasion, proliferation, and growth and facilitates evasion of chemotherapeutic cell death. We summarize data from in vitro studies, 2D-, 3D- and organotypic cell culture, animal models and human tissue, which collectively point to pH-regulation in general, and NHE1 in particular, as potential targets in combination chemotherapy. Finally, we discuss the possible pitfalls, side effects and cellular escape mechanisms that need to be considered in the process of translating the plethora of basic research data into a clinical setting. Copyright © 2016 Elsevier Ltd. All rights reserved.

  11. Dissociative excitation of H2, HD, and D2 by electron impact

    NASA Technical Reports Server (NTRS)

    Carnahan, B. L.; Zipf, E. C.

    1977-01-01

    Time-of-flight techniques have been used to investigate the electron-impact dissociation of H2, HD, and D2 in order to determine the effect of isotopic mass variation in the target molecule on the dissociative excitation process. At incident electron energies near 100 eV, the time-of-flight spectrum produced from each molecule consists of atoms in the metastable 2s state and in high-lying long-lived Rydberg levels. The individual time-of-flight distributions, kinetic-energy spectra, and relative differential cross sections for these two species resulting from each molecule have been measured. The kinetic-energy spectrum of the Rydberg atoms produced from dissociative excitation of H2 was notably dissimilar in shape from the corresponding distributions produced from HD and D2. Also the 2s and Rydberg production cross sections differed between the three molecules. In the dissociation of the heteronuclear HD molecule, the ratio of fast H(2s) atoms to D(2s) atoms was about 1 to 1, while the same ratio comparing the Rydberg atoms was nearly 2 to 1. These differences indicate the influence of the mass variation on the position of the Franck-Condon region in the production of 2s atoms and on the competition between autoionization and dissociation in the formation of Rydberg fragments.

  12. First Measurements of 15N Fractionation in N2H+ toward High-mass Star-forming Cores

    NASA Astrophysics Data System (ADS)

    Fontani, F.; Caselli, P.; Palau, A.; Bizzocchi, L.; Ceccarelli, C.

    2015-08-01

    We report on the first measurements of the isotopic ratio 14N/15N in N2H+ toward a statistically significant sample of high-mass star-forming cores. The sources belong to the three main evolutionary categories of the high-mass star formation process: high-mass starless cores, high-mass protostellar objects, and ultracompact H ii regions. Simultaneous measurements of the 14N/15N ratio in CN have been made. The 14N/15N ratios derived from N2H+ show a large spread (from ∼180 up to ∼1300), while those derived from CN are in between the value measured in the terrestrial atmosphere (∼270) and that of the proto-solar nebula (∼440) for the large majority of the sources within the errors. However, this different spread might be due to the fact that the sources detected in the N2H+ isotopologues are more than those detected in the CN ones. The 14N/15N ratio does not change significantly with the source evolutionary stage, which indicates that time seems to be irrelevant for the fractionation of nitrogen. We also find a possible anticorrelation between the 14N/15N (as derived from N2H+) and the H/D isotopic ratios. This suggests that 15N enrichment could not be linked to the parameters that cause D enrichment, in agreement with the prediction by recent chemical models. These models, however, are not able to reproduce the observed large spread in 14N/15N, pointing out that some important routes of nitrogen fractionation could be still missing in the models. Based on observations carried out with the IRAM-30 m Telescope. IRAM is supported by INSU/CNRS (France), MPG (Germany), and IGN (Spain).

  13. Proton-detected 3D {sup 1}H/{sup 13}C/{sup 1}H correlation experiment for structural analysis in rigid solids under ultrafast-MAS above 60 kHz

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

    Zhang, Rongchun; Ramamoorthy, Ayyalusamy, E-mail: ramamoor@umich.edu; Nishiyama, Yusuke

    2015-10-28

    A proton-detected 3D {sup 1}H/{sup 13}C/{sup 1}H chemical shift correlation experiment is proposed for the assignment of chemical shift resonances, identification of {sup 13}C-{sup 1}H connectivities, and proximities of {sup 13}C-{sup 1}H and {sup 1}H-{sup 1}H nuclei under ultrafast magic-angle-spinning (ultrafast-MAS) conditions. Ultrafast-MAS is used to suppress all anisotropic interactions including {sup 1}H-{sup 1}H dipolar couplings, while the finite-pulse radio frequency driven dipolar recoupling (fp-RFDR) pulse sequence is used to recouple dipolar couplings among protons and the insensitive nuclei enhanced by polarization transfer technique is used to transfer magnetization between heteronuclear spins. The 3D experiment eliminates signals from non-carbon-bonded protonsmore » and non-proton-bonded carbons to enhance spectral resolution. The 2D (F1/F3) {sup 1}H/{sup 1}H and 2D {sup 13}C/{sup 1}H (F2/F3) chemical shift correlation spectra extracted from the 3D spectrum enable the identification of {sup 1}H-{sup 1}H proximity and {sup 13}C-{sup 1}H connectivity. In addition, the 2D (F1/F2) {sup 1}H/{sup 13}C chemical shift correlation spectrum, incorporated with proton magnetization exchange via the fp-RFDR recoupling of {sup 1}H-{sup 1}H dipolar couplings, enables the measurement of proximities between {sup 13}C and even the remote non-carbon-bonded protons. The 3D experiment also gives three-spin proximities of {sup 1}H-{sup 1}H-{sup 13}C chains. Experimental results obtained from powder samples of L-alanine and L-histidine ⋅ H{sub 2}O ⋅ HCl demonstrate the efficiency of the 3D experiment.« less

  14. Observations of D/H ratios in H2O, HCl, and HF on Venus and new DCl and DF line strengths

    NASA Astrophysics Data System (ADS)

    Krasnopolsky, V. A.; Belyaev, D. A.; Gordon, I. E.; Li, G.; Rothman, L. S.

    2013-05-01

    , W.J. [2012]. Icarus 217, 561-569). Equivalent widths of the HDO and H2O lines are similar in our observations; therefore some errors cancel out in their ratios. Photochemistry of HCl in the mesosphere tends to enrich D in HCl and deplete it in H2O. This may be an explanation of the twofold difference between the observed D/H in HCl and H2O. An alternative explanation is based on (D/H)H2O ≈ 200 observed in the mesosphere by Bjoraker et al. (Bjoraker, G.L., Larson, H.P., Mumma, M.J., Timmermann, R., Montani, J.L. [1992]. Bull. Am. Astron. Soc. 24, 995) and Fedorova et al. (Fedorova, A. et al. J. Geophys. Res. 113, E00B22). This means an effective exchange of D between H2O and HCl and almost equal D/H in both species. However, this requires a twofold increase in D/H from the lower atmosphere to the mesosphere. This increase is not supported by theory; furthermore, condensation processes usually deplete D/H above the clouds. Photochemistry of HF has not been studied; it proceeds mostly in the lower thermosphere, and D/H in HF may be very different from that in H2O. Overall, the observational data on D/H in all hydrogen-bearing species on Venus are helpful to solve the problem of deuterium fractionation on Venus.

  15. Intensification of heat and mass transfer by ultrasound: application to heat exchangers and membrane separation processes.

    PubMed

    Gondrexon, N; Cheze, L; Jin, Y; Legay, M; Tissot, Q; Hengl, N; Baup, S; Boldo, P; Pignon, F; Talansier, E

    2015-07-01

    This paper aims to illustrate the interest of ultrasound technology as an efficient technique for both heat and mass transfer intensification. It is demonstrated that the use of ultrasound results in an increase of heat exchanger performances and in a possible fouling monitoring in heat exchangers. Mass transfer intensification was observed in the case of cross-flow ultrafiltration. It is shown that the enhancement of the membrane separation process strongly depends on the physico-chemical properties of the filtered suspensions. Copyright © 2014 Elsevier B.V. All rights reserved.

  16. Luminosity and Stellar Mass Functions from the 6dF Galaxy Survey

    NASA Astrophysics Data System (ADS)

    Colless, M.; Jones, D. H.; Peterson, B. A.; Campbell, L.; Saunders, W.; Lah, P.

    2007-12-01

    The completed 6dF Galaxy Survey includes redshifts for over 124,000 galaxies. We present luminosity functions in optical and near-infrared passbands that span a range of 10^4 in luminosity. These luminosity functions show systematic deviations from the Schechter form. The corresponding luminosity densities in the optical and near-infrared are consistent with an old stellar population and a moderately declining star formation rate. Stellar mass functions, derived from the K band luminosities and simple stellar population models selected by b_J-r_F colour, lead to an estimate of the present-day stellar mass density of ρ_* = (5.00 ± 0.11) × 10^8 h M_⊙ Mpc^{-3}, corresponding to Ω_* h = (1.80 ± 0.04) × 10^{-3}.

  17. Influence of nuclear exchange on nonadiabatic electron processes in H(+)+H2 collisions.

    PubMed

    Errea, L F; Illescas, Clara; Macías, A; Méndez, L; Pons, B; Rabadán, I; Riera, A

    2010-12-28

    H(+)+H(2) collisions are studied by means of a semiclassical approach that explicitly accounts for nuclear rearrangement channels in nonadiabatic electron processes. A set of classical trajectories is used to describe the nuclear motion, while the electronic degrees of freedom are treated quantum mechanically in terms of a three-state expansion of the collision wavefunction. We describe electron capture and vibrational excitation, which can also involve nuclear exchange and dissociation, in the E = 2-1000 eV impact energy range. We compare dynamical results obtained with two parametrizations of the potential energy surface of H(3)(+) ground electronic state. Total cross sections for E > 10 eV agree with previous results using a vibronic close-coupling expansion, and with experimental data for E < 10 eV. Additionally, some prototypical features of both nuclear and electron dynamics at low E are discussed.

  18. A Numerical Model of Exchange Chromatography Through 3D Lattice Structures

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

    Salloum, Maher; Robinson, David B.

    Rapid progress in the development of additive manufacturing technologies is opening new opportunities to fabricate structures that control mass transport in three dimensions across a broad range of length scales. We describe a structure that can be fabricated by newly available commercial 3D printers. It contains an array of regular three-dimensional flow paths that are in intimate contact with a solid phase, and thoroughly shuffle material among the paths. We implement a chemically reacting flow model to study its behavior as an exchange chromatography column, and compare it to an array of one-dimensional flow paths that resemble more traditional honeycombmore » monoliths. A reaction front moves through the columns and then elutes. Here, the front is sharper at all flow rates for the structure with three-dimensional flow paths, and this structure is more robust to channel width defects than the one-dimensional array.« less

  19. A Numerical Model of Exchange Chromatography Through 3D Lattice Structures

    DOE PAGES

    Salloum, Maher; Robinson, David B.

    2018-01-30

    Rapid progress in the development of additive manufacturing technologies is opening new opportunities to fabricate structures that control mass transport in three dimensions across a broad range of length scales. We describe a structure that can be fabricated by newly available commercial 3D printers. It contains an array of regular three-dimensional flow paths that are in intimate contact with a solid phase, and thoroughly shuffle material among the paths. We implement a chemically reacting flow model to study its behavior as an exchange chromatography column, and compare it to an array of one-dimensional flow paths that resemble more traditional honeycombmore » monoliths. A reaction front moves through the columns and then elutes. Here, the front is sharper at all flow rates for the structure with three-dimensional flow paths, and this structure is more robust to channel width defects than the one-dimensional array.« less

  20. A massive hydrogen-rich Martian greenhouse recorded in D/H

    NASA Astrophysics Data System (ADS)

    Pahlevan, K.; Schaefer, L. K.; Desch, S. J.; Elkins-Tanton, L. T.

    2017-12-01

    The deuterium-to-hydrogen (D/H) ratio in Martian atmospheric water ( 6x standard mean ocean water, SMOW) [1,2] is higher than that of known sources [3,4] alluding to a planetary enrichment process. A recent measurement by the Curiosity rover of Hesperian clays yields a D/H value 3x higher than SMOW [5], demonstrating that most enrichment occurred early in planetary history, buttressing the conclusions of Martian meteorite studies [6,7]. Extant models of the isotopic evolution of the Martian hydrosphere have not incorporated primordial H2, despite its likely abundance on early Mars. Here, we report the first 1D climate calculations with an atmospheric composition determined via degassing from a reducing magma ocean to study Martian climate during an early water ocean stage. A reducing Martian magma ocean is expected based on experimental petrology [8], the degassing of which gives rise to an H2-rich steam atmosphere [9] with strong attendant greenhouse warming [10,11] even after the removal of steam via condensation. At the pressures and temperatures prevailing in such a degassed greenhouse, we find that isotopic exchange in the fluid envelope is rapid, strongly concentrating deuterium in water molecules over molecular hydrogen [12]. The subsequent loss of the isotopically light H2-rich atmosphere results in a 2x D/H enrichment in the oceans via isotopic equilibration alone. These calculations suggest that most of the D/H enrichment observed in the first billion years of Martian history is produced by the evolution of a massive ( 100 bar) H2-rich greenhouse in the aftermath of magma ocean crystallization. The proposed link between early planetary process and modern isotopic observable opens a new window into the earliest history of Mars. [1] Owen, T. et al. Science 240, 1767-1770 (1988). [2] Webster, C. R. et al. Science 341, 260-263 (2013). [3] Lunine, J. I. et al. Icarus 165, 1-8, (2003). [4] Marty, B. et al. EPSL 441, 91-102, (2016). [5] Mahaffy, P. et al

  1. [Characteristics of soil pH and exchangeable acidity in red soil profile under different vegetation types].

    PubMed

    Ji, Gang; Xu, Ming-gang; Wen, Shi-lin; Wang, Bo-ren; Zhang, Lu; Liu, Li-sheng

    2015-09-01

    The characteristics of soil pH and exchangeable acidity in soil profile under different vegetation types were studied in hilly red soil regions of southern Hunan Province, China. The soil samples from red soil profiles within 0-100 cm depth at fertilized plots and unfertilized plots were collected and analyzed to understand the profile distribution of soil pH and exchangeable acidity. The results showed that, pH in 0-60 cm soil from the fertilized plots decreased as the following sequence: citrus orchard > Arachis hypogaea field > tea garden. As for exchangeable acidity content, the sequence was A. hypogaea field ≤ citrus orchard < tea garden. After tea tree and A. hypogaea were planted for long time, acidification occurred in surface soil (0-40 cm), compared with the deep soil (60-100 cm), and soil pH decreased by 0.55 and 0.17 respectively, but such changes did not occur in citrus orchard. Soil pH in 0-40 cm soil from the natural recovery vegetation unfertilized plots decreased as the following sequence: Imperata cylindrica land > Castanea mollissima garden > Pinus elliottii forest ≥ Loropetalum chinensis forest. As for exchangeable acidity content, the sequence was L cylindrica land < C. mollissima garden < L. chinensis forest ≤ P. elliottii forest. Soil pH in surface soil (0-20 cm) from natural forest plots, secondary forest and Camellia oleifera forest were significantly lower than that from P. massoniana forest, decreased by 0.34 and 0.20 respectively. For exchangeable acidity content in 0-20 cm soil from natural forest plot, P. massoniana forest and secondary forest were significantly lower than C. oleifera forest. Compared with bare land, surface soil acidification in unfertilized plots except I. cylindrica land had been accelerated, and the natural secondary forest was the most serious among them, with surface soil pH decreasing by 0.52. However, the pH increased in deep soils from unfertilized plots except natural secondary forest, and I. cylindrica

  2. Long range ferromagnetism in (Zn, Mn, Li)Se with competition between double exchange and p-d exchange

    NASA Astrophysics Data System (ADS)

    Zhu, Y.; Liu, T.; Zhang, X. Y.; Pan, Y. F.; Wei, X. Y.; Ma, C. L.; Shi, D. N.; Fan, J. Y.

    2017-04-01

    In this paper, we elucidate the mechanism for Li co-dopant induced enhancement of the ferromagnetism in 2 × 2 × 2 and 3 × 3 × 3 cubic (Zn, Mn)Se using density functional calculations. The doping atoms tend to congregate together according to the ferromagnetic (FM) energy. All configurations are strongly FM ones due to double exchange (DE) and p-d exchange (PE). DE and PE are shown in the partial density of states. The hole is uniformly distributed in the cubic (Zn, Mn, Li)Se, and it is the one and only parameter to decide the exchange energy, when impurity atoms stay further away from each other. The average exchange energy of these configurations is considered to be a function of the square root of the hole concentration. The fitting data to a polynomial function shows that DE and PE have roles of similar importance in the exchange energy.

  3. D/H and Water Concentrations of Submarine MORB Glass Around the World: Analytical Aspects, Standardization, and (re)defining Mantle D/H Ranges

    NASA Astrophysics Data System (ADS)

    Bindeman, I. N.; Dixon, J. E.; Langmuir, C. H.; Palandri, J. L.

    2015-12-01

    The advent and calibration of the Thermal Combustion Element Analyzer (TCEA) continuous flow system coupled with the large-radius mass spectrometer MAT253 permits precise (±0.02 wt.% H2O, ±1-3‰ D/H) measurements in 1-10 mg of volcanic glass (0.1 wt.% H2O requires ~10 mg glass), which permits the targeting of small amounts of the freshest concentrate. This is a >100 factor reduction in sample size over conventional methods, four times over more common Delta series instruments. We investigated in triplicate 115 samples of submarine MORB glasses ranging from water-poor (0.1-0.2wt%) to water-rich (1.2-1.5wt%). These samples were previously investigated for major and trace elements, radiogenic isotopes; a large subset of these samples coming from the FAZAR expedition were studied previously by FTIR for water concentration. We also ran samples previously studied by the conventional off-line technique: MORB glass including those from the Easter Platform and the Alvin 526-1 standard (0.2wt% H2O). We observe excellent 1:1 correspondence (1.02x+0.02, R2=0.94) of wt% water by FTIR and TCEA suggesting complete extraction of water and no dependence on water concentration. We measure 51‰ total range in D/H that correlates with all other chemical and isotopic indicators of mantle enrichment, with the heaviest values occurring in the most enriched samples. When used uncorrected values of H2 gas run against H2 gas of known composition, this range agrees nicely with previous D/H range for MORB (-30 to -90‰), measured for samples run conventionally. Uncorrected analyses of Alvin glass 526-1 gives -66‰. When run against SMOW, SLAP and -41‰ water sealed in silver cups, the range is shifted by -15‰; when standardization is done by with three commonly used mica standards as is done most commonly in different labs, the range is shifted downward by -30-32‰. There are no isotopic offsets related to total water or D/H range requiring different slope or non-linear correction

  4. Final Hazard Categorization for the Remediation of the 118-D-1, 118-D-2, 118-D-3, 118-H-1, 118-H-2, and 118-H-3 Solid Waste Burial Grounds

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

    T. J. Rodovsky

    2006-12-06

    This report presents the final hazard categorization (FHC) for the remediation of the 118-D-1, 118-D-2, and 118-D-3 Burial Grounds located within the 100-D/DR Area of the Hanford Site and the 118-H-1, 118-H-2, and 118-H-3 Burial Grounds located within the 100-H Area of the Hanford Site.

  5. Final Hazard Categorization for the Remediation of the 118-D-1, 118-D-2, 118-D-3, 118-H-1, 118-H-2, and 118-H-3 Solid Waste Burial Grounds

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

    T. J. Rodovsky

    2007-04-12

    This report presents the final hazard categorization (FHC) for the remediation of the 118-D-1, 118-D-2, and 118-D-3 Burial Grounds located within the 100-D/DR Area of the Hanford Site and the 118-H-1, 118-H-2, and 118-H-3 Burial Grounds located within the 100-H Area of the Hanford Site.

  6. Absolute Charge Exchange Cross Sections for ^3He^2+ Collisions with ^4He and H_2

    NASA Astrophysics Data System (ADS)

    Mawhorter, R. J.; Greenwood, J.; Smith, S. J.; Chutjian, A.

    2002-05-01

    The JPL charge exchange beam-line(J.B. Greenwood, et al., Phys. Rev A 63), 062707 (2001) was modified to increase the forward acceptance angle and enable the measurement of total charge-exchange cross sections for slow, light, highly-charged ion collisions with neutral targets(R. E. Olson and M. Kimura, J. Phys. B 15), 4231 (1982). Data are presented for single charge exchange cross sections for ^3He^2+ nuclei scattered by ^4He and H2 in the energy range 0.33-4.67 keV/amu. For both targets there is good agreement with Kusakabe, et al.(T. Kusakabe, et al., J. Phys. Soc. Japan 59), 1218 (1990). Angular collection is studied by a comparison with differential measurements(D. Bordenave-Montesquieu and R. Dagnac, J. Phys. B 27), 543 (1994), as well as with earlier JPL results(J.B. Greenwood, et al., Ap. J. 533), L175 (2000), ibid. 529, 605 (2000) using heavier projectiles and targets. This work was carried out at JPL/Caltech, and was supported through contract with NASA. RJM thanks the NRC for a Senior Associateship at JPL.

  7. Creatine ( methyl-d3) dilution in urine for estimation of total body skeletal muscle mass: accuracy and variability vs. MRI and DXA.

    PubMed

    Clark, Richard V; Walker, Ann C; Miller, Ram R; O'Connor-Semmes, Robin L; Ravussin, Eric; Cefalu, William T

    2018-01-01

    A noninvasive method to estimate muscle mass based on creatine ( methyl-d 3 ) (D 3 -creatine) dilution using fasting morning urine was evaluated for accuracy and variability over a 3- to 4-mo period. Healthy older (67- to 80-yr-old) subjects ( n = 14) with muscle wasting secondary to aging and four patients with chronic disease (58-76 yr old) fasted overnight and then received an oral 30-mg dose of D 3 -creatine at 8 AM ( day 1). Urine was collected during 4 h of continued fasting and then at consecutive 4- to 8-h intervals through day 5. Assessment was repeated 3-4 mo later in 13 healthy subjects and 1 patient with congestive heart failure. Deuterated and unlabeled creatine and creatinine were measured using liquid chromatography-tandem mass spectrometry. Total body creatine pool size and muscle mass were calculated from D 3 -creatinine enrichment in urine. Muscle mass was also measured by whole body MRI and 24-h urine creatinine, and lean body mass (LBM) was measured by dual-energy X-ray absorptiometry (DXA). D 3 -creatinine urinary enrichment from day 5 provided muscle mass estimates that correlated with MRI for all subjects ( r = 0.88, P < 0.0001), with less bias [difference from MRI = -3.00 ± 2.75 (SD) kg] than total LBM assessment by DXA, which overestimated muscle mass vs. MRI (+22.5 ± 3.7 kg). However, intraindividual variability was high with the D 3 -creatine dilution method, with intrasubject SD for estimated muscle mass of 2.5 kg vs. MRI (0.5 kg) and DXA (0.8 kg). This study supports further clinical validation of the D 3 -creatine method for estimating muscle mass. NEW & NOTEWORTHY Measurement of creatine ( methyl-d 3 ) (D 3 -creatine) and D 3 -creatinine excretion in fasted morning urine samples may be a simple, less costly alternative to MRI or dual-energy X-ray absorptiometry (DXA) to calculate total body muscle mass. The D 3 -creatine enrichment method provides estimates of muscle mass that correlate well with MRI, and with less

  8. Variable-temperature Fourier transform near-infrared imaging spectroscopy of the deuterium/hydrogen exchange in liquid D₂O.

    PubMed

    Unger, Miriam; Ozaki, Yukihiro; Siesler, Heinz W

    2014-01-01

    In the present publication, the deuterium/hydrogen (D/H) exchange of liquid D2O exposed to water vapor of the surrounding atmosphere has been studied by variable-temperature Fourier transform near-infrared (FT-NIR) imaging spectroscopy. Apart from the visualization of the exchange process in the time-resolved FT-NIR images, kinetic parameters and the activation energy for this D/H exchange reaction have been derived from the Arrhenius plot of the variable-temperature spectroscopic data.

  9. What is Neptune's D/H ratio really telling us about its water abundance?

    NASA Astrophysics Data System (ADS)

    Ali-Dib, Mohamad; Lakhlani, Gunjan

    2018-05-01

    We investigate the deep-water abundance of Neptune using a simple two-component (core + envelope) toy model. The free parameters of the model are the total mass of heavy elements in the planet (Z), the mass fraction of Z in the envelope (fenv), and the D/H ratio of the accreted building blocks (D/Hbuild).We systematically search the allowed parameter space on a grid and constrain it using Neptune's bulk carbon abundance, D/H ratio, and interior structure models. Assuming solar C/O ratio and cometary D/H for the accreted building blocks are forming the planet, we can fit all of the constraints if less than ˜15 per cent of Z is in the envelope (f_{env}^{median} ˜ 7 per cent), and the rest is locked in a solid core. This model predicts a maximum bulk oxygen abundance in Neptune of 65× solar value. If we assume a C/O of 0.17, corresponding to clathrate-hydrates building blocks, we predict a maximum oxygen abundance of 200× solar value with a median value of ˜140. Thus, both cases lead to oxygen abundance significantly lower than the preferred value of Cavalié et al. (˜540× solar), inferred from model-dependent deep CO observations. Such high-water abundances are excluded by our simple but robust model. We attribute this discrepancy to our imperfect understanding of either the interior structure of Neptune or the chemistry of the primordial protosolar nebula.

  10. Construction of chiral ligand exchange capillary electrochromatography for d,l-amino acids enantioseparation and its application in glutaminase kinetics study.

    PubMed

    Zhao, Liping; Qiao, Juan; Zhang, Ke; Li, Dan; Zhang, Hongyi; Qi, Li

    2018-05-04

    A chiral ligand exchange capillary electrochromatography (CLE-CEC) protocol was designed and implemented for d,l-amino acids enantioseparation with poly(maleic anhydride-styrene-methacryloyl-l-arginine methyl ester) as the coating. The block copolymer was synthesized through the reversible addition fragmentation chain transfer reaction. In the constructed CLE-CEC system, poly (methacryloyl-l-arginine methyl ester) moiety of the block copolymer played the role as the immobilized chiral ligand and Zn (II) was used as the central ion. Key factors, including pH of buffer solution, ratio of Zn (II) to ligands, the mass ratio of monomers in the block copolymer, which affect the enantioresolution were investigated. Comparing with the bare capillary, the CLE-CEC enantioresolution was enhanced greatly with the coating one. 5 Pairs of d,l-amino acids enantiomers obtained baseline separation with 5 pairs partly separated. The mechanism of enhancement enantioresolution of the developed CLE-CEC system was explored briefly. Further, good linearities were achieved in the range of 25.0 μM-5.0 mM for quantitative analysis of d-glutamine (r 2  = 0.997) and l-glutamine (r 2  = 0.991). Moreover, the proposed CLE-CEC assay was successfully applied in the kinetics study of glutaminase by using l-glutamine as the substrate. Copyright © 2018 Elsevier B.V. All rights reserved.

  11. New Insights into Active Site Conformation Dynamics of E. coli PNP Revealed by Combined H/D Exchange Approach and Molecular Dynamics Simulations.

    PubMed

    Kazazić, Saša; Bertoša, Branimir; Luić, Marija; Mikleušević, Goran; Tarnowski, Krzysztof; Dadlez, Michal; Narczyk, Marta; Bzowska, Agnieszka

    2016-01-01

    The biologically active form of purine nucleoside phosphorylase (PNP) from Escherichia coli (EC 2.4.2.1) is a homohexamer unit, assembled as a trimer of dimers. Upon binding of phosphate, neighboring monomers adopt different active site conformations, described as open and closed. To get insight into the functions of the two distinctive active site conformations, virtually inactive Arg24Ala mutant is complexed with phosphate; all active sites are found to be in the open conformation. To understand how the sites of neighboring monomers communicate with each other, we have combined H/D exchange (H/DX) experiments with molecular dynamics (MD) simulations. Both methods point to the mobility of the enzyme, associated with a few flexible regions situated at the surface and within the dimer interface. Although H/DX provides an average extent of deuterium uptake for all six hexamer active sites, it was able to indicate the dynamic mechanism of cross-talk between monomers, allostery. Using this technique, it was found that phosphate binding to the wild type (WT) causes arrest of the molecular motion in backbone fragments that are flexible in a ligand-free state. This was not the case for the Arg24Ala mutant. Upon nucleoside substrate/inhibitor binding, some release of the phosphate-induced arrest is observed for the WT, whereas the opposite effects occur for the Arg24Ala mutant. MD simulations confirmed that phosphate is bound tightly in the closed active sites of the WT; conversely, in the open conformation of the active site of the WT phosphate is bound loosely moving towards the exit of the active site. In Arg24Ala mutant binary complex Pi is bound loosely, too.

  12. Longitudinal relaxation optimized amide 1H-CEST experiments for studying slow chemical exchange processes in fully protonated proteins.

    PubMed

    Yuwen, Tairan; Kay, Lewis E

    2017-04-01

    Chemical Exchange Saturation Transfer (CEST) experiments are increasingly used to study slow timescale exchange processes in biomolecules. Although 15 N- and 13 C-CEST have been the approaches of choice, the development of spin state selective 1 H-CEST pulse sequences that separate the effects of chemical and dipolar exchange [T. Yuwen, A. Sekhar and L. E. Kay, Angew Chem Int Ed Engl 2016 doi: 10.1002/anie.201610759 (Yuwen et al. 2017)] significantly increases the utility of 1 H-based experiments. Pulse schemes have been described previously for studies of highly deuterated proteins. We present here longitudinal-relaxation optimized amide 1 H-CEST experiments for probing chemical exchange in protonated proteins. Applications involving a pair of proteins are presented establishing that accurate 1 H chemical shifts of sparsely populated conformers can be obtained from simple analyses of 1 H-CEST profiles. A discussion of the inherent differences between 15 N-/ 13 C- and 1 H-CEST experiments is presented, leading to an optimal strategy for recording 1 H-CEST experiments.

  13. Measurements of ion-molecule reactions of He plus, H plus, HeH plus with H sub 2 and D sub 2

    NASA Technical Reports Server (NTRS)

    Johnsen, R.; Biondi, M. A.

    1974-01-01

    A drift tube mass spectrometer apparatus has been used to determine the rate coefficient, energy dependence and product ions of the reaction He(+) +H2. The total rate coefficient at 300 K is 1.1 plus or minus 0.1) 10 to minus 13th power cu cm/sec. The reaction proceeds principally by dissociative charge transfer to produce H(+), with the small remainder going by charge transfer to produce H2(+) and by atom rearrangement to produce HeH(+). The rate coefficient increases slowly with increasing ion mean energy, reaching a value of 2.8 x ten to the minus 13th power cu cm sec at 0.18 eV. The corresponding reaction with deuterium, He(+) + D2, exhibits a value (5 plus or minus 1) x 10 to the minus 14th cu cm/sec at 300K. The reaction rates for conversion of H(+) and HeH(+) to H3(+) on collisions with H2 molecules are found to agree well with results of previous investigations.

  14. Diffusion Monte Carlo simulations of gas phase and adsorbed D2-(H2)n clusters

    NASA Astrophysics Data System (ADS)

    Curotto, E.; Mella, M.

    2018-03-01

    We have computed ground state energies and analyzed radial distributions for several gas phase and adsorbed D2(H2)n and HD(H2)n clusters. An external model potential designed to mimic ionic adsorption sites inside porous materials is used [M. Mella and E. Curotto, J. Phys. Chem. A 121, 5005 (2017)]. The isotopic substitution lowers the ground state energies by the expected amount based on the mass differences when these are compared with the energies of the pure clusters in the gas phase. A similar impact is found for adsorbed aggregates. The dissociation energy of D2 from the adsorbed clusters is always much higher than that of H2 from both pure and doped aggregates. Radial distributions of D2 and H2 are compared for both the gas phase and adsorbed species. For the gas phase clusters, two types of hydrogen-hydrogen interactions are considered: one based on the assumption that rotations and translations are adiabatically decoupled and the other based on nonisotropic four-dimensional potential. In the gas phase clusters of sufficiently large size, we find the heavier isotopomer more likely to be near the center of mass. However, there is a considerable overlap among the radial distributions of the two species. For the adsorbed clusters, we invariably find the heavy isotope located closer to the attractive interaction source than H2, and at the periphery of the aggregate, H2 molecules being substantially excluded from the interaction with the source. This finding rationalizes the dissociation energy results. For D2-(H2)n clusters with n ≥12 , such preference leads to the desorption of D2 from the aggregate, a phenomenon driven by the minimization of the total energy that can be obtained by reducing the confinement of (H2)12. The same happens for (H2)13, indicating that such an effect may be quite general and impact on the absorption of quantum species inside porous materials.

  15. Isomerization and fragmentation reactions of gaseous phenylarsane radical cations and phenylarsanyl cations. A study by tandem mass spectrometry and theoretical calculations.

    PubMed

    Letzel, Matthias; Kirchhoff, Dirk; Grützmacher, Hans-Friedrich; Stein, Daniel; Grützmacher, Hansjörg

    2006-04-28

    The unimolecular reactions of radical cations and cations derived from phenylarsane, C6H5AsH2 (1) and dideutero phenylarsane, C6H5AsD2 (1-d2), were investigated by methods of tandem mass spectrometry and theoretical calculations. The mass spectrometric experiments reveal that the molecular ion of phenylarsane, 1*+, exhibits different reactivity at low and high internal excess energy. Only at low internal energy the observed fragmentations are as expected, that is the molecular ion 1*+ decomposes almost exclusively by loss of an H atom. The deuterated derivative 1-d2 with an AsD2 group eliminates selectively a D atom under these conditions. The resulting phenylarsenium ion [C6H5AsH]+, 2+, decomposes rather easily by loss of the As atom to give the benzene radical cation [C6H6]*+ and is therefore of low abundance in the 70 eV EI mass spectrum. At high internal excess energy, the ion 1*+ decomposes very differently either by elimination of an H2 molecule, or by release of the As atom, or by loss of an AsH fragment. Final products of these reactions are either the benzoarsenium ion 4*+, or the benzonium ion [C6H7]+, or the benzene radical cation, [C6H6]*+. As key-steps, these fragmentations contain reductive eliminations from the central As atom under H-H or C-H bond formation. Labeling experiments show that H/D exchange reactions precede these fragmentations and, specifically, that complete positional exchange of the H atoms in 1*+ occurs. Computations at the UMP2/6-311+G(d)//UHF/6-311+G(d) level agree best with the experimental results and suggest: (i) 1*+ rearranges (activation enthalpy of 93 kJ mol(-1)) to a distinctly more stable (DeltaH(r)(298) = -64 kJ mol(-1)) isomer 1 sigma*+ with a structure best represented as a distonic radical cation sigma complex between AsH and benzene. (ii) The six H atoms of the benzene moiety of 1 sigma*+ become equivalent by a fast ring walk of the AsH group. (iii) A reversible isomerization 1+<==>1 sigma*+ scrambles eventually all H

  16. Observing mass exchange with the Lofoten Basin using surface drifters

    NASA Astrophysics Data System (ADS)

    Dugstad, Johannes S.; LaCasce, Joe; Koszalka, Inga M.; Fer, Ilker

    2017-04-01

    The Lofoten Basin in the Nordic Seas plays a central role in the global overturning circulation, acting as a reservoir for northward-flowing Atlantic water. Substantial heat loss occurs here, permitting the waters to become denser and eventually sink nearer the Arctic. Idealized modeling studies and theoretical arguments suggest the warm water enters the Lofoten Basin via eddy transport from the boundary current over the adjacent continental slope. But there is no observational evidence that this is the major contribution to mass exchange between the warm Atlantic Current and the Basin. How the basin waters exit also remains a mystery. Surface drifters offer an unique possibility to study the pathways of the boundary-basin exchange of mass and heat. We thereby examine trajectories of surface drifters released in the Nordic Seas in the POLEWARD and PROVOLO experiments, and supplemented by historical data from the Global Drifter Array. Contrary to the idea that the boundary current eddies are the main source, the results suggest that fluid is entering the Lofoten Basin from all sides. However, the drifters exit preferentially in the northeast corner of the basin. This asymmetry likely contributes to the extended residence times of the warm Atlantic waters in the Lofoten Basin. We consider various measures to quantify the effect, and test whether this is captured in a high resolution numerical model.

  17. Dissociative charge transfer of H/+/ ions with H2 and D2 molecules from 78 to 330 K

    NASA Technical Reports Server (NTRS)

    Johnsen, R.; Chen, A.; Biondi, M. A.

    1980-01-01

    The dissociative charge transfer of He(+) ions with H2 and D2 molecules has been studied using a temperature-variable drift-tube mass-spectrometer apparatus over the temperature range 78 to 330 K. The binary rate coefficients are small at 300 K, approximately 10 to the -13th to 10 to the -14th cu cm/sec, and only slightly larger at 78 K. Termolecular contributions to the binary rate coefficients are found to be small at 330 K but increase substantially with decreasing temperature. Two-body charge transfer with D2 is found to be slower than with H2 by a factor of 10, in good agreement with recent theoretical predictions, although the measured values of the rate coefficients are larger by a factor of about 4 than the predicted values.

  18. Water-deuterium oxide exchange in polymers used in spacecraft applications. [outgassing from Mylar and Kapton

    NASA Technical Reports Server (NTRS)

    Carre, D. J.

    1980-01-01

    The replacement of water (H2O) by deuterium oxide (D2O) and the exchange between atmospheric water and adsorbed or absorbed D2O were investigated for the polymeric materials Kapton and Mylar using thermal gravimetric analysis and infrared spectroscopy. Replacement of H2O by D2O is easily accomplished. However, exposure of D2O samples to the ambient atmosphere or gases containing H2O results in rapid proton and deuteron exchange between H2O vapor and adsorbed D2O. Replacement of H2O by D2O would not be a practical solution to alleviate spectral interferences that would result from water outgassing in spacecraft orbital environments. Maintaining the materials of interest in a dehydrated state is a more reasonable approach.

  19. Characteristics of stratosphere-troposphere exchange in a general circulation model

    NASA Technical Reports Server (NTRS)

    Mote, Philip W.; Holton, James R.; Boville, Byron A.

    1994-01-01

    In this study we examine mass exchange, water vapor exchange, and the behavior of idealized tracers and parcels to diagnose Stratosphere-Troposphere Exchange (STE) in the National Center for Atmospheric Research (NCAR) General Circulation Model (GCM), the Community Climate Model (CCM2). The CCM2 correctly represents the seasonality of mass exchange across 100 hPa, but values are uniformly too strong. Water vapor, however, indicates that tropical STE is not well represented in the CCM2; even though mean tropopause temperatures are colder than observed, the lower stratosphere is too moist. Most net mass flux occurs at water vapor mixing ratios of about 4-5 parts per million by volume (ppmv), about 1 ppmv too moist. Vertical resolution has little impact on the nature of tropical STE. In midlatitudes, CCM2 more successfully represents STE, which occurs in developing baroclinic waves and stationary anticyclones. Exchange from troposphere to stratosphere does occur but only influences the lowest few kilometers of the extratropical stratosphere, even for tracers with large vertical gradients.

  20. Optimization of heat and mass transfers in counterflow corrugated-plate liquid-gas exchangers used in a greenhouse dehumidifier

    NASA Astrophysics Data System (ADS)

    Bentounes, N.; Jaffrin, A.

    1998-09-01

    Heat and mass transfers occuring in a counterflow direct contact liquid-gas exchanger determine the performance of a new greenhouse air dehumidifier designed at INRA. This prototype uses triethylene glycol (TEG) as the desiccant fluid which extracts water vapor from the air. The regeneration of the TEG desiccant fluid is then performed by direct contact with combustion gas from a high efficiency boiler equipped with a condensor. The heat and mass transfers between the thin film of diluted TEG and the hot gas were simulated by a model which uses correlation formula from the literature specifically relevant to the present cross-corrugated plates geometry. A simple set of analytical solutions is first derived, which explains why some possible processes can clearly be far from optimal. Then, more exact numerical calculations confirm that some undesirable water recondensations on the upper part of the exchanger were limiting the performance of this prototype. More suitable conditions were defined for the process, which lead to a new design of the apparatus. In this second prototype, a gas-gas exchanger provides dryer and cooler gas to the basis of the regenerators, while a warmer TEG is fed on the top. A whole range of operating conditions was experimented and measured parameters were compared with numerical simulations of this new configuration: recondensation did not occur any more. As a consequence, this second prototype was able to concentrate the desiccant fluid at the desired rate of 20 kg H_{2O}/hour, under temperature and humidity conditions which correspond to the dehumidification of a 1000 m2 greenhouse heated at night during the winter season.

  1. 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.

    PubMed

    Gershon, P D

    2010-12-15

    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.

  2. 26 CFR 1.168(h)-1 - Like-kind exchanges involving tax-exempt use property.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... property. 1.168(h)-1 Section 1.168(h)-1 Internal Revenue INTERNAL REVENUE SERVICE, DEPARTMENT OF THE... and Corporations § 1.168(h)-1 Like-kind exchanges involving tax-exempt use property. (a) Scope. (1... property (as defined in section 168(h)) at the time of the transfer; and (ii) Property that does not become...

  3. Zero Launch Mass 3D printer

    NASA Image and Video Library

    2018-05-01

    Packing light is the idea behind the Zero Launch Mass 3-D Printer. Instead of loading up on heavy building supplies, a large scale 3-D printer capable of using recycled plastic waste and dirt at the destination as construction material would save mass and money when launching robotic precursor missions to build infrastructure on the Moon or Mars in preparation for human habitation. To make this a reality, Nathan Gelino, a researcher engineer with NASA’s Swamp Works at Kennedy Space Center, measured the temperature of a test specimen from the 3-D printer Tuesday as an early step in characterizing printed material strength properties. Material temperature plays a large role in the strength of bonds between layers.

  4. Mass spectrometry and tandem mass spectrometry of citrus limonoids.

    PubMed

    Tian, Qingguo; Schwartz, Steven J

    2003-10-15

    Methods for atmospheric pressure chemical ionization tandem mass spectrometry (APCI-MS/MS) of citrus limonoid aglycones and electrospray ionization tandem mass spectrometry (ESI-MS/MS) of limonoid glucosides are reported. The fragmentation patterns of four citrus limonoid aglycones (limonin, nomilin, obacunone, and deacetylnomilin) and six limonoid glucosides, that is, limonin 17-beta-D-glucopyranoside (LG), nomilin 17-beta-D-glucopyranoside (NG), nomilinic acid 17-beta-D-glucopyranoside (NAG), deacetyl nomilinic acid 17-beta-D-glucopyranoside (DNAG), obacunone 17-beta-D-glucopyranoside (OG), and obacunoic acid 17-beta-D-glucopyranoside (OAG) were investigated using a quadruple mass spectrometer in low-energy collisionally activated dissociation (CAD). The four limonoid aglycones and four limonoid glucosides (LG, OG, NAG, and DNAG) were purified from citrus seeds; the other two limonoid glucosides (NG and OAG) were tentatively identified in the crude extract of grapefruit seeds by ESI mass spectrometry in both positive and negative ion analysis. Ammonium hydroxide or acetic acid was added to the mobile phase to facilitate ionization. During positive ion APCI analysis of limonoid aglycones, protonated molecular ion, [M + H]+, or adduct ion, [M + NH3 + H]-, was formed as base peaks when ammonium hydroxide was added to the mobile phase. Molecular anions or adduct ions with acetic acid ([M + HOAc - H] and [M + HOAc]-) or a deprotonated molecular ion were produced during negative ion APCI analysis of limonoid aglycones, depending on the mobile-phase modifier used. Positive ion ESI-MS of limonoid glucosides produced adduct ions of [M + H + NH3]+, [M + Na]+, and [M + K]+ when ammonium hydroxide was added to the mobile phase. After collisionally activated dissociation (CAD) of the limonoid aglycone molecular ions in negative ion APCI analysis, fragment ions indicated structural information of the precursor ions, showing the presence of methyl, carboxyl, and oxygenated ring

  5. Effective Mass Theory of 2D Excitons Revisited

    NASA Astrophysics Data System (ADS)

    Gonzalez, Joseph; Oleynik, Ivan

    Two-dimensional (2D) semiconducting materials possess an exceptionally unique set of electronic and excitonic properties due to the combined effects of quantum and dielectric confinement. Reliable determination of exciton binding energies from both first-principles many-body perturbation theory (GW/BSE) and experiment is very challenging due to the enormous computational expense as well as the tremendous technical difficulties in experiment.. Very recently, effective mass theories of 2D excitons have been developed as an attractive alternative for inexpensive and accurate evaluation of the exciton binding energies. In this presentation, we evaluate two effective mass theory approaches by Velizhanin et al and Olsen et al in predicting exciton binding energies across a wide range of 2D materials. We specifically analyze the trends related to the varying screening lengths and exciton effective masses. We also extended the effective mass theory of 2D excitons to include effects of electron and hole mass anisotropies (mx ≠ my) , the latter showing a substantial influence on exciton binding energies. The recent predictions of exciton binding energies being independent of the exciton effective mass and a linear correlation with the band gap of a specific material are also critically reexamined.

  6. Kinetic Investigation of Homogeneous H(2)-D(2) Equilibration Catalyzed by Pt-Au Cluster Compounds. Characterization of the Cluster [(H)Pt(AuPPh(3))(9)](NO(3))(2).

    PubMed

    Rubinstein, Leon I.; Pignolet, Louis H.

    1996-11-06

    The new Pt-Au hydrido cluster compound [(H)Pt(AuPPh(3))(9)](NO(3))(2) (3) has been synthesized and characterized by NMR, FABMS, and single-crystal X-ray diffraction [triclinic, P&onemacr;, a = 17.0452(1) Å, b = 17.4045(2) Å, c = 55.2353(1) Å, alpha = 89.891(1) degrees, beta = 85.287(1) degrees, gamma = 75.173(1) degrees, V = 15784.0(2) Å(3), Z = 4 (two molecules in asymmetric unit), residual R = 0.089 for 45 929 observed reflections and 3367 variables, Mo Kalpha radiation]. The Pt(AuP)(9) core geometry is a distorted icosahedron with three vertices vacant. The Pt-Au, Au-Au, and Au-P distances are within the normal ranges observed in other Pt-Au clusters. This cluster is a catalyst for H(2)-D(2) equilibration in homogeneous solution phase and has been used in a general mechanistic study of this reaction catalyzed by Pt-Au clusters. We previously proposed that a key step in the mechanism for catalytic H(2)-D(2) equilibration is the dissociation of a PPh(3) ligand to give a cluster with an open Au site for bonding of H(2) or D(2). This was based on qualitative observations that PPh(3) inhibited the rate of HD production with [Pt(AuPPh(3))(8)](NO(3))(2) (1) as catalyst. In order to test this hypothesis, phosphine inhibition (on the rate of HD production) and phosphine ligand exchange kinetic experiments were carried out with [(H)(PPh(3))Pt(AuPPh(3))(7)](NO(3))(2) (2) and 3. In this paper we show that the rate constant for phosphine dissociation determined from the PPh(3) inhibition rate study of H(2)-D(2) equilibration with cluster 2 is nearly identical to the rate constant for dissociative phosphine ligand exchange. The slower rate for H(2)-D(2) equilibration observed with 3 compared with 2 (5.5 x 10(-3) vs 7.7 x 10(-2) turnover s(-1)) is explained by its smaller rate constant for phosphine dissociation (2.8 x 10(-5) vs 2.9 x 10(-4) s(-1)). The fact that clusters 2 and 3 show similar kinetic behaviors suggests that the PPh(3) dissociation step in the catalytic H(2

  7. Estimating an exchange rate between the EQ-5D-3L and ASCOT.

    PubMed

    Stevens, Katherine; Brazier, John; Rowen, Donna

    2018-06-01

    The aim was to estimate an exchange rate between EQ-5D-3L and the Adult Social Care Outcome Tool (ASCOT) using preference-based mapping via common time trade-off (TTO) valuations. EQ-5D and ASCOT are useful for examining cost-effectiveness within the health and social care sectors, respectively, but there is a policy need to understand overall benefits and compare across sectors to assess relative value for money. Standard statistical mapping is unsuitable since it relies on conceptual overlap of the measures but EQ-5D and ASCOT have different conceptualisations of quality of life. We use a preference-based mapping approach to estimate the exchange rate using common TTO valuations for both measures. A sample of health states from each measure was valued using TTO by 200 members of the UK adult general population. Regression analyses are used to generate separate equations between EQ-5D-3L and ASCOT values using their original value set and TTO values elicited here. These are solved as simultaneous equations to estimate the relationship between EQ-5D-3L and ASCOT. The relationship for moving from ASCOT to EQ-5D-3L is a linear transformation with an intercept of -0.0488 and gradient of 0.978. This enables QALY gains generated by ASCOT and EQ-5D to be compared across different interventions. This paper estimated an exchange rate between ASCOT and EQ-5D-3L using a preference-based mapping approach that does not compromise the descriptive systems of the two measures. This contributes to the development of preference-based mapping through the use of TTO as the common metric used to estimate the exchange rate between measures.

  8. 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.

    PubMed

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

    2015-01-01

    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.

  9. Modelling non-adiabatic effects in H{sub 3}{sup +}: Solution of the rovibrational Schrödinger equation with motion-dependent masses and mass surfaces

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

    Mátyus, Edit, E-mail: matyus@chem.elte.hu; Szidarovszky, Tamás; Császár, Attila G., E-mail: csaszar@chem.elte.hu

    2014-10-21

    Introducing different rotational and vibrational masses in the nuclear-motion Hamiltonian is a simple phenomenological way to model rovibrational non-adiabaticity. It is shown on the example of the molecular ion H{sub 3}{sup +}, for which a global adiabatic potential energy surface accurate to better than 0.1 cm{sup −1} exists [M. Pavanello, L. Adamowicz, A. Alijah, N. F. Zobov, I. I. Mizus, O. L. Polyansky, J. Tennyson, T. Szidarovszky, A. G. Császár, M. Berg et al., Phys. Rev. Lett. 108, 023002 (2012)], that the motion-dependent mass concept yields much more accurate rovibrational energy levels but, unusually, the results are dependent upon themore » choice of the embedding of the molecule-fixed frame. Correct degeneracies and an improved agreement with experimental data are obtained if an Eckart embedding corresponding to a reference structure of D{sub 3h} point-group symmetry is employed. The vibrational mass of the proton in H{sub 3}{sup +} is optimized by minimizing the root-mean-square (rms) deviation between the computed and recent high-accuracy experimental transitions. The best vibrational mass obtained is larger than the nuclear mass of the proton by approximately one third of an electron mass, m{sub opt,p}{sup (v)}=m{sub nuc,p}+0.31224 m{sub e}. This optimized vibrational mass, along with a nuclear rotational mass, reduces the rms deviation of the experimental and computed rovibrational transitions by an order of magnitude. Finally, it is shown that an extension of the algorithm allowing the use of motion-dependent masses can deal with coordinate-dependent mass surfaces in the rovibrational Hamiltonian, as well.« less

  10. Reconstructing the history of water ice formation from HDO/H2O and D2O/HDO ratios in protostellar cores

    NASA Astrophysics Data System (ADS)

    Furuya, K.; van Dishoeck, E. F.; Aikawa, Y.

    2016-02-01

    Recent interferometer observations have found that the D2O/HDO abundance ratio is higher than that of HDO/H2O by about one order of magnitude in the vicinity of low-mass protostar NGC 1333-IRAS 2A, where water ice has sublimated. Previous laboratory and theoretical studies show that the D2O/HDO ice ratio should be lower than the HDO/H2O ice ratio, if HDO and D2O ices are formed simultaneously with H2O ice. In this work, we propose that the observed feature, D2O/HDO > HDO/H2O, is a natural consequence of chemical evolution in the early cold stages of low-mass star formation as follows: 1) majority of oxygen is locked up in water ice and other molecules in molecular clouds, where water deuteration is not efficient; and 2) water ice formation continues with much reduced efficiency in cold prestellar/protostellar cores, where deuteration processes are highly enhanced as a result of the drop of the ortho-para ratio of H2, the weaker UV radiation field, etc. Using a simple analytical model and gas-ice astrochemical simulations, which traces the evolution from the formation of molecular clouds to protostellar cores, we show that the proposed scenario can quantitatively explain the observed HDO/H2O and D2O/HDO ratios. We also find that the majority of HDO and D2O ices are likely formed in cold prestellar/protostellar cores rather than in molecular clouds, where the majority of H2O ice is formed. This work demonstrates the power of the combination of the HDO/H2O and D2O/HDO ratios as a tool to reveal the past history of water ice formation in the early cold stages of star formation, and when the enrichment of deuterium in the bulk of water occurred. Further observations are needed to explore if the relation, D2O/HDO > HDO/H2O, is common in low-mass protostellar sources.

  11. Na+-H+ exchange activity in taste receptor cells.

    PubMed

    Vinnikova, Anna K; Alam, Rammy I; Malik, Shahbaz A; Ereso, Glenn L; Feldman, George M; McCarty, John M; Knepper, Mark A; Heck, Gerard L; DeSimone, John A; Lyall, Vijay

    2004-03-01

    mRNA for two Na(+)-H(+)-exchanger isoforms 1 and 3 (NHE-1 and NHE-3) was detected by RT-PCR in fungiform and circumvallate taste receptor cells (TRCs). Anti-NHE-1 antibody binding was localized to the basolateral membranes, and the anti-NHE-3 antibody was localized in the apical membranes of fungiform and circumvallate TRCs. In a subset of TRCs, NHE-3 immunoreactivity was also detected in the intracellular compartment. For functional studies, an isolated lingual epithelium containing a single fungiform papilla was mounted with apical and basolateral sides isolated and perfused with nominally CO(2)/HCO(3)(-)-free physiological media (pH 7.4). The TRCs were monitored for changes in intracellular pH (pH(i)) and Na(+) ([Na(+)](i)) using fluorescence ratio imaging. At constant external pH, 1) removal of basolateral Na(+) reversibly decreased pH(i) and [Na(+)](i); 2) HOE642, a specific blocker, and amiloride, a nonspecific blocker of basolateral NHE-1, attenuated the decrease in pH(i) and [Na(+)](i); 3) exposure of TRCs to basolateral NH(4)Cl or sodium acetate pulses induced transient decreases in pH(i) that recovered spontaneously to baseline; 4) pH(i) recovery was inhibited by basolateral amiloride, 5-(N-methyl-N-isobutyl)-amiloride (MIA), 5-(N-ethyl-N-isopropyl)-amiloride (EIPA), HOE642, and by Na(+) removal; 5) HOE642, MIA, EIPA, and amiloride inhibited pH(i) recovery with K(i) values of 0.23, 0.46, 0.84, and 29 microM, respectively; and 6) a decrease in apical or basolateral pH acidified TRC pH(i) and inhibited spontaneous pH(i) recovery. The results indicate the presence of a functional NHE-1 in the basolateral membranes of TRCs. We hypothesize that NHE-1 is involved in sour taste transduction since its activity is modulated during acid stimulation.

  12. 3-D indium(III)-btc channel frameworks and their ion-exchange properties (btc=1,3,5-benzenetricarboxylate)

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

    Lin Zhengzhong; Chen Lian; Yue Chengyang

    2006-04-15

    Assembly of InCl{sub 3} with 1,3,5-benzenetricarboxylic acid (H{sub 3}btc) and pyridine or pyridine derivatives under hydrothermal conditions produces a series of isostructural coordination polymers with the interesting frameworks: {l_brace}(HL)[In{sub 4}(OH){sub 4}(btc){sub 3}].L.3H{sub 2}O{r_brace} {sub n} {sub ,} L=pyridine (1); L=2-picoline (2); L=4-picoline (3) and {l_brace}(Hdpea)[In{sub 4}(OH){sub 4}(btc){sub 3}].3H{sub 2}O{r_brace} {sub n} (4) (dpea=1,2-di(4-pyridyl)ethane). In these four complexes, carboxyl and hydroxyl oxygen atoms bridge indium(III) centers to form octahedral chain-like sinusoidal curves, which are further interlinked by btc{sup 3-} moieties to generate 3-D frameworks with 1-D channels. The protonated guests HL in 1-3 located at the channels can be fully exchangedmore » by K{sup +} ion or partially exchanged by Sr{sup 2+}, and Ba{sup 2+} ions.« less

  13. H(D) → D(H) + Cu(111) collision system: Molecular dynamics study of surface temperature effects

    PubMed Central

    Vurdu, Can D.; Güvenç, Ziya B.

    2011-01-01

    All the channels of the reaction dynamics of gas-phase H (or D) atoms with D (or H) atoms adsorbed onto a Cu(111) surface have been studied by quasiclassical constant energy molecular dynamics simulations. The surface is flexible and is prepared at different temperature values, such as 30 K, 94 K, and 160 K. The adsorbates were distributed randomly on the surface to create 0.18 ML, 0.28 ML, and 0.50 ML of coverages. The multi-layer slab is mimicked by a many-body embedded-atom potential energy function. The slab atoms can move according to the exerted external forces. Treating the slab atoms non-rigid has an important effect on the dynamics of the projectile atom and adsorbates. Significant energy transfer from the projectile atom to the surface lattice atoms takes place especially during the first impact that modifies significantly the details of the dynamics of the collisions. Effects of the different temperatures of the slab are investigated in this study. Interaction between the surface atoms and the adsorbates is modeled by a modified London–Eyring–Polanyi–Sato (LEPS) function. The LEPS parameters are determined by using the total energy values which were calculated by a density functional theory and a generalized gradient approximation for an exchange-correlation energy for many different orientations, and locations of one- and two-hydrogen atoms on the Cu(111) surface. The rms value of the fitting procedure is about 0.16 eV. Many different channels of the processes on the surface have been examined, such as inelastic reflection of the incident hydrogen, subsurface penetration of the incident projectile and adsorbates, sticking of the incident atom on the surface. In addition, hot-atom and Eley-Rideal direct processes are investigated. The hot-atom process is found to be more significant than the Eley-Rideal process. Furthermore, the rate of subsurface penetration is larger than the sticking rate on the surface. In addition, these results are compared

  14. H(D) → D(H) + Cu(111) collision system: molecular dynamics study of surface temperature effects.

    PubMed

    Vurdu, Can D; Güvenç, Ziya B

    2011-04-28

    All the channels of the reaction dynamics of gas-phase H (or D) atoms with D (or H) atoms adsorbed onto a Cu(111) surface have been studied by quasiclassical constant energy molecular dynamics simulations. The surface is flexible and is prepared at different temperature values, such as 30 K, 94 K, and 160 K. The adsorbates were distributed randomly on the surface to create 0.18 ML, 0.28 ML, and 0.50 ML of coverages. The multi-layer slab is mimicked by a many-body embedded-atom potential energy function. The slab atoms can move according to the exerted external forces. Treating the slab atoms non-rigid has an important effect on the dynamics of the projectile atom and adsorbates. Significant energy transfer from the projectile atom to the surface lattice atoms takes place especially during the first impact that modifies significantly the details of the dynamics of the collisions. Effects of the different temperatures of the slab are investigated in this study. Interaction between the surface atoms and the adsorbates is modeled by a modified London-Eyring-Polanyi-Sato (LEPS) function. The LEPS parameters are determined by using the total energy values which were calculated by a density functional theory and a generalized gradient approximation for an exchange-correlation energy for many different orientations, and locations of one- and two-hydrogen atoms on the Cu(111) surface. The rms value of the fitting procedure is about 0.16 eV. Many different channels of the processes on the surface have been examined, such as inelastic reflection of the incident hydrogen, subsurface penetration of the incident projectile and adsorbates, sticking of the incident atom on the surface. In addition, hot-atom and Eley-Rideal direct processes are investigated. The hot-atom process is found to be more significant than the Eley-Rideal process. Furthermore, the rate of subsurface penetration is larger than the sticking rate on the surface. In addition, these results are compared and

  15. Surfactant control of air-sea gas exchange across contrasting biogeochemical regimes

    NASA Astrophysics Data System (ADS)

    Pereira, Ryan; Schneider-Zapp, Klaus; Upstill-Goddard, Robert

    2014-05-01

    months likely from primary production and spatially there is less suppression of air-sea gas exchange with increasing distance from the shoreline, which is likely due to riverine inputs. REFERENCES Bock, E. J., Hara, T., Frew, N. M., and McGillis, W. R., 1999. Relationship between air-sea gas transfer and short wind waves. Journal of Geophysical Research-Oceans 104, 25821-25831. Brockmann, U. H., Huhnerfuss, H., Kattner, G., Broecker, H. C., and Hentzschel, G., 1982. Artificial surface-films in the sea area near sylt. Limnology and Oceanography 27, 1050-1058. Goldman, J. C., Dennett, M. R., and Frew, N. M., 1988. Surfactant effects on air sea gas-exchange under turbulent conditions. Deep-Sea Research Part a-Oceanographic Research Papers 35, 1953-1970. McKenna, S. P. and McGillis, W. R., 2004. The role of free-surface turbulence and surfactants in air-water gas transfer. International Journal of Heat and Mass Transfer 47, 539-553. Salter, M. E., R. C. Upstill-Goddard, P. D. Nightingale, S. D. Archer, B. Blomquist, D. T. Ho, B. Huebert, P. Schlosser, and M. Yang (2011), Impact of an artificial surfactant release on air-sea gas fluxes during Deep Ocean Gas Exchange Experiment II, J. Geophys. Res., 116, C11016, doi:10.1029/2011JC00702 Takahashi, T., Sutherland, S. C., Wanninkhof, R., Sweeney, C., Feely, R. A., Chipman, D. W., Hales, B., Friederich, G., Chavez, F., Sabine, C., Watson, A., Bakker, D. C. E., Schuster, U., Metzl, N., Yoshikawa-Inoue, H., Ishii, M., Midorikawa, T., Nojiri, Y., Körtzinger, A., Steinhoff, T., Hoppema, M., Olafsson, J., Arnarson, T. S., Tilbrook, B., Johannessen, T., Olsen, A., Bellerby, R., Wong, C. S., Delille, B., Bates, N. R., and de Baar, H. J. W., 2009. Climatological mean and decadal change in surface ocean pCO 2, and net sea-air CO 2 flux over the global oceans. Deep-Sea Research Part II: Topical Studies in Oceanography 56, 554-577.

  16. Higher cation exchange capacity determined lower critical soil pH and higher Al concentration for soybean.

    PubMed

    Baquy, M Abdulaha-Al; Li, Jiu-Yu; Shi, Ren-Yong; Kamran, Muhammad Aqeel; Xu, Ren-Kou

    2018-03-01

    Low soil pH and aluminum (Al) toxicity induced by soil acidification are the main obstacles in many regions of the world for crop production. The purpose of this study was to reveal the mechanisms on how the properties of the soils derived from different parent materials play role on the determination of critical soil pH and Al concentration for soybean crops. A set of soybean pot experiment was executed in greenhouse with a soil pH gradient as treatment for each of four soils to fulfill the objectives of this study. The results indicated that plant growth parameters were affected adversely due to Al toxicity at low soil pH level in all soils. The critical soil pH varied with soil type and parent materials. They were 4.38, 4.63, 4.74, and 4.95 in the Alfisol derived from loss deposit, and the Ultisols derived from Quaternary red earth, granite, and Tertiary red sandstone, respectively. The critical soil exchangeable Al was 2.42, 1.82, 1.55, and 1.44 cmol c /kg for the corresponding soils. At 90% yield level, the critical Al saturation was 6.94, 10.36, 17.79, and 22.75% for the corresponding soils. The lower critical soil pH and Al saturation, and higher soil exchangeable Al were mainly due to greater soil CEC and exchangeable base cations. Therefore, we recommended that critical soil pH, soil exchangeable Al, and Al saturation should be considered during judicious liming approach for soybean production.

  17. Suppression of H-/O2- exchange by incorporated nitride anions in the perovskite lattice

    NASA Astrophysics Data System (ADS)

    Takeiri, Fumitaka; Yajima, Takeshi; Yamamoto, Takafumi; Kobayashi, Yoji; Matsui, Toshiaki; Hester, James; Kageyama, Hiroshi

    2017-12-01

    We investigate the low temperature anion exchange behavior of hydride and oxide in perovskite oxynitrides. CaH2 reduction of (Sr1-xLax)Ti(O3-xNx) (0exchange of hydride for oxide rather than nitride, yielding the oxyhydride-nitride (Sr1-xLax)Ti(O3-x-yHyNx). However, the exchange of hydride is drastically suppressed with increasing nitrogen content and is completely impeded when the nitride content reaches 10% of the anionic site. This implies that the N3- anions in the oxide lattice play a crucial role in lowering diffusion of O2- (and H-). The present study indicates the necessity to consider kinetic aspects when manipulating anion compositions, in particular in a mixed anion system with a small amount of anion vacancies.

  18. Photodissociation dynamics of gaseous CpCo(CO)2 and ligand exchange reactions of CpCoH2 with C3H4, C3H6, and NH3.

    PubMed

    Oana, Melania; Nakatsuka, Yumiko; Albert, Daniel R; Davis, H Floyd

    2012-05-31

    The photodissociation dynamics of CpCo(CO)(2) was studied in a molecular beam using photofragment translational energy spectroscopy with 157 nm photoionization detection of the metallic products. At 532 and 355 nm excitation, the dominant one-photon channel involved loss of a single CO ligand producing CpCoCO. The product angular distributions were isotropic, and a large fraction of excess energy appeared as product vibrational excitation. Production of CpCO + 2CO resulted from two-photon absorption processes. The two-photon dissociation of mixtures containing CpCo(CO)(2) and H(2) at the orifice of a pulsed nozzle was used to produce a novel 16-electron unsaturated species, CpCoH(2). Transition metal ligand exchange reactions, CpCoH(2) + L → CpCoL + H(2) (L = propyne, propene, or ammonia), were studied under single-collision conditions for the first time. In all cases, ligand exchange occurred via 18-electron association complexes with lifetimes comparable to their rotational periods. Although ligand exchange reactions were not detected from CpCoH(2) collisions with methane or propane (L = CH(4) or C(3)H(8)), a molecular beam containing CpCoCH(4) was produced by photolysis of mixtures containing CpCo(CO)(2) and CH(4).

  19. Numerical study of heat transfer characteristics in BOG heat exchanger

    NASA Astrophysics Data System (ADS)

    Yan, Yan; Pfotenhauer, John M.; Miller, Franklin; Ni, Zhonghua; Zhi, Xiaoqin

    2016-12-01

    In this study, a numerical study of turbulent flow and the heat transfer process in a boil-off liquefied natural gas (BOG) heat exchanger was performed. Finite volume computational fluid dynamics and the k - ω based shear stress transport model were applied to simulate thermal flow of BOG and ethylene glycol in a full-sized 3D tubular heat exchanger. The simulation model has been validated and compared with the engineering specification data from its supplier. In order to investigate thermal characteristics of the heat exchanger, velocity, temperature, heat flux and thermal response were studied under different mass flowrates in the shell-side. The shell-side flow pattern is mostly determined by viscous forces, which lead to a small velocity and low temperature buffer area in the bottom-right corner of the heat exchanger. Changing the shell-side mass flowrate could result in different distributions of the shell-side flow. However, the distribution in the BOG will remain in a relatively stable pattern. Heat flux increases along with the shell-side mass flowrate, but the increase is not linear. The ratio of increased heat flux to the mass flow interval is superior at lower mass flow conditions, and the threshold mass flow for stable working conditions is defined as greater than 0.41 kg/s.

  20. Fragility of ferromagnetic double exchange interactions and pressure tuning of magnetism in 3 d -5 d double perovskite Sr2FeOsO6

    NASA Astrophysics Data System (ADS)

    Veiga, L. S. I.; Fabbris, G.; van Veenendaal, M.; Souza-Neto, N. M.; Feng, H. L.; Yamaura, K.; Haskel, D.

    2015-06-01

    The ability to tune exchange (magnetic) interactions between 3 d transition metals in perovskite structures has proven to be a powerful route to discovery of novel properties. Here we demonstrate that the introduction of 3 d -5 d exchange pathways in double perovskites enables additional tunability, a result of the large spatial extent of 5 d wave functions. Using x-ray probes of magnetism and structure at high pressure, we show that compression of Sr2FeOsO6 drives an unexpected continuous change in the sign of Fe-Os exchange interactions and a transition from antiferromagnetic to ferrimagnetic order. We analyze the relevant electron-electron interactions, shedding light into fundamental differences with the more thoroughly studied 3 d -3 d systems.

  1. Letter: Observation of the 16O/18O exchange during electrospray ionization.

    PubMed

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

    2015-01-01

    Isotopic exchange approach coupled to high-resolution mass spectrometry has become the power analytical approach for a wide range of analytical and bioanalyticall applications. Considerable efforts have been dedicated to developing fast exchange techniques directly in the ionization source. But all such methods are limited to the hydrogen/deuterium exchange approaches. In this paper we demonstrate that certain types of oxygen atoms can also be exchanged for (18)O on the time scale of the ionization process. Using HIO(3) and NaIO(4) and by infusing the heavy water H(2)(18)O in the ESI source we have demonstrated that it is possible to obtain a high level of oxygen exchange. It was observed that the rate of this exchange depends to a large extent on the temperature of the desolvating capillary of the mass spectrometer. Several other species, such as peptides, oligonucleotides and low weight organic molecules, were subjected to in-ESI (16)O/(18)O exchange but the exchange was not observed.

  2. Hydrogen exchange mass spectrometry of functional membrane-bound chemotaxis receptor complexes.

    PubMed

    Koshy, Seena S; Eyles, Stephen J; Weis, Robert M; Thompson, Lynmarie K

    2013-12-10

    The transmembrane signaling mechanism of bacterial chemotaxis receptors is thought to involve changes in receptor conformation and dynamics. The receptors function in ternary complexes with two other proteins, CheA and CheW, that form extended membrane-bound arrays. Previous studies have shown that attractant binding induces a small (∼2 Å) piston displacement of one helix of the periplasmic and transmembrane domains toward the cytoplasm, but it is not clear how this signal propagates through the cytoplasmic domain to control the kinase activity of the CheA bound at the membrane-distal tip, nearly 200 Å away. The cytoplasmic domain has been shown to be highly dynamic, which raises the question of how a small piston motion could propagate through a dynamic domain to control CheA kinase activity. To address this, we have developed a method for measuring dynamics of the receptor cytoplasmic fragment (CF) in functional complexes with CheA and CheW. Hydrogen-deuterium exchange mass spectrometry (HDX-MS) measurements of global exchange of the CF demonstrate that the CF exhibits significantly slower exchange in functional complexes than in solution. Because the exchange rates in functional complexes are comparable to those of other proteins with similar structures, the CF appears to be a well-structured protein within these complexes, which is compatible with its role in propagating a signal that appears to be a tiny conformational change in the periplasmic and transmembrane domains of the receptor. We also demonstrate the feasibility of this protocol for local exchange measurements by incorporating a pepsin digest step to produce peptides with 87% sequence coverage and only 20% back exchange. This method extends HDX-MS to membrane-bound functional complexes without detergents that may perturb the stability or structure of the system.

  3. Hydrogen Exchange Mass Spectrometry of Functional Membrane-bound Chemotaxis Receptor Complexes

    PubMed Central

    Koshy, Seena S.; Eyles, Stephen J.; Weis, Robert M.; Thompson, Lynmarie K.

    2014-01-01

    The transmembrane signaling mechanism of bacterial chemotaxis receptors is thought to involve changes in receptor conformation and dynamics. The receptors function in ternary complexes with two other proteins, CheA and CheW, that form extended membrane-bound arrays. Previous studies have shown that attractant binding induces a small (~2 Å) piston displacement of one helix of the periplasmic and transmembrane domains towards the cytoplasm, but it is not clear how this signal propagates through the cytoplasmic domain to control the kinase activity of the CheA bound at the membrane-distal tip, nearly 200 Å away. The cytoplasmic domain has been shown to be highly dynamic, which raises the question of how a small piston motion could propagate through a dynamic domain to control CheA kinase activity. To address this, we have developed a method for measuring dynamics of the receptor cytoplasmic fragment (CF) in functional complexes with CheA and CheW. Hydrogen exchange mass spectrometry (HDX-MS) measurements of global exchange of CF demonstrate that CF exhibits significantly slower exchange in functional complexes than in solution. Since the exchange rates in functional complexes are comparable to that of other proteins of similar structure, the CF appears to be a well-structured protein within these complexes, which is compatible with its role in propagating a signal that appears to be a tiny conformational change in the periplasmic and transmembrane domains of the receptor. We also demonstrate the feasibility of this protocol for local exchange measurements, by incorporating a pepsin digest step to produce peptides with 87% sequence coverage and only 20% back exchange. This method extends HDX-MS to membrane-bound functional complexes without detergents that may perturb the stability or structure of the system. PMID:24274333

  4. Differential Stimulation of the Na+/H+ Exchanger Determines Chloroquine Uptake in Plasmodium falciparum

    PubMed Central

    Wünsch, Stefan; Sanchez, Cecilia P.; Gekle, Michael; Große-Wortmann, Lars; Wiesner, Jochen; Lanzer, Michael

    1998-01-01

    Here we describe the identification and characterization of a physiological marker that is associated with the chloroquine-resistant (CQR) phenotype in the human malarial parasite Plasmodium falciparum. Single cell in vivo pH measurements revealed that CQR parasites consistently have an elevated cytoplasmic pH compared to that of chloroquine-sensitive (CQS) parasites because of a constitutively activated Na+/H+ exchanger (NHE). Together, biochemical and physiological data suggest that chloroquine activates the plasmodial NHE of CQS parasites, resulting in a transitory phase of rapid sodium/hydrogen ion exchange during which chloroquine is taken up by this protein. The constitutively stimulated NHE of CQR parasites are capable of little or no further activation by chloroquine. We propose that the inability of chloroquine to stimulate its own uptake through the constitutively activated NHE of resistant parasites constitutes a minimal and necessary event in the generation of the chloroquine-resistant phenotype. PMID:9442109

  5. The simulation of 3D mass models in 2D digital mammography and breast tomosynthesis

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

    Shaheen, Eman, E-mail: eman.shaheen@uzleuven.be; De Keyzer, Frederik; Bosmans, Hilde

    2014-08-15

    Purpose: This work proposes a new method of building 3D breast mass models with different morphological shapes and describes the validation of the realism of their appearance after simulation into 2D digital mammograms and breast tomosynthesis images. Methods: Twenty-five contrast enhanced MRI breast lesions were collected and each mass was manually segmented in the three orthogonal views: sagittal, coronal, and transversal. The segmented models were combined, resampled to have isotropic voxel sizes, triangularly meshed, and scaled to different sizes. These masses were referred to as nonspiculated masses and were then used as nuclei onto which spicules were grown with anmore » iterative branching algorithm forming a total of 30 spiculated masses. These 55 mass models were projected into 2D projection images to obtain mammograms after image processing and into tomographic sequences of projection images, which were then reconstructed to form 3D tomosynthesis datasets. The realism of the appearance of these mass models was assessed by five radiologists via receiver operating characteristic (ROC) analysis when compared to 54 real masses. All lesions were also given a breast imaging reporting and data system (BIRADS) score. The data sets of 2D mammography and tomosynthesis were read separately. The Kendall's coefficient of concordance was used for the interrater observer agreement assessment for the BIRADS scores per modality. Further paired analysis, using the Wilcoxon signed rank test, of the BIRADS assessment between 2D and tomosynthesis was separately performed for the real masses and for the simulated masses. Results: The area under the ROC curves, averaged over all observers, was 0.54 (95% confidence interval [0.50, 0.66]) for the 2D study, and 0.67 (95% confidence interval [0.55, 0.79]) for the tomosynthesis study. According to the BIRADS scores, the nonspiculated and the spiculated masses varied in their degrees of malignancy from normal (BIRADS 1) to highly

  6. Elucidation of the binding sites of sodium dodecyl sulfate to β-lactoglobulin using hydrogen/deuterium exchange mass spectrometry combined with docking simulation.

    PubMed

    Hu, Wenbing; Liu, Jianan; Luo, Qun; Han, Yumiao; Wu, Kui; Lv, Shuang; Xiong, Shaoxiang; Wang, Fuyi

    2011-05-30

    Hydrogen/deuterium exchange mass spectrometry (H/DX MS) has become a powerful tool to investigate protein-protein and protein-ligand interactions, but it is still challenging to localize the interaction regions/sites of ligands with pepsin-resistant proteins such as lipocalins. β-Lactoglobulin (BLG), a member of the lipocalin family, can bind a variety of small hydrophobic molecules including retinols, retinoic acids, and long linear fatty acids. However, whether the binding site of linear molecules locates in the external groove or internal cavity of BLG is controversial. In this study we used H/DX MS combined with docking simulation to localize the interaction sites of a tested ligand, sodium dodecyl sulfate (SDS), binding to BLG. H/DX MS results indicated that SDS can bind to both the external and the internal sites in BLG. However, neither of the sites is saturated with SDS, allowing a dynamic ligand exchange to occur between the sites at equilibrium state. Docking studies revealed that SDS forms H-bonds with Lys69 in the internal site and Lys138 and Lys141 in the external site in BLG via the sulfate group, and interacts with the hydrophobic residues valine, leucine, isoleucine and methionine within both of the sites via its hydrocarbon tail, stabilizing the BLG-SDS complex. Copyright © 2011 John Wiley & Sons, Ltd.

  7. The 3H(d,gamma) Reaction and the 3 H(d,gamma)/ 3H(d, n) Branching Ratio for Ec.m. 300 keV

    NASA Astrophysics Data System (ADS)

    Parker, Cody E.

    The 3H(d, gamma)5He reaction and the 3H(d, gamma)/3H(d, n) branching ratio have been measured using a 500-keV pulsed deuteron beam incident on a titanium tritide target of stopping thickness at the Edwards Accelerator Laboratory. The time-of-flight technique has been used to distinguish the gamma-rays from neutrons in the bismuth germinate (BGO) gamma-ray detector. A stilbene scintillator and an NE-213 scintillator have been used to detect the neutrons from the 3H(d, n)alpha reaction using both the pulse-shape discrimination and time-of-flight techniques. A target holder with an ion-implanted silicon detector at a fixed angle of 135° to the beam axis to simultaneously measure alpha-particles as a normalization for the number of neutrons was incorporated to reduce the uncertainty in the neutron yield over the preliminary measurement. The gamma-rays have been measured at laboratory angles of 0°, 4°, 9°, and 15°. Information about the gamma-ray energy distribution for the unbound ground state and first excited state of 5He have been obtained experimentally by comparing the BGO data to Monte Carlo simulations. The reported branching ratios for each angle contain only contributions from the ground-state gamma-ray branch.

  8. Proton Translocation in Cytochrome c Oxidase: Insights from Proton Exchange Kinetics and Vibrational Spectroscopy

    PubMed Central

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

    2014-01-01

    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. PMID:25268561

  9. Uncoupling and Turnover in a Cl−/H+ Exchange Transporter

    PubMed Central

    Walden, Michael; Accardi, Alessio; Wu, Fang; Xu, Chen; Williams, Carole; Miller, Christopher

    2007-01-01

    The CLC-family protein CLC-ec1, a bacterial homologue of known structure, stoichiometrically exchanges two Cl− for one H+ via an unknown membrane transport mechanism. This study examines mutations at a conserved tyrosine residue, Y445, that directly coordinates a Cl− ion located near the center of the membrane. Mutations at this position lead to “uncoupling,” such that the H+/Cl− transport ratio decreases roughly with the volume of the substituted side chain. The uncoupled proteins are still able to pump protons uphill when driven by a Cl− gradient, but the extent and rate of this H+ pumping is weaker in the more uncoupled variants. Uncoupling is accompanied by conductive Cl− transport that is not linked to counter-movement of H+, i.e., a “leak.” The unitary Cl− transport rate, measured in reconstituted liposomes by both a conventional initial-velocity method and a novel Poisson dilution approach, is ∼4,000 s−1 for wild-type protein, and the uncoupled mutants transport Cl− at similar rates. PMID:17389248

  10. D/H on Mars: Effects of floods, volcanism, impacts, and polar processes

    USGS Publications Warehouse

    Carr, M.H.

    1990-01-01

    Water in the Martian atmosphere is 5.1 times more enriched in deuterium than terrestial water. The enrichment has been previously attributed to either a massive loss of water early in the planet's history or the presence of only a very small reservoir of water that has exchanged with the atmosphere over geologic time. Both these interpretations appear inconsistent with geologic evidence of large floods and sustained volcanism. Large floods are believed to have episodically introduced large amounts of water onto the surface. During a large flood roughly 1017 g of water would almost immediately sublime into the atmospher and be frozen out on polar terrain, to form a new layer several centimeters thick. The long-term effect of a flood would depend on where the water pooled after the flood. If the water pooled at low latitudes, all the water would slowly sublime into the atmosphers and ultimately be frozen out at the poles, thereby adding several meters to the polar deposits for each flood. If the water pooled at high latitude, it would form a permanent ice deposit, largely isolated from further interchange with the atmosphere. Volcanism has also episodically introduced water into the atmosphere. Most of this water has become incorporated into the polar deposits. That released over the last 3.5 Ga could have added a few kilometers to the polar deposits, depending on the amount of dust incorporated along with the ice. Large cometary impacts would have introduced additional large amounts of water into the atmosphere. The long-term evolution of D/H in the atmosphere depends on the rate of exchange of water between the atmosphere and the polar deposits. If exchange is active, then loss rates of hydrogen from the upper atmosphere are substantially higher than those estimated by Y. L. Yung, J. Wen, J. P. Pinto, M. Allen, K. K. Pierce, and S. Paulsen [Icarus 76, 146-159 (1988)]. More plausibly, exchange of water between the atmosphere and the polar deposits is limited, so

  11. Emerging roles of Na+/H+ exchangers in epilepsy and developmental brain disorders

    PubMed Central

    Falgoust, Lindsay; Pan, Jullie W.; Sun, Dandan; Zhang, Zhongling

    2016-01-01

    Epilepsy is a common central nervous system (CNS) disease characterized by recurrent transient neurological events occurring due to abnormally excessive or synchronous neuronal activity in the brain. The CNS is affected by systemic acid–base disorders, and epileptic seizures are sensitive indicators of underlying imbalances in cellular pH regulation. Na+/H+ exchangers (NHEs) are a family of membrane transporter proteins actively involved in regulating intracellular and organellar pH by extruding H+ in exchange for Na+ influx. Altering NHE function significantly influences neuronal excitability and plays a role in epilepsy. This review gives an overview of pH regulatory mechanisms in the brain with a special focus on the NHE family and the relationship between epilepsy and dysfunction of NHE isoforms. We first discuss how cells translocate acids and bases across the membrane and establish pH homeostasis as a result of the concerted effort of enzymes and ion transporters. We focus on the specific roles of the NHE family by detailing how the loss of NHE1 in two NHE mutant mice results in enhanced neuronal excitability in these animals. Furthermore, we highlight new findings on the link between mutations of NHE6 and NHE9 and developmental brain disorders including epilepsy, autism, and attention deficit hyperactivity disorder (ADHD). These studies demonstrate the importance of NHE proteins in maintaining H+ homeostasis and their intricate roles in the regulation of neuronal function. A better understanding of the mechanisms underlying NHE1, 6, and 9 dysfunctions in epilepsy formation may advance the development of new epilepsy treatment strategies. PMID:26965387

  12. Integrating Mass Spectrometry of Intact Protein Complexes into Structural Proteomics

    PubMed Central

    Hyung, Suk-Joon; Ruotolo, Brandon T.

    2013-01-01

    Summary Mass spectrometry analysis of intact protein complexes has emerged as an established technology for assessing the composition and connectivity within dynamic, heterogeneous multiprotein complexes at low concentrations and in the context of mixtures. As this technology continues to move forward, one of the main challenges is to integrate the information content of such intact protein complex measurements with other mass spectrometry approaches in structural biology. Methods such as H/D exchange, oxidative foot-printing, chemical cross-linking, affinity purification, and ion mobility separation add complementary information that allows access to every level of protein structure and organization. Here, we survey the structural information that can be retrieved by such experiments, demonstrate the applicability of integrative mass spectrometry approaches in structural proteomics, and look to the future to explore upcoming innovations in this rapidly-advancing area. PMID:22611037

  13. Actin Isoform-specific Conformational Differences Observed with Hydrogen/Deuterium Exchange and Mass Spectrometry*

    PubMed Central

    Stokasimov, Ema; Rubenstein, Peter A.

    2009-01-01

    Actin can exist in multiple conformations necessary for normal function. Actin isoforms, although highly conserved in sequence, exhibit different biochemical properties and cellular roles. We used amide proton hydrogen/deuterium (HD) exchange detected by mass spectrometry to analyze conformational differences between Saccharomyces cerevisiae and muscle actins in the G and F forms to gain insight into these differences. We also utilized HD exchange to study interdomain and allosteric communication in yeast-muscle hybrid actins to better understand the conformational dynamics of actin. Areas showing differences in HD exchange between G- and F-actins are areas of intermonomer contacts, consistent with the current filament models. Our results showed greater exchange for yeast G-actin compared with muscle actin in the barbed end pivot region and areas in subdomains 1 and 2 and for F-actin in monomer-monomer contact areas. These results suggest greater flexibility of the yeast actin monomer and filament compared with muscle actin. For hybrid G-actins, the muscle-like and yeastlike parts of the molecule generally showed exchange characteristics resembling their parent actins. A few exceptions were a peptide on top of subdomain 2 and the pivot region between subdomains 1 and 3 with muscle actin-like exchange characteristics although the areas were yeastlike. These results demonstrate that there is cross-talk between subdomains 1 and 2 and the large and small domains. Hybrid F-actin data showing greater exchange compared with both yeast and muscle actins are consistent with mismatched yeast-muscle interfaces resulting in decreased stability of the hybrid filament contacts. PMID:19605362

  14. Polarization IR spectra of hydrogen bonded pyrazole crystals: self-organization effects in proton and deuteron mixture systems. Long-range H/D isotopic effects

    NASA Astrophysics Data System (ADS)

    Flakus, Henryk T.; Machelska, Aleksandra

    2002-02-01

    This paper deals with experimental studies of the polarization IR spectra of solid-state pyrazole H1345, as well as of its H1D345, D1H345 and D1345 deuterium derivatives. Spectra were measured for the νNH and νND band frequency ranges at temperatures of 298 and 77 K. The spectra were found to strongly change their intensity distribution and their polarization properties with the decrease of temperature. These effects were ascribed to some temperature-induced conformational changes in the hydrogen bond lattices. The studies reported allowed the finding of new kind of isotopic effects H/D in the open-chain hydrogen bond systems, i.e. the self-organization effects. It was found that the spectrally active aggregates of hydrogen bonds remain unchanged despite the growing isotope H/D exchange rate. This statement was supported by analysis of the residual polarized νNH and νND band properties, measured for the isotopically diluted crystalline samples. Analysis of the band shapes of the four hydrogen isotope derivative crystals proved the existence of another kind of H/D isotopic effect, i.e. the long-range isotopic effect. It depends on an influence of the pyrazole ring hydrogen atoms onto the νNH and νND band widths and onto the band fine structures.

  15. Phospholipase A2-treated human high-density lipoprotein and cholesterol movements: exchange processes and lecithin: cholesterol acyltransferase reactivity.

    PubMed

    Chollet, F; Perret, B P; Chap, H; Douste-Blazy, L

    1986-02-12

    Human HDL3 (d 1.125-1.21 g/ml) were treated by an exogenous phospholipase A2 from Crotalus adamenteus in the presence of albumin. Phosphatidylcholine hydrolysis ranged between 30 and 90% and the reisolated particle was essentially devoid of lipolysis products. (1) An exchange of free cholesterol was recorded between radiolabelled erythrocytes at 5-10% haematocrit and HDL3 (0.6 mM total cholesterol) from 0 to 12-15 h. Isotopic equilibration was reached. Kinetic analysis of the data indicated a constant rate of free cholesterol exchange of 13.0 microM/h with a half-time of equilibration around 3 h. Very similar values of cholesterol exchange, specific radioactivities and kinetic parameters were measured when phospholipase-treated HDL replaced control HDL. (2) The lecithin: cholesterol acyltransferase reactivity of HDL3, containing different amounts of phosphatidylcholine, as achieved by various degrees of phospholipase A2 treatment, was measured using a crude preparation of lecithin: cholesterol acyltransferase (the d 1.21-1.25 g/ml plasma fraction). The rate of esterification was determined between 0 and 12 h. Following a 15-30% lipolysis, the lecithin: cholesterol acyltransferase reactivity of HDL3 was reduced about 30-40%, and then continued to decrease, though more slowly, as the phospholipid content was further lowered in the particle. (3) The addition of the lecithin: cholesterol acyltransferase preparation into an incubation medium made of labelled erythrocytes and HDL3 promoted a movement of radioactive cholesterol out of cells, above the values of exchange, and an accumulation of cholesteryl esters in HDL. This reflected a mass consumption of free cholesterol, from both the cellular and the lipoprotein compartments upon the lecithin: cholesterol acyltransferase action. As a consequence of a decreased reactivity, phospholipase-treated HDL (with 2/3 of phosphatidylcholine hydrolyzed) proved much less effective in the lecithin: cholesterol acyltransferase

  16. Acid precipitation effects on soil pH and base saturation of exchange sites

    Treesearch

    W. W. McFee; J. M. Kelly; R. H. Beck

    1976-01-01

    The typical values and probable ranges of acid-precipitation are evaluated in terms of their theoretical effects on pH and cation exchange equilibrium of soils characteristic of the humid temperature region. The extent of probable change in soil pH and the time required to cause such a change are calculated for a range of common soils. Hydrogen ion input by acid...

  17. Improved protein hydrogen/deuterium exchange mass spectrometry platform with fully automated data processing.

    PubMed

    Zhang, Zhongqi; Zhang, Aming; Xiao, Gang

    2012-06-05

    Protein hydrogen/deuterium exchange (HDX) followed by protease digestion and mass spectrometric (MS) analysis is accepted as a standard method for studying protein conformation and conformational dynamics. In this article, an improved HDX MS platform with fully automated data processing is described. The platform significantly reduces systematic and random errors in the measurement by introducing two types of corrections in HDX data analysis. First, a mixture of short peptides with fast HDX rates is introduced as internal standards to adjust the variations in the extent of back exchange from run to run. Second, a designed unique peptide (PPPI) with slow intrinsic HDX rate is employed as another internal standard to reflect the possible differences in protein intrinsic HDX rates when protein conformations at different solution conditions are compared. HDX data processing is achieved with a comprehensive HDX model to simulate the deuterium labeling and back exchange process. The HDX model is implemented into the in-house developed software MassAnalyzer and enables fully unattended analysis of the entire protein HDX MS data set starting from ion detection and peptide identification to final processed HDX output, typically within 1 day. The final output of the automated data processing is a set (or the average) of the most possible protection factors for each backbone amide hydrogen. The utility of the HDX MS platform is demonstrated by exploring the conformational transition of a monoclonal antibody by increasing concentrations of guanidine.

  18. Detection of Interstellar Ortho-D2H+ with SOFIA

    NASA Astrophysics Data System (ADS)

    Harju, Jorma; Sipilä, Olli; Brünken, Sandra; Schlemmer, Stephan; Caselli, Paola; Juvela, Mika; Menten, Karl M.; Stutzki, Jürgen; Asvany, Oskar; Kamiński, Tomasz; Okada, Yoko; Higgins, Ronan

    2017-05-01

    We report on the detection of the ground-state rotational line of ortho-D2H+ at 1.477 THz (203 μm) using the German REceiver for Astronomy at Terahertz frequencies (GREAT) on board the Stratospheric Observatory For Infrared Astronomy (SOFIA). The line is seen in absorption against far-infrared continuum from the protostellar binary IRAS 16293-2422 in Ophiuchus. The para-D2H+ line at 691.7 GHz was not detected with the APEX telescope toward this position. These D2H+ observations complement our previous detections of para-H2D+ and ortho-H2D+ using SOFIA and APEX. By modeling chemistry and radiative transfer in the dense core surrounding the protostars, we find that the ortho-D2H+ and para-H2D+ absorption features mainly originate in the cool (T < 18 K) outer envelope of the core. In contrast, the ortho-H2D+ emission from the core is significantly absorbed by the ambient molecular cloud. Analyses of the combined D2H+ and H2D+ data result in an age estimate of ˜5 × 105 yr for the core, with an uncertainty of ˜2 × 105 yr. The core material has probably been pre-processed for another 5 × 105 years in conditions corresponding to those in the ambient molecular cloud. The inferred timescale is more than 10 times the age of the embedded protobinary. The D2H+ and H2D+ ions have large and nearly equal total (ortho+para) fractional abundances of ˜10-9 in the outer envelope. This confirms the central role of {{{H}}}3+ in the deuterium chemistry in cool, dense gas, and adds support to the prediction of chemistry models that also {{{D}}}3+ should be abundant in these conditions.

  19. Determination of exchangeable protons in natural organic matter using a home-made hydrogen/carbon analyser.

    PubMed

    Haiber, S; Barth, U

    2001-01-01

    A home made hydrogen/carbon analyser was used to determine the portion of exchangeable protons in aquatic humic substances. For this purpose, equal sample amounts were dissolved in H2O and D2O, respectively, dried and combusted in a stream of oxygen. The amount of water resulting from combustion was measured by an infrared detector which recorded the OH bending vibration of H2O. The bands stemming from HOD or D2O were not registered by the detection unit. Thus, combustion of organic samples containing exchangeable protons dissolved in D2O resulted in a significantly smaller signal compared to the signal observed for the same sample dissolved in H2O. The relative intensity loss of the H2O signal observed after combustion was used to derive the portion of exchangeable protons in a standard reference material, a humic substance isolated by the International Humic Substances Society (Suwannee River fulvic acid). According to this method about 20% of the sample protons could be identified as exchangeable protons. With regard to titration data the portion of protons bound to non acidic hydroxy functions could be estimated. The validity of this procedure was proved by combustion experiments using commercially available deuterated substances as well as organic model compounds dissolved in D2O and H2O, respectively.

  20. Final Hazard Categorization and Auditable Safety Analysis for the Remediation of the 118-D-1, 118-D-2, 118-D-3, 118-H-1, 118-H-2 and 118-H-3 Solid Waste Burial Grounds

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

    T. J. Rodovsky

    2006-03-01

    This report presents the initial hazard categorization, final hazard categorization and auditable safety analysis for the remediation of the 118-D-1, 118-D-2, and 118-D-3 Burial Grounds located within the 100-D/DR Area of the Hanford Site and the 118-H-1, 118-H-2, and 118-H-3 Burial Grounds located within the 100-H Area of the Hanford Site.

  1. Differentiation of regioisomeric aromatic ketocarboxylic acids by atmospheric pressure chemical ionization CAD tandem mass spectrometry in a linear quadrupole ion trap mass spectrometer

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

    Amundson, Lucas M.; Owen, Ben C.; Gallardo, Vanessa A.

    2011-01-01

    Positive-mode atmospheric pressure chemical ionization tandem mass spectrometry (APCI-MS n ) was tested for the differentiation of regioisomeric aromatic ketocarboxylic acids. Each analyte forms exclusively an abundant protonated molecule upon ionization via positive-mode APCI in a commercial linear quadrupole ion trap (LQIT) mass spectrometer. Energy-resolved collision-activated dissociation (CAD) experiments carried out on the protonated analytes revealed fragmentation patterns that varied based on the location of the functional groups. Unambiguous differentiation between the regioisomers was achieved in each case by observing different fragmentation patterns, different relative abundances of ion-molecule reaction products, or different relative abundances of fragment ions formed at differentmore » collision energies. The mechanisms of some of the reactions were examined by H/D exchange reactions and molecular orbital calculations.« less

  2. BiPACE 2D--graph-based multiple alignment for comprehensive 2D gas chromatography-mass spectrometry.

    PubMed

    Hoffmann, Nils; Wilhelm, Mathias; Doebbe, Anja; Niehaus, Karsten; Stoye, Jens

    2014-04-01

    Comprehensive 2D gas chromatography-mass spectrometry is an established method for the analysis of complex mixtures in analytical chemistry and metabolomics. It produces large amounts of data that require semiautomatic, but preferably automatic handling. This involves the location of significant signals (peaks) and their matching and alignment across different measurements. To date, there exist only a few openly available algorithms for the retention time alignment of peaks originating from such experiments that scale well with increasing sample and peak numbers, while providing reliable alignment results. We describe BiPACE 2D, an automated algorithm for retention time alignment of peaks from 2D gas chromatography-mass spectrometry experiments and evaluate it on three previously published datasets against the mSPA, SWPA and Guineu algorithms. We also provide a fourth dataset from an experiment studying the H2 production of two different strains of Chlamydomonas reinhardtii that is available from the MetaboLights database together with the experimental protocol, peak-detection results and manually curated multiple peak alignment for future comparability with newly developed algorithms. BiPACE 2D is contained in the freely available Maltcms framework, version 1.3, hosted at http://maltcms.sf.net, under the terms of the L-GPL v3 or Eclipse Open Source licenses. The software used for the evaluation along with the underlying datasets is available at the same location. The C.reinhardtii dataset is freely available at http://www.ebi.ac.uk/metabolights/MTBLS37.

  3. Mass exchange in an experimental new-generation life support system model based on biological regeneration of environment.

    PubMed

    Tikhomirov, A A; Ushakova, S A; Manukovsky, N S; Lisovsky, G M; Kudenko, Yu A; Kovalev, V S; Gubanov, V G; Barkhatov, Yu V; Gribovskaya, I V; Zolotukhin, I G; Gros, J B; Lasseur, Ch

    2003-01-01

    An experimental model of a biological life support system was used to evaluate qualitative and quantitative parameters of the internal mass exchange. The photosynthesizing unit included the higher plant component (wheat and radish), and the heterotrophic unit consisted of a soil-like substrate, California worms, mushrooms and microbial microflora. The gas mass exchange involved evolution of oxygen by the photosynthesizing component and its uptake by the heterotroph component along with the formation and maintaining of the SLS structure, growth of mushrooms and California worms, human respiration, and some other processes. Human presence in the system in the form of "virtual human" that at regular intervals took part in the respirative gas exchange during the experiment. Experimental data demonstrated good oxygen/carbon dioxide balance, and the closure of the cycles of these gases was almost complete. The water cycle was nearly 100% closed. The main components in the water mass exchange were transpiration water and the watering solution with mineral elements. Human consumption of the edible plant biomass (grains and roots) was simulated by processing these products by a unique physicochemical method of oxidizing them to inorganic mineral compounds, which were then returned into the system and fully assimilated by the plants. The oxidation was achieved by "wet combustion" of organic biomass, using hydrogen peroxide following a special procedure, which does not require high temperature and pressure. Hydrogen peroxide is produced from the water inside the system. The closure of the cycle was estimated for individual elements and compounds. Stoichiometric proportions are given for the main components included in the experimental model of the system. Approaches to the mathematical modeling of the cycling processes are discussed, using the data of the experimental model. Nitrogen, as a representative of biogenic elements, shows an almost 100% closure of the cycle inside

  4. Low band gap frequencies and multiplexing properties in 1D and 2D mass spring structures

    NASA Astrophysics Data System (ADS)

    Aly, Arafa H.; Mehaney, Ahmed

    2016-11-01

    This study reports on the propagation of elastic waves in 1D and 2D mass spring structures. An analytical and computation model is presented for the 1D and 2D mass spring systems with different examples. An enhancement in the band gap values was obtained by modeling the structures to obtain low frequency band gaps at small dimensions. Additionally, the evolution of the band gap as a function of mass value is discussed. Special attention is devoted to the local resonance property in frequency ranges within the gaps in the band structure for the corresponding infinite periodic lattice in the 1D and 2D mass spring system. A linear defect formed of a row of specific masses produces an elastic waveguide that transmits at the narrow pass band frequency. The frequency of the waveguides can be selected by adjusting the mass and stiffness coefficients of the materials constituting the waveguide. Moreover, we pay more attention to analyze the wave multiplexer and DE-multiplexer in the 2D mass spring system. We show that two of these tunable waveguides with alternating materials can be employed to filter and separate specific frequencies from a broad band input signal. The presented simulation data is validated through comparison with the published research, and can be extended in the development of resonators and MEMS verification.

  5. The intracellular Na(+)/H(+) exchanger NHE7 effects a Na(+)-coupled, but not K(+)-coupled proton-loading mechanism in endocytosis.

    PubMed

    Milosavljevic, Nina; Monet, Michaël; Léna, Isabelle; Brau, Frédéric; Lacas-Gervais, Sandra; Feliciangeli, Sylvain; Counillon, Laurent; Poët, Mallorie

    2014-05-08

    Vesicular H(+)-ATPases and ClC-chloride transporters are described to acidify intracellular compartments, which also express the highly conserved Na(+)/H(+) exchangers NHE6, NHE7, and NHE9. Mutations of these exchangers cause autism-spectrum disorders and neurodegeneration. NHE6, NHE7, and NHE9 are hypothesized to exchange cytosolic K(+) for H(+) and alkalinize vesicles, but this notion has remained untested in K(+) because their intracellular localization prevents functional measurements. Using proton-killing techniques, we selected a cell line that expresses wild-type NHE7 at the plasma membrane, enabling measurement of the exchanger's transport parameters. We found that NHE7 transports Li(+) and Na(+), but not K(+), is nonreversible in physiological conditions and is constitutively activated by cytosolic H(+). Therefore, NHE7 acts as a proton-loading transporter rather than a proton leak. NHE7 mediates an acidification of intracellular vesicles that is additive to that of V-ATPases and that accelerates endocytosis. This study reveals an unexpected function for vesicular Na(+)/H(+) exchangers and provides clues for understanding NHE-linked neurological disorders. Copyright © 2014 The Authors. Published by Elsevier Inc. All rights reserved.

  6. Reduced white matter MRI transverse relaxation rate in cognitively normal H63D-HFE human carriers and H67D-HFE mice.

    PubMed

    Meadowcroft, Mark D; Wang, Jianli; Purnell, Carson J; Peters, Douglas G; Eslinger, Paul J; Neely, Elizabeth B; Gill, David J; Vasavada, Megha; Ali-Rahmani, Fatima; Yang, Qing X; Connor, James R

    2016-12-01

    Mutations within the HFE protein gene sequence have been associated with increased risk of developing a number of neurodegenerative disorders. To this effect, an animal model has been created which incorporates the mouse homologue to the human H63D-HFE mutation: the H67D-HFE knock-in mouse. These mice exhibit alterations in iron management proteins, have increased neuronal oxidative stress, and a disruption in cholesterol regulation. However, it remains undetermined how these differences translate to human H63D carriers in regards to white matter (WM) integrity. To this endeavor, MRI transverse relaxation rate (R 2 ) parametrics were employed to test the hypothesis that WM alterations are present in H63D human carriers and are recapitulated in the H67D mice. H63D carriers exhibit widespread reductions in brain R 2 compared to non-carriers within white matter association fibers in the brain. Similar R 2 decreases within white matter tracts were observed in the H67D mouse brain. Additionally, an exacerbation of age-related R 2 decrease is found in the H67D animal model in white matter regions of interest. The decrease in R 2 within white matter tracts of both species is speculated to be multifaceted. The R 2 changes are hypothesized to be due to alterations in axonal biochemical tissue composition. The R 2 changes observed in both the human-H63D and mouse-H67D data suggest that modified white matter myelination is occurring in subjects with HFE mutations, potentially increasing vulnerability to neurodegenerative disorders.

  7. A mass spectrometric study of gaseous H4PO+3 and H2PO-3 ions

    NASA Astrophysics Data System (ADS)

    de Petris, Giulia; Occhiucci, Giorgio; Pepi, Federico

    1994-09-01

    H4PO+3 ions have been generated in a mass spectrometer by proton-transfer to H3PO3 from different Brønsted acids. The proton affinity of H3PO3 has been estimated by bracketing and kinetic methods to be 198.6 ± 2 kcal mol-1. Gaseous H4PO+3 ions have been structurally assessed by metastable ion kinetic energy (MIKE) and collisionally induced dissociation (CID) mass spectrometry leading to the detection of a single isomeric species. The chemistry of H2PO-3 is characterized by facile addition-elimination reactions leading to formation of polyanions. Species containing up to six P atoms have been detected.

  8. Zero Launch Mass 3D Printer

    NASA Image and Video Library

    2018-05-01

    Nathan Gelino, a research engineer, manually loads materials into the Zero Launch Mass 3-D Printer at Kennedy Space Center’s Swamp Works Tuesday. The 3-D printer heated the pellets to about 600 degrees F and extruded them to produce specimens for material strength properties testing. Automated pellet delivery system will be added to the printer soon.

  9. Manifestation of intra-atomic 5d6s-4f exchange coupling in photoexcited gadolinium

    NASA Astrophysics Data System (ADS)

    Zhang, G. P.; Jenkins, T.; Bennett, M.; Bai, Y. H.

    2017-12-01

    Intra-atomic exchange couplings (IECs) between 5d6s and 4f electrons are ubiquitous in rare-earth metals and play a critical role in spin dynamics. However, detecting them in real time domain has been difficult. Here we show the direct evidence of IEC between 5d6s and 4f electrons in gadolinium. Upon femtosecond laser excitation, 5d6s electrons are directly excited; their majority bands shift toward the Fermi level while their minority bands do the opposite. For the first time, our first-principles minority shift now agrees with the experiment quantitatively. Excited 5d6s electrons lower the exchange potential barrier for 4f electrons, so the 4f states are also shifted in energy, a prediction that can be tested experimentally. Although a significant number of 5d6s electrons, some several eV below the Fermi level, are excited out of the Fermi sea, there is no change in the 4f states, a clear manifestation of intra-atomic exchange coupling.

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

    ERIC Educational Resources Information Center

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

    2015-01-01

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

  11. Tuning exchange interactions in organometallic semiconductors

    NASA Astrophysics Data System (ADS)

    Rawat, Naveen; Manning, Lane W.; Hua, Kim-Ngan; Headrick, Randall L.; Cherian, Judy G.; Bishop, Michael M.; McGill, Stephen A.; Furis, Madalina I.

    2015-09-01

    Organic semiconductors are emerging as a leading area of research as they are expected to overcome limitations of inorganic semiconductor devices for certain applications where low cost manufacturing, device transparency in the visible range or mechanical flexibility are more important than fast switching times. Solution processing methods produce thin films with millimeter sized crystalline grains at very low cost manufacturing prices, ideally suited for optical spectroscopy investigations of long range many-body effects in organic systems. To this end, we synthesized an entire family of organosoluble 3-d transition metal Pc's and successfully employed a novel solution-based pen-writing deposition technique to fabricate long range ordered thin films of mixtures of metal-free (H2Pc) molecule and organometallic phthalocyanines (MPc's). Our previous studies on the parent MPc crystalline thin films identified different electronic states mediating exchange interactions in these materials. This understanding of spin-dependent exchange interaction between delocalized π-electrons with unpaired d spins enabled the further tuning of these interactions by mixing CoPc and H2Pc in different ratios ranging from 1:1 to 1000:1 H2Pc:MPc. The magnitude of the exchange is also tunable as a function of the average distance between unpaired spins in these materials. Furthermore, high magnetic field (B < 25T) MCD and magneto-photoluminescence show evidence of spin-polarized band-edge excitons in the same materials.

  12. Hydrogen-Exchange Mass Spectrometry for the Study of Intrinsic Disorder in Proteins

    PubMed Central

    Balasubramaniam, Deepa; Komives, Elizabeth A.

    2012-01-01

    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 posttranslational modifications affect weak structuring of disordered regions, the study of coupled folding and binding, and the characterization of amyloid formation. PMID:23099262

  13. Anion- or Cation-Exchange Membranes for NaBH4/H2O2 Fuel Cells?

    PubMed

    Sljukić, Biljana; Morais, Ana L; Santos, Diogo M F; Sequeira, César A C

    2012-07-19

    Direct borohydride fuel cells (DBFC), which operate on sodium borohydride (NaBH4) as the fuel, and hydrogen peroxide (H2O2) as the oxidant, are receiving increasing attention. This is due to their promising use as power sources for space and underwater applications, where air is not available and gas storage poses obvious problems. One key factor to improve the performance of DBFCs concerns the type of separator used. Both anion- and cation-exchange membranes may be considered as potential separators for DBFC. In the present paper, the effect of the membrane type on the performance of laboratory NaBH4/H2O2 fuel cells using Pt electrodes is studied at room temperature. Two commercial ion-exchange membranes from Membranes International Inc., an anion-exchange membrane (AMI-7001S) and a cation-exchange membrane (CMI-7000S), are tested as ionic separators for the DBFC. The membranes are compared directly by the observation and analysis of the corresponding DBFC's performance. Cell polarization, power density, stability, and durability tests are used in the membranes' evaluation. Energy densities and specific capacities are estimated. Most tests conducted, clearly indicate a superior performance of the cation-exchange membranes over the anion-exchange membrane. The two membranes are also compared with several other previously tested commercial membranes. For long term cell operation, these membranes seem to outperform the stability of the benchmark Nafion membranes but further studies are still required to improve their instantaneous power load.

  14. Mechanism of pyridine-ligand exchanges at the different labile sites of 3d heterometallic and mixed valence mu3-oxo trinuclear clusters.

    PubMed

    Novitchi, Ghenadie; Riblet, Fabrice; Scopelliti, Rosario; Helm, Lothar; Gulea, Aurelian; Merbach, André E

    2008-11-17

    The syntheses and single crystal X-ray structural analysis of five novel hetero- and homometallic mu 3-oxo trinuclear cluster with the formula [Fe (III) 2M (II)(mu 3-O)(mu-O 2CCH 3) 6(4-Rpy) 3]. x(4-Rpy). y(CH 3CN) where R = Ph for 1(Fe 2Mn), 2(Fe 2Fe), 3(Fe 2Co), 4(Fe 2Ni) and R = CF 3 for 5(Fe 2Co), are reported. The persistence of the structure for compounds 2- 5 in dichloromethane solution in the temperature range 190-320 K is demonstrated by (1)H and (19)F NMR spectroscopy. Even at the lowest temperature, the electron exchange in the homometallic mixed-valence compound 2(Fe 2Fe) is in the fast regime at the NMR time scale. Variable temperature and pressure NMR line broadening allowed quantifying the fast coordinated/free 4-Rpy exchanges at the two labile metal centers in these clusters: 2: Fe (III)( k (298)/10 (3) s (-1) = 16.6; Delta H (++) = 60.32 kJ mol (-1); Delta S (++) = + 34.8 J K (-1) mol (-1); Delta V (++) = + 12.5 cm (3) mol (-1)); 3: Fe (11.9; 58.92; +30.7; +10.6) and Co (2.8; 68.24; +49.8; +13.9); 4: Fe(12.2; 67.91; +61.0; -) and Ni (0.37; 78.62; +67.8; +12.3); 5: Fe (46; 58.21; +39.3; +14.2) and Co (4.7; 55.37; +11.2; +10.9). A limiting D mechanism is assigned to these exchange reactions. This assignment is based on a first-order rate law, the detection of intermediates, the positive and large entropies and volumes of activation. The order of reactivity k (Co) > k (Ni) is expected for a D mechanism at these metal centers: their low exchange rates are due to their strong binding with the 4-Rpy donor. Surrounded by oxygen donors the d (5) iron(III) usually reacts associatively; however, here due to low affinity of this ion for nitrogen the mechanism is D and the rate of exchange is very fast, even faster than on the divalent ions. There is no significant effect of the divalent ion in cluster 2, 3, and 5 on the exchange rates of 4-Phpy at the iron center, which seems to indicate that the specific electronic interactions between the three ions making

  15. Absolute detection efficiencies of low energy H, H -, H +, H 2+ and H 3+ incident on a multichannel plate detector

    NASA Astrophysics Data System (ADS)

    Peko, B. L.; Stephen, T. M.

    2000-12-01

    Measured absolute detection efficiencies are presented for H, H - and H n+ ( n=1,2,3) impacting a commercially available, dual multichannel plate (MCP) electron multiplier at kinetic energies ranging from 30 to 1000 eV. Measurements involving isotopic substitutions (D, D -, D n+) and Ar + are also presented. In addition, atomic hydrogen detection efficiencies relative to those of H + and H - are given, as they may have a more universal application. For the three charge states, H, H + and H -, the absolute detection efficiencies are markedly different at low energies and converge to a nearly uniform value of ˜70% with increasing projectile energy. The energy dependence is strongest for H +, varying nearly three orders of magnitude over the energy range studied, and weakest for H -, varying by less than one order of magnitude. In general, for the low energy positive ions at a given energy, the lighter the incident particle mass, the greater the probability of its detection.

  16. A Combined Desorption Ionization by Charge Exchange (DICE) and Desorption Electrospray Ionization (DESI) Source for Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Chan, Chang-Ching; Bolgar, Mark S.; Miller, Scott A.; Attygalle, Athula B.

    2011-01-01

    A source that couples the desorption ionization by charge exchange (DICE) and desorption electrospray ionization (DESI) techniques together was demonstrated to broaden the range of compounds that can be analyzed in a single mass spectrometric experiment under ambient conditions. A tee union was used to mix the spray reagents into a partially immiscible blend before this mixture was passed through a conventional electrospray (ES) probe capillary. Using this technique, compounds that are ionized more efficiently by the DICE method and those that are ionized better with the DESI procedure could be analyzed simultaneously. For example, hydroquinone, which is not detected when subjected to DESI-MS in the positive-ion generation mode, or the sodium adduct of guaifenesin, which is not detected when examined by DICE-MS, could both be detected in one experiment when the two techniques were combined. The combined technique was able to generate the molecular ion, proton and metal adduct from the same compound. When coupled to a tandem mass spectrometer, the combined source enabled the generation of product ion spectra from the molecular ion and the [M + H]+ or [M + metal]+ ions of the same compound without the need to physically change the source from DICE to DESI. The ability to record CID spectra of both the molecular ion and adduct ions in a single mass spectrometric experiment adds a new dimension to the array of mass spectrometric methods available for structural studies.

  17. 31 CFR 315.77 - Exchanges by fiduciaries.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... SERVICE, DEPARTMENT OF THE TREASURY BUREAU OF THE PUBLIC DEBT REGULATIONS GOVERNING U.S. SAVINGS BONDS, SERIES A, B, C, D, E, F, G, H, J, AND K, AND U.S. SAVINGS NOTES Fiduciaries § 315.77 Exchanges by...

  18. Cesium and strontium ion exchange on the framework titanium silicate M2Ti2O3SiO4.nH2O (M = H, Na).

    PubMed

    Solbrå, S; Allison, N; Waite, S; Mikhalovsky, S V; Bortun, A I; Bortun, L N; Clearfield, A

    2001-02-01

    The ion exchange properties of the titanium silicate, M2Ti2O3SiO4.nH2O (M = H, Na), toward stable and radioactive 137Cs+ and 89Sr2+, have been examined. By studying the cesium and strontium uptake in the presence of NaNO3, CaCl2, NaOH, and HNO3 (in the range of 0.01-6 M) the sodium titanium silicate was found to be an efficient Cs+ ion exchanger in acid, neutral, and alkaline media and an efficient Sr2+ ion exchanger in neutral and alkaline media, which makes it promising for treatment of contaminated environmental media and biological systems.

  19. Influence of Murchison Minerals on Hydrogen-Deuterium Exchange of Amino Acids

    NASA Astrophysics Data System (ADS)

    Lerner, N. R.

    1993-07-01

    The amino acids found on the Murchison meteorite are deuterium enriched. For the glycine-alanine fraction, delta D = +2448 per mil, and for the alpha-amino isobutyric acid fraction, delta D = +149 per mil [1]. In order to retain such levels of deuterium enrichment, the amino acids found in Murchison must have not only retained the deuterium enrichment of their interstellar precursors (delta D > +1500 per mil [2]) during synthesis, as has been recently shown [3], but they must have also retained their deuterium label during the aqueous alteration phase [4]. By measuring the rates of deuterium exchange of amino acids with D(sub)2O, limits can be set on the length of time and the conditions under which the Murchison parent body experienced an aqueous environment. The rates of hydrogen-deuterium exchange of nondeuterated glycine, alanine, alpha-amino isobutyric acid, and amino diacetic acid have been measured in D(sub)2O as a function of temperature, pH, and the presence of Murchison minerals. In addition to the amino and carboxylic hydrogens, only the alpha- hydrogens of glycine, alanine, and amino diacetic acid are found to exchange. Even for solutions maintained for weeks at temperatures as high as 120 degrees C, no exchange was observed with the hydrogens of the methyl groups of alanine or alpha-amino isobutyric acid. The rate of exchange for alpha-hydrogens of amino acids is first-order with respect to the amino acid concentration. Increasing the pH of the solution markedly increases the rate of exchange. For example, at 115 degrees C and pH 4.0, 7.0, and 10 the rates are 14, 30, and 125 yr^-1 respectively for glycine and 2.0, 3.5, and 14 yr^-1 respectively for alanine. In a pH-6.0 D(sub)2O solution of amino acids containing Murchison dust the rates are 135 yr^-1 for glycine and 32 yr^-1 for alanine, rates close to those for the pH 10 solution. Activation energies for exchange were obtained from Arrhenius plots constructed from measurements made between 70 degrees

  20. Non-invasive acoustic-based monitoring of uranium in solution and H/D ratio

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

    Pantea, Cristian; Beedle, Christopher Craig; Sinha, Dipen N.

    The primary objective of this project is to adapt existing non-invasive acoustic techniques (Swept-Frequency Acoustic Interferometry and Gaussian-pulse acoustic technique) for the purpose of demonstrating the ability to quantify U or H/D ratios in solution. Furthermore, a successful demonstration will provide an easily implemented, low cost, and non-invasive method for remote and unattended uranium mass measurements for International Atomic Energy Agency (IAEA).

  1. Ethylene hydrogenation catalysis on Pt(111) single-crystal surfaces studied by using mass spectrometry and in situ infrared absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Tillekaratne, Aashani; Simonovis, Juan Pablo; Zaera, Francisco

    2016-10-01

    The catalytic hydrogenation of ethylene promoted by a Pt(111) single crystal was studied by using a ultrahigh-vacuum surface-science instrument equipped with a so-called high-pressure cell. Kinetic data were acquired continuously during the catalytic conversion of atmospheric-pressure mixtures of ethylene and hydrogen by using mass spectrometry while simultaneously characterizing the surface species in operando mode by reflection-absorption infrared spectroscopy (RAIRS). Many observations reported in previous studies of this system were corroborated, including the presence of adsorbed alkylidyne intermediates during the reaction and the zero-order dependence of the rate of hydrogenation on the pressure of ethylene. In addition, the high quality of the kinetic data, which could be recorded continuously versus time and processed to calculate time-dependent turnover frequencies (TOFs), afforded a more detailed analysis of the mechanism. Specifically, deuterium labeling could be used to estimate the extent of isotope scrambling reached with mixed-isotope-substituted reactants (C2H4 + D2 and C2D4 + H2). Perhaps the most important new observation from this work is that, although extensive H-D exchange takes place on ethylene before being fully converted to ethane, the average stoichiometry of the final product retains the expected stoichiometry of the gas mixture, that is, four regular hydrogen atoms and two deuteriums per ethane molecule in the case of the experiments with C2H4 + D2. This means that no hydrogen atoms are removed from the surface via their inter-recombination to produce X2 (X = H or D). It is concluded that, under catalytic conditions, hydrogen surface recombination is much slower than ethylene hydrogenation and H-D exchange.

  2. Determination of (2)H-enrichment of rat brain interstitial fluid and rat plasma by headspace-gas-chromatography - quadrupole-mass-spectrometry.

    PubMed

    Eberl, Anita; Altendorfer-Kroath, Thomas; Kollmann, Denise; Birngruber, Thomas; Sinner, Frank; Raml, Reingard; Magnes, Christoph

    2016-09-15

    (2)H2O as nonradioactive, stable marker substance is commonly used in preclinical and clinical studies and the precise determination of (2)H2O concentration in biological samples is crucial. However, aside from isotope ratio mass spectrometry (IRMS), only a very limited number of methods to accurately measure the (2)H2O concentration in biological samples are routinely established until now. In this study, we present a straightforward method to accurately measure (2)H-enrichment of rat brain interstitial fluid (ISF) and rat plasma to determine the relative recovery of a cerebral open flow microperfusion (cOFM) probe, using headspace-gas-chromatography - quadrupole-mass-spectrometry. This method is based on basic-catalyzed hydrogen/deuterium exchange in acetone and detects the (2)H-labelled acetone directly by the headspace GC-MS. Small sample volumes and limited number of preparation steps make this method highly competitive. It has been fully validated. (2)H enriched to 8800 ppm in plasma showed an accuracy of 98.9% and %Relative Standard Deviation (RSD) of 3.1 with n = 18 over three days and with two operators. Similar performance was obtained for cerebral ISF enriched to 1100 ppm (accuracy: 96.5%, %RSD: 3.1). With this highly reproducible method we demonstrated the successful employment of (2)H2O as performance marker for a cOFM probe. Copyright © 2016. Published by Elsevier Inc.

  3. Two-dimensional liquid chromatography system for online top-down mass spectrometry

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

    Tian, Zhixin; Zhao, Rui; Tolic, Nikola

    2010-10-01

    An online metal-free weak cation exchange-hydrophilic interaction liquid chromatography/reversed phase liquid chromatography (WCX-HILIC/RPLC) system has been developed for sensitive high-throughput top-down mass spectrometry. Analyzing posttranslational modifications (PTMs) of core histones, with focus on histone H4, tested the system. Using ~24 μg of core histones (H4, H2B, H2A and H3) purified from human fibroblasts, 41 H4 isoforms were identified, with the type and locations of PTMs unambiguously mapped for 20 of these variants. Compared to corresponding offline studies reported previously, online WCXHILIC/ RPLC platform offers significant improvement in sensitivity, with several orders of magnitude reduction in sample requirements and reduction inmore » the overall analysis time. To the best of our knowledge, this study represents the first online two-dimensional (2D) LC-MS/MS characterization of core histone mixture at the intact protein level.« less

  4. Long-range p-d exchange interaction in a ferromagnet-semiconductor hybrid structure

    NASA Astrophysics Data System (ADS)

    Korenev, V. L.; Salewski, M.; Akimov, I. A.; Sapega, V. F.; Langer, L.; Kalitukha, I. V.; Debus, J.; Dzhioev, R. I.; Yakovlev, D. R.; Müller, D.; Schröder, C.; Hövel, H.; Karczewski, G.; Wiater, M.; Wojtowicz, T.; Kusrayev, Yu. G.; Bayer, M.

    2016-01-01

    Hybrid structures synthesized from different materials have attracted considerable attention because they may allow not only combination of the functionalities of the individual constituents but also mutual control of their properties. To obtain such a control an interaction between the components needs to be established. For coupling the magnetic properties, an exchange interaction has to be implemented which typically depends on wavefunction overlap and is therefore short-ranged, so that it may be compromised across the hybrid interface. Here we study a hybrid structure consisting of a ferromagnetic Co layer and a semiconducting CdTe quantum well, separated by a thin (Cd, Mg)Te barrier. In contrast to the expected p-d exchange that decreases exponentially with the wavefunction overlap of quantum well holes and magnetic atoms, we find a long-ranged, robust coupling that does not vary with barrier width up to more than 30 nm. We suggest that the resulting spin polarization of acceptor-bound holes is induced by an effective p-d exchange that is mediated by elliptically polarized phonons.

  5. [Hydrogen exchange and proteolytic degradation of ribonuclease A. Similarities and distinctions of the kinetic mechanisms].

    PubMed

    Abaturov, L V; Nosova, N G

    2007-01-01

    The studies by IR spectroscopy of the temperature dependence of the H-D exchange rate of the RNase A peptide NH atoms permit one to characterize two types of conformation fluctuations, local and global. A comparison with the temperature dependence of the proteolytic degradation rate of RNase A shows that similar in nature fluctuations allow for the H-D exchange of NH atoms and the splitting of peptide bonds of the native protein. In the low temperature region, both processes occur through local fluctuations, by way of the EX2 mechanism, and in the high temperature region, they occur through global fluctuations with the overall denaturation desorganization of the native structure, by way of the EX1 mechanism. The biphasic dependence of the rate of H-D exchange and proteolytic degradation of RNase A on urea concentration is also explained by the combination of local and global fluctuations.

  6. Enolate Stabilization by Anion-π Interactions: Deuterium Exchange in Malonate Dilactones on π-Acidic Surfaces.

    PubMed

    Miros, François N; Zhao, Yingjie; Sargsyan, Gevorg; Pupier, Marion; Besnard, Céline; Beuchat, César; Mareda, Jiri; Sakai, Naomi; Matile, Stefan

    2016-02-18

    Of central importance in chemistry and biology, enolate chemistry is an attractive topic to elaborate on possible contributions of anion-π interactions to catalysis. To demonstrate the existence of such contributions, experimental evidence for the stabilization of not only anions but also anionic intermediates and transition states on π-acidic aromatic surfaces is decisive. To tackle this challenge for enolate chemistry with maximal precision and minimal uncertainty, malonate dilactones are covalently positioned on the π-acidic surface of naphthalenediimides (NDIs). Their presence is directly visible in the upfield shifts of the α-protons in the (1) H NMR spectra. The reactivity of these protons on π-acidic surfaces is measured by hydrogen-deuterium (H-D) exchange for 11 different examples, excluding controls. The velocity of H-D exchange increases with π acidity (NDI core substituents: SO2 R>SOR>H>OR>OR/NR2 >SR>NR2 ). The H-D exchange kinetics vary with the structure of the enolate (malonates>methylmalonates, dilactones>dithiolactones). Moreover, they depend on the distance to the π surface (bridge length: 11-13 atoms). Most importantly, H-D exchange depends strongly on the chirality of the π surface (chiral sulfoxides as core substituents; the crystal structure of the enantiopure (R,R,P)-macrocycle is reported). For maximal π acidity, transition-state stabilizations up to -18.8 kJ mol(-1) are obtained for H-D exchange. The Brønsted acidity of the enols increases strongly with π acidity of the aromatic surface, the lowest measured pKa =10.9 calculates to a ΔpKa =-5.5. Corresponding to the deprotonation of arginine residues in neutral water, considered as "impossible" in biology, the found enolate-π interactions are very important. The strong dependence of enolate stabilization on the unprecedented seven-component π-acidity gradient over almost 1 eV demonstrates quantitatively that such important anion-π activities can be expected only from

  7. Geo3DML: A standard-based exchange format for 3D geological models

    NASA Astrophysics Data System (ADS)

    Wang, Zhangang; Qu, Honggang; Wu, Zixing; Wang, Xianghong

    2018-01-01

    A geological model (geomodel) in three-dimensional (3D) space is a digital representation of the Earth's subsurface, recognized by geologists and stored in resultant geological data (geodata). The increasing demand for data management and interoperable applications of geomodelscan be addressed by developing standard-based exchange formats for the representation of not only a single geological object, but also holistic geomodels. However, current standards such as GeoSciML cannot incorporate all the geomodel-related information. This paper presents Geo3DML for the exchange of 3D geomodels based on the existing Open Geospatial Consortium (OGC) standards. Geo3DML is based on a unified and formal representation of structural models, attribute models and hierarchical structures of interpreted resultant geodata in different dimensional views, including drills, cross-sections/geomaps and 3D models, which is compatible with the conceptual model of GeoSciML. Geo3DML aims to encode all geomodel-related information integrally in one framework, including the semantic and geometric information of geoobjects and their relationships, as well as visual information. At present, Geo3DML and some supporting tools have been released as a data-exchange standard by the China Geological Survey (CGS).

  8. Experimental study of heat and mass transfer in a buoyant countercurrent exchange flow

    NASA Astrophysics Data System (ADS)

    Conover, Timothy Allan

    Buoyant Countercurrent Exchange Flow occurs in a vertical vent through which two miscible fluids communicate, the higher-density fluid, residing above the lower-density fluid, separated by the vented partition. The buoyancy- driven zero net volumetric flow through the vent transports any passive scalars, such as heat and toxic fumes, between the two compartments as the fluids seek thermodynamic and gravitational equilibrium. The plume rising from the vent into the top compartment resembles a pool fire plume. In some circumstances both countercurrent flows and pool fires can ``puff'' periodically, with distinct frequencies. One experimental test section containing fresh water in the top compartment and brine (NaCl solution) in the bottom compartment provided a convenient, idealized flow for study. This brine flow decayed in time as the concentrations approached equilibrium. A second test section contained fresh water that was cooled by heat exchangers above and heated by electrical elements below and operated steadily, allowing more time for data acquisition. Brine transport was reduced to a buoyancy- scaled flow coefficient, Q*, and heat transfer was reduced to an analogous coefficient, H*. Results for vent diameter D = 5.08 cm were consistent between test sections and with the literature. Some results for D = 2.54 cm were inconsistent, suggesting viscosity and/or molecular diffusion of heat become important at smaller scales. Laser Doppler Velocimetry was used to measure velocity fields in both test sections, and in thermal flow a small thermocouple measured temperature simultaneously with velocity. Measurement fields were restricted to the plume base region, above the vent proper. In baseline periodic flow, instantaneous velocity and temperature were ensemble averaged, producing a movie of the average variation of each measure during a puffing flow cycle. The temperature movie revealed the previously unknown cold core of the puff during its early development. The

  9. The influence of cryogenic mass exchange on the distribution of viable microfauna in cryozems

    NASA Astrophysics Data System (ADS)

    Gubin, S. V.; Lupachev, A. V.; Shatilovich, A. V.; Myl'nikov, A. P.; Ryss, A. Yu.; Veremeeva, A. A.

    2016-12-01

    The role of cryogenic mass exchange in the distribution of the viable microfauna (ciliates, heterotrophic flagellates, and nematodes) in the profiles of cryoturbated cryogenic soils and in the upper layers of permafrost was revealed. The material for microbiological investigations was collected from the main horizons of cryozem profiles, including the zones with morphologically manifested processes of cryogenic mass exchange (the development of barren spots, cryoturbation, and suprapermafrost accumulation) and the zones affected by solifluction. The radiocarbon dating of the soil samples showed that the age of the organic cryogenic material and material buried in the course of solifluction varied from 2100 to 4500 years. Some zones with specific ecological conditions promoting the preservation of species diversity of the microfauna were found to develop in the cryozem profiles. A considerable part of the community (38% of ciliates, 58% of flagellates, and 50% of nematodes) maintained its viability in the dormant state, and in some cases, it could pass to the state of long-term cryobiosis in the upper layer of permafrost.

  10. Effect of the type of ion exchange membrane on performance, ion transport, and pH in biocatalyzed electrolysis of wastewater.

    PubMed

    Rozendal, R A; Sleutels, T H J A; Hamelers, H V M; Buisman, C J N

    2008-01-01

    Previous studies have shown that the application of cation exchange membranes (CEMs) in bioelectrochemical systems running on wastewater can cause operational problems. In this paper the effect of alternative types of ion exchange membrane is studied in biocatalyzed electrolysis cells. Four types of ion exchange membranes are used: (i) a CEM, (ii) an anion exchange membrane (AEM), (iii) a bipolar membrane (BPM), and (iv) a charge mosaic membrane (CMM). With respect to the electrochemical performance of the four biocatalyzed electrolysis configurations, the ion exchange membranes are rated in the order AEM > CEM > CMM > BPM. However, with respect to the transport numbers for protons and/or hydroxyl ions (t(H/OH)) and the ability to prevent pH increase in the cathode chamber, the ion exchange membranes are rated in the order BPM > AEM > CMM > CEM.

  11. Structure and dynamics of a detergent-solubilized membrane protein: measurement of amide hydrogen exchange rates in M13 coat protein by /sub 1/H NMR spectroscopy

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

    O'Neil, J.D.J.; Sykes, B.D.

    The coat protein of bacteriophage M13 is inserted into the inner membrane of Escherichia coli where it exists as an integral membrane protein during the reproductive cycle of the phage. The protein sequence consists of a highly hydrophobic 19-residue central segment flanked by an acidic 20-residue N-terminus and a basic 11-residue C-terminus. The authors have measured backbone amide hydrogen exchange of the protein solubilized in perdeuteriated sodium dodecyl sulfate using /sup 1/H nuclear magnetic resonance (NMR) spectroscopy. Direct proton exchange-out measurements in D/sub 2/O at 24 /sup 0/C were used to follow the exchange of the slowest amides in themore » protein. Multiple exponential fitting of the exchange data showed that these amides exchanged in two kinetic sets with exchange rates that differed by more than 100-fold. Steady-state saturation-transfer techniques were also used to measure exchange. These methods showed that 15-20 amides in the protein are very stable at 55/sup 0/C and that bout 30 amides have exchange rates retarded by at least 10/sup 5/-fold at 24/sup 0/C. Saturation-transfer studies also showed that the pH dependence of exchange in the hydrophilic termini was unusual. Relaxation and solid-state NMR experiments have previously shown that the majority of the protein backbone is rigid on the picosecond to microsecond time scale, except for the extreme ends of the molecule which are mobile. The hydrogen exchange results, which are sensitive to a much longer time scale, suggest a stable core with a progressive increase in amplitude or frequency of motions as the ends of the protein are approached.« less

  12. Contribution of the amiloride-sensitive component and the Na+/H+ exchanger to renal responsiveness to vasoconstrictors.

    PubMed

    Vargas, Pablo; Wangensteen, Rosemary; Rodríguez-Gómez, Isabel; Perez-Abud, Rocío; Osuna, Antonio; Quesada, Andrés; Vargas, Félix

    2011-01-01

    This study analyzed the role of the amiloride-sensitive component and the participation of the Na(+)/H(+) exchanger in renal responsiveness to vasoconstrictors in the isolated perfused rat kidney. The renal responses to vasoconstrictors (angiotensin II, phenylephrine, vasopressin and KCl) were studied under baseline conditions and after the administration of amiloride (10 and 100 μmol/l) or the specific Na(+)/H(+) exchange inhibitor ethylisopropylamiloride (EIPA, 10 μmol/l). The effects of amiloride and EIPA on renal responsiveness to vasoconstrictors were also analyzed in endothelium-denuded preparations. Amiloride reduced renal responsiveness to all vasoconstrictors in a dose-related manner, whereas EIPA did not affect the renal pressor response to KCl. The inhibitory effects of amiloride and EIPA on renal responsiveness to vasoconstrictors persisted after endothelium removal. These results indicate that the amiloride-sensitive component and the Na(+)/H(+) exchanger play an important role in responsiveness to the main endogenous vasoconstrictors in the renal vasculature. These results also suggest that amiloride might be useful as an inhibitor of renal vasoconstriction, even in diseases with endothelial dysfunction. Copyright © 2011 S. Karger AG, Basel.

  13. Anion- or Cation-Exchange Membranes for NaBH4/H2O2 Fuel Cells?

    PubMed Central

    Šljukić, Biljana; Morais, Ana L.; Santos, Diogo M. F.; Sequeira, César A. C.

    2012-01-01

    Direct borohydride fuel cells (DBFC), which operate on sodium borohydride (NaBH4) as the fuel, and hydrogen peroxide (H2O2) as the oxidant, are receiving increasing attention. This is due to their promising use as power sources for space and underwater applications, where air is not available and gas storage poses obvious problems. One key factor to improve the performance of DBFCs concerns the type of separator used. Both anion- and cation-exchange membranes may be considered as potential separators for DBFC. In the present paper, the effect of the membrane type on the performance of laboratory NaBH4/H2O2 fuel cells using Pt electrodes is studied at room temperature. Two commercial ion-exchange membranes from Membranes International Inc., an anion-exchange membrane (AMI-7001S) and a cation-exchange membrane (CMI-7000S), are tested as ionic separators for the DBFC. The membranes are compared directly by the observation and analysis of the corresponding DBFC’s performance. Cell polarization, power density, stability, and durability tests are used in the membranes’ evaluation. Energy densities and specific capacities are estimated. Most tests conducted, clearly indicate a superior performance of the cation-exchange membranes over the anion-exchange membrane. The two membranes are also compared with several other previously tested commercial membranes. For long term cell operation, these membranes seem to outperform the stability of the benchmark Nafion membranes but further studies are still required to improve their instantaneous power load. PMID:24958292

  14. New insights into proton surface mobility processes in PEMFC catalysts using isotopic exchange methods.

    PubMed

    Ferreira-Aparicio, Paloma

    2009-09-01

    The surface chemistry and the adsorption/desorption/exchange behavior of a proton-exchange membrane fuel cell catalyst are analyzed as a case study for the development of tailor-made support materials of enhanced performance and stability. By using H2, D2, and CO as probe molecules, the relevance of some surface functional groups of the catalyst support on several diffusion processes taking place during the adsorption is shown. Sulfonic groups associated with the vulcanized carbon black surface have been detected by means of spectroscopic techniques (X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy) and by analysis of the desorbed products during temperature-programmed desorption tests by mass spectrometry. Such hydrophilic species have been observed to favor proton surface mobility and exchange with Pt-adsorbed deuterium even in the presence of adsorbed CO. This behavior is relevant both for the proper characterization of these kinds of catalysts using adsorption probes and for the design of new surface-modified carbon supports, enabling alternative proton-transfer pathways throughout the catalytic layers toward the membrane.

  15. Localizing Carbohydrate Binding Sites in Proteins Using Hydrogen/Deuterium Exchange Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Zhang, Jingjing; Kitova, Elena N.; Li, Jun; Eugenio, Luiz; Ng, Kenneth; Klassen, John S.

    2016-01-01

    The application of hydrogen/deuterium exchange mass spectrometry (HDX-MS) to localize ligand binding sites in carbohydrate-binding proteins is described. Proteins from three bacterial toxins, the B subunit homopentamers of Cholera toxin and Shiga toxin type 1 and a fragment of Clostridium difficile toxin A, and their interactions with native carbohydrate receptors, GM1 pentasaccharides (β-Gal-(1→3)-β-GalNAc-(1→4)[α-Neu5Ac-(2→3)]-β-Gal-(1→4)-Glc), Pk trisaccharide (α-Gal-(1→4)-β-Gal-(1→4)-Glc) and CD-grease (α-Gal-(1→3)-β-Gal-(1→4)-β-GlcNAcO(CH2)8CO2CH3), respectively, served as model systems for this study. Comparison of the differences in deuterium uptake for peptic peptides produced in the absence and presence of ligand revealed regions of the proteins that are protected against deuterium exchange upon ligand binding. Notably, protected regions generally coincide with the carbohydrate binding sites identified by X-ray crystallography. However, ligand binding can also result in increased deuterium exchange in other parts of the protein, presumably through allosteric effects. Overall, the results of this study suggest that HDX-MS can serve as a useful tool for localizing the ligand binding sites in carbohydrate-binding proteins. However, a detailed interpretation of the changes in deuterium exchange upon ligand binding can be challenging because of the presence of ligand-induced changes in protein structure and dynamics.

  16. Deuterium charge exchange recombination spectroscopy from the top of the pedestal to the scrape off layer in H-mode plasmas

    DOE PAGES

    Haskey, S. R.; Grierson, B. A.; Stagner, L.; ...

    2017-10-25

    Recent completion of the thirty two channel main-ion (deuterium) charge exchange recombination spectroscopy (CER) diagnostic on DIII-D enables detailed comparisons between impurity and main-ion temperature, density, and toroidal rotation. Sixteen sightlines cover the core of the plasma and another sixteen are densely packed towards the edge, providing high resolution measurements of the pedestal and steep gradient edge region of H-mode plasmas. The complexities of the D α spectrum require fitting with a comprehensive model, as well as using iterative collisional radiative modeling to determine the underlying thermal deuterium ion properties. Large differences in the structure and magnitude of impurity (Cmore » 6+) and main-ion (D +) toroidal rotation profiles are seen in the H-mode pedestal. Additionally the D + temperature can be half the value of the C 6+ temperature at the separatrix and shows more of a pedestal structure. Typically only the impurity properties are measured and the main-ion properties are either assumed to be the same, or inferred using neoclassical models, which require validation in the steep gradient region. Furthermore, these measured differences have implications for transport model validation, intrinsic rotation studies, pedestal stability, and the boundary conditions for scrape off layer and plasma material interactions studies.« less

  17. Precision determination of the D0 mass.

    PubMed

    Cawlfield, C; Eisenstein, B I; Karliner, I; Kim, D; Lowrey, N; Naik, P; Selen, M; White, E J; Wiss, J; Mitchell, R E; Shepherd, M R; Besson, D; Pedlar, T K; Cronin-Hennessy, D; Gao, K Y; Hietala, J; Kubota, Y; Klein, T; Lang, B W; Poling, R; Scott, A W; Smith, A; Zweber, P; Dobbs, S; Metreveli, Z; Seth, K K; Tomaradze, A; Ernst, J; Ecklund, K M; Severini, H; Love, W; Savinov, V; Aquines, O; Li, Z; Lopez, A; Mehrabyan, S; Mendez, H; Ramirez, J; Huang, G S; Miller, D H; Pavlunin, V; Sanghi, B; Shipsey, I P J; Xin, B; Adams, G S; Anderson, M; Cummings, J P; Danko, I; Hu, D; Moziak, B; Napolitano, J; He, Q; Insler, J; Muramatsu, H; Park, C S; Thorndike, E H; Yang, F; Coan, T E; Gao, Y S; Artuso, M; Blusk, S; Butt, J; Li, J; Menaa, N; Mountain, R; Nisar, S; Randrianarivony, K; Sia, R; Skwarnicki, T; Stone, S; Wang, J C; Zhang, K; Bonvicini, G; Cinabro, D; Dubrovin, M; Lincoln, A; Asner, D M; Edwards, K W; Briere, R A; Ferguson, T; Tatishvili, G; Vogel, H; Watkins, M E; Rosner, J L; Adam, N E; Alexander, J P; Cassel, D G; Duboscq, J E; Ehrlich, R; Fields, L; Galik, R S; Gibbons, L; Gray, R; Gray, S W; Hartill, D L; Heltsley, B K; Hertz, D; Jones, C D; Kandaswamy, J; Kreinick, D L; Kuznetsov, V E; Mahlke-Krüger, H; Onyisi, P U E; Patterson, J R; Peterson, D; Pivarski, J; Riley, D; Ryd, A; Sadoff, A J; Schwarthoff, H; Shi, X; Stroiney, S; Sun, W M; Wilksen, T; Athar, S B; Patel, R; Potlia, V; Yelton, J; Rubin, P

    2007-03-02

    A precision measurement of the D0 meson mass has been made using approximately 281 pb(-1) of e+e- annihilation data taken with the CLEO-c detector at the psi(3770) resonance. The exclusive decay D0-->K_{S}phi has been used to obtain M(D0)=1864.847+/-0.150(stat)+/-0.095(syst) MeV. This corresponds to M(D0D*0)=3871.81+/-0.36 MeV, and leads to a well-constrained determination of the binding energy of the proposed D0D*0 molecule X(3872), as Eb=0.6+/-0.6 MeV.

  18. Exchange and Inelastic OH(+) + H Collisions on the Doublet and Quartet Electronic States.

    PubMed

    Bulut, Niyazi; Lique, François; Roncero, Octavio

    2015-12-17

    The exchange and inelastic state-to-state cross sections for the OH(+) + H collisions are computed from wave packet calculations using the doublet and quartet ground electronic potential energy surface (PES) correlating to the open shell reactants, for collision energies in the range of 1 meV to 0.7 eV. The doublet PES presents a deep insertion well, of ≈6 eV, but the exchange reaction has a rather low probability, showing that the mechanism is not statistical. This well is also responsible of a rather high rotational energy transfer, which makes the rigid-rotor approach overestimate the cross section for low Δj transitions and for high collisonal energies. The quartet PES, with a much shallower well, also presents a low exchange reaction cross section, but the inelastic state-to-state cross sections are very well reproduced by rigid-rotor calculations. When the electronic partition is used to obtain the total state-to-state cross section, the contribution of the doublet state becomes small, and the resulting total cross sections become close to those obtained for the quartet state. Thus, the total (quartet and doublet) cross sections for this open shell system can be reproduced rather satisfactorily by those obtained with the rigid-rotor approximation on the quartet state. Finally, we compare the new OH(+)-H cross sections with OH(+)-He ones recently computed. We found significant differences, especially for transitions with large Δj showing that specific OH(+)-H calculations had to be performed to accurately analyze the OH(+) emission from interstellar molecular clouds.

  19. Integrating mass spectrometry with MD simulations reveals the role of lipids in Na+/H+ antiporters

    NASA Astrophysics Data System (ADS)

    Landreh, Michael; Marklund, Erik G.; Uzdavinys, Povilas; Degiacomi, Matteo T.; Coincon, Mathieu; Gault, Joseph; Gupta, Kallol; Liko, Idlir; Benesch, Justin L. P.; Drew, David; Robinson, Carol V.

    2017-01-01

    Na+/H+ antiporters are found in all kingdoms of life and exhibit catalysis rates that are among the fastest of all known secondary-active transporters. Here we combine ion mobility mass spectrometry and molecular dynamics simulations to study the conformational stability and lipid-binding properties of the Na+/H+ exchanger NapA from Thermus thermophilus and compare this to the prototypical antiporter NhaA from Escherichia coli and the human homologue NHA2. We find that NapA and NHA2, but not NhaA, form stable dimers and do not selectively retain membrane lipids. By comparing wild-type NapA with engineered variants, we show that the unfolding of the protein in the gas phase involves the disruption of inter-domain contacts. Lipids around the domain interface protect the native fold in the gas phase by mediating contacts between the mobile protein segments. We speculate that elevator-type antiporters such as NapA, and likely NHA2, use a subset of annular lipids as structural support to facilitate large-scale conformational changes within the membrane.

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

    PubMed

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

    2016-06-15

    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. Jak2 and Ca2+/calmodulin are key intermediates for bradykinin B2 receptor-mediated activation of Na+/H+ exchange in KNRK and CHO cells.

    PubMed

    Lefler, David; Mukhin, Yurii V; Pettus, Tobiah; Leeb-Lundberg, L M Fredrik; Garnovskaya, Maria N; Raymond, John R

    2003-04-01

    Na(+)/H(+) exchangers are ubiquitous in mammalian cells, carrying out key functions, such as cell volume defense, acid-base homeostasis, and regulation of the cytoskeleton. We used two screening technologies (FLIPR and microphysiometry) to characterize the signal transduction pathway used by the bradykinin B(2) receptor to activate Na(+)/H(+) exchange in two cell lines, KNRK and CHO. In both cell types, B(2) receptor activation resulted in rapid increases in the rate of proton extrusion that were sodium-dependent and could be blocked by the Na(+)/H(+) exchange inhibitors EIPA and MIA or by replacing extracellular sodium with TMA. Activation of Na(+)/H(+) exchange by bradykinin was concentration-dependent and could be blocked by the selective B(2) receptor antagonist HOE140, but not by the B(1) receptor antagonist des-Arg10-HOE140. Inhibitors of Jak2 tyrosine kinase (genistein and AG490) and of CAM (W-7 and calmidazolium) attenuated bradykinin-induced activation of Na(+)/H(+) exchange. Bradykinin induced formation of a complex between CAM and Jak2, supporting a regulatory role for Jak2 and CAM in the activation of Na(+)/H(+) exchange in KNRK and CHO cells. We propose that this pathway (B(2) receptor --> Jak2 --> CAM --> Na(+)/H(+) exchanger) is a fundamental regulator of Na(+)/H(+) exchange activity.

  2. Optimizing Higgs factories by modifying the recoil mass

    NASA Astrophysics Data System (ADS)

    Gu, Jiayin; Li, Ying-Ying

    2018-02-01

    It is difficult to measure the WW-fusion Higgs production process ({{{e}}}+{{{e}}}-\\to {{ν }}\\bar{{{ν }}}{{h}}) at a lepton collider with a center of mass energy of 240-250 GeV due to its small rate and the large background from the Higgsstrahlung process with an invisible Z ({{{e}}}+{{{e}}}-\\to {{hZ}},{{Z}}\\to {{ν }}\\bar{{{ν }}}). We construct a modified recoil mass variable, {m}{{recoil}}p, defined using only the 3-momentum of the reconstructed Higgs particle, and show that it can separate the WW-fusion and Higgsstrahlung events better than the original recoil mass variable m recoil. Consequently, the {m}{{recoil}}p variable can be used to improve the overall precisions of the extracted Higgs couplings, in both the conventional framework and the effective-field-theory framework. We also explore the application of the {m}{{recoil}}p variable in the inclusive cross section measurements of the Higgsstrahlung process, while a quantitive analysis is left for future studies. JG is Supported by an International Postdoctoral Exchange Fellowship Program between the Office of the National Administrative Committee of Postdoctoral Researchers of China (ONACPR) and DESY. YYL is Supported by Hong Kong PhD Fellowship (HKPFS) and the Collaborative Research Fund (CRF) (HUKST4/CRF/13G)

  3. Thermal dissociation of ions limits the degree of the gas-phase H/D exchange at the atmospheric pressure.

    PubMed

    Kostyukevich, Y; Kononikhin, A; Popov, I; Nikolaev, E

    2017-04-01

    We present the application of the extended desolvating capillaries for increasing the degree of the gas-phase hydrogen/deuterium exchange reaction at atmospheric pressure. The use of the extended capillaries results in the increase of the time that ions spend in the high pressure region, what leads to the significant improvement of the efficiency of the reaction. For the small protein ubiquitin, it was observed that for the same temperature, the number of exchanges increases with the decrease of the charge state so that the lowest charge state can exchange twice the number of hydrogen than the highest one. With the increase of the temperature, the difference decreases, and eventually, the number of exchanges equalizes for all charge states. The value of this temperature and the corresponding number of exchanges depend on the geometric parameters of the capillary. Further increase of the temperature leads to the thermal dissociation of the protein ion. The observed b/y fragments are identical to those produced by collision-induced dissociation performed in the ion trap. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

  4. Cardiac-specific expression and hypertrophic upregulation of the feline Na(+)-Ca(2+) exchanger gene H1-promoter in a transgenic mouse model.

    PubMed

    Müller, Joachim G; Isomatsu, Yukihisa; Koushik, Srinagesh V; O'Quinn, Michael; Xu, Lin; Kappler, Christiana S; Hapke, Elizabeth; Zile, Michael R; Conway, Simon J; Menick, Donald R

    2002-02-08

    The NCX1 gene contains three promoters (H1, K1, and Br1), and as a result of alternative promoter usage and alternative splicing, there are multiple tissue-specific variants of the Na(+)-Ca(2+) exchanger. We have proposed that for NCX1, the H1 promoter regulates expression in the heart, the K1 promoter regulates expression in the kidney, and the Br1 promoter regulates expression in the brain as well as low-level ubiquitous expression. Here, using a transgenic mouse model, we test the role of the DNA region including -1831 to 67 bp of intron 1, encompassing exon H1 of the feline NCX1 gene (NCX1H1). The NCX1H1 promoter was sufficient for driving the normal spatiotemporal pattern of NCX1 expression in cardiac development. The luciferase reporter gene was expressed in a heart-restricted pattern both in early embryos (embryonic days 8 to 14) and in later embryos (after embryonic day 14), when NCX1 is also expressed in other tissues. In the adult, no luciferase activity was detected in the kidney, liver, spleen, uterus, or skeletal muscle; minimal activity was detected in the brain; and very high levels of luciferase expression were detected in the heart. Transverse aortic constriction-operated mice showed significantly increased left ventricular mass after 7 days. In addition, there was a 2-fold upregulation of NCX1H1 promoter activity in the left ventricle in animals after 7 days of pressure overload compared with both control and sham-operated animals. This work demonstrates that the NCX1H1 promoter directs cardiac-specific expression of the exchanger in both the embryo and adult and is also sufficient for the upregulation of NCX1 in response to pressure overload.

  5. Delivering strong 1H nuclear hyperpolarization levels and long magnetic lifetimes through signal amplification by reversible exchange

    PubMed Central

    Rayner, Peter J.; Burns, Michael J.; Olaru, Alexandra M.; Norcott, Philip; Fekete, Marianna; Green, Gary G. R.; Highton, Louise A. R.; Mewis, Ryan E.

    2017-01-01

    Hyperpolarization turns typically weak NMR and MRI responses into strong signals so that ordinarily impractical measurements become possible. The potential to revolutionize analytical NMR and clinical diagnosis through this approach reflect this area's most compelling outcomes. Methods to optimize the low-cost parahydrogen-based approach signal amplification by reversible exchange with studies on a series of biologically relevant nicotinamides and methyl nicotinates are detailed. These procedures involve specific 2H labeling in both the agent and catalyst and achieve polarization lifetimes of ca. 2 min with 50% polarization in the case of methyl-4,6-d2-nicotinate. Because a 1.5-T hospital scanner has an effective 1H polarization level of just 0.0005% this strategy should result in compressed detection times for chemically discerning measurements that probe disease. To demonstrate this technique’s generality, we exemplify further studies on a range of pyridazine, pyrimidine, pyrazine, and isonicotinamide analogs that feature as building blocks in biochemistry and many disease-treating drugs. PMID:28377523

  6. Dual Studies on a Hydrogen-Deuterium Exchange of Resorcinol and the Subsequent Kinetic Isotope Effect

    ERIC Educational Resources Information Center

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

    2014-01-01

    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…

  7. Surfactant exfoliated 2D hexagonal Boron Nitride (2D-hBN) explored as a potential electrochemical sensor for dopamine: surfactants significantly influence sensor capabilities.

    PubMed

    Khan, Aamar F; Brownson, Dale A C; Foster, Christopher W; Smith, Graham C; Banks, Craig E

    2017-05-21

    Surfactant exfoliated 2D hexagonal Boron Nitride (2D-hBN) nanosheets are explored as a potential electrochemical sensing platform and evaluated towards the electroanalytical sensing of dopamine (DA) in the presence of the common interferents, ascorbic acid (AA) and uric acid (UA). Surfactant exfoliated 2D-hBN nanosheets (2-4 layers) fabricated using sodium cholate in aqueous media are electrically wired via a drop-casting modification process onto disposable screen-printed graphite electrodes (SPEs). We critically evaluate the performance of these 2D-hBN modified SPEs and demonstrate the effect of 'mass coverage' towards the detection of DA, AA and UA. Previous studies utilising surfactant-free (pristine) 2D-hBN modified SPEs have shown a beneficial effect towards the detection of DA, AA and UA when compared to the underlying/unmodified graphite-based electrode. We show that the fabrication route utilised to prepare 2D-hBN is a vital experimental consideration, such that the beneficial effect previously reported is considerably reduced when surfactant exfoliated 2D-hBN is utilised. We demonstrate for the first time, through implementation of control experiments in the form of surfactant modified graphite electrodes, that sodium cholate is a major contributing factor to the aforementioned detrimental behaviour. The significance here is not in the material per se, but the fundamental knowledge of the surfactant and surface coverage changing the electrochemical properties of the material under investigation. Given the wide variety of ionic and non-ionic surfactants that are utilised in the manufacture of novel 2D materials, the control experiments reported herein need to be performed in order to de-convolute the electrochemical response and effectively evaluate the 'underlying surface/surfactant/2D materials' electrocatalytic contribution.

  8. GAMA/H-ATLAS: The Local Dust Mass Function and Cosmic Density as a Function of Galaxy Type - A Benchmark for Models of Galaxy Evolution

    NASA Astrophysics Data System (ADS)

    Beeston, R. A.; Wright, A. H.; Maddox, S.; Gomez, H. L.; Dunne, L.; Driver, S. P.; Robotham, A.; Clark, C. J. R.; Vinsen, K.; Takeuchi, T. T.; Popping, G.; Bourne, N.; Bremer, M. N.; Phillipps, S.; Moffett, A. J.; Baes, M.; Bland-Hawthorn, J.; Brough, S.; De Vis, P.; Eales, S. A.; Holwerda, B. W.; Loveday, J.; Liske, J.; Smith, M. W. L.; Smith, D. J. B.; Valiante, E.; Vlahakis, C.; Wang, L.

    2018-06-01

    We present the dust mass function (DMF) of 15,750 galaxies with redshift z < 0.1, drawn from the overlapping area of the GAMA and H-ATLAS surveys. The DMF is derived using the density corrected Vmax method, where we estimate Vmax using: (i) the normal photometric selection limit (pVmax) and (ii) a bivariate brightness distribution (BBD) technique, which accounts for two selection effects. We fit the data with a Schechter function, and find M^{*}=(4.65 ± 0.18)× 107 h^2_{70} M_{⊙ }, α = ( - 1.22 ± 0.01), φ ^{*}=(6.26 ± 0.28)× 10^{-3} h^3_{70} Mpc^{-3} dex^{-1}. The resulting dust mass density parameter integrated down to 104 M⊙ is Ωd = (1.11 ± 0.02) × 10-6 which implies the mass fraction of baryons in dust is f_{m_b}=(2.40± 0.04)× 10^{-5}; cosmic variance adds an extra 7-17 per cent uncertainty to the quoted statistical errors. Our measurements have fewer galaxies with high dust mass than predicted by semi-analytic models. This is because the models include too much dust in high stellar mass galaxies. Conversely, our measurements find more galaxies with high dust mass than predicted by hydrodynamical cosmological simulations. This is likely to be from the long timescales for grain growth assumed in the models. We calculate DMFs split by galaxy type and find dust mass densities of Ωd = (0.88 ± 0.03) × 10-6 and Ωd = (0.060 ± 0.005) × 10-6 for late-types and early-types respectively. Comparing to the equivalent galaxy stellar mass functions (GSMF) we find that the DMF for late-types is well matched by the GMSF scaled by (8.07 ± 0.35) × 10-4.

  9. Analysis of phosphoinositide 3-kinase inhibitors by bottom-up electron-transfer dissociation hydrogen/deuterium exchange mass spectrometry

    PubMed Central

    Masson, Glenn R.; Maslen, Sarah L.

    2017-01-01

    Until recently, one of the major limitations of hydrogen/deuterium exchange mass spectrometry (HDX-MS) was the peptide-level resolution afforded by proteolytic digestion. This limitation can be selectively overcome through the use of electron-transfer dissociation to fragment peptides in a manner that allows the retention of the deuterium signal to produce hydrogen/deuterium exchange tandem mass spectrometry (HDX-MS/MS). Here, we describe the application of HDX-MS/MS to structurally screen inhibitors of the oncogene phosphoinositide 3-kinase catalytic p110α subunit. HDX-MS/MS analysis is able to discern a conserved mechanism of inhibition common to a range of inhibitors. Owing to the relatively minor amounts of protein required, this technique may be utilised in pharmaceutical development for screening potential therapeutics. PMID:28381646

  10. Nitroxyl Radical plus Hydroxylamine Pseudo Self-Exchange Reactions: Tunneling in Hydrogen Atom Transfer

    PubMed Central

    Wu, Adam; Mader, Elizabeth A.; Datta, Ayan; Hrovat, David A.; Borden, Weston Thatcher; Mayer, James M.

    2009-01-01

    Bimolecular rate constants have been measured for reactions that involve hydrogen atom transfer (HAT) from hydroxylamines to nitroxyl radicals, using the stable radicals TEMPO• (2,2,6,6-tetramethylpiperidine-1-oxyl radical), 4-oxo-TEMPO• (2,2,6,6-tetramethyl-4-oxo-piperidine-1-oxyl radical), di-tert-butylnitroxyl (tBu2NO•), and the hydroxylamines TEMPO-H, 4-oxo-TEMPO-H, 4-MeO-TEMPO-H (2,2,6,6-tetramethyl-N-hydroxy-4-methoxy-piperidine), and tBu2NOH. The reactions have been monitored by UV-vis stopped-flow methods, using the different optical spectra of nitroxyl radicals. The HAT reactions all have |ΔGo| ≤ 1.4 kcal mol−1 and therefore are close to self-exchange reactions. The reaction of 4-oxo-TEMPO• + TEMPO-H → 4-oxo-TEMPO-H + TEMPO• occurs with k2H,MeCN = 10 ± 1 M−1 s−1 in MeCN at 298 K (K2H,MeCN = 4.5 ± 1.8). Surprisingly, the rate constant for the analogous deuterium atom transfer reaction is much slower: k2D,MeCN = 0.44 ± 0.05 M−1 s−1 with k2H,MeCN/k2D,MeCN = 23 ± 3 at 298 K. The same large kinetic isotope effect (KIE) is found in CH2Cl2, 23 ± 4, suggesting that the large KIE is not caused by solvent dynamics or hydrogen bonding to solvent. The related reaction of 4-oxo-TEMPO• with 4-MeO-TEMPO-H(D) also has a large KIE, k3H/k3D = 21 ± 3 in MeCN. For these three reactions, the EaD – EaH values, between 0.3 ± 0.6 and 1.3 ± 0.6 kcal mol−1, and the log(AH/AD) values, between 0.5 ± 0.7 and 1.1 ± 0.6, indicate that hydrogen tunneling plays an important role. The related reaction of tBu2NO• + TEMPO-H(D) in MeCN has a large KIE, 16 ± 3 in MeCN, and very unusual isotopic activation parameters, EaD – EaH = −2.6 ± 0.4 and log(AH/AD) = 3.1 ± 0.6. Computational studies, using POLYRATE, also indicate substantial tunneling in the (CH3)2NO• + (CH3)2NOH model reaction for the experimental self-exchange processes. Additional calculations on TEMPO(•/H), tBu2NO(•/H), and Ph2NO(•/H) self-exchange reactions reveal why the

  11. Direct analysis of ultra-trace semiconductor gas by inductively coupled plasma mass spectrometry coupled with gas to particle conversion-gas exchange technique.

    PubMed

    Ohata, Masaki; Sakurai, Hiromu; Nishiguchi, Kohei; Utani, Keisuke; Günther, Detlef

    2015-09-03

    An inductively coupled plasma mass spectrometry (ICPMS) coupled with gas to particle conversion-gas exchange technique was applied to the direct analysis of ultra-trace semiconductor gas in ambient air. The ultra-trace semiconductor gases such as arsine (AsH3) and phosphine (PH3) were converted to particles by reaction with ozone (O3) and ammonia (NH3) gases within a gas to particle conversion device (GPD). The converted particles were directly introduced and measured by ICPMS through a gas exchange device (GED), which could penetrate the particles as well as exchange to Ar from either non-reacted gases such as an air or remaining gases of O3 and NH3. The particle size distribution of converted particles was measured by scanning mobility particle sizer (SMPS) and the results supported the elucidation of particle agglomeration between the particle converted from semiconductor gas and the particle of ammonium nitrate (NH4NO3) which was produced as major particle in GPD. Stable time-resolved signals from AsH3 and PH3 in air were obtained by GPD-GED-ICPMS with continuous gas introduction; however, the slightly larger fluctuation, which could be due to the ionization fluctuation of particles in ICP, was observed compared to that of metal carbonyl gas in Ar introduced directly into ICPMS. The linear regression lines were obtained and the limits of detection (LODs) of 1.5 pL L(-1) and 2.4 nL L(-1) for AsH3 and PH3, respectively, were estimated. Since these LODs revealed sufficiently lower values than the measurement concentrations required from semiconductor industry such as 0.5 nL L(-1) and 30 nL L(-1) for AsH3 and PH3, respectively, the GPD-GED-ICPMS could be useful for direct and high sensitive analysis of ultra-trace semiconductor gas in air. Copyright © 2015 Elsevier B.V. All rights reserved.

  12. Selective Adsorption Resonances in the Scattering of n-H2 p-H2 n-D2 and o-D2 from Ag(111)

    NASA Astrophysics Data System (ADS)

    Yu, Chien-Fan; Whaley, K. Birgitta; Hogg, Charles S.; Sibener, Steven J.

    1983-12-01

    Diffractive and rotationally mediated selective adsorption scattering resonances are reported for n-H2 p-H2 n-D2 and o-D2 on Ag(111). Small resonance shifts and line-width differences are observed between n-H2 and p-H2 indicating a weak orientation dependence of the laterally averaged H2/Ag(111) potential. The p-H2 and o-D2 levels were used to determine the isotropic component of this potential, yielding a well depth of ~ 32 meV.

  13. 3d-4f magnetic interaction with density functional theory plus u approach: local Coulomb correlation and exchange pathways.

    PubMed

    Zhang, Yachao; Yang, Yang; Jiang, Hong

    2013-12-12

    The 3d-4f exchange interaction plays an important role in many lanthanide based molecular magnetic materials such as single-molecule magnets and magnetic refrigerants. In this work, we study the 3d-4f magnetic exchange interactions in a series of Cu(II)-Gd(III) (3d(9)-4f(7)) dinuclear complexes based on the numerical atomic basis-norm-conserving pseudopotential method and density functional theory plus the Hubbard U correction approach (DFT+U). We obtain improved description of the 4f electrons by including the semicore 5s5p states in the valence part of the Gd-pseudopotential. The Hubbard U correction is employed to treat the strongly correlated Cu-3d and Gd-4f electrons, which significantly improve the agreement of the predicted exchange constants, J, with experiment, indicating the importance of accurate description of the local Coulomb correlation. The high efficiency of the DFT+U approach enables us to perform calculations with molecular crystals, which in general improve the agreement between theory and experiment, achieving a mean absolute error smaller than 2 cm(-1). In addition, through analyzing the physical effects of U, we identify two magnetic exchange pathways. One is ferromagnetic and involves an interaction between the Cu-3d, O-2p (bridge ligand), and the majority-spin Gd-5d orbitals. The other one is antiferromagnetic and involves Cu-3d, O-2p, and the empty minority-spin Gd-4f orbitals, which is suppressed by the planar Cu-O-O-Gd structure. This study demonstrates the accuracy of the DFT+U method for evaluating the 3d-4f exchange interactions, provides a better understanding of the exchange mechanism in the Cu(II)-Gd(III) complexes, and paves the way for exploiting the magnetic properties of the 3d-4f compounds containing lanthanides other than Gd.

  14. A Comprehensive Study on the Electronic State of Hydrogen in α-Phase PdH(D)x-Does a Chemical Bond Between Pd and H(D) Exist?

    PubMed

    Dekura, Shun; Kobayashi, Hirokazu; Ikeda, Ryuichi; Maesato, Mitsuhiko; Yoshino, Haruka; Ohba, Masaaki; Ishimoto, Takayoshi; Kawaguchi, Shogo; Kubota, Yoshiki; Yoshioka, Satoru; Matsumura, Syo; Sugiyama, Takeharu; Kitagawa, Hiroshi

    2018-06-12

    The palladium(Pd)-hydrogen(H) system is one of the most famous hydrogen storage systems. Although there has been much research on β-phase PdH(D)x, we comprehensively investigated the nature of the interaction between Pd and H(D) in α-phase PdH(D)x (x < 0.03 at 303 K), and revealed the existence of Pd-H(D) chemical bond for the first time, by various in situ experimental techniques and first-principles theoretical calculations. The lattice expansion by H(D) dissolution in the α-phase lattice suggests the existence of interaction between Pd and H(D). The decrease of magnetic susceptibility and the increase of electrical resistivity indicate that the electronic states are changed by the H(D) dissolution in the α phase. In situ solid-state 1H and 2H NMR results and first-principles theoretical calculations revealed that a Pd-H(D) chemical bond exists in the α phase, but the bonding character of the Pd-H(D) chemical bond in the α phase is quite different from that in the β phase; the nature of the Pd-H(D) chemical bond in the α phase is a localized covalent bond whereas that in the β phase is a metallic bond. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. pH-Dependent isotope exchange and hydrogenation catalysed by water-soluble NiRu complexes as functional models for [NiFe]hydrogenases.

    PubMed

    Kure, Bunsho; Matsumoto, Takahiro; Ichikawa, Koji; Fukuzumi, Shunichi; Higuchi, Yoshiki; Yagi, Tatsuhiko; Ogo, Seiji

    2008-09-21

    The pH-dependent hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes and hydrogenation of the carbonyl compounds have been investigated with water-soluble bis(mu-thiolate)(mu-hydride)NiRu complexes, Ni(II)(mu-SR)(2)(mu-H)Ru(II) {(mu-SR)(2) = N,N'-dimethyl-N,N'-bis(2-mercaptoethyl)-1,3-propanediamine}, as functional models for [NiFe]hydrogenases. In acidic media (at pH 4-6), the mu-H ligand of the Ni(II)(mu-SR)(2)(mu-H)Ru(II) complexes has H(+) properties, and the complexes catalyse the hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes. A mechanism of the hydrogen isotope exchange reaction between gaseous isotopes and medium isotopes through a low-valent Ni(I)(mu-SR)(2)Ru(I) complex is proposed. In contrast, in neutral-basic media (at pH 7-10), the mu-H ligand of the Ni(II)(mu-SR)(2)(mu-H)Ru(II) complexes acts as H(-), and the complexes catalyse the hydrogenation of carbonyl compounds.

  16. Solution structure, mutagenesis, and NH exchange studies of the MutT enzyme-Mg 2+-8-oxo-dGMP complex

    NASA Astrophysics Data System (ADS)

    Massiah, M. A.; Saraswat, V.; Azurmendi, H. F.; Mildvan, A. S.

    2004-08-01

    The MutT pyrophosphohydrolase from E. coli (129 residues) catalyzes the hydrolysis of nucleoside triphosphates (NTP), including 8-oxo-dGTP, by substitution at Pβ, to yield NMP and pyrophosphate. The product, 8-oxo-dGMP is an unusually tight binding, slowly exchanging inhibitor with a KD=52 nM, (Δ G°=-9.8 kcal/mol) which is 6.1 kcal/mol tighter than the binding of dGMP (Δ G°=-3.7 kcal/mol). The higher affinity for 8-oxo-dGMP results from a more favorable Δ Hbinding (-32 kcal/mol) despite an unfavorable - TΔ S° binding (+22 kcal/mol). The solution structure of the MutT-Mg 2+-8-oxo-dGMP complex shows a narrowed, hydrophobic nucleotide-binding cleft with Asn-119 and Arg-78 among the few polar residues. The N119A, N119D, R78K and R78A single mutations, and the R78K+N119A double mutant all showed largely intact active sites, on the basis of small changes in the kinetic parameters of dGTP hydrolysis and in 1H- 15N HSQC spectra. However, the N119A mutation profoundly weakened the active site binding of 8-oxo-dGMP by 4.3 kcal/mol (1650-fold). The N119D mutation also weakened 8-oxo-dGMP binding but only by 2.1 kcal/mol (37-fold), suggesting that Asn-119 functioned both as a hydrogen bond donor to C8O, and a hydrogen bond acceptor from N7H of 8-oxo-dGMP, while aspartate at position -119 functioned as an acceptor of a single hydrogen bond. Much smaller weakening effects (0.3-0.4 kcal/mol) on the binding of dGMP and dAMP were found, indicating specific hydrogen bonding of Asn-119 to 8-oxo-dGMP. While formation of the wild type MutT-Mg 2+-8-oxo-dGMP complex slowed the backbone NH exchange rates of 45 residues distributed throughout the protein, the same complex of the N119A mutant slowed the exchange rates of only 11 residues at or near the active site, indicating an increase in conformational flexibility of the N119A mutant. The R78K and R78A mutations weakened the binding of 8-oxo-dGMP by 1.7 and 1.1 kcal/mol, respectively, indicating a lesser role of Arg-78 than of

  17. Biotic Control of Surface pH and Evidence of Light-Induced H+ Pumping and Ca2+-H+ Exchange in a Tropical Crustose Coralline Alga.

    PubMed

    Hofmann, Laurie C; Koch, Marguerite; de Beer, Dirk

    2016-01-01

    Presently, an incomplete mechanistic understanding of tropical reef macroalgae photosynthesis and calcification restricts predictions of how these important autotrophs will respond to global change. Therefore, we investigated the mechanistic link between inorganic carbon uptake pathways, photosynthesis and calcification in a tropical crustose coralline alga (CCA) using microsensors. We measured pH, oxygen (O2), and calcium (Ca2+) dynamics and fluxes at the thallus surface under ambient (8.1) and low (7.8) seawater pH (pHSW) and across a range of irradiances. Acetazolamide (AZ) was used to inhibit extracellular carbonic anhydrase (CAext), which mediates hydrolysis of HCO3-, and 4,4' diisothiocyanatostilbene-2,2'-disulphonate (DIDS) that blocks direct HCO3- uptake by anion exchange transport. Both inhibited photosynthesis, suggesting both diffusive uptake of CO2 via HCO3- hydrolysis to CO2 and direct HCO3- ion transport are important in this CCA. Surface pH was raised approximately 0.3 units at saturating irradiance, but less when CAext was inhibited. Surface pH was lower at pHSW 7.8 than pHSW 8.1 in the dark, but not in the light. The Ca2+ fluxes were large, complex and temporally variable, but revealed net Ca2+ uptake under all conditions. The temporal variability in Ca2+ dynamics was potentially related to localized dissolution during epithallial cell sloughing, a strategy of CCA to remove epiphytes. Simultaneous Ca2+ and pH dynamics suggest the presence of Ca2+/H+ exchange. Rapid light-induced H+ surface dynamics that continued after inhibition of photosynthesis revealed the presence of a light-mediated, but photosynthesis-independent, proton pump. Thus, the study indicates metabolic control of surface pH can occur in CCA through photosynthesis and light-inducible H+ pumps. Our results suggest that complex light-induced ion pumps play an important role in biological processes related to inorganic carbon uptake and calcification in CCA.

  18. Biotic Control of Surface pH and Evidence of Light-Induced H+ Pumping and Ca2+-H+ Exchange in a Tropical Crustose Coralline Alga

    PubMed Central

    Hofmann, Laurie C.; Koch, Marguerite; de Beer, Dirk

    2016-01-01

    Presently, an incomplete mechanistic understanding of tropical reef macroalgae photosynthesis and calcification restricts predictions of how these important autotrophs will respond to global change. Therefore, we investigated the mechanistic link between inorganic carbon uptake pathways, photosynthesis and calcification in a tropical crustose coralline alga (CCA) using microsensors. We measured pH, oxygen (O2), and calcium (Ca2+) dynamics and fluxes at the thallus surface under ambient (8.1) and low (7.8) seawater pH (pHSW) and across a range of irradiances. Acetazolamide (AZ) was used to inhibit extracellular carbonic anhydrase (CAext), which mediates hydrolysis of HCO3-, and 4,4′ diisothiocyanatostilbene-2,2′-disulphonate (DIDS) that blocks direct HCO3- uptake by anion exchange transport. Both inhibited photosynthesis, suggesting both diffusive uptake of CO2 via HCO3- hydrolysis to CO2 and direct HCO3- ion transport are important in this CCA. Surface pH was raised approximately 0.3 units at saturating irradiance, but less when CAext was inhibited. Surface pH was lower at pHSW 7.8 than pHSW 8.1 in the dark, but not in the light. The Ca2+ fluxes were large, complex and temporally variable, but revealed net Ca2+ uptake under all conditions. The temporal variability in Ca2+ dynamics was potentially related to localized dissolution during epithallial cell sloughing, a strategy of CCA to remove epiphytes. Simultaneous Ca2+ and pH dynamics suggest the presence of Ca2+/H+ exchange. Rapid light-induced H+ surface dynamics that continued after inhibition of photosynthesis revealed the presence of a light-mediated, but photosynthesis-independent, proton pump. Thus, the study indicates metabolic control of surface pH can occur in CCA through photosynthesis and light-inducible H+ pumps. Our results suggest that complex light-induced ion pumps play an important role in biological processes related to inorganic carbon uptake and calcification in CCA. PMID:27459463

  19. Modeling and simulation of protein elution in linear pH and salt gradients on weak, strong and mixed cation exchange resins applying an extended Donnan ion exchange model.

    PubMed

    Wittkopp, Felix; Peeck, Lars; Hafner, Mathias; Frech, Christian

    2018-04-13

    Process development and characterization based on mathematic modeling provides several advantages and has been applied more frequently over the last few years. In this work, a Donnan equilibrium ion exchange (DIX) model is applied for modelling and simulation of ion exchange chromatography of a monoclonal antibody in linear chromatography. Four different cation exchange resin prototypes consisting of weak, strong and mixed ligands are characterized using pH and salt gradient elution experiments applying the extended DIX model. The modelling results are compared with the results using a classic stoichiometric displacement model. The Donnan equilibrium model is able to describe all four prototype resins while the stoichiometric displacement model fails for the weak and mixed weak/strong ligands. Finally, in silico chromatogram simulations of pH and pH/salt dual gradients are performed to verify the results and to show the consistency of the developed model. Copyright © 2018 Elsevier B.V. All rights reserved.

  20. Applications of 3D visualization : peer exchange summary report : Raleigh, North Carolina July 8-9, 2009

    DOT National Transportation Integrated Search

    2009-11-01

    This report provides a summary of a 1.5-day peer exchange held in July 2009 focusing on select transportation agencies' applications of 3D visualization techniques. FHWA's Office of Interstate and Border Planning sponsored the peer exchange.

  1. Design and operation of the pellet charge exchange diagnostic for measurement of energetic confined alphas and tritons on TFTR

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

    Medley, S.S.; Duong, H.H.; Fisher, R.K.

    1996-05-01

    Radially-resolved energy and density distributions of the energetic confined alpha particles in D-T experiments on TFTR are being measured by active neutral particle analysis using low-Z impurity pellet injection. When injected into a high temperature plasma, an impurity pellet (e.g. Lithium or Boron) rapidly ablates forming an elongated cloud which is aligned with the magnetic field and moves with the pellet. This ablation cloud provides a dense target with which the alpha particles produced in D-T fusion reactions can charge exchange. A small fraction of the alpha particles incident on the pellet ablation cloud will be converted to helium neutralsmore » whose energy is essentially unchanged by the charge transfer process. By measuring the resultant helium neutrals escaping from the plasma using a mass and energy resolving charge exchange analyzer, this technique offers a direct measurement of the energy distribution of the incident high-energy alpha particles. Other energetic ion species can be detected as well, such as tritons generated in D-D plasmas and H or He{sup 3} RF-driven minority ion tails. The diagnostic technique and its application on TFTR are described in detail.« less

  2. Protein hydrogen exchange at residue resolution by proteolytic fragmentation mass spectrometry analysis

    PubMed Central

    Kan, Zhong-Yuan; Walters, Benjamin T.; Mayne, Leland; Englander, S. Walter

    2013-01-01

    Hydrogen exchange technology provides a uniquely powerful instrument for measuring protein structural and biophysical properties, quantitatively and in a nonperturbing way, and determining how these properties are implemented to produce protein function. A developing hydrogen exchange–mass spectrometry method (HX MS) is able to analyze large biologically important protein systems while requiring only minuscule amounts of experimental material. The major remaining deficiency of the HX MS method is the inability to deconvolve HX results to individual amino acid residue resolution. To pursue this goal we used an iterative optimization program (HDsite) that integrates recent progress in multiple peptide acquisition together with previously unexamined isotopic envelope-shape information and a site-resolved back-exchange correction. To test this approach, residue-resolved HX rates computed from HX MS data were compared with extensive HX NMR measurements, and analogous comparisons were made in simulation trials. These tests found excellent agreement and revealed the important computational determinants. PMID:24019478

  3. Sc2C2@D3h(14246)-C74: A Missing Piece of the Clusterfullerene Puzzle.

    PubMed

    Wang, Yaofeng; Tang, Qiangqiang; Feng, Lai; Chen, Ning

    2017-02-20

    Clusterfullerenes with variable carbon cages have been extensively studied in recent years. However, despite all these efforts, C 74 cage-based clusterfullerene remains a missing piece of the puzzle. Herein, we show that single-crystal X-ray crystallographic analysis unambiguously assigns the previously reported dimetallofullerene Sc 2 @C 76 to a novel carbide clusterfullerene, Sc 2 C 2 @D 3h (14246)-C 74 , the first experimentally proven clusterfullerene with a C 74 cage. In addition, Sc 2 C 2 @D 3h (14246)-C 74 was charaterized by mass spectrometry, ultraviolet-visible-near-infrared absorption spectroscopy, 45 Sc nuclear magnetic resonance, and cyclic voltammetry. Comparative studies of the motion of the carbide cluster in Sc 2 C 2 @D 3h (14246)-C 74 and Sc 2 C 2 @C 2n (n = 40-44) revealed that a combination of factors, involving both the shape and size of the cage, is crucial in dictating the cluster motion. Moreover, structural studies of D 3h (14246)-C 74 revealed that it can be easily converted to C s (10528)-C 72 and T d (19151)-C 76 cages via C 2 desertion/insertion and Stone-Wales transformation. This suggests that D 3h (14246)-C 74 might play an important role in the growth pathway of clusterfullerenes.

  4. Cometary science. 67P/Churyumov-Gerasimenko, a Jupiter family comet with a high D/H ratio.

    PubMed

    Altwegg, K; Balsiger, H; Bar-Nun, A; Berthelier, J J; Bieler, A; Bochsler, P; Briois, C; Calmonte, U; Combi, M; De Keyser, J; Eberhardt, P; Fiethe, B; Fuselier, S; Gasc, S; Gombosi, T I; Hansen, K C; Hässig, M; Jäckel, A; Kopp, E; Korth, A; LeRoy, L; Mall, U; Marty, B; Mousis, O; Neefs, E; Owen, T; Rème, H; Rubin, M; Sémon, T; Tzou, C-Y; Waite, H; Wurz, P

    2015-01-23

    The provenance of water and organic compounds on Earth and other terrestrial planets has been discussed for a long time without reaching a consensus. One of the best means to distinguish between different scenarios is by determining the deuterium-to-hydrogen (D/H) ratios in the reservoirs for comets and Earth's oceans. Here, we report the direct in situ measurement of the D/H ratio in the Jupiter family comet 67P/Churyumov-Gerasimenko by the ROSINA mass spectrometer aboard the European Space Agency's Rosetta spacecraft, which is found to be (5.3 ± 0.7) × 10(-4)—that is, approximately three times the terrestrial value. Previous cometary measurements and our new finding suggest a wide range of D/H ratios in the water within Jupiter family objects and preclude the idea that this reservoir is solely composed of Earth ocean-like water. Copyright © 2015, American Association for the Advancement of Science.

  5. Characterisation of DEFB107 by mass spectrometry

    NASA Astrophysics Data System (ADS)

    McCullough, Bryan J.; Eastwood, Hayden; Clark, Dave J.; Polfer, Nick C.; Campopiano, Dominic J.; Dorin, Julia A.; Maxwell, Alison; Langley, Ross J.; Govan, John R. W.; Bernstein, Summer L.; Bowers, Michael T.; Barran, Perdita E.

    2006-05-01

    Mammalian defensins are small endogenous cationic proteins which form a class of antimicrobial peptides that is part of the innate immune response of all mammalian species [R. Lehrer, Nat. Rev. Microbiol. 2 (9) (2004) 727; T. Ganz, R.I. Lehrer, Curr. Opin. Immunol. 6 (4) (1994) 584] [1] and [2]. We have developed mass spectrometry based strategies for characterising the structure-activity relationship of defensins [D.J. Campopiano, D.J. Clarke, N.C. Polfer, P.E. Barran, R.J. Langley, J.R.W. Govan, A. Maxwell, J.R. Dorin, J. Biol. Chem. 279 (47) (2004) 48671; P.E. Barran, N.C. Polfer, D.J. Campopiano, D.J. Clarke, P.R.R. Langridge-Smith, R.J. Langley, J.R.W. Govan, A. Maxwell, J.R. Dorin, R.P. Millar, M.T. Bowers, Int. J. Mass Spectrom. 240 (2005) 273] [3] and [4], and here we present data obtained from a five cysteine containing [beta]-defensin, DEFB107. The synthetic product of this human defensin exists with a glutathione capping group, its oxidation state and disulphide connectivity have been determined via accurate mass measurements and peptide mass mapping respectively, and despite possessing three disulphide bridges, it does not fit the [beta]-defensin canonical motif. With the use of molecular modelling, we have generated candidate geometries to discern the influence of disulphide bridging on the overall tertiary structure of DEFB107. These are compared with experimental results from ion mobility measurements. Defensins display activity against a wide variety of pathogens including both gram-negative and gram-positive bacteria. Their mechanism of mode of action is unknown, but is believed to involve defensin aggregation at cell surfaces, followed by cell permeabilisation and hence deathE To probe this mechanism, the localisation of DEFB107 in synthetic vesicles was studied using H/D exchange and mass spectrometry. The results obtained are used to analyse the antimicrobial activity of DEFB107.

  6. D/H ratios of the inner Solar System.

    PubMed

    Hallis, L J

    2017-05-28

    The original hydrogen isotope (D/H) ratios of different planetary bodies may indicate where each body formed in the Solar System. However, geological and atmospheric processes can alter these ratios through time. Over the past few decades, D/H ratios in meteorites from Vesta and Mars, as well as from S- and C-type asteroids, have been measured. The aim of this article is to bring together all previously published data from these bodies, as well as the Earth, in order to determine the original D/H ratio for each of these inner Solar System planetary bodies. Once all secondary processes have been stripped away, the inner Solar System appears to be relatively homogeneous in terms of water D/H, with the original water D/H ratios of Vesta, Mars, the Earth, and S- and C-type asteroids all falling between δD values of -100‰ and -590‰. This homogeneity is in accord with the 'Grand tack' model of Solar System formation, where giant planet migration causes the S- and C-type asteroids to be mixed within 1 AU to eventually form the terrestrial planets.This article is part of the themed issue 'The origin, history and role of water in the evolution of the inner Solar System'. © 2017 The Authors.

  7. D/H ratios of the inner Solar System

    NASA Astrophysics Data System (ADS)

    Hallis, L. J.

    2017-04-01

    The original hydrogen isotope (D/H) ratios of different planetary bodies may indicate where each body formed in the Solar System. However, geological and atmospheric processes can alter these ratios through time. Over the past few decades, D/H ratios in meteorites from Vesta and Mars, as well as from S- and C-type asteroids, have been measured. The aim of this article is to bring together all previously published data from these bodies, as well as the Earth, in order to determine the original D/H ratio for each of these inner Solar System planetary bodies. Once all secondary processes have been stripped away, the inner Solar System appears to be relatively homogeneous in terms of water D/H, with the original water D/H ratios of Vesta, Mars, the Earth, and S- and C-type asteroids all falling between δD values of -100‰ and -590‰. This homogeneity is in accord with the `Grand tack' model of Solar System formation, where giant planet migration causes the S- and C-type asteroids to be mixed within 1 AU to eventually form the terrestrial planets. This article is part of the themed issue 'The origin, history and role of water in the evolution of the inner Solar System'.

  8. Non-thermal escape rates of atmospheric H and D from Mars using MAVEN data

    NASA Astrophysics Data System (ADS)

    Gacesa, M.; Zahnle, K. J.

    2017-12-01

    Geological evidence suggests that an ocean of liquid water existed on Mars until at least middle to late Noachian era (4.1 to 3.8 Ga) and possibly, at least episodically, as late as Hesperian. Between 67% and 87% of the total primordial amount of water, equal to about 70 to 110 meters equivalent (spread over the entire Mars' surface), is believed to have escape to space, while about 35 meters remains on or beneath the surface as water ice. Establishing better constraints on these numbers and identifying the responsible atmospheric loss processes remains the major objective of NASA's Mars Atmosphere and Volatile EvolutioN (MAVEN) mission. The ratio of atmospheric Deuterium and Hydrogen (D/H) on Mars is one of the best indicators of water loss to space. While majority of H and D escape through thermal Jeans escape, up to 10% of D can escape to space via non-thermal mechanisms, such as collisions with superthermal neutral atoms. In this study, we present new estimates of non-thermal escape rates of light molecules of interest to the water evolution, including H2, HD, OH, and OD, based on recent measurements of atmospheric density and temperature profiles by MAVEN. The escape mechanisms considered include photochemical sources of hot O, as well as collisions with energetic neutral atoms produced in charge-exchange of solar wind ions with atmospheric gases1,2. Energy transport and escape rates are modeled using quantum reactive scattering formalism3 and seasonal variations are illustrated. Finally, a simple estimate of the role of the non-thermal escape mechanisms in previous eras is given. We conclude that D escape rates can be affected by the non-thermal processes with consequences on the estimates of primordial water inventory based on the D/H ratio. [1] N. Lewkow and V. Kharchenko, Astroph. J., 790, 98 (2014) [2] M. Gacesa, N. Lewkow, V. Kharchenko, Icarus 284, 90 (2017) [3] M. Gacesa and V. Kharchenko, Geophys. Res. Lett., 39, L10203 (2012)

  9. 2D fluorescence spectroscopy for monitoring ion-exchange membrane based technologies - Reverse electrodialysis (RED).

    PubMed

    Pawlowski, Sylwin; Galinha, Claudia F; Crespo, João G; Velizarov, Svetlozar

    2016-01-01

    Reverse electrodialysis (RED) is one of the emerging, membrane-based technologies for harvesting salinity gradient energy. In RED process, fouling is an undesirable operation constraint since it leads to a decrease of the obtainable net power density due to increasing stack electric resistance and pressure drop. Therefore, early fouling detection is one of the main challenges for successful RED technology implementation. In the present study, two-dimensional (2D) fluorescence spectroscopy was used, for the first time, as a tool for fouling monitoring in RED. Fluorescence excitation-emission matrices (EEMs) of ion-exchange membrane surfaces and of natural aqueous streams were acquired during one month of a RED stack operation. Fouling evolvement on the ion-exchange membrane surfaces was successfully followed by 2D fluorescence spectroscopy and quantified using principal components analysis (PCA). Additionally, the efficiency of cleaning strategy was assessed by measuring the membrane fluorescence emission intensity before and after cleaning. The anion-exchange membrane (AEM) surface in contact with river water showed to be significantly affected due to fouling by humic compounds, which were found to cross through the membrane from the lower salinity (river water) to higher salinity (sea water) stream. The results obtained show that the combined approach of using 2D fluorescence spectroscopy and PCA has a high potential for studying fouling development and membrane cleaning efficiency in ion exchange membrane processes. Copyright © 2015 Elsevier Ltd. All rights reserved.

  10. Determination of the delta(2H/1H)of Water: RSIL Lab Code 1574

    USGS Publications Warehouse

    Revesz, Kinga; Coplen, Tyler B.

    2008-01-01

    Reston Stable Isotope Laboratory (RSIL) lab code 1574 describes a method used to determine the relative hydrogen isotope-ratio delta(2H,1H), abbreviated hereafter as d2H of water. The d2H measurement of water also is a component of the National Water Quality Laboratory (NWQL) schedules 1142 and 1172. The water is collected unfiltered in a 60-mL glass bottle and capped with a Polyseal cap. In the laboratory, the water sample is equilibrated with gaseous hydrogen using a platinum catalyst (Horita, 1988; Horita and others, 1989; Coplen and others, 1991). The reaction for the exchange of one hydrogen atom is shown in equation 1.

  11. (1→3)-β-d-Glucan oligosaccharides monomers purification and its H2O2 induction effect study.

    PubMed

    Fu, Yunbin; Wang, Mengyu; Wang, Wenxia; Tuo, Yaqin; Guo, Zhimou; Du, Yuguang; Yin, Heng

    2015-11-01

    In order to produce highly purified (1→3)-β-d-glucan oligosaccharides ((1→3)-β-d-GOS) monomers, a hydrophilic interaction liquid chromatography (HILIC) system with X-Amide stationary phase was performed. Nine (1→3)-β-d-GOS monomers with degree of polymerization (DP) from 2 to 10 were successfully separated. Matrix-assisted laser desorption/ionization time of flight mass spectrometry (MALDI-TOF-MS) demonstrated that these monomers were with high purity. Furthermore, a hydrogen peroxide (H2O2) online detection method was established to monitor H2O2 releases in tobacco cells. This is the first report on nine consecutive (1→3)-β-d-GOS monomers purification and its effect upon H2O2-releasing in plants. It was found that (1→3)-β-d-GOS monomers with higher DP induced stronger defense responses in plants, which will pave the way for elucidating the relationship between (1→3)-β-d-GOS and biological activities. Copyright © 2015 Elsevier B.V. All rights reserved.

  12. Study of X(3872) from effective field theory with pion-exchange interaction.

    PubMed

    Wang, P; Wang, X G

    2013-07-26

    We study DD[over ¯]* (D*D[over ¯]) scattering in the framework of unitarized heavy meson chiral perturbation theory with pion exchange and a contact interaction. 3S1-3D1 mixing effects are taken into account. A loosely bound state X(3872), with the pole position being Mpole}=(3871.70-i0.39)  MeV, is found. The result is not sensitive to the strength of the contact interaction. Our calculation provides a theoretical confirmation of the existence of the 1++ state X(3872). The light quark mass dependence of the pole position indicates it has a predominately DD[over ¯]* (D*D[over ¯]) molecular nature. When the π mass is larger than 142 MeV, the pole disappears, which makes impossible the lattice simulation of this state at large quark mass.

  13. Genes encoding the vacuolar Na+/H+ exchanger and flower coloration.

    PubMed

    Yamaguchi, T; Fukada-Tanaka, S; Inagaki, Y; Saito, N; Yonekura-Sakakibara, K; Tanaka, Y; Kusumi, T; Iida, S

    2001-05-01

    Vacuolar pH plays an important role in flower coloration: an increase in the vacuolar pH causes blueing of flower color. In the Japanese morning glory (Ipomoea nil or Pharbitis nil), a shift from reddish-purple buds to blue open flowers correlates with an increase in the vacuolar pH. We describe details of the characterization of a mutant that carries a recessive mutation in the Purple (Pr) gene encoding a vacuolar Na+/H+ exchanger termed InNHX1. The genome of I. nil carries one copy of the Pr (or InNHX1) gene and its pseudogene, and it showed functional complementation to the yeast nhx1 mutation. The mutant of I. nil, called purple (pr), showed a partial increase in the vacuolar pH during flower-opening and its reddish-purple buds change into purple open flowers. The vacuolar pH in the purple open flowers of the mutant was significantly lower than that in the blue open flowers. The InNHX1 gene is most abundantly expressed in the petals at around 12 h before flower-opening, accompanying the increase in the vacuolar pH for the blue flower coloration. No such massive expression was observed in the petunia flowers. Since the NHX1 genes that promote the transport of Na+ into the vacuoles have been regarded to be involved in salt tolerance by accumulating Na+ in the vacuoles, we can add a new biological role for blue flower coloration in the Japanese morning glory by the vacuolar alkalization.

  14. D/H ratios of the inner Solar System

    PubMed Central

    2017-01-01

    The original hydrogen isotope (D/H) ratios of different planetary bodies may indicate where each body formed in the Solar System. However, geological and atmospheric processes can alter these ratios through time. Over the past few decades, D/H ratios in meteorites from Vesta and Mars, as well as from S- and C-type asteroids, have been measured. The aim of this article is to bring together all previously published data from these bodies, as well as the Earth, in order to determine the original D/H ratio for each of these inner Solar System planetary bodies. Once all secondary processes have been stripped away, the inner Solar System appears to be relatively homogeneous in terms of water D/H, with the original water D/H ratios of Vesta, Mars, the Earth, and S- and C-type asteroids all falling between δD values of −100‰ and −590‰. This homogeneity is in accord with the ‘Grand tack’ model of Solar System formation, where giant planet migration causes the S- and C-type asteroids to be mixed within 1 AU to eventually form the terrestrial planets. This article is part of the themed issue ‘The origin, history and role of water in the evolution of the inner Solar System’. PMID:28416726

  15. Deuterium charge exchange recombination spectroscopy from the top of the pedestal to the scrape off layer in H-mode plasmas

    NASA Astrophysics Data System (ADS)

    Haskey, S. R.; Grierson, B. A.; Stagner, L.; Burrell, K. H.; Chrystal, C.; Groebner, R. J.; Ashourvan, A.; Pablant, N. A.

    2017-10-01

    Recent completion of the thirty two channel main-ion (deuterium) charge exchange recombination spectroscopy (CER) diagnostic on DIII-D [J.L. Luxon, Nucl. Fusion 42 (2002) 614] enables detailed comparisons between impurity and main-ion temperature, density, and toroidal rotation. Sixteen sightlines cover the core of the plasma and another sixteen are densely packed towards the edge, providing high resolution measurements of the pedestal and steep gradient edge region of H-mode plasmas. The complexities of the Dα spectrum require fitting with a comprehensive model, as well as using iterative collisional radiative modeling to determine the underlying thermal deuterium ion properties. Large differences in the structure and magnitude of impurity (C6+) and main-ion (D+) toroidal rotation profiles are seen in the H-mode pedestal. Additionally the D+ temperature can be half the value of the C6+ temperature at the separatrix and shows more of a pedestal structure. Typically only the impurity properties are measured and the main-ion properties are either assumed to be the same, or inferred using neoclassical models, which require validation in the steep gradient region. These measured differences have implications for transport model validation, intrinsic rotation studies, pedestal stability, and the boundary conditions for scrape off layer and plasma material interactions studies.

  16. Seasonal change in CO2 and H2O exchange between grassland and atmosphere

    NASA Astrophysics Data System (ADS)

    Saigusa, N.; Liu, S.; Oikawa, T.; Watanabe, T.

    1996-03-01

    The seasonal change in CO2 flux over an artificial grassland was analyzed from the ecological and meteorological point of view. This grassland contains C3 and C4 plants; the three dominant species belonging to the Gramineae; Festuca elatior (C3) dominated in early spring, and Imperata cylindrica (C4) and Andropogon virginicus (C4) grew during early summer and became dominant in mid-summer. CO2 flux was measured by the gradient method, and the routinely observed data for the surface-heat budget were used to analyze the CO2 and H2O exchange between the grassland and atmosphere. From August to October in 1993, CO2 flux was reduced to around half under the same solar-radiation conditions, while H2O flux decreased 20% during the same period. The monthly values of water use efficiency, i.e., ratio of CO2 flux to H2O flux decreased from 5.8 to 3.3 mg CO2/g H2O from August to October, the Bowen ratio increased from 0.20 to 0.30, and the ratio of the bulk latent heat transfer coefficient CE to the sensible heat transfer coefficient CH was maintained around 0.40-0.50. The increase in the Bowen ratio was explained by the decrease in air temperature from 22.3 °C in August to 16.6 °C in October without considering biological effects such as stomatal closure on the individual leaves. The nearly constant CE/CH ratios suggested that the contribution ratio of canopy resistance to aerodynamic resistance did not change markedly, although the meteorological conditions changed seasonally. The decrease in the water use efficiency, however, suggested that the photosynthetic rate decreased for individual leaves from August to October under the same radiation conditions. Diurnal variations of CO2 exchange were simulated by the multi-layer canopy model taking into account the differences in the stomatal conductance and photosynthetic pathway between C3 and C4 plants. The results suggested that C4 plants played a major role in the CO2 exchange in August, the contribution of C4 plants

  17. Differential and integral cross sections for the rotationally inelastic scattering of methyl radicals with H2 and D2

    NASA Astrophysics Data System (ADS)

    Tkáč, Ondřej; Ma, Qianli; Rusher, Cassandra A.; Greaves, Stuart J.; Orr-Ewing, Andrew J.; Dagdigian, Paul J.

    2014-05-01

    Comparisons are presented of experimental and theoretical studies of the rotationally inelastic scattering of CD3 radicals with H2 and D2 collision partners at respective collision energies of 680 ± 75 and 640 ± 60 cm-1. Close-coupling quantum-mechanical calculations performed using a newly constructed ab initio potential energy surface (PES) provide initial-to-final CD3 rotational level (n, k → n', k') integral and differential cross sections (ICSs and DCSs). The DCSs are compared with crossed molecular beam and velocity map imaging measurements of angular scattering distributions, which serve as a critical test of the accuracy of the new PES. In general, there is very good agreement between the experimental measurements and the calculations. The DCSs for CD3 scattering from both H2 and D2 peak in the forward hemisphere for n' = 2-4 and shift more to sideways and backward scattering for n' = 5. For n' = 6-8, the DCSs are dominated by backward scattering. DCSs for a particular CD3 n → n' transition have a similar angular dependence with either D2 or H2 as collision partner. Any differences between DCSs or ICSs can be attributed to mass effects because the PES is unchanged for CD3-H2 and CD3-D2 collisions. Further comparisons are drawn between the CD3-D2 scattering and results for CD3-He presented in our recent paper [O. Tkáč, A. G. Sage, S. J. Greaves, A. J. Orr-Ewing, P. J. Dagdigian, Q. Ma, and M. H. Alexander, Chem. Sci. 4, 4199 (2013)]. These systems have the same reduced mass, but are governed by different PESs.

  18. The flushing and exchange of the South China Sea derived from salt and mass conservation

    NASA Astrophysics Data System (ADS)

    Liu, Yang; Bye, John A. T.; You, Yuzhu; Bao, Xianwen; Wu, Dexing

    2010-07-01

    In this paper, we use two kinds of hydrographic data, historical cruise data, Array for Real-time Geostrophic Oceanography (Argo) float data, and atmospheric data to study the water exchange between the South China Sea (SCS) and the Pacific Ocean through the Luzon Strait. The annual mean distributions of temperature and salinity at five different levels in the SCS and the adjacent Pacific Ocean are presented, which indicate the occurrence of active water exchange through the Luzon Strait. The flushing and exchange of the SCS are then determined by the application of salt and mass conservation in a multi-layered thermohaline system, using an estimate of the net rainfall obtained from reanalysis data. The results show that the annual mean flushing time is 44±8 months with an inflow rate of 11±2 Sv (1 Sv=10 6 m 3 s -1), part of which recirculates at a deeper level through the Luzon Strait, the remainder (6±2 Sv) forming the SCS throughflow. The diffusive influx of salt is also estimated and accounts for about 10% of the total influx, and hence advection dominates over diffusion in the water exchange through the Luzon Strait. The seasonal cycle of exchange shows a maximum in autumn and winter of about twice the annual mean rate.

  19. Effect of kinetic and electronic energy on the reactions of Mn + with H2, HD, and D2

    NASA Astrophysics Data System (ADS)

    Elkind, J. L.; Armentrout, P. B.

    1986-05-01

    Reactions of several electronic states of Mn+ with H2, HD, and D2 have been examined using guided ion beam mass spectroscopy. The excitation function for the ground state of Mn+(7S) has two regions: one of very low reactivity at threshold and another more efficient pathway at higher energies. In contrast, the 5S and 5D states react efficiently at their thermodynamic thresholds. In reaction with HD, the 5S and 5D states produce ≊3 times as much MnH+ as MnD+ in the threshold region. This isotope effect is similar to that seen in previous studies of transition metal ion reactions. Reaction of Mn+(7S) with HD, on the other hand, exhibits an extreme isotope effect such that MnD+ is formed almost exclusively. The state dependence of the reactivity and reaction mechanisms is explained using simple molecular orbital concepts. The results are analyzed to yield a bond dissociation energy at 0 K for MnH+ of 2.06±0.15 eV (47.5±3.4 kcal/mol).

  20. Hydrogen-deuterium exchange mass spectrometry reveals folding and allostery in protein-protein interactions.

    PubMed

    Ramirez-Sarmiento, Cesar A; Komives, Elizabeth A

    2018-04-06

    Hydrogen-deuterium exchange mass spectrometry (HDXMS) has emerged as a powerful approach for revealing folding and allostery in protein-protein interactions. The advent of higher resolution mass spectrometers combined with ion mobility separation and ultra performance liquid chromatographic separations have allowed the complete coverage of large protein sequences and multi-protein complexes. Liquid-handling robots have improved the reproducibility and accurate temperature control of the sample preparation. Many researchers are also appreciating the power of combining biophysical approaches such as stopped-flow fluorescence, single molecule FRET, and molecular dynamics simulations with HDXMS. In this review, we focus on studies that have used a combination of approaches to reveal (re)folding of proteins as well as on long-distance allosteric changes upon interaction. Copyright © 2018 Elsevier Inc. All rights reserved.

  1. Dynamic Reactive Ionization with Cluster Secondary Ion Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Tian, Hua; Wucher, Andreas; Winograd, Nicholas

    2016-02-01

    Gas cluster ion beams (GCIB) have been tuned to enhance secondary ion yields by doping small gas molecules such as CH4, CO2, and O2 into an Ar cluster projectile, Arn + ( n = 1000-10,000) to form a mixed cluster. The `tailored beam' has the potential to expand the application of secondary ion mass spectrometry for two- and three-dimensional molecular specific imaging. Here, we examine the possibility of further enhancing the ionization by doping HCl into the Ar cluster. Water deposited on the target surface facilitates the dissociation of HCl. This concerted effect, occurring only at the impact site of the cluster, arises since the HCl is chemically induced to ionize to H+ and Cl- , allowing improved protonation of neutral molecular species. This hypothesis is confirmed by depth profiling through a trehalose thin film exposed to D2O vapor, resulting in ~20-fold increase in protonated molecules. The results show that it is possible to dynamically maintain optimum ionization conditions during depth profiling by proper adjustment of the water vapor pressure. H-D exchange in the trehalose molecule M was monitored upon deposition of D2O on the target surface, leading to the observation of [Mn* + H]+ or [Mn* + D]+ ions, where n = 1-8 hydrogen atoms in the trehalose molecule M have been replaced by deuterium. In general, we discuss the role of surface chemistry and dynamic reactive ionization of organic molecules in increasing the secondary ion yield.

  2. 3D numerical modeling of hyporheic exchange processes in fractal riverbed

    NASA Astrophysics Data System (ADS)

    Lee, A.; Aubeneau, A.

    2017-12-01

    The subsurface region receiving stream water is known as the hyporheic zone and the flow of water in and out of this zone is called hyporheic exchange. The hyporheic zone is populated by biofilms and is a hotspot for nutrient uptake and contaminant transformation. Traditionally, pumping models predicting the head distribution over the riverbed boundary are used to obtain the velocity field in the subsurface. However, past research has largely overlooked the nonlinearity of the turbulent flow above the bumpy riverbed. The main objective of this research is to investigate the effect of spatial and temporal heterogeneity created by turbulent flow on hyporheic exchange and residence time distribution in fractal channel beds. The 3-D fractal riverbed is created from the power spectrum. Large-Eddy Simulation is used to provide the pressure field over the benthic boundary. Finally, Darcian fluxes in the sub-surface are calculated and hyporheic travel times computed using random walks. Surface and subsurface transport processes are represented explicitly and can be studied in detail. Our results suggest that (1) Eddies and wakes around the dunes force the exchange (2) The bigger the dunes, the greater the influence of turbulence (3) Turbulence induces more exchange than pumping predicts.

  3. Dissociative recombination of HCl+, H2Cl+, DCl+, and D2Cl+ in a flowing afterglow

    NASA Astrophysics Data System (ADS)

    Wiens, Justin P.; Miller, Thomas M.; Shuman, Nicholas S.; Viggiano, Albert A.

    2016-12-01

    Dissociative recombination of electrons with HCl+, H2Cl+, DCl+, and D2Cl+ has been measured under thermal conditions at 300, 400, and 500 K using a flowing afterglow-Langmuir probe apparatus. Measurements for HCl+ and DCl+ employed the variable electron and neutral density attachment mass spectrometry (VENDAMS) method, while those for H2Cl+ and D2Cl+ employed both VENDAMS and the more traditional technique of monitoring electron density as a function of reaction time. At 300 K, HCl+ and H2Cl+ recombine with kDR = 7.7±2.14.5 × 10-8 cm3 s-1 and 2.6 ± 0.8 × 10-7 cm3 s-1, respectively, whereas D2Cl+ is roughly half as fast as H2Cl+ with kDR = 1.1 ± 0.3 × 10-7 cm3 s-1 (2 σ confidence intervals). DCl+ recombines with a rate coefficient below the approximate detection limit of the method (≲5 × 10-8 cm3 s-1) at all temperatures. Relatively slow dissociative recombination rates have been speculated to be responsible for the large HCl+ and H2Cl+ abundances in interstellar clouds compared to current astrochemical models, but our results imply that the discrepancy must originate elsewhere.

  4. A deep search for H2D+ in protoplanetary disks. Perspectives for ALMA

    NASA Astrophysics Data System (ADS)

    Chapillon, E.; Parise, B.; Guilloteau, S.; Du, F.

    2011-09-01

    Context. The structure in density and temperature of protoplanetary disks surrounding low-mass stars is not well known yet. The protoplanetary disks' midplane are expected to be very cold and thus depleted in molecules in gas phase, especially CO. Recent observations of molecules at very low apparent temperatures (~6 K) challenge this current picture of the protoplanetary disk structures. Aims: We aim at constraining the physical conditions and, in particular, the gas-phase CO abundance in the midplane of protoplanetary disks. Methods: The light molecule H2D+ is a tracer of cold and CO-depleted environment. It is therefore a good candidate for exploring the disks midplanes. We performed a deep search for H2D+ in the two well-known disks surrounding TW Hya and DM Tau using the APEX and JCMT telescopes. The analysis of the observations was done with DISKFIT, a radiative transfer code dedicated to disks. In addition, we used a chemical model describing deuterium chemistry to infer the implications of our observations on the level of CO depletion and on the ionization rate in the disk midplane. Results: The ortho-H2D+ (11,0-11,1) line at 372 GHz was not detected. Although our limit is three times better than previous observations, comparison with the chemical modeling indicates that it is still insufficient for putting useful constraints on the CO abundance in the disk midplane. Conclusions: Even with ALMA, the detection of H2D+ may not be straightforward, and H2D+ may not be sensitive enough to trace the protoplanetary disks midplane. Based on observations carried out with the Atacama Pathfinder Experiment and the James Clerk Maxwell Telescope. APEX is a collaboration between the Max-Planck-Institut für Radioastronomie, the European Southern Observatory, and the Onsala Space Observatory. The JCMT is operated by the Joint Astronomy Centre on behalf of the Science and Technology Facilities Council of the United Kingdom, the Netherlands Organisation for Scientific

  5. THE SURVEY OF H I IN EXTREMELY LOW-MASS DWARFS (SHIELD)

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

    Cannon, John M.; Engstrom, Eric; Allan, John

    We present first results from the Survey of H I in Extremely Low-mass Dwarfs (SHIELD), a multi-configuration Expanded Very Large Array (EVLA) study of the neutral gas contents and dynamics of galaxies with H I masses in the 10{sup 6}-10{sup 7} M{sub sun} range detected by the Arecibo Legacy Fast ALFA (ALFALFA) survey. We describe the survey motivation and concept demonstration using Very Large Array imaging of six low-mass galaxies detected in early ALFALFA data products. We then describe the primary scientific goals of SHIELD and present preliminary EVLA and WIYN 3.5 m imaging of the 12 SHIELD galaxies. Withmore » only a few exceptions, the neutral gas distributions of these extremely low-mass galaxies are centrally concentrated. In only one system have we detected H I column densities higher than 10{sup 21} cm{sup -2}. Despite this, the stellar populations of all of these systems are dominated by blue stars. Further, we find ongoing star formation as traced by H{alpha} emission in 10 of the 11 galaxies with H{alpha} imaging obtained to date. Taken together these results suggest that extremely low-mass galaxies are forming stars in conditions different from those found in more massive systems. While detailed dynamical analysis requires the completion of data acquisition, the most well-resolved system is amenable to meaningful position-velocity analysis. For AGC 749237, we find well-ordered rotation of 30 km s{sup -1} at {approx}40'' distance from the dynamical center. At the adopted distance of 3.2 Mpc, this implies the presence of a {approx}>1 x 10{sup 8} M{sub sun} dark matter halo and a baryon fraction {approx}<0.1.« less

  6. Detachable strong cation exchange monolith, integrated with capillary zone electrophoresis and coupled with pH gradient elution, produces improved sensitivity and numbers of peptide identifications during bottom-up analysis of complex proteomes.

    PubMed

    Zhang, Zhenbin; Yan, Xiaojing; Sun, Liangliang; Zhu, Guijie; Dovichi, Norman J

    2015-04-21

    A detachable sulfonate-silica hybrid strong cation-exchange monolith was synthesized in a fused silica capillary, and used for solid phase extraction with online pH gradient elution during capillary zone electrophoresis-tandem mass spectrometry (CZE-MS/MS) proteomic analysis. Tryptic digests were prepared in 50 mM formic acid and loaded onto the strong cation-exchange monolith. Fractions were eluted using a series of buffers with lower concentration but higher pH values than the 50 mM formic acid background electrolyte. This combination of elution and background electrolytes results in both sample stacking and formation of a dynamic pH junction and allows use of relatively large elution buffer volumes while maintaining reasonable peak efficiency and resolution. A series of five pH bumps were applied to elute E. coli tryptic peptides from the monolith, followed by analysis using CZE coupled to an LTQ-Orbitrap Velos mass spectrometer; 799 protein groups and 3381 peptides were identified from 50 ng of the digest in a 2.5 h analysis, which approaches the identification rate for this organism that was obtained with an Orbitrap Fusion. We attribute the improved numbers of peptide and protein identifications to the efficient fractionation by the online pH gradient elution, which decreased the complexity of the sample in each elution step and improved the signal intensity of low abundance peptides. We also performed a comparative analysis using a nanoACQUITY UltraPerformance LCH system. Similar numbers of protein and peptide identifications were produced by the two methods. Protein identifications showed significant overlap between the two methods, whereas peptide identifications were complementary.

  7. Branching fractions of the CN + C3H6 reaction using synchrotron photoionization mass spectrometry: evidence for the 3-cyanopropene product.

    PubMed

    Trevitt, Adam J; Soorkia, Satchin; Savee, John D; Selby, Talitha S; Osborn, David L; Taatjes, Craig A; Leone, Stephen R

    2011-11-24

    The gas-phase CN + propene reaction is investigated using synchrotron photoionization mass spectrometry (SPIMS) over the 9.8-11.5 eV photon energy range. Experiments are conducted at room temperature in 4 Torr of He buffer gas. The CN + propene addition reaction produces two distinct product mass channels, C(3)H(3)N and C(4)H(5)N, corresponding to CH(3) and H elimination, respectively. The CH(3) and H elimination channels are measured to have branching fractions of 0.59 ± 0.15 and 0.41 ± 0.10, respectively. The absolute photoionization cross sections between 9.8 and 11.5 eV are measured for the three considered H-elimination coproducts: 1-, 2-, and 3-cyanopropene. Based on fits using the experimentally measured photoionization spectra for the C(4)H(5)N mass channel and contrary to the previous study (Int. J. Mass. Spectrom.2009, 280, 113-118), where it was concluded that 3-cyanopropene was not a significant product, the new data suggests 3-cyanopropene is produced in significant quantity along with 1-cyanopropene, with isomer branching fractions from this mass channel of 0.50 ± 0.12 and 0.50 ± 0.24, respectively. However, similarities between the 1-, 2-, and 3-cyanopropene photoionization spectra make an unequivocal assignment difficult based solely on photoionization spectra. The CN + CH(2)CHCD(3) reaction is studied and shows, in addition to the H-elimination product signal, a D-elimination product channel (m/z 69, consistent with CH(2)CHCD(2)CN), providing further evidence for the formation of the 3-cyanopropene reaction product.

  8. Multiscale Kinetic Modeling Reveals an Ensemble of Cl–/H+ Exchange Pathways in ClC-ec1 Antiporter

    PubMed Central

    2018-01-01

    Despite several years of research, the ion exchange mechanisms in chloride/proton antiporters and many other coupled transporters are not yet understood at the molecular level. Here, we present a novel approach to kinetic modeling and apply it to ion exchange in ClC-ec1. Our multiscale kinetic model is developed by (1) calculating the state-to-state rate coefficients with reactive and polarizable molecular dynamics simulations, (2) optimizing these rates in a global kinetic network, and (3) predicting new electrophysiological results. The model shows that the robust Cl:H exchange ratio (2.2:1) can indeed arise from kinetic coupling without large protein conformational changes, indicating a possible facile evolutionary connection to chloride channels. The E148 amino acid residue is shown to couple chloride and proton transport through protonation-dependent blockage of the central anion binding site and an anion-dependent pKa value, which influences proton transport. The results demonstrate how an ensemble of different exchange pathways, as opposed to a single series of transitions, culminates in the macroscopic observables of the antiporter, such as transport rates, chloride/proton stoichiometry, and pH dependence. PMID:29332400

  9. Ion Mobility Spectrometry-Hydrogen Deuterium Exchange Mass Spectrometry of Anions: Part 1. Peptides to Proteins

    NASA Astrophysics Data System (ADS)

    Donohoe, Gregory C.; Khakinejad, Mahdiar; Valentine, Stephen J.

    2015-04-01

    Ion mobility spectrometry (IMS) coupled with hydrogen deuterium exchange (HDX)-mass spectrometry (MS) has been used to study the conformations of negatively-charged peptide and protein ions. Results are presented for ion conformers of angiotensin 1, a synthetic peptide (SP), bovine insulin, ubiquitin, and equine cytochrome c. In general, the SP ion conformers demonstrate a greater level of HDX efficiency as a greater proportion of the sites undergo HDX. Additionally, these ions exhibit the fastest rates of exchange. Comparatively, the angiotensin 1 ions exhibit a lower rate of exchange and HDX level presumably because of decreased accessibility of exchange sites by charge sites. The latter are likely confined to the peptide termini. Insulin ions show dramatically reduced HDX levels and exchange rates, which can be attributed to decreased conformational flexibility resulting from the disulfide bonds. For the larger ubiquitin and protein ions, increased HDX is observed for larger ions of higher charge state. For ubiquitin, a conformational transition from compact to more elongated species (from lower to higher charge states) is reflected by an increase in HDX levels. These results can be explained by a combination of interior site protection by compact conformers as well as decreased access by charge sites. The elongated cytochrome c ions provide the largest HDX levels where higher values correlate with charge state. These results are consistent with increased exchange site accessibility by additional charge sites. The data from these enhanced IMS-HDX experiments are described in terms of charge site location, conformer rigidity, and interior site protection.

  10. Organic environments on Saturn's moon, Titan: simulating chemical reactions and analyzing products by FT-ICR and ion-trap mass spectrometry.

    PubMed

    Somogyi, Arpad; Oh, Chu-Ha; Smith, Mark A; Lunine, Jonathan I

    2005-06-01

    Laboratory simulations have been carried out to model chemical reactions that possibly take place in the stratosphere of Saturn's moon, Titan. The aerosol products of these reactions (tholin samples) have been systematically analyzed by mass spectrometry using electrospray ionization (ESI) and laser desorption (LD). A wide variety of ions with a general formula C(x)H(y)N(z) detected by ultrahigh resolution and accurate mass measurements in a Fourier transform/ion cyclotron resonance (FT-ICR) cell reflect the complexity of these polymeric products, both in chemical compositions and isomeric distributions. As a common feature, however, tandem mass spectral (MS/MS) data and H/D exchange products in the solution phase support the presence of amino and nitrile functionalities in these (highly unsaturated) "tholin" compounds. The present work demonstrates that ESI-MS coupled with FT-ICR is a suitable and "intact" method to analyze tholin components formed under anaerobic conditions; only species with C(x)H(y)N(z) are detected for freshly prepared and harvested samples. However, when intentionally exposed to water, oxygen-containing compounds are unambiguously detected.

  11. A Mn(III) triplesalen-based 1D pearl necklace: exchange interactions and zero-field splittings in a C3-symmetric Mn(III)6 complex.

    PubMed

    Glaser, Thorsten; Heidemeier, Maik; Theil, Hubert; Stammler, Anja; Bögge, Hartmut; Schnack, Jürgen

    2010-01-07

    The reaction of the tert-butyl-substituted triplesalen ligand H(6)talen(t-Bu(2)) with 2.8 equivalents of Mn(OAc)(2) x 4 H(2)O in MeOH in the presence of NaBPh(4) results in the formation of the one-dimensional (1D) coordination polymer {[{(talen(t-Bu(2)))Mn(3)(MeOH)}(2)(mu(2)-OAc)(3)](mu(2)-OAc)}(n)(BPh(4))(2n) ({[Mn(III)(6)](OAc)}(n)(BPh(4))(2n)) which has been characterized by FTIR, elemental analysis, ESI-MS, single-crystal X-ray diffraction and magnetic measurements. The triplesalen ligand (talen(t-Bu(2)))(6-) provides three salen-like coordination compartments bridged in a meta-phenylene arrangement by a phloroglucinol backbone resulting in the trinuclear Mn(III) base unit {(talen(t-Bu(2)))Mn(3)}(3+). Two of these base units are bridged by three inner acetate ligands giving rise to the hexanuclear complex [{(talen(t-Bu(2)))Mn(3)(MeOH)}(2)(mu(2)-OAc)(3)](3+) ([Mn(III)(6)](3+)). These complexes are bridged by a single external acetate to form a 1D chain as pearls in a pearl necklace. Variable temperature-variable field and mu(eff)vs. T magnetic data have been analyzed in detail by full-matrix diagonalization of the appropriate spin-Hamiltonian consisting of isotropic exchange, zero-field splitting, and Zeeman interaction taking into account the relative orientation of the D-tensors. Satisfactory reproduction of the experimental data have been obtained for parameters sets J(1) = -(0.60 +/- 0.15) cm(-1), J(2) = -(1.05 +/- 0.15) cm(-1), and D(Mn) = -(3.0 +/- 0.7) cm(-1) with J(1) describing the exchange through the phloroglucinol backbone and J(2) describing the exchange through the inner acetates. The non-necessity to incorporate the bridging outer acetates correlates with the longer Mn-O bonds. The experimental data can neither be analyzed without incorporating zero-field splitting nor by the application of a single effective spin ground state.

  12. Reduced flavin: NMR investigation of N5-H exchange mechanism, estimation of ionisation constants and assessment of properties as biological catalyst.

    PubMed

    Macheroux, Peter; Ghisla, Sandro; Sanner, Christoph; Rüterjans, Heinz; Müller, Franz

    2005-11-25

    The flavin in its FMN and FAD forms is a versatile cofactor that is involved in catalysis of most disparate types of biological reactions. These include redox reactions such as dehydrogenations, activation of dioxygen, electron transfer, bioluminescence, blue light reception, photobiochemistry (as in photolyases), redox signaling etc. Recently, hitherto unrecognized types of biological reactions have been uncovered that do not involve redox shuffles, and might involve the reduced form of the flavin as a catalyst. The present work addresses properties of reduced flavin relevant in this context. N(5)-H exchange reactions of the flavin reduced form and its pH dependence were studied using the 15N-NMR-signals of 15N-enriched, reduced flavin in the pH range from 5 to 12. The chemical shifts of the N(3) and N(5) resonances are not affected to a relevant extent in this pH range. This contrasts with the multiplicity of the N(5)-resonance, which strongly depends on pH. It is a doublet between pH 8.45 and 10.25 that coalesces into a singlet at lower and higher pH values. From the line width of the 15N(5) signal the pH-dependent rate of hydrogen exchange was deduced. The multiplicity of the 15N(5) signal and the proton exchange rates are little dependent on the buffer system used. The exchange rates allow an estimation of the pKa value of N(5)-H deprotonation in reduced flavin to be >or= 20. This value imposes specific constraints for mechanisms of flavoprotein catalysis based on this process. On the other hand the pK asymptotically equal to 4 for N(5)-H protonation (to form N(5)+-H2) would be consistent with a role of N(5)-H as a base.

  13. Masses and decay constants of D(s) * and B(s) * mesons with Nf=2 +1 +1 twisted mass fermions

    NASA Astrophysics Data System (ADS)

    Lubicz, V.; Melis, A.; Simula, S.; ETM Collaboration

    2017-08-01

    We present a lattice calculation of the masses and decay constants of D(s) * and B(s) * mesons using the gauge configurations produced by the European Twisted Mass Collaboration (ETMC) with Nf=2 +1 +1 dynamical quarks at three values of the lattice spacing a ˜(0.06 -0.09 ) fm . Pion masses are simulated in the range Mπ≃(210 - 450 ) MeV , while the strange and charm sea-quark masses are close to their physical values. We compute the ratios of vector to pseudoscalar masses and decay constants for various values of the heavy-quark mass mh in the range 0.7 mcphys≲mh≲3 mcphys . In order to reach the physical b -quark mass, we exploit the heavy quark effective theory prediction that, in the static limit of infinite heavy-quark mass, the considered ratios are equal to one. At the physical point our results are MD*/MD=1.0769 (79 ) , MDs*/MDs=1.0751(56 ), fD*/fD=1.078 (36 ), fDs*/fD s=1.087 (20 ), MB*/MB=1.0078 (15 ), MBs*/MBs=1.0083(10 ), fB*/fB=0.958 (22 ) and fBs*/fB s=0.974 (10 ). Combining them with the experimental values of the pseudoscalar meson masses (used as input to fix the quark masses) and the values of the pseudoscalar decay constants calculated by ETMC, we get MD*=2013 (14 ), MDs*=2116 (11 ), fD*=223.5 (8.4 ), fDs*=268.8 (6.6 ), MB*=5320.5 (7.6 ), MBs*=5411.36 (5.3 ), fB*=185.9 (7.2 ) and fBs*=223.1 (5.4 ) MeV .

  14. THz spectroscopy of D2H+

    NASA Astrophysics Data System (ADS)

    Yu, S.; Pearson, J. C.; Amano, T.; Matsushima, F.

    2017-01-01

    We extended the measurements of the rotational transitions of D2H+ up to 3 THz by using the JPL frequency multiplier chains and a TuFIR system at Toyama. D2H+ was generated in an extended negative glow discharge cell cooled to liquid nitrogen temperature. We observed five new THz lines. All the available rotational transition frequencies together with the combination differences derived from the three fundamental bands were subject to least square analysis to determine the molecular constants. New THz measurements are definitely useful for better characterization of spectroscopic properties. The improved molecular constants provide better predictions of other unobserved rotational transitions.

  15. Quark-mass dependence of the H dibaryon in Λ Λ scattering

    NASA Astrophysics Data System (ADS)

    Yamaguchi, Yasuhiro; Hyodo, Tetsuo

    2016-12-01

    We study the quark mass dependence of the H dibaryon in the strangeness S =-2 baryon-baryon scattering. A low-energy effective field theory is used to describe the coupled-channel scattering, in which the quark mass dependence is incorporated so as to reproduce the lattice QCD data by the HAL QCD collaboration in the SU(3) limit. We point out the existence of the Castillejo-Dalitz-Dyson pole in the Λ Λ scattering amplitude below the threshold in the SU(3) limit, which may cause the Ramsauer-Townsend effect near the N Ξ threshold at the physical point. The H dibaryon is unbound at the physical point, and a resonance appears just below the N Ξ threshold. As a consequence of the coupled-channel dynamics, the pole associated with the resonance is not continuously connected to the bound state in the SU(3) limit. Through the extrapolation in quark masses, we show that the unitary limit of the Λ Λ scattering is achieved between the physical point and the SU(3) limit. We discuss the possible realization of the "H matter" in the unphysical quark mass region.

  16. Modeling of salt and pH gradient elution in ion-exchange chromatography.

    PubMed

    Schmidt, Michael; Hafner, Mathias; Frech, Christian

    2014-01-01

    The separation of proteins by internally and externally generated pH gradients in chromatofocusing on ion-exchange columns is a well-established analytical method with a large number of applications. In this work, a stoichiometric displacement model was used to describe the retention behavior of lysozyme on SP Sepharose FF and a monoclonal antibody on Fractogel SO3 (S) in linear salt and pH gradient elution. The pH dependence of the binding charge B in the linear gradient elution model is introduced using a protein net charge model, while the pH dependence of the equilibrium constant is based on a thermodynamic approach. The model parameter and pH dependences are calculated from linear salt gradient elutions at different pH values as well as from linear pH gradient elutions at different fixed salt concentrations. The application of the model for the well-characterized protein lysozyme resulted in almost identical model parameters based on either linear salt or pH gradient elution data. For the antibody, only the approach based on linear pH gradients is feasible because of the limited pH range useful for salt gradient elution. The application of the model for the separation of an acid variant of the antibody from the major monomeric form is discussed. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. An NMR-based quenched hydrogen exchange investigation of model amyloid fibrils formed by cold shock protein A.

    PubMed

    Alexandrescu, A T

    2001-01-01

    Acid-denatured cold shock protein A (CspA) self-assembles into polymers with properties typical of amyloid fibrils. In the present work, a quenched hydrogen exchange experiment was used to probe the interactions of CspA fibrils with solvent. Exchange was initiated by incubating suspensions of fibrils in D2O, and quenched by flash freezing. Following lyophilization, exchange-quenched samples were dissolved in 90% DMSO/10% D2O, giving DMSO-denatured monomers. Intrinsic exchange rates for denatured CspA in 90% DMSO/10% D2O (pH* 4.5) were sufficiently slow (approximately 1 x 10(-3) min-1) to enable quantification of NMR signal intensity decays due to H/D exchange in the fibrils. Hydrogen exchange rate constants for CspA fibrils were found to vary less than 3-fold from a mean value of 5 x 10(-5) min-1. The uniformity of rate constants suggests that exchange is in the EX1 limit, and that the mechanism of exchange involves a cooperative dissociation of CspA monomers from fibrils, concomitant with unfolding. Previous studies indicated that the highest protection factors in native CspA are approximately 10(3), and that protection factors for the acid-denatured monomer precursors of CspA fibrils are close to unity. Because exchange in is in the EX1 regime, it is only possible to place a lower limit of at least 10(5) on protection factors in CspA fibrils. The observation that all amide protons are protected from exchange indicates that the entire CspA polypeptide chain is structured in the fibrils.

  18. Extended screened exchange functional derived from transcorrelated density functional theory.

    PubMed

    Umezawa, Naoto

    2017-09-14

    We propose a new formulation of the correlation energy functional derived from the transcorrelated method in use in density functional theory (TC-DFT). An effective Hamiltonian, H TC , is introduced by a similarity transformation of a many-body Hamiltonian, H, with respect to a complex function F: H TC =1FHF. It is proved that an expectation value of H TC for a normalized single Slater determinant, D n , corresponds to the total energy: E[n] = ⟨Ψ n |H|Ψ n ⟩/⟨Ψ n |Ψ n ⟩ = ⟨D n |H TC |D n ⟩ under the two assumptions: (1) The electron density nr associated with a trial wave function Ψ n = D n F is v-representable and (2) Ψ n and D n give rise to the same electron density nr. This formulation, therefore, provides an alternative expression of the total energy that is useful for the development of novel correlation energy functionals. By substituting a specific function for F, we successfully derived a model correlation energy functional, which resembles the functional form of the screened exchange method. The proposed functional, named the extended screened exchange (ESX) functional, is described within two-body integrals and is parametrized for a numerically exact correlation energy of the homogeneous electron gas. The ESX functional does not contain any ingredients of (semi-)local functionals and thus is totally free from self-interactions. The computational cost for solving the self-consistent-field equation is comparable to that of the Hartree-Fock method. We apply the ESX functional to electronic structure calculations for a solid silicon, H - ion, and small atoms. The results demonstrate that the TC-DFT formulation is promising for the systematic improvement of the correlation energy functional.

  19. Characterization of D-tagatose-3-epimerase from Rhodobacter sphaeroides that converts D-fructose into D-psicose.

    PubMed

    Zhang, Longtao; Mu, Wanmeng; Jiang, Bo; Zhang, Tao

    2009-06-01

    A non-characterized gene, previously proposed as the D-tagatose-3-epimerase gene from Rhodobacter sphaeroides, was cloned and expressed in Escherichia coli. Its molecular mass was estimated to be 64 kDa with two identical subunits. The enzyme specificity was highest with D-fructose and decreased for other substrates in the order: D-tagatose, D-psicose, D-ribulose, D-xylulose and D-sorbose. Its activity was maximal at pH 9 and 40 degrees C while being enhanced by Mn(2+). At pH 9 and 40 degrees C, 118 g D-psicose l(-1) was produced from 700 g D-fructose l(-1) after 3 h.

  20. Calculation of Scattering Amplitude Without Partial Analysis. II; Inclusion of Exchange

    NASA Technical Reports Server (NTRS)

    Temkin, Aaron; Shertzer, J.; Fisher, Richard R. (Technical Monitor)

    2002-01-01

    There was a method for calculating the whole scattering amplitude, f(Omega(sub k)), directly. The idea was to calculate the complete wave function Psi numerically, and use it in an integral expression for f, which can be reduced to a 2 dimensional quadrature. The original application was for e-H scattering without exchange. There the Schrodinger reduces a 2-d partial differential equation (pde), which was solved using the finite element method (FEM). Here we extend the method to the exchange approximation. The S.E. can be reduced to a pair of coupled pde's, which are again solved by the FEM. The formal expression for f(Omega(sub k)) consists two integrals, f+/- = f(sub d) +/- f(sub e); f(sub d) is formally the same integral as the no-exchange f. We have also succeeded in reducing f(sub e) to a 2-d integral. Results will be presented at the meeting.

  1. Nuclear spin polarized H and D by means of spin-exchange optical pumping

    NASA Astrophysics Data System (ADS)

    Stenger, Jörn; Grosshauser, Carsten; Kilian, Wolfgang; Nagengast, Wolfgang; Ranzenberger, Bernd; Rith, Klaus; Schmidt, Frank

    1998-01-01

    Optically pumped spin-exchange sources for polarized hydrogen and deuterium atoms have been demonstrated to yield high atomic flow and high electron spin polarization. For maximum nuclear polarization the source has to be operated in spin temperature equilibrium, which has already been demonstrated for hydrogen. In spin temperature equilibrium the nuclear spin polarization PI equals the electron spin polarization PS for hydrogen and is even larger than PS for deuterium. We discuss the general properties of spin temperature equilibrium for a sample of deuterium atoms. One result are the equations PI=4PS/(3+PS2) and Pzz=PSṡPI, where Pzz is the nuclear tensor polarization. Furthermore we demonstrate that the deuterium atoms from our source are in spin temperature equilibrium within the experimental accuracy.

  2. Combining high-throughput MALDI-TOF mass spectrometry and isoelectric focusing gel electrophoresis for virtual 2D gel-based proteomics.

    PubMed

    Lohnes, Karen; Quebbemann, Neil R; Liu, Kate; Kobzeff, Fred; Loo, Joseph A; Ogorzalek Loo, Rachel R

    2016-07-15

    The virtual two-dimensional gel electrophoresis/mass spectrometry (virtual 2D gel/MS) technology combines the premier, high-resolution capabilities of 2D gel electrophoresis with the sensitivity and high mass accuracy of mass spectrometry (MS). Intact proteins separated by isoelectric focusing (IEF) gel electrophoresis are imaged from immobilized pH gradient (IPG) polyacrylamide gels (the first dimension of classic 2D-PAGE) by matrix-assisted laser desorption/ionization (MALDI) MS. Obtaining accurate intact masses from sub-picomole-level proteins embedded in 2D-PAGE gels or in IPG strips is desirable to elucidate how the protein of one spot identified as protein 'A' on a 2D gel differs from the protein of another spot identified as the same protein, whenever tryptic peptide maps fail to resolve the issue. This task, however, has been extremely challenging. Virtual 2D gel/MS provides access to these intact masses. Modifications to our matrix deposition procedure improve the reliability with which IPG gels can be prepared; the new procedure is described. Development of this MALDI MS imaging (MSI) method for high-throughput MS with integrated 'top-down' MS to elucidate protein isoforms from complex biological samples is described and it is demonstrated that a 4-cm IPG gel segment can now be imaged in approximately 5min. Gel-wide chemical and enzymatic methods with further interrogation by MALDI MS/MS provide identifications, sequence-related information, and post-translational/transcriptional modification information. The MSI-based virtual 2D gel/MS platform may potentially link the benefits of 'top-down' and 'bottom-up' proteomics. Copyright © 2016 Elsevier Inc. All rights reserved.

  3. Charge exchange in slow collisions of Si3+ with H

    NASA Astrophysics Data System (ADS)

    Joseph, D. C.; Saha, B. C.

    2010-10-01

    Low energy electron capture from atomic hydrogen by multi-charged ions continues to be of interest and has wide applications including both magnetically confined^ fusion and astrophysical plasmas. The charge exchange process reported here, Si^3+ + H -- Si^2+ + H^+ is an important destruction mechanism of Si^3+ in photo-ionized gas. The soft X-ray emission from comets has been explained by charge transfer of solar wind ions, among them Si^3+, with neutrals in the cometary gas vapor. The state selective cross sections are evaluated using the semi-classical molecular orbital close coupling (MOCC) [1] methods. Adiabatic potentials and wave functions for a number of low-lying singlet and triplet states are calculated using the MRD-CI package [2]. Details will be presented at the conference. [1] M. Kimura and N. F. Lane, At. Mol. Opt. Phys 26, 79 (1990). [3] R. J. Buenker, ``Current Aspects of Quantum Chemistry'' 1981, Vol 21, edited by R. Carbo (Elsevier, Amsterdam) p 17.

  4. Dim Light at Night Increases Body Mass of Female Mice

    PubMed Central

    Aubrecht, Taryn G.; Jenkins, Richelle; Nelson, Randy J.

    2016-01-01

    During the past century the prevalence of light at night has increased in parallel with obesity rates. Dim light at night (dLAN) increases body mass in male mice. However, the effects of light at night on female body mass remain unspecified. Thus, female mice were exposed to a standard light/dark (LD; 16h light at ~150 lux/8h dark at ~0 lux) cycle or to light/dim light at night (dLAN; 16h light at ~150 lux/8h dim light at ~5 lux) cycles for six weeks. Females exposed to dLAN increased the rate of change in body mass compared to LD mice despite reduced total food intake during weeks five and six, suggesting that dLAN disrupted circadian rhythms resulting in deranged metabolism. PMID:25431079

  5. A measurement of the difference between the single-nucleon cross sections for J/ψmuoproduction in iron and in H2, D2 targets

    NASA Astrophysics Data System (ADS)

    Aubert, J. J.; Bassompierre, G.; Becks, K. H.; Benchouk, C.; Best, C.; Bird, I. G.; Böhm, E.; de Bouard, X.; Brasse, F. W.; Broll, C.; Brown, S.; Carr, J.; Clifft, R.; Cobb, J. H.; Coignet, G.; Combley, F.; Court, G. R.; D'Agostini, G.; Dau, W. D.; Davies, J. K.; Déclais, Y.; Dosselli, U.; Drees, J.; Edwards, A.; Edwards, M.; Favier, J.; Ferrero, M. I.; Flauger, W.; Forsbach, H.; Gabathuler, E.; Gamet, R.; Gayler, J.; Gerhardt, V.; Gössling, C.; Haas, J.; Hamacher, K.; Hayman, P.; Henckes, M.; Korbel, V.; Landgraf, U.; Leenen, M.; Maire, M.; Mohr, W.; Montgomery, H. E.; Moser, K.; Mount, R. P.; Nagy, E.; Nassalski, J.; Norton, P. R.; McNicholas, J.; Osborne, A. M.; Payre, P.; Peroni, C.; Pessard, H.; Pietrzyk, U.; Rith, K.; Schneegans, M.; Sloan, T.; Stier, H. E.; Stockhausen, W.; Thénard, J. M.; Thompson, J. C.; Urban, L.; Villers, M.; Wahlen, H.; Walley, M.; Williams, D.; Williams, W. S. C.; Williamson, J.; Wimpenny, S.

    1985-03-01

    The cross sections for J/ψ production have been measured in interactions of 280 GeV μ+ on hydrogen and deuterium (H, D) and also in interactions of 250 GeV μ+ on iron. The single-nucleon cross sections in iron are found to be larger than those in H, D. The mean ratio of the iron to H, D photoproduction cross sections in the range 60 < v < 200 GeV is 1.45 +/-0.12 (statistical) +/-0.22 (systematic error). Within the framework of the photon-gluon fusion model, this indicates that the gluon density per nucleon is ~45% larger in iron than in H, D in the range 0.026 < x < 0.085, on a mass scale Q2eff ~M2J/ψ.

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

    PubMed

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

    2018-03-07

    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.

  7. Na+/H+ and Na+/NH4+ exchange activities of zebrafish NHE3b expressed in Xenopus oocytes

    PubMed Central

    Ito, Yusuke; Kato, Akira; Hirata, Taku; Hirose, Shigehisa

    2014-01-01

    Zebrafish Na+/H+ exchanger 3b (zNHE3b) is highly expressed in the apical membrane of ionocytes where Na+ is absorbed from ion-poor fresh water against a concentration gradient. Much in vivo data indicated that zNHE3b is involved in Na+ absorption but not leakage. However, zNHE3b-mediated Na+ absorption has not been thermodynamically explained, and zNHE3b activity has not been measured. To address this issue, we overexpressed zNHE3b in Xenopus oocytes and characterized its activity by electrophysiology. Exposure of zNHE3b oocytes to Na+-free media resulted in significant decrease in intracellular pH (pHi) and intracellular Na+ activity (aNai). aNai increased significantly when the cytoplasm was acidified by media containing CO2-HCO3− or butyrate. Activity of zNHE3b was inhibited by amiloride or 5-ethylisopropyl amiloride (EIPA). Although the activity was accompanied by a large hyperpolarization of ∼50 mV, voltage-clamp experiments showed that Na+/H+ exchange activity of zNHE3b is electroneutral. Exposure of zNHE3b oocytes to medium containing NH3/NH4+ resulted in significant decreases in pHi and aNai and significant increase in intracellular NH4+ activity, indicating that zNHE3b mediates the Na+/NH4+ exchange. In low-Na+ (0.5 mM) media, zNHE3b oocytes maintained aNai of 1.3 mM, and Na+-influx was observed when pHi was decreased by media containing CO2-HCO3− or butyrate. These results provide thermodynamic evidence that zNHE3b mediates Na+ absorption from ion-poor fresh water by its Na+/H+ and Na+/NH4+ exchange activities. PMID:24401990

  8. Design, synthesis, and structure-activity relationships of 3,4-dihydropyridopyrimidin-2(1H)-one derivatives as a novel class of sodium/calcium exchanger inhibitor.

    PubMed

    Hasegawa, Hirohiko; Muraoka, Masami; Ohmori, Mikiko; Matsui, Kazuki; Kojima, Atsuyuki

    2005-10-01

    Design, synthesis, and structure-activity relationships for 3,4-dihydropyridopyrimidin-2(1H)-one derivatives, which are aza-3,4-dihydro-2(1H)-quinazolinone derivatives, as the sodium/calcium (Na+/Ca2+) exchanger inhibitors are discussed. These studies based on 3,4-dihydro-2(1H)-quinazolinone derivatives led to the discovery of a structurally novel and potent Na+/Ca2+ exchanger inhibitor, 3,4-dihydropyridopyrimidin-2(1H)-one derivative (26), with an IC30 value of 0.02 microM. Compound 26 directly inhibited the Na+-dependent Ca2+ influx via the Na+/Ca2+ exchanger after Na+-free treatment in cardiomyocytes.

  9. Temperature-dependent kinetic measurements and quasi-classical trajectory studies for the OH(+) + H2/D2 → H2O(+)/HDO(+) + H/D reactions.

    PubMed

    Martinez, Oscar; Ard, Shaun G; Li, Anyang; Shuman, Nicholas S; Guo, Hua; Viggiano, Albert A

    2015-09-21

    We have measured the temperature-dependent kinetics for the reactions of OH(+) with H2 and D2 using a selected ion flow tube apparatus. Reaction occurs via atom abstraction to result in H2O(+)/HDO(+) + H/D. Room temperature rate coefficients are in agreement with prior measurements and resulting temperature dependences are T(0.11) for the hydrogen and T(0.25) for the deuterated reactions. This work is prompted in part by recent theoretical work that mapped a full-dimensional global potential energy surface of H3O(+) for the OH(+) + H2 → H + H2O(+) reaction [A. Li and H. Guo, J. Phys. Chem. A 118, 11168 (2014)], and reported results of quasi-classical trajectory calculations, which are extended to a wider temperature range and initial rotational state specification here. Our experimental results are in excellent agreement with these calculations which accurately predict the isotope effect in addition to an enhancement of the reaction rate constant due to the molecular rotation of OH(+). The title reaction is of high importance to astrophysical models, and the temperature dependence of the rate coefficients determined here should now allow for better understanding of this reaction at temperatures more relevant to the interstellar medium.

  10. Hyperfine excitation of C2H and C2D by para-H2

    NASA Astrophysics Data System (ADS)

    Dumouchel, Fabien; Lique, François; Spielfiedel, Annie; Feautrier, Nicole

    2017-10-01

    The [C2H]/[C2D] abundance ratio is a useful tool to explore the physical and chemical conditions of cold molecular clouds. Hence, an accurate determination of both the C2H and C2D abundances is of fundamental interest. Due to the low density of the interstellar medium, the population of the energy levels of the molecules is not at local thermodynamical equilibrium. Thus, the accurate modelling of the emission spectra requires the calculation of collisional rate coefficients with the most abundant interstellar species. Hence, we provide rate coefficients for the hyperfine excitation of C2H and C2D by para-H2(j=0), the most abundant collisional partner in cold molecular clouds. State-to-state rate coefficients between the lowest levels were computed for temperatures ranging from 5 to 80 K. For both isotopologues, the Δj = ΔF propensity rule is observed. The comparison between C2H and C2D rate coefficients shows that differences by up to a factor of two exist, mainly for Δj = ΔN = 1 transitions. The new rate coefficients will significantly help in the interpretation of recent observed spectra.

  11. Exchangers man the pumps

    PubMed Central

    Barkla, Bronwyn J; Hirschi, Kendal D

    2008-01-01

    Tonoplast-localised proton-coupled Ca2+ transporters encoded by cation/H+ exchanger (CAX) genes play a critical role in sequestering Ca2+ into the vacuole. These transporters may function in coordination with Ca2+ release channels, to shape stimulus-induced cytosolic Ca2+ elevations. Recent analysis of Arabidopsis CAX knockout mutants, particularly cax1 and cax3, identified a variety of phenotypes including sensitivity to abiotic stresses, which indicated that these transporters might play a role in mediating the plant's stress response. A common feature of these mutants was the perturbation of H+-ATPase activity at both the tonoplast and the plasma membrane, suggesting a tight interplay between the Ca2+/H+ exchangers and H+ pumps. We speculate that indirect regulation of proton flux by the exchangers may be as important as the direct regulation of Ca2+ flux. These results suggest cautious interpretation of mutant Ca2+/H+ exchanger phenotypes that may be due to either perturbed Ca2+ or H+ transport. PMID:19841670

  12. Simulation of density fluctuations before the L-H transition for Hydrogen and Deuterium plasmas in the DIII-D tokamak using the BOUT++ code

    NASA Astrophysics Data System (ADS)

    Wang, Y. M.; Xu, X. Q.; Yan, Z.; Mckee, G. R.; Grierson, B. A.; Xia, T. Y.; Gao, X.

    2018-02-01

    A six-field two-fluid model has been used to simulate density fluctuations. The equilibrium is generated by experimental measurements for both Deuterium (D) and Hydrogen (H) plasmas at the lowest densities of DIII-D low to high confinement (L-H) transition experiments. In linear simulations, the unstable modes are found to be resistive ballooning modes with the most unstable mode number n  =  30 or k_θρ_i˜0.12 . The ion diamagnetic drift and E× B convection flow are balanced when the radial electric field (E r ) is calculated from the pressure profile without net flow. The curvature drift plays an important role in this stage. Two poloidally counter propagating modes are found in the nonlinear simulation of the D plasma at electron density n_e˜1.5×1019 m-3 near the separatrix while a single ion mode is found in the H plasma at the similar lower density, which are consistent with the experimental results measured by the beam emission spectroscopy (BES) diagnostic on the DIII-D tokamak. The frequency of the electron modes and the ion modes are about 40 kHz and 10 kHz respectively. The poloidal wave number k_θ is about 0.2 cm -1 (k_θρ_i˜0.05 ) for both ion and electron modes. The particle flux, ion and electron heat fluxes are  ˜3.5-6 times larger for the H plasma than the D plasma, which makes it harder to achieve H-mode for the same heating power. The change of the atomic mass number A from 2 to 1 using D plasma equilibrium make little difference on the flux. Increase the electric field will suppress the density fluctuation. The electric field scan and ion mass scan results show that the dual-mode results primarily from differences in the profiles rather than the ion mass.

  13. Simulation of density fluctuations before the L-H transition for Hydrogen and Deuterium plasmas in the DIII-D tokamak using the BOUT++ code

    DOE PAGES

    Wang, Y. M.; Xu, X. Q.; Yan, Z.; ...

    2018-01-05

    A six-field two-fluid model has been used to simulate density fluctuations. The equilibrium is generated by experimental measurements for both Deuterium (D) and Hydrogen (H) plasmas at the lowest densities of DIII-D low to high confinement (L-H) transition experiments. In linear simulations, the unstable modes are found to be resistive ballooning modes with the most unstable mode number n=30 ormore » $$k_\\theta\\rho_i\\sim0.12$$ . The ion diamagnetic drift and $$E\\times B$$ convection flow are balanced when the radial electric field (E r) is calculated from the pressure profile without net flow. The curvature drift plays an important role in this stage. Two poloidally counter propagating modes are found in the nonlinear simulation of the D plasma at electron density $$n_e\\sim1.5\\times10^{19}$$ m -3 near the separatrix while a single ion mode is found in the H plasma at the similar lower density, which are consistent with the experimental results measured by the beam emission spectroscopy (BES) diagnostic on the DIII-D tokamak. The frequency of the electron modes and the ion modes are about 40kHz and 10 kHz respectively. The poloidal wave number $$k_\\theta$$ is about 0.2 cm -1 ($$k_\\theta\\rho_i\\sim0.05$$ ) for both ion and electron modes. The particle flux, ion and electron heat fluxes are~3.5–6 times larger for the H plasma than the D plasma, which makes it harder to achieve H-mode for the same heating power. The change of the atomic mass number A from 2 to 1 using D plasma equilibrium make little difference on the flux. Increase the electric field will suppress the density fluctuation. In conclusion, the electric field scan and ion mass scan results show that the dual-mode results primarily from differences in the profiles rather than the ion mass.« less

  14. Simulation of density fluctuations before the L-H transition for Hydrogen and Deuterium plasmas in the DIII-D tokamak using the BOUT++ code

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

    Wang, Y. M.; Xu, X. Q.; Yan, Z.

    A six-field two-fluid model has been used to simulate density fluctuations. The equilibrium is generated by experimental measurements for both Deuterium (D) and Hydrogen (H) plasmas at the lowest densities of DIII-D low to high confinement (L-H) transition experiments. In linear simulations, the unstable modes are found to be resistive ballooning modes with the most unstable mode number n=30 ormore » $$k_\\theta\\rho_i\\sim0.12$$ . The ion diamagnetic drift and $$E\\times B$$ convection flow are balanced when the radial electric field (E r) is calculated from the pressure profile without net flow. The curvature drift plays an important role in this stage. Two poloidally counter propagating modes are found in the nonlinear simulation of the D plasma at electron density $$n_e\\sim1.5\\times10^{19}$$ m -3 near the separatrix while a single ion mode is found in the H plasma at the similar lower density, which are consistent with the experimental results measured by the beam emission spectroscopy (BES) diagnostic on the DIII-D tokamak. The frequency of the electron modes and the ion modes are about 40kHz and 10 kHz respectively. The poloidal wave number $$k_\\theta$$ is about 0.2 cm -1 ($$k_\\theta\\rho_i\\sim0.05$$ ) for both ion and electron modes. The particle flux, ion and electron heat fluxes are~3.5–6 times larger for the H plasma than the D plasma, which makes it harder to achieve H-mode for the same heating power. The change of the atomic mass number A from 2 to 1 using D plasma equilibrium make little difference on the flux. Increase the electric field will suppress the density fluctuation. In conclusion, the electric field scan and ion mass scan results show that the dual-mode results primarily from differences in the profiles rather than the ion mass.« less

  15. Effect of Isotope Mass in Simulations of JET H-mode Discharges

    NASA Astrophysics Data System (ADS)

    Snyder, S. E.; Onjun, T.; Kritz, A. H.; Bateman, G.; Parail, V.

    2004-11-01

    In JET type-I ELMy H-mode discharges, it is found that the height of the pressure pedestal increases and the frequency of the ELMs decreases with increasing isotope mass. These experimentally observed trends are obtained in these simulations only if the pedestal width increases with isotope mass. Simulations are carried out using the JETTO integrated modeling code with a dynamic model for the H-mode pedestal and the ELMs.(T. Onjun et al, Phys. Plasmas 11 (2004) 1469 and 3006.) The HELENA and MISHKA stability codes are applied to calibrate the stability criteria used to trigger ELM crashes in the JETTO code and to explore possible access to second stability in the pedestal. In the simulations, transport in the pedestal is given by the ion thermal neoclassical diffusivity, which increases with isotope mass. Consequently, as the isotope mass is increased, the pressure gradient and the bootstrap current in the pedestal rebuild more slowly after each ELM crash. Several models are explored in which the pedestal width increases with isotope mass.

  16. Towards a theory of tropical/midlatitude mass exchange from the earth's surface through the stratosphere

    NASA Technical Reports Server (NTRS)

    Hartley, Dana

    1995-01-01

    The main focus of this work is to understand the dynamics of mass exchange between the tropics and the midlatitudes and to determine any links between tropospheric exchange and that in the stratosphere. We have approached this problem from two different perspectives. The first is aimed towards understanding the troposphere's role in inducing lower stratospheric tropical/midlatitude exchange. For this project we focus on observational analysis of the lower stratosphere to assess the key regions of transport in/out of the tropics and to what extent this transport is driven by tropospheric processes. The second approach is to determine the extent to which stratospheric processes influence the troposphere. In this project we are performing potential vorticity (PV) inversions to assess the winds induced near the tropopause when the stratospheric polar vortex is displaced equatorward. These are each discussed in more detail in the subsections below. Also, we have organized a session on Tropical/Midlatitude Interaction and Transport at the Fall AGU where we will be showing our latest results.

  17. Theory and applications of a novel ion exchange chromatographic technology using controlled pH gradients for separating proteins on anionic and cationic stationary phases.

    PubMed

    Tsonev, Latchezar I; Hirsh, Allen G

    2008-07-25

    pISep is a major new advance in low ionic strength ion exchange chromatography. It enables the formation of externally controlled pH gradients over the very broad pH range from 2 to 12. The gradients can be generated on either cationic or anionic exchangers over arbitrary pH ranges wherein the stationary phases remain totally charged. Associated pISep software makes possible the calculation of either linear, nonlinear or combined, multi-step, multi-slope pH gradients. These highly reproducible pH gradients, while separating proteins and glycoproteins in the order of their electrophoretic pIs, provide superior chromatographic resolution compared to salt. This paper also presents a statistical mechanical model for protein binding to ion exchange stationary phases enhancing the electrostatic interaction theory for the general dependence of retention factor k, on both salt and pH simultaneously. It is shown that the retention factors computed from short time isocratic salt elution data of a model protein can be used to accurately predict its salt elution concentration in varying slope salt elution gradients formed at varying isocratic pH as well as the pH at which it will be eluted from an anionic exchange column by a pISep pH gradient in the absence of salt.

  18. Pyruvate and ketone-body transport across the mitochondrial membrane. Exchange properties, pH-dependence and mechanism of the carrier.

    PubMed

    Halestrap, A P

    1978-06-15

    The effects of exchangeable ions and pH on the efflux of pyruvate from preloaded mitochondria are reported. Efflux obeys first-order kinetics, and the stimulation of efflux by exchangeable ions such as acetoacetate and lactate obeys Michaelis--Menten kinetics. The apparent Km value +/- S.E. for acetoacetate was 0.56 +/- 0.14 mM (n = 5) and that for lactate 12.3 +/- 2.3 mM (n = 6). The Vmax. values +/- S.E. at 0 degrees C were 16.2 +/- 2.0 and 21.9 +/- 2.7 nmol/min per mg of protein. The exchange of a variety of other substituted monocarboxylates was also studied. Efflux was also stimulated by increasing the external pH. The data gave a pK for the transport process of 8.35 and a Vmax. of 3.31 +/- 0.14 nmol/min per mg. The similarity of the Vmax. values for various exchangeable ions but the difference of this from the Vmax. in the absence of exchangeable ions may indicate that transport of pyruvate occurs with H+ and not in exchange for an OH- ion. The inhibition of transport by alpha-cyano-4-hydroxycinnamate took several seconds to reach completion at 0 degrees C. It is proposed that inhibition occurs by binding to the substrate site and subsequent reaction with an -SH group on the inside of the membrane. The inhibitor can be displaced by substrates that can also enter the mitochondria independently of the carrier and so compete with the inhibitor for the substrate-binding site on the inside of the membrane. A mechanism for transport is proposed that invokes a transition state of pyruvate involving addition of an -SH group to the 2-carbon of pyruvate. Evidence is presented that suggests that ketone bodies may cross the mitochondrial membrane either on the carrier or by free diffusion. The physiological involvement of the carrier in ketone-body metabolism is discussed. The role of ketone bodies and pH in the physiological regulation of pyruvate transport is considered.

  19. NMR analysis of t-butyl-catalyzed deuterium exchange at unactivated arene localities.

    PubMed

    Stack, Douglas E; Eastman, Rachel

    2016-10-01

    Regioselective labelling of arene rings via electrophilic exchange is often dictated by the electronic environment caused by substituents present on the aromatic system. Previously, we observed the presence of a t-butyl group, either covalently bond or added as an external reagent, could impart deuterium exchange to the unactivated, C1-position of estrone. Here, we provide nuclear magnetic resonance analysis of this exchange in a solvent system composed of 50:50 trifluoroacetic acid and D 2 O with either 2-t-butylestrone or estrone in the presence of t-butyl alcohol has shed insights into the mechanism of this t-butyl-catalyzed exchange. Fast exchange of the t-butyl group concurrent with the gradual reduction of the H1 proton signal in both systems suggest a mechanism involving ipso attack of the t-butyl position by deuterium. The reversible addition/elimination of the t-butyl group activates the H1 proton towards exchange by a mechanism of t-butyl incorporation, H1 activation and exchange, followed by eventual t-butyl elimination. Density functional calculations are consistent with the observation of fast t-butyl exchange concurrent with slower H1 exchange. The σ-complex resulting from ipso attack of deuterium at the t-butyl carbon was 6.6 kcal/mol lower in energy than that of the σ-complex resulting from deuterium attack at C1. A better understanding of the t-butyl-catalyzed exchange could help in the design of labelling recipes for other phenolic metabolites. Copyright © 2016 The Authors. Journal of Labelled Compounds and Radiopharmaceuticals published by John Wiley & Sons, Ltd.

  20. Molecular Basis for Differential Anion Binding and Proton Coupling in the Cl−/H+ Exchanger ClC-ec1

    PubMed Central

    Jiang, Tao; Han, Wei; Maduke, Merritt; Tajkhorshid, Emad

    2016-01-01

    Cl−/H+ transporters of the CLC superfamily form a ubiquitous class of membrane proteins that catalyze stoichiometrically coupled exchange of Cl− and H+ across biological membranes. CLC transporters exchange H+ for halides and certain polyatomic anions, but exclude cations, F−, and larger physiological anions, such as PO43− and SO42−. Despite comparable transport rates of different anions, the H+ coupling in CLC transporters varies significantly depending on the chemical nature of the transported anion. Although the molecular mechanism of exchange remains unknown, studies on bacterial ClC-ec1 transporter revealed that Cl− binding to the central anion-binding site (Scen) is crucial for the anion-coupled H+ transport. Here, we show that Cl−, F−, NO3−, and SCN− display distinct binding coordinations at the Scen site and are hydrated in different manners. Consistent with the observation of differential bindings, ClC-ec1 exhibits markedly variable ability to support the formation of the transient water wires, which are necessary to support the connection of the two H+ transfer sites (Gluin and Gluex), in the presence of different anions. While continuous water wires are frequently observed in the presence of physiologically transported Cl−, binding of F− or NO3− leads to the formation of pseudo-water-wires that are substantially different from the wires formed with Cl−. Binding of SCN−, however, eliminates the water wires altogether. These findings provide structural details of anion binding in ClC-ec1 and reveal a putative atomic-level mechanism for the decoupling of H+ transport to the transport of anions other than Cl−. PMID:26880377

  1. Dynamic studies of H-Ras•GTPγS interactions with nucleotide exchange factor Sos reveal a transient ternary complex formation in solution

    PubMed Central

    Vo, Uybach; Vajpai, Navratna; Embrey, Kevin J.; Golovanov, Alexander P.

    2016-01-01

    The cycling between GDP- and GTP- bound forms of the Ras protein is partly regulated by the binding of Sos. The structural/dynamic behavior of the complex formed between activated Sos and Ras at the point of the functional cycle where the nucleotide exchange is completed has not been described to date. Here we show that solution NMR spectra of H-Ras∙GTPγS mixed with a functional fragment of Sos (SosCat) at a 2:1 ratio are consistent with the formation of a rather dynamic assembly. H-Ras∙GTPγS binding was in fast exchange on the NMR timescale and retained a significant degree of molecular tumbling independent of SosCat, while SosCat also tumbled largely independently of H-Ras. Estimates of apparent molecular weight from both NMR data and SEC-MALS revealed that, at most, only one H-Ras∙GTPγS molecule appears stably bound to Sos. The weak transient interaction between Sos and the second H-Ras∙GTPγS may provide a necessary mechanism for complex dissociation upon the completion of the native GDP → GTP exchange reaction, but also explains measurable GTP → GTP exchange activity of Sos routinely observed in in vitro assays that use fluorescently-labelled analogs of GTP. Overall, the data presents the first dynamic snapshot of Ras functional cycle as controlled by Sos. PMID:27412770

  2. Dynamic studies of H-Ras•GTPγS interactions with nucleotide exchange factor Sos reveal a transient ternary complex formation in solution.

    PubMed

    Vo, Uybach; Vajpai, Navratna; Embrey, Kevin J; Golovanov, Alexander P

    2016-07-14

    The cycling between GDP- and GTP- bound forms of the Ras protein is partly regulated by the binding of Sos. The structural/dynamic behavior of the complex formed between activated Sos and Ras at the point of the functional cycle where the nucleotide exchange is completed has not been described to date. Here we show that solution NMR spectra of H-Ras∙GTPγS mixed with a functional fragment of Sos (Sos(Cat)) at a 2:1 ratio are consistent with the formation of a rather dynamic assembly. H-Ras∙GTPγS binding was in fast exchange on the NMR timescale and retained a significant degree of molecular tumbling independent of Sos(Cat), while Sos(Cat) also tumbled largely independently of H-Ras. Estimates of apparent molecular weight from both NMR data and SEC-MALS revealed that, at most, only one H-Ras∙GTPγS molecule appears stably bound to Sos. The weak transient interaction between Sos and the second H-Ras∙GTPγS may provide a necessary mechanism for complex dissociation upon the completion of the native GDP → GTP exchange reaction, but also explains measurable GTP → GTP exchange activity of Sos routinely observed in in vitro assays that use fluorescently-labelled analogs of GTP. Overall, the data presents the first dynamic snapshot of Ras functional cycle as controlled by Sos.

  3. High efficiency laser-assisted H - charge exchange for microsecond duration beams

    DOE PAGES

    Cousineau, Sarah; Rakhman, Abdurahim; Kay, Martin; ...

    2017-12-26

    Laser-assisted stripping is a novel approach to H - charge exchange that overcomes long-standing limitations associated with the traditional, foil-based method of producing high-intensity, time-structured beams of protons. This paper reports on the first successful demonstration of the laser stripping technique for microsecond duration beams. The experiment represents a factor of 1000 increase in the stripped pulse duration compared with the previous proof-of-principle demonstration. The central theme of the experiment is the implementation of methods to reduce the required average laser power such that high efficiency stripping can be accomplished for microsecond duration beams using conventional laser technology. In conclusion,more » the experiment was performed on the Spallation Neutron Source 1 GeV H - beam using a 1 MW peak power UV laser and resulted in ~95% stripping efficiency.« less

  4. High efficiency laser-assisted H - charge exchange for microsecond duration beams

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

    Cousineau, Sarah; Rakhman, Abdurahim; Kay, Martin

    Laser-assisted stripping is a novel approach to H - charge exchange that overcomes long-standing limitations associated with the traditional, foil-based method of producing high-intensity, time-structured beams of protons. This paper reports on the first successful demonstration of the laser stripping technique for microsecond duration beams. The experiment represents a factor of 1000 increase in the stripped pulse duration compared with the previous proof-of-principle demonstration. The central theme of the experiment is the implementation of methods to reduce the required average laser power such that high efficiency stripping can be accomplished for microsecond duration beams using conventional laser technology. In conclusion,more » the experiment was performed on the Spallation Neutron Source 1 GeV H - beam using a 1 MW peak power UV laser and resulted in ~95% stripping efficiency.« less

  5. Patterns of structural dynamics in RACK1 protein retained throughout evolution: A hydrogen-deuterium exchange study of three orthologs

    PubMed Central

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

    2014-01-01

    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. PMID:24591271

  6. Geometric phase effects in ultracold hydrogen exchange reaction

    DOE PAGES

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

    2016-10-14

    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+H 2 product or in the D+H 2more » $$(v=4,j=0)\\,\\to $$ 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. In conclusion, experimental detection of the resonance may allow a sensitive probe of the GP effect in the H+HD reaction.« less

  7. Deuterium Exchange in Ethyl Acetoacetate: An Undergraduate GC-MS [Gas Chromatography-Mass Spectroscopy] Experiment

    ERIC Educational Resources Information Center

    Heinson, C. D.; Williams, J. M.; Tinnerman, W. N.; Malloy, T. B.

    2005-01-01

    The role of ethanol O-d in nullifying the deuterolysis may be demonstrated by determining that transesterification of methyl acetoacetate of the ethyl ester occurs as well as deuterium exchange of the five acetoacetate hydrogens. The significant acidity of the methylene protons in the acetoacetate group, the efficacy of base catalysis, the role of…

  8. Oxygen Atom Exchange between H2O and Non-Heme Oxoiron(IV) Complexes: Ligand Dependence and Mechanism.

    PubMed

    Puri, Mayank; Company, Anna; Sabenya, Gerard; Costas, Miquel; Que, Lawrence

    2016-06-20

    Detailed studies of oxygen atom exchange (OAE) between H2(18)O and synthetic non-heme oxoiron(IV) complexes supported by tetradentate and pentadentate ligands provide evidence that they proceed by a common mechanism but within two different kinetic regimes, with OAE rates that span 2 orders of magnitude. The first kinetic regime involves initial reversible water association to the Fe(IV) complex, which is evidenced by OAE rates that are linearly dependent on [H2(18)O] and H2O/D2O KIEs of 1.6, while the second kinetic regime involves a subsequent rate determining proton-transfer step between the bound aqua and oxo ligands that is associated with saturation behavior with [H2(18)O] and much larger H2O/D2O KIEs of 5-6. [Fe(IV)(O)(TMC)(MeCN)](2+) (1) and [Fe(IV)(O)(MePy2TACN)](2+) (9) are examples of complexes that exhibit kinetic behavior in the first regime, while [Fe(IV)(O)(N4Py)](2+) (3), [Fe(IV)(O)(BnTPEN)](2+) (4), [Fe(IV)(O)(1Py-BnTPEN)](2+) (5), [Fe(IV)(O)(3Py-BnTPEN)](2+) (6), and [Fe(IV)(O)(Me2Py2TACN)](2+) (8) represent complexes that fall in the second kinetic regime. Interestingly, [Fe(IV)(O)(PyTACN)(MeCN)](2+) (7) exhibits a linear [H2(18)O] dependence below 0.6 M and saturation above 0.6 M. Analysis of the temperature dependence of the OAE rates shows that most of these complexes exhibit large and negative activation entropies, consistent with the proposed mechanism. One exception is complex 9, which has a near-zero activation entropy and is proposed to undergo ligand-arm dissociation during the RDS to accommodate H2(18)O binding. These results show that the observed OAE kinetic behavior is highly dependent on the nature of the supporting ligand and are of relevance to studies of non-heme oxoiron(IV) complexes in water or acetonitrile/water mixtures for applications in photocatalysis and water oxidation chemistry.

  9. Dim light at night increases body mass of female mice.

    PubMed

    Aubrecht, Taryn G; Jenkins, Richelle; Nelson, Randy J

    2015-05-01

    During the past century, the prevalence of light at night has increased in parallel with obesity rates. Dim light at night (dLAN) increases body mass in male mice. However, the effects of light at night on female body mass remain unspecified. Thus, female mice were exposed to a standard light/dark (LD; 16 h light at ∼150 lux/8 h dark at ∼0 lux) cycle or to light/dim light at night (dLAN; 16 h light at ∼150 lux/8 h dim light at ∼5 lux) cycles for six weeks. Females exposed to dLAN increased the rate of change in body mass compared to LD mice despite reduced total food intake during weeks five and six, suggesting that dLAN disrupted circadian rhythms resulting in deranged metabolism.

  10. The role of nonmagnetic d{sup 0} vs. d{sup 10}B-type cations on the magnetic exchange interactions in osmium double perovskites

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

    Feng, Hai L., E-mail: Hai.Feng@cpfs.mpg.de; Yamaura, Kazunari; Tjeng, Liu Hao

    Polycrystalline samples of double perovskites Ba{sub 2}BOsO{sub 6} (B=Sc, Y, In) were synthesized by solid state reactions. They adopt the cubic double perovskite structures (space group, Fm-3m) with ordered B and Os arrangements. Ba{sub 2}BOsO{sub 6} (B=Sc, Y, In) show antiferromagnetic transitions at 93 K, 69 K, and 28 K, respectively. The Weiss-temperatures are −590 K for Ba{sub 2}ScOsO{sub 6}, −571 K for Ba{sub 2}YOsO{sub 6}, and −155 K for Ba{sub 2}InOsO{sub 6}. Sc{sup 3+} and Y{sup 3+} have the open-shell d{sup 0} electronic configuration, while In{sup 3+} has the closed-shell d{sup 10}. This indicates that a d{sup 0} B-typemore » cation induces stronger overall magnetic exchange interactions in comparison to a d{sup 10}. Comparison of Ba{sub 2}BOsO{sub 6} (B=Sc, Y, In) to their Sr and Ca analogues shows that the structural distortions weaken the overall magnetic exchange interactions. - Graphical abstract: Magnetic properties of osmium double perovskites Ba{sub 2}BOsO{sub 6} (B=Sc, Y, In) were studied. Comparison of Ba{sub 2}BOsO{sub 6}indicates that a d{sup 0} B-type cation induces stronger overall magnetic exchange interactions in comparison to a d{sup 10}. - Highlights: • Magnetic properties of double perovskites Ba{sub 2}BOsO{sub 6} (B=Sc, Y, In) were studied. • A d{sup 0}B-type cation induces stronger magnetic interactions than a d{sup 10}. • Structural distortions weaken the overall Os{sup 5+}-Os{sup 5+} magnetic interactions.« less

  11. Fragility of ferromagnetic double exchange interactions and pressure tuning of magnetism in 3d–5d double perovskite Sr₂FeOsO₆

    DOE PAGES

    Veiga, L. S. I.; Fabbris, G.; van Veenendaal, M.; ...

    2015-06-19

    The ability to tune exchange (magnetic) interactions between 3d transition metals in perovskite structures has proven to be a powerful route to discovery of novel properties. Here we demonstrate that the introduction of 3d-5d exchange pathways in double perovskites enables additional tunability, a result of the large spatial extent of 5d wave functions. Using x-ray probes of magnetism and structure at high pressure, we show that compression of Sr₂FeOsO₆ drives an unexpected continuous change in the sign of Fe-Os exchange interactions and a transition from antiferromagnetic to ferrimagnetic order. We analyze the relevant electron-electron interactions, shedding light into fundamental differencesmore » with the more thoroughly studied 3d-3d systems.« less

  12. Multi-layer membrane model for mass transport in a direct ethanol fuel cell using an alkaline anion exchange membrane

    NASA Astrophysics Data System (ADS)

    Bahrami, Hafez; Faghri, Amir

    2012-11-01

    A one-dimensional, isothermal, single-phase model is presented to investigate the mass transport in a direct ethanol fuel cell incorporating an alkaline anion exchange membrane. The electrochemistry is analytically solved and the closed-form solution is provided for two limiting cases assuming Tafel expressions for both oxygen reduction and ethanol oxidation. A multi-layer membrane model is proposed to properly account for the diffusive and electroosmotic transport of ethanol through the membrane. The fundamental differences in fuel crossover for positive and negative electroosmotic drag coefficients are discussed. It is found that ethanol crossover is significantly reduced upon using an alkaline anion exchange membrane instead of a proton exchange membrane, especially at current densities higher than 500 A m

  13. Novel two-step laser ablation and ionization mass spectrometry (2S-LAIMS) of actor-spectator ice layers: Probing chemical composition of D{sub 2}O ice beneath a H{sub 2}O ice layer

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

    Yang, Rui, E-mail: ryang73@ustc.edu; Gudipati, Murthy S., E-mail: gudipati@jpl.nasa.gov

    2014-03-14

    In this work, we report for the first time successful analysis of organic aromatic analytes imbedded in D{sub 2}O ices by novel infrared (IR) laser ablation of a layered non-absorbing D{sub 2}O ice (spectator) containing the analytes and an ablation-active IR-absorbing H{sub 2}O ice layer (actor) without the analyte. With these studies we have opened up a new method for the in situ analysis of solids containing analytes when covered with an IR laser-absorbing layer that can be resonantly ablated. This soft ejection method takes advantage of the tenability of two-step infrared laser ablation and ultraviolet laser ionization mass spectrometry,more » previously demonstrated in this lab to study chemical reactions of polycyclic aromatic hydrocarbons (PAHs) in cryogenic ices. The IR laser pulse tuned to resonantly excite only the upper H{sub 2}O ice layer (actor) generates a shockwave upon impact. This shockwave penetrates the lower analyte-containing D{sub 2}O ice layer (spectator, a non-absorbing ice that cannot be ablated directly with the wavelength of the IR laser employed) and is reflected back, ejecting the contents of the D{sub 2}O layer into the vacuum where they are intersected by a UV laser for ionization and detection by a time-of-flight mass spectrometer. Thus, energy is transmitted from the laser-absorbing actor layer into the non-absorbing spectator layer resulting its ablation. We found that isotope cross-contamination between layers was negligible. We also did not see any evidence for thermal or collisional chemistry of PAH molecules with H{sub 2}O molecules in the shockwave. We call this “shockwave mediated surface resonance enhanced subsurface ablation” technique as “two-step laser ablation and ionization mass spectrometry of actor-spectator ice layers.” This method has its roots in the well-established MALDI (matrix assisted laser desorption and ionization) method. Our method offers more flexibility to optimize both the processes

  14. MSX-3D: a tool to validate 3D protein models using mass spectrometry.

    PubMed

    Heymann, Michaël; Paramelle, David; Subra, Gilles; Forest, Eric; Martinez, Jean; Geourjon, Christophe; Deléage, Gilbert

    2008-12-01

    The technique of chemical cross-linking followed by mass spectrometry has proven to bring valuable information about the protein structure and interactions between proteic subunits. It is an effective and efficient way to experimentally investigate some aspects of a protein structure when NMR and X-ray crystallography data are lacking. We introduce MSX-3D, a tool specifically geared to validate protein models using mass spectrometry. In addition to classical peptides identifications, it allows an interactive 3D visualization of the distance constraints derived from a cross-linking experiment. Freely available at http://proteomics-pbil.ibcp.fr

  15. Commensurate Superstructure of the {Cu(NO3)(H2O)}(HTae)(Bpy) Coordination Polymer: An Example of 2D Hydrogen-Bonding Networks as Magnetic Exchange Pathway.

    PubMed

    Fernández de Luis, Roberto; Larrea, Edurne S; Orive, Joseba; Lezama, Luis; Arriortua, María I

    2016-11-21

    The average and commensurate superstructures of the one-dimensional coordination polymer {Cu(NO 3 )(H 2 O)}(HTae)(Bpy) (H 2 Tae = 1,1,2,2-tetraacetylethane, Bpy = 4,4'-bipyridine) were determined by single-crystal X-ray diffraction, and the possible symmetry relations between the space group of the average structure and the superstructure were checked. The crystal structure consists in parallel and oblique {Cu(HTae)(Bpy)} zigzag metal-organic chains stacked along the [100] crystallographic direction. The origin of the fivefold c axis in the commensurate superstructure is ascribed to a commensurate modulation of the coordination environment of the copper atoms. The commensurately ordered nitrate groups and coordinated water molecules establish a two-dimensional hydrogen-bonding network. Moreover, the crystal structure shows a commensurate to incommensurate transition at room temperature. The release of the coordination water molecules destabilizes the crystal framework, and the compound shows an irreversible structure transformation above 100 °C. Despite the loss of crystallinity, the spectroscopic studies indicate that the main building blocks of the crystal framework are retained after the transformation. The hydrogen-bonding network not only plays a crucial role stabilizing the crystal structure but also is an important pathway for magnetic exchange transmission. In fact, the magnetic susceptibility curves indicate that after the loss of coordinated water molecules, and hence the collapse of the hydrogen-bonding network, the weak anti-ferromagnetic coupling observed in the initial compound is broken. The electron paramagnetic resonance spectra are the consequence of the average signals from Cu(II) with different orientations, indicating that the magnetic coupling is effective between them. In fact, X- and Q-band data are reflecting different situations; the X-band spectra show the characteristics of an exchange g-tensor, while the Q-band signals are coming from

  16. Molecular characterization and expression analysis of the Na+/H+ exchanger gene family in Medicago truncatula

    USDA-ARS?s Scientific Manuscript database

    One important mechanism plants use to cope with salinity is keeping the cytosolic Na+ concentration low by sequestering Na+ in vacuoles, a process facilitated by Na+/H+ exchangers (NHX). There are eight NHX genes (NHX1 through NHX8) identified and characterized in Arabidopsis. Bioinformatic analysis...

  17. Plio-Pleistocene evolution of water mass exchange and erosional input at the Atlantic-Arctic gateway

    NASA Astrophysics Data System (ADS)

    Teschner, Claudia; Frank, Martin; Haley, Brian A.; Knies, Jochen

    2016-05-01

    Water mass exchange between the Arctic Ocean and the Norwegian-Greenland Seas has played an important role for the Atlantic thermohaline circulation and Northern Hemisphere climate. We reconstruct past water mass mixing and erosional inputs from the radiogenic isotope compositions of neodymium (Nd), lead (Pb), and strontium (Sr) at Ocean Drilling Program site 911 (leg 151) from 906 m water depth on Yermak Plateau in the Fram Strait over the past 5.2 Myr. The isotopic compositions of past bottom waters were extracted from authigenic oxyhydroxide coatings of the bulk sediments. Neodymium isotope signatures obtained from surface sediments agree well with present-day deepwater ɛNd signature of -11.0 ± 0.2. Prior to 2.7 Ma the Nd and Pb isotope compositions of the bottom waters only show small variations indicative of a consistent influence of Atlantic waters. Since the major intensification of the Northern Hemisphere Glaciation at 2.7 Ma the seawater Nd isotope composition has varied more pronouncedly due to changes in weathering inputs related to the waxing and waning of the ice sheets on Svalbard, the Barents Sea, and the Eurasian shelf, due to changes in water mass exchange and due to the increasing supply of ice-rafted debris (IRD) originating from the Arctic Ocean. The seawater Pb isotope record also exhibits a higher short-term variability after 2.7 Ma, but there is also a trend toward more radiogenic values, which reflects a combination of changes in input sources and enhanced incongruent weathering inputs of Pb released from freshly eroded old continental rocks.

  18. The Effect of Halo Mass on the H I Content of Galaxies in Groups and Clusters

    NASA Astrophysics Data System (ADS)

    Yoon, Ilsang; Rosenberg, Jessica L.

    2015-10-01

    We combine data from the Sloan Digital Sky Survey (SDSS) and the Arecibo Legacy Fast ALFA Survey (ALFALFA) to study the cold atomic gas content of galaxies in groups and clusters in the local universe. A careful cross-matching of galaxies in the SDSS, ALFALFA, and SDSS group catalogs provides a sample of group galaxies with stellar masses {10}8.4{M}⊙ ≤slant {M}*≤slant {10}10.6{M}⊙ and group halo masses {10}12.5{h}-1{M}⊙ ≤slant {M}h≤slant {10}15.0{h}-1{M}⊙ . Controlling our sample in stellar mass and redshift, we find no significant radial variation in the galaxy H i gas-to-stellar mass ratio for the halo mass range in our sample. However, the fraction of galaxies detected in ALFALFA declines steadily toward the centers of groups, with the effect being most prominent in the most massive halos. In the outskirts of massive halos a hint of a depressed detection fraction for low-mass galaxies suggests pre-processing that decreases the H i in these galaxies before they fall into massive clusters. We interpret the decline in the ALFALFA detection of galaxies in the context of a threshold halo mass for ram pressure stripping for a given galaxy stellar mass. The lack of an observable decrease in the galaxy H i gas-to-stellar mass ratio with the position of galaxies within groups and clusters highlights the difficulty of detecting the impact of environment on the galaxy H i content in a shallow H i survey.

  19. H2 Emission Nebulosity Associated with KH 15D

    NASA Astrophysics Data System (ADS)

    Tokunaga, A. T.; Dahm, S.; Gässler, W.; Hayano, Yutaka; Hayashi, Masahiko; Iye, Masanori; Kanzawa, Tomio; Kobayashi, Naoto; Kamata, Yukiko; Minowa, Yosuke; Nedachi, Ko; Oya, Shin; Pyo, Tae-Soo; Saint-Jacques, D.; Terada, Hiroshi; Takami, Hideki; Takato, Naruhisa

    2004-01-01

    An H2 emission filament is found in close proximity to the unique object KH 15D using the adaptive optics system of the Subaru Telescope. The morphology of the filament, the presence of spectroscopic outflow signatures observed by Hamilton et al., and the detection of extended H2 emission from KH 15D by Deming, Charbonneau, & Harrington suggest that this filament arises from shocked H2 in an outflow. The filament extends about 15" to the north of KH 15D. Based on data collected at Subaru Telescope, which is operated by the National AstronomiObservatory of Japan.

  20. Glauber exchange amplitudes. [electron scattering from H atoms

    NASA Technical Reports Server (NTRS)

    Madan, R. N.

    1975-01-01

    The extrapolation method of Ochkur, valid for intermediate energies (about 50 eV), is applied to the exchange form of the Glauber amplitudes. In the case of elastic scattering of electrons from hydrogen atoms at 54.4 Ev the 'post' and 'prior' forms of the exchange amplitude are equivalent, whereas for the case of inelastic scattering there is a minute discrepancy between the two forms of the amplitude. The results are compared with the close-coupling calculation. The investigation is expected to be useful for optically forbidden exchange-allowed transitions due to electron impact at intermediate energies.

  1. Super (a,d)-H-antimagic covering of möbius ladder graph

    NASA Astrophysics Data System (ADS)

    Indriyani, Novia; Sri Martini, Titin

    2018-04-01

    Let G = (V(G), E(G)) be a simple graph. Let H-covering of G is a subgraph H 1, H 2, …, Hj with every edge in G is contained in at least one graph Hi for 1 ≤ i ≤ j. If every Hi is isomorphic, then G admits an H-covering. Furthermore, an (a,d)-H-antimagic covering if there bijective function ξ :V(G)\\cup E(G)\\to \\{1,2,3,\\ldots,|V(G)|+|E(G)|\\}. The H‑-weights for all subgraphs H‑ isomorphic to H ω ({H}^{\\prime })={\\sum }v\\in V({H^{\\prime })}ξ (v)+{\\sum }e\\in E({H^{\\prime })}ξ (e). The weights of subgraphs constitutes an arithmatic progression {a, a + d, …, a + (t ‑ 1)d} where a and d are positive integers and t is the number of subgraphs G isomorphic to H. If ξ (V(G))=\\{1,2,\\ldots,|V(G)|\\} then ξ is called super (a, d)-H-antimagic covering. The research provides super (a, d)-H-antimagic covering with d = {1, 3} of Möbius ladder graph Mn for n > 5 and n is odd.

  2. Conformational Specific Infrared and Ultraviolet Spectroscopy of Cold YA(D-Pro)AA\\cdotH+ Ions: a Sterochemical "twist" on the Proline Effect

    NASA Astrophysics Data System (ADS)

    Harrilal, Christopher P.; DeBlase, Andrew F.; Burke, Nicole L.; McLuckey, Scott A.; Zwier, Timothy S.

    2016-06-01

    The "proline effect" is a well-known fragmentation phenomenon in mass spectrometry, in which y-fragments are produced preferentially over b-fragments during the collision induced dissociation of protonated L-proline containing peptide ions. This specific fragmentation channel is favored because of the high basicity of the secondary amine intermediate and the ring instability in alternative bn+ products [ASMS 2014, 25, 1705]. In contrast, peptides containing the D-Pro stereoisomer have been shown to largely favor the production of b4+ ions over y3+ ions. This strongly suggests that differences in the conformational preferences between the D-Pro and L-Pro diastereomers are likely to be responsible but structural evidence has been lacking to date. Using tandem mass spectrometry and IR-UV double resonant action spectroscopy we are able to compare the 3D structures of cold [YA(D-Pro)AA+H]+ to [YA(L-Pro)AA+H]+ ions. The UV action spectra reveals two major conformers in [YA(D-Pro)AA+H]+ and one major conformer in [YA(L-Pro)AA+H]+. Clear differences in the hydrogen bonding patterns are apparent between the two conformers observed in the D-Pro specie which are both distinct from the L-Pro diastereomer. Furthermore, conformer and diastereomer specific photofragmentation patterns are observed. It is also noted that a ten-fold photofragment enhancement unique to one of the D-Pro conformers is observed upon absorption of a resonant IR photon after UV excitation. Differences in the excited state photophysics between the two D-Pro conformers suggest that vibrational excitation of S1 turns on coupling to the dissociative -Tyr channel in one conformer, while this coupling is already present in the vibronic ground state of the other. Calculated harmonic spectra (M052X/6-31+G*) of conformers obtained from Monte Carlo searches to the experimental spectra.

  3. New measurements of D/H on Mars using EXES aboard SOFIA

    NASA Astrophysics Data System (ADS)

    Encrenaz, T.; DeWitt, C.; Richter, M. J.; Greathouse, T. K.; Fouchet, T.; Montmessin, F.; Lefèvre, F.; Bézard, B.; Atreya, S. K.; Aoki, S.; Sagawa, H.

    2018-05-01

    The global D/H ratio on Mars is an important measurement for understanding the past history of water on Mars; locally, through condensation and sublimation processes, it is a possible tracer of the sources and sinks of water vapor on Mars. Measuring D/H as a function of longitude, latitude and season is necessary for determining the present averaged value of D/H on Mars. Following an earlier measurement in April 2014, we used the Echelon Cross Echelle Spectrograph (EXES) instrument on board the Stratospheric Observatory for Infrared Astronomy (SOFIA) facility to map D/H on Mars on two occasions, on March 24, 2016 (Ls = 127°), and January 24, 2017 (Ls = 304°), by measuring simultaneously the abundances of H2O and HDO in the 1383-1391 cm-1 range (7.2 μm). The D/H disk-integrated values are 4.0 (+0.8, -0.6) × Vienna Standard Mean Ocean Water (VSMOW) and 4.5 (+0.7, -0.6) × VSMOW, respectively, in agreement with our earlier result. The main result of this study is that there is no evidence of strong local variations in the D/H ratio nor for seasonal variations in the global D/H ratio between northern summer and southern summer.

  4. Understanding the Reactive Adsorption of H 2S and CO 2 in Sodium-Exchanged Zeolites

    DOE PAGES

    Fetisov, Evgenii O.; Shah, Mansi S; Knight, Christopher; ...

    2018-02-19

    Purifying sour natural gas streams containing hydrogen sulfide and carbon dioxide has been a long-standing environmental and economic challenge. In the presence of cation-exchanged zeolites, these two acid gases can react to form carbonyl sulfide and water (H 2S+CO 2H 2O+COS), but this reaction is rarely accounted for. In this work, we carry out reactive first-principles Monte Carlo (RxFPMC) simulations for mixtures of H 2S and CO 2 in all-silica and Na-exchanged forms of zeolite beta to understand the governing principles driving the enhanced conversion. The RxFPMC simulations show that the presence of Na + cations can change the equilibriummore » constant by several orders of magnitude compared to the gas phase or in all-silica beta. The shift in the reaction equilibrium is caused by very strong interactions of H 2O with Na + that reduce the reaction enthalpy by about 20 kJmol -1. The simulations also demonstrate that the siting of Al atoms in the framework plays an important role. Lastly, the RxFPMC method presented here is applicable to any chemical conversion in any confined environment, where strong interactions of guest molecules with the host framework and high activation energies limit the use of other computational approaches to study reaction equilibria.« less

  5. Electron mass stopping power in H2

    NASA Astrophysics Data System (ADS)

    Fursa, Dmitry V.; Zammit, Mark C.; Threlfall, Robert L.; Savage, Jeremy S.; Bray, Igor

    2017-08-01

    Calculations of electron mass stopping power (SP) of electrons in H2 have been performed using the convergent close-coupling method for incident electron energies up to 2000 eV. Convergence of the calculated SP has been established by increasing the size of the close-coupling expansion from 9 to 491 states. Good agreement was found with the SP measurements of Munoz et al. [Chem. Phys. Lett. 433, 253 (2007), 10.1016/j.cplett.2006.10.114].

  6. Search for doubly-charged Higgs Boson production in the decay H ++ H -- → μ +μ +μ -μ - with the D0 detector at √s = 1.96-TeV

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

    Zdrazil, Marian

    2004-08-01

    This work presents a search for the pair production of doubly-charged Higgs Bosons in the process pmore » $$\\bar{p}$$ → H ++H -- → μ +μ +μ -μ - using inclusive dimuon events. These data correspond to an integrated luminosity of about 113 pb 1 and were recorded by the D0 experiment between August 2002 and June 2003. In the absence of a signal, 95% confidence level mass limits of M(H$$±±\\atop{L}$$) > 118.6 GeV/c 2 and M(H R ±±) > 98.1 GeV/c 2 are set for left-handed and right-handed doubly-charged Higgs boson, assuming 100% branching into muons and hypercharge |Y| = 2 and Yukawa coupling h μμ > 10 -7. This is the first search for doubly-charged Higgs bosons at hadron colliders. It significantly extends the previous mass limit of 100.5 GeV/c 2 for a left-handed doubly-charged Higgs boson measured in the muon final states by the OPAL collaboration.« less

  7. THE ARECIBO LEGACY FAST ALFA SURVEY. IX. THE LEO REGION H I CATALOG, GROUP MEMBERSHIP, AND THE H I MASS FUNCTION FOR THE LEO I GROUP

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

    Stierwalt, Sabrina; Haynes, Martha P.; Giovanelli, Riccardo

    We present the catalog of H I sources extracted from the ongoing Arecibo Legacy Fast ALFA (ALFALFA) extragalactic H I line survey, found within the sky region bounded by 9{sup h}36{sup m} < {alpha} < 11{sup h}36{sup m} and +08{sup 0} < {delta} < +12{sup 0}. The H I catalog presented here for this 118 deg{sup 2} region is combined with the ones derived from surrounding regions also covered by the ALFALFA survey to examine the large-scale structure in the complex Leo region. Because of the combination of wide sky coverage and superior sensitivity, spatial and spectral resolution, the ALFALFAmore » H I catalog of the Leo region improves significantly on the numbers of low H I mass sources as compared with those found in previous H I surveys. The H I mass function of the Leo I group presented here is dominated by low-mass objects: 45 of the 65 Leo I members have M{sub H{sub l}}<10{sup 8} M-odot, yielding tight constraints on the low-mass slope of the Leo I H I mass function. The best-fit slope is {alpha} {approx_equal} -1.41 + 0.2 - 0.1. A direct comparison between the ALFALFA H I line detections and an optical search of the Leo I region proves the advantage of the ALFALFA strategy in finding low-mass, gas-rich dwarfs. These results suggest the existence of a significant population of low surface brightness, gas-rich, yet still very low H I mass galaxies, and may reflect the same type of morphological segregation as is seen in the Local Group. While the low-mass end slope of the Leo I H I mass function is steeper than that determined for luminosity functions of the group, the slope still falls short of the values predicted by simulations of structure formation in the lambda cold dark matter paradigm.« less

  8. The Mass Function in h+(chi) Persei

    NASA Astrophysics Data System (ADS)

    Bragg, Ann; Kenyon, Scott

    2000-08-01

    Knowledge of the stellar initial mass function (IMF) is critical to understanding star formation and galaxy evolution. Past studies of the IMF in open clusters have primarily used luminosity functions to determine mass functions, frequently in relatively sparse clusters. Our goal with this project is to derive a reliable, well- sampled IMF for a pair of very dense young clusters (h+(chi) Persei) with ages, 1-2 × 10^7 yr (e.g., Vogt A& A 11:359), where stellar evolution theory is robust. We will construct the HR diagram using both photometry and spectral types to derive more accurate stellar masses and ages than are possible using photometry alone. Results from the two clusters will be compared to examine the universality of the IMF. We currently have a spectroscopic sample covering an area within 9 arc-minutes of the center of each cluster taken with the FAST Spectrograph. The sample is complete to V=15.4 and contains ~ 1000 stars. We request 2 nights at WIYN/HYDRA to extend this sample to deeper magnitudes, allowing us to determine the IMF of the clusters to a lower limiting mass and to search for a pre-main sequence, theoretically predicted to be present for clusters of this age. Note that both clusters are contained within a single HYDRA field.

  9. 2D Bayesian automated tilted-ring fitting of disc galaxies in large H I galaxy surveys: 2DBAT

    NASA Astrophysics Data System (ADS)

    Oh, Se-Heon; Staveley-Smith, Lister; Spekkens, Kristine; Kamphuis, Peter; Koribalski, Bärbel S.

    2018-01-01

    We present a novel algorithm based on a Bayesian method for 2D tilted-ring analysis of disc galaxy velocity fields. Compared to the conventional algorithms based on a chi-squared minimization procedure, this new Bayesian-based algorithm suffers less from local minima of the model parameters even with highly multimodal posterior distributions. Moreover, the Bayesian analysis, implemented via Markov Chain Monte Carlo sampling, only requires broad ranges of posterior distributions of the parameters, which makes the fitting procedure fully automated. This feature will be essential when performing kinematic analysis on the large number of resolved galaxies expected to be detected in neutral hydrogen (H I) surveys with the Square Kilometre Array and its pathfinders. The so-called 2D Bayesian Automated Tilted-ring fitter (2DBAT) implements Bayesian fits of 2D tilted-ring models in order to derive rotation curves of galaxies. We explore 2DBAT performance on (a) artificial H I data cubes built based on representative rotation curves of intermediate-mass and massive spiral galaxies, and (b) Australia Telescope Compact Array H I data from the Local Volume H I Survey. We find that 2DBAT works best for well-resolved galaxies with intermediate inclinations (20° < i < 70°), complementing 3D techniques better suited to modelling inclined galaxies.

  10. THE ARECIBO LEGACY FAST ALFA SURVEY. X. THE H I MASS FUNCTION AND {Omega}{sub H{sub i}} FROM THE 40% ALFALFA SURVEY

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

    Martin, Ann M.; Papastergis, Emmanouil; Giovanelli, Riccardo

    The Arecibo Legacy Fast ALFA (ALFALFA) survey has completed source extraction for 40% of its total sky area, resulting in the largest sample of H I-selected galaxies to date. We measure the H I mass function from a sample of 10,119 galaxies with 6.2 < log (M{sub H{sub i}}/M{sub sun}) < 11.0 and with well-described mass errors that accurately reflect our knowledge of low-mass systems. We characterize the survey sensitivity and its dependence on profile velocity width, the effect of large-scale structure, and the impact of radio frequency interference in order to calculate the H I mass function with bothmore » the 1/V{sub max} and 2DSWML methods. We also assess a flux-limited sample to test the robustness of the methods applied to the full sample. These measurements are in excellent agreement with one another; the derived Schechter function parameters are {phi}{sub *} (h {sup 3}{sub 70} Mpc{sup -3} dex{sup -1}) = 4.8 {+-} 0.3 x 10{sup -3}, log (M{sub *}/M{sub sun}) + 2 log h{sub 70} = 9.96 {+-} 0.02, and {alpha} = -1.33 {+-} 0.02. We find {Omega}{sub H{sub i}}= 4.3 {+-} 0.3 x10{sup -4} h {sup -1}{sub 70}, 16% larger than the 2005 HIPASS result, and our Schechter function fit extrapolated to log (M{sub H{sub i}}/M{sub sun}) = 11.0 predicts an order of magnitude more galaxies than HIPASS. The larger values of {Omega}{sub H{sub i}} and of M{sub *} imply an upward adjustment for estimates of the detection rate of future large-scale H I line surveys with, e.g., the Square Kilometer Array. A comparison with simulated galaxies from the Millennium Run and a treatment of photoheating as a method of baryon removal from H I-selected halos indicate that the disagreement between dark matter mass functions and baryonic mass functions may soon be resolved.« less

  11. Crystal structures of D-psicose 3-epimerase from Clostridium cellulolyticum H10 and its complex with ketohexose sugars.

    PubMed

    Chan, Hsiu-Chien; Zhu, Yueming; Hu, Yumei; Ko, Tzu-Ping; Huang, Chun-Hsiang; Ren, Feifei; Chen, Chun-Chi; Ma, Yanhe; Guo, Rey-Ting; Sun, Yuanxia

    2012-02-01

    D-psicose 3-epimerase (DPEase) is demonstrated to be useful in the bioproduction of D-psicose, a rare hexose sugar, from D-fructose, found plenty in nature. Clostridium cellulolyticum H10 has recently been identified as a DPEase that can epimerize D-fructose to yield D-psicose with a much higher conversion rate when compared with the conventionally used DTEase. In this study, the crystal structure of the C. cellulolyticum DPEase was determined. The enzyme assembles into a tetramer and each subunit shows a (β/α)(8) TIM barrel fold with a Mn(2+) metal ion in the active site. Additional crystal structures of the enzyme in complex with substrates/products (D-psicose, D-fructose, D-tagatose and D-sorbose) were also determined. From the complex structures of C. cellulolyticum DPEase with D-psicose and D-fructose, the enzyme has much more interactions with D-psicose than D-fructose by forming more hydrogen bonds between the substrate and the active site residues. Accordingly, based on these ketohexose-bound complex structures, a C3-O3 proton-exchange mechanism for the conversion between D-psicose and D-fructose is proposed here. These results provide a clear idea for the deprotonation/protonation roles of E150 and E244 in catalysis.

  12. Capture and isotopic exchange method for water and hydrogen isotopes on zeolite catalysts up to technical scale for pre-study of processing highly tritiated water

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

    Michling, R.; Braun, A.; Cristescu, I.

    2015-03-15

    Highly tritiated water (HTW) may be generated at ITER by various processes and, due to the excessive radio toxicity, the self-radiolysis and the exceedingly corrosive property of HTW, a potential hazard is associated with its storage and process. Therefore, the capture and exchange method for HTW utilizing Molecular Sieve Beds (MSB) was investigated in view of adsorption capacity, isotopic exchange performance and process parameters. For the MSB, different types of zeolite were selected. All zeolite materials were additionally coated with platinum. The following work comprised the selection of the most efficient zeolite candidate based on detailed parametric studies during themore » H{sub 2}/D{sub 2}O laboratory scale exchange experiments (about 25 g zeolite per bed) at the Tritium Laboratory Karlsruhe (TLK). For the zeolite, characterization analytical techniques such as Infrared Spectroscopy, Thermogravimetry and online mass spectrometry were implemented. Followed by further investigation of the selected zeolite catalyst under full technical operation, a MSB (about 22 kg zeolite) was processed with hydrogen flow rates up to 60 mol*h{sup -1} and deuterated water loads up to 1.6 kg in view of later ITER processing of arising HTW. (authors)« less

  13. How well does CO emission measure the H2 mass of MCs?

    NASA Astrophysics Data System (ADS)

    Szűcs, László; Glover, Simon C. O.; Klessen, Ralf S.

    2016-07-01

    We present numerical simulations of molecular clouds (MCs) with self-consistent CO gas-phase and isotope chemistry in various environments. The simulations are post-processed with a line radiative transfer code to obtain 12CO and 13CO emission maps for the J = 1 → 0 rotational transition. The emission maps are analysed with commonly used observational methods, I.e. the 13CO column density measurement, the virial mass estimate and the so-called XCO (also CO-to-H2) conversion factor, and then the inferred quantities (I.e. mass and column density) are compared to the physical values. We generally find that most methods examined here recover the CO-emitting H2 gas mass of MCs within a factor of 2 uncertainty if the metallicity is not too low. The exception is the 13CO column density method. It is affected by chemical and optical depth issues, and it measures both the true H2 column density distribution and the molecular mass poorly. The virial mass estimate seems to work the best in the considered metallicity and radiation field strength range, even when the overall virial parameter of the cloud is above the equilibrium value. This is explained by a systematically lower virial parameter (I.e. closer to equilibrium) in the CO-emitting regions; in CO emission, clouds might seem (sub-)virial, even when, in fact, they are expanding or being dispersed. A single CO-to-H2 conversion factor appears to be a robust choice over relatively wide ranges of cloud conditions, unless the metallicity is low. The methods which try to take the metallicity dependence of the conversion factor into account tend to systematically overestimate the true cloud masses.

  14. Exchangers man the pumps: Functional interplay between proton pumps and proton-coupled Ca exchangers.

    PubMed

    Barkla, Bronwyn J; Hirschi, Kendal D; Pittman, Jon K

    2008-05-01

    Tonoplast-localised proton-coupled Ca(2+) transporters encoded by cation/H(+)exchanger (CAX) genes play a critical role in sequestering Ca(2+) into the vacuole. These transporters may function in coordination with Ca(2+) release channels, to shape stimulus-induced cytosolic Ca(2+) elevations. Recent analysis of Arabidopsis CAX knockout mutants, particularly cax1 and cax3, identified a variety of phenotypes including sensitivity to abiotic stresses, which indicated that these transporters might play a role in mediating the plant's stress response. A common feature of these mutants was the perturbation of H(+)-ATPase activity at both the tonoplast and the plasma membrane, suggesting a tight interplay between the Ca(2+)/H(+) exchangers and H(+) pumps. We speculate that indirect regulation of proton flux by the exchangers may be as important as the direct regulation of Ca(2+) flux. These results suggest cautious interpretation of mutant Ca(2+)/H(+) exchanger phenotypes that may be due to either perturbed Ca(2+) or H(+) transport.

  15. Preoperative evaluation of renal anatomy and renal masses with helical CT, 3D-CT and 3D-CT angiography.

    PubMed

    Toprak, Uğur; Erdoğan, Aysun; Gülbay, Mutlu; Karademir, Mehmet Alp; Paşaoğlu, Eşref; Akar, Okkeş Emrah

    2005-03-01

    The aim of this prospective study was to determine the efficacy of three-dimensional computed tomography (3D-CT) and three-dimensional computed tomographic angiography (3D-CTA) that were reconstructed by using the axial images of the multiphasic helical CT in the preoperative evaluation of renal masses and demonstration of renal anatomy. Twenty patients that were suspected of having renal masses upon initial physical examination and ultrasonographic evaluation were examined through multiphasic helical CT. Two authors executed CT evaluations. Axial images were first examined and then used to reconstruct 3D-CT and 3D- CTA images. Number, location and size of the renal masses and other findings were noted. Renal vascularization and relationships of the renal masses with the neighboring renal structures were further investigated with 3D-CT and 3D-CTA images. Out of 20 patients, 13 had histopathologically proven renal cell carcinoma. The diagnoses of the remaining seven patients were xanthogranulomatous pyelonephritis, abscess, simple cyst, infected cyst, angiomyolipoma, oncocytoma and arteriovenous fistula. In the renal cell carcinoma group, 3 patients had stage I, 7 patients had stage II, and 3 patients had stage III disease. Sizes of renal cell carcinoma masses were between 23 mm to 60 mm (mean, 36 mm). Vascular invasion was shown in 2 renal cell carcinoma patients. Collecting system invasion was identified in 11 of 13 renal cell patients. These radiologic findings were confirmed with surgical specimens. Three-dimensional CT and 3D-CTA are non-invasive, effective imaging techniques for the preoperative evaluation of renal masses.

  16. The D/H ratio in Saturn's atmosphere from Voyager IRIS spectra

    NASA Technical Reports Server (NTRS)

    Courtin, R.; Gautier, D.; Marten, A.; Bezard, B.; Hanel, R.

    1985-01-01

    A selection of 1656 spectra recorded between 180 and 2300 mm in the 20 to 40 N latitude range by the Voyager interferometer IRIS were analyzed. The CH3D/H2 and CH4/H2 ratios are determined from a best fit of the radiances measured in the nu6 and nu4 fundamental bands, respectively centered at 1161 and 1304 mm. Results are CH3D/H2 = 3.9 + or - 2.5 times 10 to the minus 7th power and CH4/H2 = 4.5 + 2.4, -1.9 x 0.001. The uncertainty includes random errors due to instrumental noise and possible systematic errors in the assumed temperature profile and spectroscopic parameters. The D/H isotopic ratio is determined from abundance ratios from the expression D/H = 1/4f (CH3D/H2)/(CH4/H2) where f accounts for equilibrium deuterium fractionation between the molecular hydrogen and methane phases. Beer and Taylor (1973, 1978) estimated f = 1.37 + or - 0.07 for Jupiter assuming a wide range of convective velocities and neglecting catalytic effects from dust particles. The same value was adopted for Saturn and yields D/H = 1.6 +1.3, -1.2 times 10 to the minus 5th power.

  17. In-pore exchange and diffusion of carbonate solvent mixtures in nanoporous carbon

    DOE PAGES

    Alam, Todd M.; Osborn Popp, Thomas M.

    2016-06-04

    High resolution magic angle spinning (HRMAS) 1H NMR spectroscopy has been used to resolve different surface and in-pore solvent environments of ethylene carbonate (EC) and dimethyl carbonate (DMC) mixtures absorbed within nanoporous carbon (NPC). Two dimensional (2D) 1H HRMAS NMR exchange measurements revealed that the inhomogeneous broadened in-pore resonances have pore-to-pore exchange rates on the millisecond timescale. Pulsed-field gradient (PFG) NMR diffusometry revealed the in-pore self-diffusion constants for both EC and DMC were reduced by up to a factor of five with respect to the diffusion in the non-absorbed solvent mixtures.

  18. High sodium intake increases HCO3− absorption in medullary thick ascending limb through adaptations in basolateral and apical Na+/H+ exchangers

    PubMed Central

    George, Thampi; Watts, Bruns A.

    2011-01-01

    A high sodium intake increases the capacity of the medullary thick ascending limb (MTAL) to absorb HCO3−. Here, we examined the role of the apical NHE3 and basolateral NHE1 Na+/H+ exchangers in this adaptation. MTALs from rats drinking H2O or 0.28 M NaCl for 5–7 days were perfused in vitro. High sodium intake increased HCO3− absorption rate by 60%. The increased HCO3− absorptive capacity was mediated by an increase in apical NHE3 activity. Inhibiting basolateral NHE1 with bath amiloride eliminated 60% of the adaptive increase in HCO3− absorption. Thus the majority of the increase in NHE3 activity was dependent on NHE1. A high sodium intake increased basolateral Na+/H+ exchange activity by 89% in association with an increase in NHE1 expression. High sodium intake increased apical Na+/H+ exchange activity by 30% under conditions in which basolateral Na+/H+ exchange was inhibited but did not change NHE3 abundance. These results suggest that high sodium intake increases HCO3− absorptive capacity in the MTAL through 1) an adaptive increase in basolateral NHE1 activity that results secondarily in an increase in apical NHE3 activity; and 2) an adaptive increase in NHE3 activity, independent of NHE1 activity. These studies support a role for NHE1 in the long-term regulation of renal tubule function and suggest that the regulatory interaction whereby NHE1 enhances the activity of NHE3 in the MTAL plays a role in the chronic regulation of HCO3− absorption. The adaptive increases in Na+/H+ exchange activity and HCO3− absorption in the MTAL may play a role in enabling the kidneys to regulate acid-base balance during changes in sodium and volume balance. PMID:21613418

  19. Theoretical/experimental comparison of deep tunneling decay of quasi-bound H(D)OCO to H(D) + CO₂.

    PubMed

    Wagner, Albert F; Dawes, Richard; Continetti, Robert E; Guo, Hua

    2014-08-07

    The measured H(D)OCO survival fractions of the photoelectron-photofragment coincidence experiments by the Continetti group are qualitatively reproduced by tunneling calculations to H(D) + CO2 on several recent ab initio potential energy surfaces for the HOCO system. The tunneling calculations involve effective one-dimensional barriers based on steepest descent paths computed on each potential energy surface. The resulting tunneling probabilities are converted into H(D)OCO survival fractions using a model developed by the Continetti group in which every oscillation of the H(D)-OCO stretch provides an opportunity to tunnel. Four different potential energy surfaces are examined with the best qualitative agreement with experiment occurring for the PIP-NN surface based on UCCSD(T)-F12a/AVTZ electronic structure calculations and also a partial surface constructed for this study based on CASPT2/AVDZ electronic structure calculations. These two surfaces differ in barrier height by 1.6 kcal/mol but when matched at the saddle point have an almost identical shape along their reaction paths. The PIP surface is a less accurate fit to a smaller ab initio data set than that used for PIP-NN and its computed survival fractions are somewhat inferior to PIP-NN. The LTSH potential energy surface is the oldest surface examined and is qualitatively incompatible with experiment. This surface also has a small discontinuity that is easily repaired. On each surface, four different approximate tunneling methods are compared but only the small curvature tunneling method and the improved semiclassical transition state method produce useful results on all four surfaces. The results of these two methods are generally comparable and in qualitative agreement with experiment on the PIP-NN and CASPT2 surfaces. The original semiclassical transition state theory method produces qualitatively incorrect tunneling probabilities on all surfaces except the PIP. The Eckart tunneling method uses the least

  20. Evidence for Sequence Scrambling and Divergent H/D Exchange Reactions of Doubly-Charged Isobaric b-Type Fragment Ions

    NASA Astrophysics Data System (ADS)

    Zekavat, Behrooz; Miladi, Mahsan; Al-Fdeilat, Abdullah H.; Somogyi, Arpad; Solouki, Touradj

    2014-02-01

    To date, only a limited number of reports are available on structural variants of multiply-charged b-fragment ions. We report on observed bimodal gas-phase hydrogen/deuterium exchange (HDX) reaction kinetics and patterns for substance P b10 2+ that point to presence of isomeric structures. We also compare HDX reactions, post-ion mobility/collision-induced dissociation (post-IM/CID), and sustained off-resonance irradiation-collision induced dissociation (SORI-CID) of substance P b10 2+ and a cyclic peptide with an identical amino acid (AA) sequence order to substance P b10. The observed HDX patterns and reaction kinetics and SORI-CID pattern for the doubly charged head-to-tail cyclized peptide were different from either of the presumed isomers of substance P b10 2+, suggesting that b10 2+ may not exist exclusively as a head-to-tail cyclized structure. Ultra-high mass measurement accuracy was used to assign identities of the observed SORI-CID fragment ions of substance P b10 2+; over 30 % of the observed SORI-CID fragment ions from substance P b10 2+ had rearranged (scrambled) AA sequences. Moreover, post-IM/CID experiments revealed the presence of two conformer types for substance P b10 2+, whereas only one conformer type was observed for the head-to-tail cyclized peptide. We also show that AA sequence scrambling from CID of doubly-charged b-fragment ions is not unique to substance P b10 2+.

  1. Evidence for sequence scrambling and divergent H/D exchange reactions of doubly-charged isobaric b-type fragment ions.

    PubMed

    Zekavat, Behrooz; Miladi, Mahsan; Al-Fdeilat, Abdullah H; Somogyi, Arpad; Solouki, Touradj

    2014-02-01

    To date, only a limited number of reports are available on structural variants of multiply-charged b-fragment ions. We report on observed bimodal gas-phase hydrogen/deuterium exchange (HDX) reaction kinetics and patterns for substance P b10(2+) that point to presence of isomeric structures. We also compare HDX reactions, post-ion mobility/collision-induced dissociation (post-IM/CID), and sustained off-resonance irradiation-collision induced dissociation (SORI-CID) of substance P b10(2+) and a cyclic peptide with an identical amino acid (AA) sequence order to substance P b10. The observed HDX patterns and reaction kinetics and SORI-CID pattern for the doubly charged head-to-tail cyclized peptide were different from either of the presumed isomers of substance P b10(2+), suggesting that b10(2+) may not exist exclusively as a head-to-tail cyclized structure. Ultra-high mass measurement accuracy was used to assign identities of the observed SORI-CID fragment ions of substance P b10(2+); over 30% of the observed SORI-CID fragment ions from substance P b10(2+) had rearranged (scrambled) AA sequences. Moreover, post-IM/CID experiments revealed the presence of two conformer types for substance P b10(2+), whereas only one conformer type was observed for the head-to-tail cyclized peptide. We also show that AA sequence scrambling from CID of doubly-charged b-fragment ions is not unique to substance P b10(2+).

  2. Mapping the contact surfaces in the Lamin A:AIMP3 complex by hydrogen/deuterium exchange FT-ICR mass spectrometry.

    PubMed

    Tao, Yeqing; Fang, Pengfei; Kim, Sunghoon; Guo, Min; Young, Nicolas L; Marshall, Alan G

    2017-01-01

    Aminoacyl-tRNA synthetases-interacting multifunctional protein3 (AIMP3/p18) is involved in the macromolecular tRNA synthetase complex via its interaction with several aminoacyl-tRNA synthetases. Recent reports reveal a novel function of AIMP3 as a tumor suppressor by accelerating cellular senescence and causing defects in nuclear morphology. AIMP3 specifically mediates degradation of mature Lamin A (LmnA), a major component of the nuclear envelope matrix; however, the mechanism of how AIMP3 interacts with LmnA is unclear. Here we report solution-phase hydrogen/deuterium exchange (HDX) for AIMP3, LmnA, and AIMP3 in association with the LmnA C-terminus. Reversed-phase LC coupled with LTQ 14.5 T Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) results in high mass accuracy and resolving power for comparing the D-uptake profiles for AIMP3, LmnA, and their complex. The results show that the AIMP3-LmnA interaction involves one of the two putative binding sites and an adjacent novel interface on AIMP3. LmnA binds AIMP3 via its extreme C-terminus. Together these findings provide a structural insight for understanding the interaction between AIMP3 and LmnA in AIMP3 degradation.

  3. Separation of 'Uncharged' Oligodeoxynucleotide Analogs by Anion-Exchange Chromatography at High pH

    NASA Technical Reports Server (NTRS)

    Schmidt, Jurgen G.; Orgel, Leslie E.; Nielsen, Peter E.

    1996-01-01

    Ion-exchange chromatography is a well-established method for the analysis and purification of phosphodiester-linked oligonucleotides. If elution is carried out under alkaline conditions, the secondary structure of G- and C-rich oligomers is disrupted. Furthermore, elution times become more sensitive to the G and T content of the oligomer, because G and T are deprotonated at pH 10. In recent work on peptide-nucleic acids (PNAs) we noted that mixtures of PNA oligomers G(sub 4), G(sub 6), G(sub 8), and G9(sub 10) are readily separated by elution at pH 12 on an RPC-5 column. Here we show that this separation method is more generally applicable.

  4. Separation of Uncharged Oligodeoxynucleotide Analogs by Anion-Exchange Chromatography at High pH

    NASA Technical Reports Server (NTRS)

    Schmidt, Jurgen G.; Nielsen, Peter E.; Orgel, Leslie

    1996-01-01

    Ion-exchange chromatography is a well-established method for the analysis and purification of phosphodiester-linked oligonucleotides. If elution is carried out under alkaline conditions, the secondary structure of G- and C-rich oligomers is disrupted. Furthermore, elution times become more sensitive to the G and T content of the oligomer, because G and T are deprotonated at pH 10. In recent work on peptide-nucleic acids (PNAs) we noted that mixtures of PNA oligomers G(sub 4), G(Sub 6), G(sub 8), and G(sub 10) are readily separated by elution at pH 12 on an RPC-5 column. Here we show that this separation method is more generally applicable.

  5. 77 FR 29694 - Richard H. NG, D.O.; Decision and Order

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-05-18

    ... DEPARTMENT OF JUSTICE Drug Enforcement Administration [Docket No. 12-19] Richard H. NG, D.O....100(b), I order that DEA Certificate of Registration AN1255733, issued to Richard H. Ng, D.O., be, and it hereby is, revoked. I further order that any pending application of Richard H. Ng, D.O., to renew...

  6. Molecular Dynamics Simulations Provide Atomistic Insight into Hydrogen Exchange Mass Spectrometry Experiments.

    PubMed

    Petruk, Ariel A; Defelipe, Lucas A; Rodríguez Limardo, Ramiro G; Bucci, Hernán; Marti, Marcelo A; Turjanski, Adrian G

    2013-01-08

    It is now clear that proteins are flexible entities that in solution switch between conformations to achieve their function. Hydrogen/Deuterium Exchange Mass Spectrometry (HX/MS) is an invaluable tool to understand dynamic changes in proteins modulated by cofactor binding, post-transductional modifications, or protein-protein interactions. ERK2MAPK, a protein involved in highly conserved signal transduction pathways of paramount importance for normal cellular function, has been extensively studied by HX/MS. Experiments of the ERK2MAPK in the inactive and active states (in the presence or absence of bound ATP) have provided valuable information on the plasticity of the MAPK domain. However, interpretation of the HX/MS data is difficult, and changes are mostly explained in relation to available X-ray structures, precluding a complete atomic picture of protein dynamics. In the present work, we have used all atom Molecular Dynamics simulations (MD) to provide a theoretical framework for the interpretation of HX/MS data. Our results show that detailed analysis of protein-solvent interaction along the MD simulations allows (i) prediction of the number of protons exchanged for each peptide in the HX/MS experiments, (ii) rationalization of the experimentally observed changes in exchange rates in different protein conditions at the residue level, and (iii) that at least for ERK2MAPK, most of the functionally observed differences in protein dynamics are related to what can be considered the native state conformational ensemble. In summary, the combination of HX/MS experiments with all atom MD simulations emerges as a powerful approach to study protein native state dynamics with atomic resolution.

  7. Cold quantum-controlled rotationally inelastic scattering of HD with H2 and D2 reveals collisional partner reorientation

    NASA Astrophysics Data System (ADS)

    Perreault, William E.; Mukherjee, Nandini; Zare, Richard N.

    2018-05-01

    Molecular interactions are best probed by scattering experiments. Interpretation of these studies has been limited by lack of control over the quantum states of the incoming collision partners. We report here the rotationally inelastic collisions of quantum-state prepared deuterium hydride (HD) with H2 and D2 using a method that provides an improved control over the input states. HD was coexpanded with its partner in a single supersonic beam, which reduced the collision temperature to 0-5 K, and thereby restricted the involved incoming partial waves to s and p. By preparing HD with its bond axis preferentially aligned parallel and perpendicular to the relative velocity of the colliding partners, we observed that the rotational relaxation of HD depends strongly on the initial bond-axis orientation. We developed a partial-wave analysis that conclusively demonstrates that the scattering mechanism involves the exchange of internal angular momentum between the colliding partners. The striking differences between H2/HD and D2/HD scattering suggest the presence of anisotropically sensitive resonances.

  8. Diode laser spectroscopy of the MnD radical ( 7Σ) and the determination of mass-independent parameters

    NASA Astrophysics Data System (ADS)

    Urban, Rolf-Dieter; Jones, Harold

    1991-03-01

    The infrared spectrum of the manganese deuteride radical has been observed in its ground electronic state ( 7Σ) using a diode-laser spectrometer. The hyperfine structure of a number of infrared transitions in the bands ν=1←0, ν=2←1 and ν=3←2 were measured with a nominal accuracy of ±0.001 cm -1. In all cases, the complete structure was easily resolved. Dunham parameters, spin—rotation and spin—spin coupling parameters were determined from the MnD data. A simultaneous fit of these data with those determined previously for MnH was carried out to determine mass-independent parameters and mass-scaling coefficients.

  9. Calculating the Ionization Constant of Functional Groups of Carboxyl Ion Exchangers

    NASA Astrophysics Data System (ADS)

    Meychik, N. R.; Stepanov, S. I.; Nikolaeva, Yu. I.

    2018-02-01

    The potentiometric titration of a weakly basic carboxyl cation exchanger, obtained via alkaline hydrolysis of an acrylonitrile copolymer with divinyl benzene (degree of crosslinking, 12%) in a wide range of variation in a solution of pH (2-12) and NaCl (concentration 0.01, 0.1, 0.5, 1 M), is considered. The maximum ion-exchange capacity of the ion exchanger for Na+ is determined (10.10 ± 0.088 mmol/g of the dry mass) and found to be independent of the solution's ionic strength. It is established that in the investigated range of NaCl concentrations and pH, the acid-base balance is adequately described by Gregor's equation. The parameters of this equation are calculated as a function of the NaCl concentration: p K a = 8.13 ± 0.04, n = 1.50 ± 0.02 for 0.01 M; p K a = 6.56 ± 0.04, n = 2.60 ± 0.07 for 0.1 M; and p K a = 5.66 ± 0.6, n = 2.62 ± 0.06 for 0.5 and 1 M. It is shown that to describe the acid-base balance correctly within the proposed model we must estimate the adequacy of the experimental and calculated values of the ion exchanger's capacity at each pH value according to the calculated parameters of Gregor's equation.

  10. Infrared Spectroscopy of the H2/HD/D2-O2 Van Der Waals Complexes

    NASA Astrophysics Data System (ADS)

    Raston, Paul; Bunn, Hayley

    2016-06-01

    Hydrogen is the most abundant element in the universe and oxygen is the third, so understanding the interaction between the two in their different forms is important to understanding astrochemical processes. The interaction between H2 and O2 has been explored in low energy scattering experiments and by far infrared synchrotron spectroscopy of the van der Waals complex. The far infrared spectra suggest a parallel stacked average structure with seven bound rotationally excited states. Here, we present the far infrared spectrum of HD/D2-O2 and the mid infrared spectrum of H2-O2 at 80 K, recorded at the infrared beamline facility of the Australian Synchrotron. We observed 'sharp' peaks in the mid infrared region, corresponding to the end over end rotation of H2-O2, that are comparatively noisier than analogous peaks in the far infrared where the synchrotron light is brightest. The larger reduced mass of HD and D2 compared to H2 is expected to result in more rotational bound states and narrower bands. The latest results in our ongoing efforts to explore this system will be presented. Y. Kalugina, et al., Phys. Chem. Chem. Phys. 14, 16458 (2012) S. Chefdeville et al. Science 341, 1094 (2013) H. Bunn et al. ApJ 799, 65 (2015)

  11. Performance evaluation of elemental analysis/isotope ratio mass spectrometry methods for the determination of the D/H ratio in tetramethylurea and other compounds--results of a laboratory inter-comparison.

    PubMed

    Bréas, Olivier; Thomas, Freddy; Zeleny, Reinhard; Calderone, Giovanni; Jamin, Eric; Guillou, Claude

    2007-01-01

    Tetramethylurea (TMU) with a certified D/H ratio is the internal standard for Site-specific Natural Isotope Fractionation measured by Nuclear Magnetic Resonance (SNIF-NMR) analysis of wine ethanol for detection of possible adulterations (Commission Regulation 2676/90). A new batch of a TMU certified reference material (CRM) is currently being prepared. Whereas SNIF-NMR has been employed up to now, Elemental Analysis/Isotope Ratio Mass Spectrometry ((2)H-EA-IRMS) was envisaged as the method of choice for value assignment of the new CRM, as more precise (better repeatable) data might be obtained, resulting in lower uncertainty of the certified value. In order to evaluate the accuracy and intra- and inter-laboratory reproducibility of (2)H-EA-IRMS methods, a laboratory inter-comparison was carried out by analysing TMU and other organic compounds, as well as some waters. The results revealed that experienced laboratories are capable of generating robust and well comparable data, which highlights the emerging potential of IRMS in food authenticity testing. However, a systematic bias between IRMS and SNIF-NMR reference data was observed for TMU; this lack of data consistency rules out the (2)H-IRMS technique for the characterisation measurement of the new TMU CRM.

  12. Acid/Salt/pH Gradient Improved Resolution and Sensitivity in Proteomics Study Using 2D SCX-RP LC-MS.

    PubMed

    Zhu, Ming-Zhi; Li, Na; Wang, Yi-Tong; Liu, Ning; Guo, Ming-Quan; Sun, Bao-Qing; Zhou, Hua; Liu, Liang; Wu, Jian-Lin

    2017-09-01

    The usage of strong cation exchange (SCX) chromatography in proteomics is limited by its poor resolution and nonspecific hydrophobic interactions with peptides, which lead to peptide overlap across fractions and change of peptide retention, respectively. The application of high concentration of salt (up to 1000 mM) in SCX also restricted its use in online 2D SCX-RP LC. In the present research, we first exploited the chromatographic ability of online 2D SCX-RP LC by combination of acid, salt, and pH gradient, three relatively independent modes of eluting peptides from SCX column. 50% ACN was added to elution buffer for eliminating hydrophobic interactions between SCX matrix and peptides, and the concentration of volatile salt was reduced to 50 mM. Acid/salt/pH gradient showed superior resolution and sensitivity as well as uniform distribution across fractions, consequently leading to significant improvements in peptide and protein identification. 112 191 unique peptides and 7373 proteins were identified by acid/salt/pH fractionation, while 69 870 unique peptides and 4536 proteins were identified by salt elution, that is, 62.5 and 60.6% more proteins and unique peptides, respectively, identified by the former. Fraction overlap was also significantly minimized by acid/salt/pH approach. Furthermore, acid/salt/pH elution showed more identification for acidic peptides and hydrophilic peptides.

  13. Gauge boson exchange in AdS d+1

    NASA Astrophysics Data System (ADS)

    D'Hoker, Eric; Freedman, Daniel Z.

    1999-04-01

    We study the amplitude for exchange of massless gauge bosons between pairs of massive scalar fields in anti-de Sitter space. In the AdS/CFT correspondence this amplitude describes the contribution of conserved flavor symmetry currents to 4-point functions of scalar operators in the boundary conformal theory. A concise, covariant, Y2K compatible derivation of the gauge boson propagator in AdS d + 1 is given. Techniques are developed to calculate the two bulk integrals over AdS space leading to explicit expressions or convenient, simple integral representations for the amplitude. The amplitude contains leading power and sub-leading logarithmic singularities in the gauge boson channel and leading logarithms in the crossed channel. The new methods of this paper are expected to have other applications in the study of the Maldacena conjecture.

  14. Concerted hydrogen atom exchange between three HF molecules

    NASA Technical Reports Server (NTRS)

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

    1992-01-01

    We have investigated the termolecular reaction involving concerted hydrogen exchange between three HF molecules, with particular emphasis on the effects of correlation at the various stationary points along the reaction. Using an extended basis, we have located the geometries of the stable hydrogen-bonded trimer, which is of C(sub 3h) symmetry, and the transition state for hydrogen exchange, which is of D(sub 3h) symmetry. The energies of the exchange reation were then evaluated at the correlated level, using a large atomic natural orbital basis and correlating all valence electrons. Several correlation treatments were used, namely, configration interaction with single and double excitations, coupled-pair functional, and coupled-cluster methods. We are thus able to measure the effect of accounting for size-extensivity. Zero-point corrections to the correlated level energetics were determined using analytic second derivative techniques at the SCF level. Our best calculations, which include the effects of connected triple excitations in the coupled-cluster procedure, indicate that the trimer is bound by 9 +/- 1 kcal/mol relative to three separate monomers, in excellent agreement with previous estimates. The barrier to concerted hydrogen exchange is 15 kcal/mol above the trimer, or only 4.7 kcal/mol above three separated monomers. Thus the barrier to hydrogen exchange between HF molecules via this termolecular process is very low.

  15. 14. Photocopy of photograph. Horgan, 1922. Negative #D & H ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    14. Photocopy of photograph. Horgan, 1922. Negative #D & H 22413 Original negative can be found in D & H collection of the Anthracite Heritage Museum, Scranton, Pennsylvania. VIEW SHOWING EAST FACADE OF BREAKER, WITH RETAIL SCALES OFFICE IN FOREGROUND, LOOKING WEST - Marvine Colliery, Breaker No. 2, West side Boulevard Avenue, between East Parker Street & Route 380, Scranton, Lackawanna County, PA

  16. NHE10, a novel osteoclast-specific member of the Na{sup +}/H{sup +} exchanger family, regulates osteoclast differentiation and survival

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

    Lee, Seoung Hoon; Kim, Taesoo; Park, Eui-Soon

    2008-05-02

    Bone homeostasis is tightly regulated by the balanced actions of osteoblasts (OBs) and osteoclasts (OCs). We previously analyzed the gene expression profile of OC differentiation using a cDNA microarray, and identified a novel osteoclastogenic gene candidate, clone OCL-1-E7 [J. Rho, C.R. Altmann, N.D. Socci, L. Merkov, N. Kim, H. So, O. Lee, M. Takami, A.H. Brivanlou, Y. Choi, Gene expression profiling of osteoclast differentiation by combined suppression subtractive hybridization (SSH) and cDNA microarray analysis, DNA Cell Biol. 21 (2002) 541-549]. In this study, we have isolated full-length cDNAs corresponding to this clone from mice and humans to determine the functionalmore » roles of this gene in osteoclastogenesis. The full-length cDNA of OCL-1-E7 encodes 12 membrane-spanning domains that are typical of isoforms of the Na{sup +}/H{sup +} exchangers (NHEs), indicating that this clone is a novel member of the NHE family (hereafter referred to as NHE10). Here, we show that NHE10 is highly expressed in OCs in response to receptor activator of nuclear factor-{kappa}B ligand signaling and is required for OC differentiation and survival.« less

  17. Fourier transform spectroscopy of MnH and MnD

    NASA Astrophysics Data System (ADS)

    Balfour, W. J.; Launila, O.; Klynning, L.

    Two infrared band systems, centred near 846 nm and 1060 nm in both MnH and MnD have been rotationally analysed and shown to have a common lower state. The electronic transitions lie within the quintet manifold and are here designated c 5Σ-a 5Σ and b 5Πi-a 5Σ for the 846 and 1060 nm systems, respectively. In the 846 nm system in MnH all 10 main branches have been found in the 0-0 and 1-1 bands, while in MnD the data are complete only for 0-0. Satellite branches have been identified in the 1060 nm system and all spin and Λ-type doublings have been established. The number of assigned 0-0 branches in the 1060 nm system is 35 for MnH and 37 for MnD. Molecular constants have been determined for all three states involved. Λ-doubling diagrams are presented for b 5Πi state with v = 1, 2 levels in MnH and with the v = 2 level in MnD. Local perturbations in c5Σ (v = 1) in MnH are suspected to originate from the v = 3 level of b 5Πi.

  18. On Estimating the Mass of Keplerian Accretion Disks in H2O Maser Galaxies

    NASA Astrophysics Data System (ADS)

    Kuo, C. Y.; Reid, M. J.; Braatz, J. A.; Gao, F.; Impellizzeri, C. M. V.; Chien, W. T.

    2018-06-01

    H2O maser disks with Keplerian rotation in active galactic nuclei offer a clean way to determine accurate black hole mass and the Hubble constant. An important assumption made in using a Keplerian H2O maser disk for measuring black hole mass and the Hubble constant is that the disk mass is negligible compared to the black hole mass. A simple and useful model of Huré et al. can be used to test this assumption. In that work, the authors apply a linear disk model to a position–dynamical mass diagram and re-analyze position–velocity data from H2O maser disks associated with active galactic nuclei. They claim that a maser disk with nearly perfect Keplerian rotation could have a disk mass comparable to the black hole mass. This would imply that ignoring the effects of disk self-gravity can lead to large systematic errors in the measurement of black hole mass and the Hubble constant. We examine their methods and find that their large estimated disk masses of Keplerian disks are likely the result of their use of projected instead of three-dimensional position and velocity information. To place better constraints on the disk masses of Keplerian maser systems, we incorporate disk self-gravity into a three-dimensional Bayesian modeling program for maser disks and also evaluate constraints based on the physical conditions for disks that support water maser emission. We find that there is little evidence that disk masses are dynamically important at the ≲1% level compared to the black holes.

  19. ClC-7 is a slowly voltage-gated 2Cl−/1H+-exchanger and requires Ostm1 for transport activity

    PubMed Central

    Leisle, Lilia; Ludwig, Carmen F; Wagner, Florian A; Jentsch, Thomas J; Stauber, Tobias

    2011-01-01

    Mutations in the ClC-7/Ostm1 ion transporter lead to osteopetrosis and lysosomal storage disease. Its lysosomal localization hitherto precluded detailed functional characterization. Using a mutated ClC-7 that reaches the plasma membrane, we now show that both the aminoterminus and transmembrane span of the Ostm1 β-subunit are required for ClC-7 Cl−/H+-exchange, whereas the Ostm1 transmembrane domain suffices for its ClC-7-dependent trafficking to lysosomes. ClC-7/Ostm1 currents were strongly outwardly rectifying owing to slow gating of ion exchange, which itself displays an intrinsically almost linear voltage dependence. Reversal potentials of tail currents revealed a 2Cl−/1H+-exchange stoichiometry. Several disease-causing CLCN7 mutations accelerated gating. Such mutations cluster to the second cytosolic cystathionine-β-synthase domain and potential contact sites at the transmembrane segment. Our work suggests that gating underlies the rectification of all endosomal/lysosomal CLCs and extends the concept of voltage gating beyond channels to ion exchangers. PMID:21527911

  20. OT1_ebergin_5: A Systematic Survery of the Water D to H Ratio in Hot Molecular Cores

    NASA Astrophysics Data System (ADS)

    Bergin, E.

    2010-07-01

    The D/H ratio of water and the enrichment of HDO relative to H2O in comets, oceans, and interstellar water vapor, has been posited as one of the primary links between chemistry in the cold (T = 10-20 K) dense interstellar medium (ISM) and chemistry in the Solar Nebula. However, there are only ~10 measurements of HDO/H2O, even in hot (T > 100 K) molecular cores, which have the most favorable chemistry (due to fossil evaporation of D-enriched ices) and excitation. In addition the existing measurements have a wide range of uncertainty, making it impossible to discern the presence of source-to-source variations, which could hint at the origin of deuterium enrichments in the dense ISM. We propose here to change this statistic with a systematic survey of HDO and H2O in a sample of 20 hot molecular cores spanning a two order of magnitude range in mass and luminosity. This will increase the number of known water D/H ratios by ~200%. This program is unique in scope for Herschel and requires the uniformity in calibration and high spectral resolution offered by the HIFI instrument. With the stability of HIFI we will be able to derive D/H ratios with significantly less uncertainty. Our observations will be combined with theoretical chemical models to explore the statistics offered by this sample. By looking at a large number of objects with a range of conditions we aim to unlock the secrets of water deuteration in the interstellar space.

  1. A role for Na+/H+ exchange in contraction of guinea pig airways by endothelin-1 in vitro.

    PubMed

    Battistini, B; Filep, J G; Cragoe, E J; Fournier, A; Sirois, P

    1991-03-15

    Endothelin-1-induced contractions of guinea pig tracheal and bronchial strips were dose-dependently attenuated by the amiloride analogues 5-(N-ethyl-N-isopropyl)amiloride (EIPA, 1-10 microM) and 5-(N,N-hexamethylene)amiloride (HMA, 1-10 microM). The calculated Ki values for EIPA and HMA were 0.11 +/- 0.02 microM and 0.06 +/- 0.02 microM in the trachea, and 0.28 +/- 0.11 microM and 0.70 +/- 0.25 microM in the bronchus, respectively. These values are in the same order of magnitude as those reported for inhibition of the Na+/H+ exchange in cells. Amiloride (1-10 microM) was ineffective. These data suggest that activation of the Na+/H+ exchange by ET-1 may be involved in mediating its myotropic action in guinea pig airway smooth muscle.

  2. A decadal time series of water vapor and D / H isotope ratios above Zugspitze: transport patterns to central Europe

    NASA Astrophysics Data System (ADS)

    Hausmann, Petra; Sussmann, Ralf; Trickl, Thomas; Schneider, Matthias

    2017-06-01

    We present vertical soundings (2005-2015) of tropospheric water vapor (H2O) and its D / H isotope ratio (δD) derived from ground-based solar Fourier transform infrared (FTIR) measurements at Zugspitze (47° N, 11° E, 2964 m a.s.l.). Beside water vapor profiles with optimized vertical resolution (degrees of freedom for signal, DOFS, = 2.8), {H2O, δD} pairs with consistent vertical resolution (DOFS = 1.6 for H2O and δD) applied in this study. The integrated water vapor (IWV) trend of 2.4 [-5.8, 10.6] % decade-1 is statistically insignificant (95 % confidence interval). Under this caveat, the IWV trend estimate is conditionally consistent with the 2005-2015 temperature increase at Zugspitze (1.3 [0.5, 2.1] K decade-1), assuming constant relative humidity. Seasonal variations in free-tropospheric H2O and δD exhibit amplitudes of 140 and 50 % of the respective overall means. The minima (maxima) in January (July) are in agreement with changing sea surface temperature of the Atlantic Ocean. Using extensive backward-trajectory analysis, distinct moisture pathways are identified depending on observed δD levels: low column-based δD values (δDcol < 5th percentile) are associated with air masses originating at higher latitudes (62° N on average) and altitudes (6.5 km)than high δD values (δDcol > 95th percentile: 46° N, 4.6 km). Backward-trajectory classification indicates that {H2O, δD} observations are influenced by three long-range-transport patterns towards Zugspitze assessed in previous studies: (i) intercontinental transport from North America (TUS; source region: 25-45° N, 70-110° W, 0-2 km altitude), (ii) intercontinental transport from northern Africa (TNA; source region: 15-30° N, 15° W-35° E, 0-2 km altitude), and (iii) stratospheric air intrusions (STIs; source region: > 20° N, above zonal mean tropopause). The FTIR data exhibit significantly differing signatures in free-tropospheric {H2O, δD} pairs (5 km a.s.l.) - given as the mean with

  3. Modified ion exchange separation for tungsten isotopic measurements from kimberlite samples using multi-collector inductively coupled plasma mass spectrometry.

    PubMed

    Sahoo, Yu Vin; Nakai, Shun'ichi; Ali, Arshad

    2006-03-01

    Tungsten isotope composition of a sample of deep-seated rock can record the influence of core-mantle interaction of the parent magma. Samples of kimberlite, which is known as a carrier of diamond, from the deep mantle might exhibit effects of core-mantle interaction. Although tungsten isotope anomaly was reported for kimberlites from South Africa, a subsequent investigation did not verify the anomaly. The magnesium-rich and calcium-rich chemical composition of kimberlite might engender difficulty during chemical separation of tungsten for isotope analyses. This paper presents a simple, one-step anion exchange technique for precise and accurate determination of tungsten isotopes in kimberlites using multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). Large quantities of Ca and Mg in kimberlite samples were precipitated and removed with aqueous H(2)SO(4). Highly pure fractions of tungsten for isotopic measurements were obtained following an anion exchange chromatographic procedure involving mixed acids. That procedure enabled efficient removal of high field strength elements (HFSE), such as Hf, Zr and Ti, which are small ions that carry strong charges and develop intense electrostatic fields. The tungsten yields were 85%-95%. Advantages of this system include less time and less use of reagents. Precise and accurate isotopic measurements are possible using fractions of tungsten that are obtained using this method. The accuracy and precision of these measurements were confirmed using various silicate standard rock samples, JB-2, JB-3 and AGV-1.

  4. D/H Ratios From Sierra Nevada Varved Lake Sediments Record Decadal Hydroclimate Variability During The Medieval Period

    NASA Astrophysics Data System (ADS)

    Roach, L. D.; Cayan, D. R.; Sessions, A. L.; Charles, C. D.; Anderson, R. S.

    2009-12-01

    Assessment of the risks of persistent drought requires multiple realizations of decadal and centennial scale hydroclimate variability that extend beyond the relatively short period of instrumental record. Much remains to be learned about the so called “mega droughts” in the Sierra Nevada Mountains, where various lines of evidence point toward the occurrence of severe, decades-long droughts during Medieval times, approximately 900-1400 AD. Here we present a continuous, decadal scale record of hydroclimate variability in the Sierra Nevada Mountains that extends through the heart of the purported Medieval mega droughts. Previous work on the stable hydrogen isotope (D/H) ratios of refractory plant lipid compounds stored in lake sediments demonstrated that these compounds reflect the D/H values of lake water and/or shallow ground water--reservoirs both fed by local precipitation. Lake sediment D/H can therefore reflect the processes that determine D/H of precipitation, including temperature, humidity and moisture source. We have measured D/H of aquatic and terrestrial plant fatty acids extracted from a suite of sediment cores collected at Swamp Lake (elevation: 1554m), in Yosemite National Park, along the Sierra Nevada crest. Measurements with biennial resolution were made for two time periods: the 20th century and the 13th-15th centuries. D/H fluctuations in 20th century sediment contain relatively strong decadal structure. Comparison with instrumentally recorded climate variability reveals that lower D/H concentrations are associated with years of higher than normal annual precipitation, cooler than normal wintertime temperatures, and positive April 1 Snow Water Equivalent (SWE) anomalies throughout the Sierra Nevada, (and conversely for elevated D/H concentrations). The range of variability is approximately 50‰. These associations may be driven by the variable mass-balance impact of evaporation on the isotopic composition of lake water and shallow groundwater

  5. The use of 1H NMR microscopy to study proton-exchange membrane fuel cells.

    PubMed

    Feindel, Kirk W; Bergens, Steven H; Wasylishen, Roderick E

    2006-01-16

    To understand proton-exchange membrane fuel cells (PEMFCs) better, researchers have used several techniques to visualize their internal operation. This Concept outlines the advantages of using 1H NMR microscopy, that is, magnetic resonance imaging, to monitor the distribution of water in a working PEMFC. We describe what a PEMFC is, how it operates, and why monitoring water distribution in a fuel cell is important. We will focus on our experience in constructing PEMFCs, and demonstrate how 1H NMR microscopy is used to observe the water distribution throughout an operating hydrogen PEMFC. Research in this area is briefly reviewed, followed by some comments regarding challenges and anticipated future developments.

  6. A critical review of period analyses and implications for mass exchange in W UMa eclipsing binaries: Paper 3

    NASA Astrophysics Data System (ADS)

    Nelson, R. H.; Terrell, D.; Milone, E. F.

    2016-02-01

    This is the third of a series of four papers, the goal of which is to identify the overcontact eclipsing binary star systems for which a solid case can be made for mass exchange. To reach this goal, it is necessary first to identify those systems for which there is a strong case for period change. We have identified 60 candidate systems; in the first two papers (Nelson et al. 2014, 2016) we discussed 40 individual cases; this paper continues with the last 20. For each system, we present a detailed discussion and evaluation concerning the observational and interpretive material presented in the literature. At least one eclipse timing (ET) diagram, commonly referred to as an "O-C diagram", that includes the latest available data, accompanies each discussion. In paper 4, we will discuss the mechanisms that can cause period change and which of the 60 systems can be reliably concluded to exhibit mass exchange; we will also provide a list of marginal and rejected cases - suitable for future work.

  7. Compact hydrogen/helium isotope mass spectrometer

    DOEpatents

    Funsten, Herbert O.; McComas, David J.; Scime, Earl E.

    1996-01-01

    The compact hydrogen and helium isotope mass spectrometer of the present invention combines low mass-resolution ion mass spectrometry and beam-foil interaction technology to unambiguously detect and quantify deuterium (D), tritium (T), hydrogen molecule (H.sub.2, HD, D.sub.2, HT, DT, and T.sub.2), .sup.3 He, and .sup.4 He concentrations and concentration variations. The spectrometer provides real-time, high sensitivity, and high accuracy measurements. Currently, no fieldable D or molecular speciation detectors exist. Furthermore, the present spectrometer has a significant advantage over traditional T detectors: no confusion of the measurements by other beta-emitters, and complete separation of atomic and molecular species of equivalent atomic mass (e.g., HD and .sup.3 He).

  8. Analysis of Hydrogen Isotopic Exchange: Lava Creek Tuff Ash and Isotopically Labeled Water

    NASA Astrophysics Data System (ADS)

    Ross, A. M.; Seligman, A. N.; Bindeman, I. N.; Nolan, G. S.

    2015-12-01

    Nolan and Bindeman (2013) placed secondarily hydrated ash from the 7.7 ka eruption of Mt. Mazama (δD=-149‰, 2.3wt% H2Ot) in isotopically labeled water (+650 ‰ δD, +56 ‰ δ18O) and observed that the H2Ot and δ18O values remained constant, but the δD values of ash increased with the surrounding water at 20, 40 and 70 °C. We expand on this work by conducting a similar experiment with ash from the 640 ka Lava Creek Tuff (LCT, δD of -128 ‰; 2.1 wt.% H2Ot) eruption of Yellowstone to see if significantly older glass (with a hypothesized gel layer on the surface shielding the interior from alteration) produces the same results. We have experiments running at 70, 24, and 5 °C, and periodically remove ~1.5 mg of glass to measure the δD (‰) and H2Ot (wt.%) of water extracted from the glass on a TC/EA MAT 253 continuous flow system. After 600 hours, the δD of the samples left at 5 and 24 °C remains at -128 ‰, but increased 8‰ for the 70 °C run series. However, there is no measurable change in wt.% of H2Ot, indicating that hydrogen exchange is not dictated by the addition of water. We are measuring and will report further progress of isotope exchange. We also plan to analyze the water in the LCT glass for δ18O (‰) to see if, as is the case for the Mt. Mazama glass, the δ18O (‰) remains constant. We also analyzed Mt. Mazama glass from the Nolan and Bindeman (2013) experiments that have now been sitting in isotopically labeled water at room temperature for ~5 years. The water concentration is still unchanged (2.3 wt.% H2Ot), and the δD of the water in the glass is now -111 ‰, causing an increase of 38 ‰. Our preliminary results show that exchange of hydrogen isotopes of hydrated glass is not limited by the age of the glass, and that the testing of hydrogen isotopes of secondarily hydrated glass, regardless of age, may not be a reliable paleoclimate indicator.

  9. Mars atmospheric D/H - Consistent with polar volatile theory?

    NASA Technical Reports Server (NTRS)

    Jakosky, Bruce M.

    1990-01-01

    Current theories on the Martian water history are discussed on the basis of data for the D/H ratio in the Martian atmosphere (which was found to be enhanced by a factor of 6 + or - relative to the value on earth). In particular, the calculations of Yung et al. (1988), on the basis of their photochemical model, are found to be inconsistent with current theories for the evolution of the polar deposits on Mars. While the photochemical model predicts that about 95 percent of the Martian water has escaped over geologic time and the nonatmospheric reservoir is now only 02 m thick, the polar volatile theory suggest that polar deposits contain the equivalent of tens of meters of water, requiring a more rapid escape of H and D to space than predicted by the photochemical model to match the observed D/H ratio. The paper examines the behavior of the polar caps and the atmospheric water vapor over geologic time and the loss of H and D to space. It is concluded that, at present, it is premature to accept a specific history for water on Mars.

  10. A novel xylan degrading β-D-xylosidase: purification and biochemical characterization.

    PubMed

    Michelin, Michele; Peixoto-Nogueira, Simone C; Silva, Tony M; Jorge, João A; Terenzi, Héctor F; Teixeira, José A; Polizeli, Maria de Lourdes T M

    2012-11-01

    Aspergillus ochraceus, a thermotolerant fungus isolated in Brazil from decomposing materials, produced an extracellular β-xylosidase that was purified using DEAE-cellulose ion exchange chromatography, Sephadex G-100 and Biogel P-60 gel filtration. β-xylosidase is a glycoprotein (39 % carbohydrate content) and has a molecular mass of 137 kDa by SDS-PAGE, with optimal temperature and pH at 70 °C and 3.0-5.5, respectively. β-xylosidase was stable in acidic pH (3.0-6.0) and 70 °C for 1 h. The enzyme was activated by 5 mM MnCl₂ (28 %) and MgCl₂ (20 %) salts. The β-xylosidase produced by A. ochraceus preferentially hydrolyzed p-nitrophenyl-β-D-xylopyranoside, exhibiting apparent K(m) and V(max) values of 0.66 mM and 39 U (mg protein)⁻¹ respectively, and to a lesser extent p-nitrophenyl-β-D-glucopyranoside. The enzyme was able to hydrolyze xylan from different sources, suggesting a novel β-D-xylosidase that degrades xylan. HPLC analysis revealed xylans of different compositions which allowed explaining the differences in specificity observed by β-xylosidase. TLC confirmed the capacity of the enzyme in hydrolyzing xylan and larger xylo-oligosaccharides, as xylopentaose.

  11. Multicomponent DFT study of geometrical H/D isotope effect on hydrogen-bonded organic conductor, κ-H3(Cat EDT-ST)2

    NASA Astrophysics Data System (ADS)

    Yamamoto, Kaichi; Kanematsu, Yusuke; Nagashima, Umpei; Ueda, Akira; Mori, Hatsumi; Tachikawa, Masanori

    2017-04-01

    We theoretically investigated a significant contraction of the hydrogen-bonding O⋯O distance upon H/D substitution in our recently developed purely organic crystals, κ-H3(Cat-EDT-ST)2 (H-ST) and its isotopologue κ-D3(Cat-EDT-ST)2 (D-ST), having π-electron systems coupled with hydrogen-bonding fluctuation. The origin of this geometrical H/D isotope effect was elucidated by using the multicomponent DFT method, which takes the H/D nuclear quantum effect into account. The optimized O⋯O distance in H-ST was found to be longer than that in D-ST due to the anharmonicity of the potential energy curve along the Osbnd H bond direction, which was in reasonable agreement with the experimental trend.

  12. Near-infrared emission bands of TeH and TeD

    NASA Astrophysics Data System (ADS)

    Fink, E. H.; Setzer, K. D.; Ramsay, D. A.; Vervloet, M.

    1989-11-01

    High-resolution emission spectra of TeH and TeD have been obtained in the region 4200 to 3600 cm -1 using a Bomem DA3.002 Fourier transform spectrometer. Analyses are given for the 0-0 and 1-1 bands of the X 22Π{1}/{2}-X 12Π{3}/{2} system of TeH and for the 0-0 band of TeD. In addition the 2-0 vibrational overtone bands of 130TeH, 128TeH, and 126TeH are observed and analyzed. Accurate molecular constants are given for the first time.

  13. Adsorption of virus-like particles on ion exchange surface: Conformational changes at different pH detected by dual polarization interferometry.

    PubMed

    Yang, Yanli; Mengran Yu; Zhang, Songping; Ma, Guanghui; Su, Zhiguo

    2015-08-21

    Disassembling of virus-like particles (VLPs) like hepatitis B virus surface antigen (HB-VLPs) during chromatographic process has been identified as a major cause of loss of antigen activity. In this study, dual polarization interferometry (DPI) measurement, together with chromatography experiments, were performed to study the adsorption and conformational change of HB-VLPs on ion exchange surface at three different pHs. Changes in pH values of buffer solution showed only minimal effect on the HB-VLPs assembly and antigen activity, while significantly different degree of HB-VLPs disassembling was observed after ion exchange chromatography (IEC) at different pHs, indicating the conformational change of HB-VLPs caused mainly by its interactions with the adsorbent surface. By creating an ion exchange surface on chip surface, the conformational changes of HB-VLPs during adsorption to the surface were monitored in real time by DPI for the first time. As pH increased from 7.0 to 9.0, strong electrostatic interactions between oppositely charged HB-VLPs and the ion exchange surface make the HB-VLPs spread thinly or even adsorbed in disassembled formation on the surface as revealed by significant decrease in thickness of the adsorbed layer measured by DPI. Such findings were consistent with the results of IEC experiments operated at different pHs, that more disassembled HB-VLPs were detected in the eluted proteins at pH 9.0. At low pH like pH 5.0, however, possible bi-layer adsorption was involved as evidenced by an adsorbed layer thickness higher than average diameter of the HB-VLPs. The "lateral" protein-protein interactions might be unfavorable and would make additional contribution to the disassembling of HB-VLPs besides the primary mechanism related to the protein-surface interactions; therefore, the lowest antigen activity was observed after IEC at pH 5.0. Such real-time information on conformational change of VLPs is helpful for better understanding the real mechanism

  14. Modélisation du champ magnétique d'un propulseur M.H.D. annulaire

    NASA Astrophysics Data System (ADS)

    Kom, C. H.; Brunet, Y.

    1995-01-01

    Stray fields have to be as small as possible to reduce the magnetic signature of the vessel in M.H.D. propulsion where the magnetic field has to be very high. The calculation of the magnetic field of an angular M.H.D. thruster is presented. The field is produced by a distribution of superconducting magnets in the shape of sectors. An analytical formulation of the field can be used in the active zone, outside the coil ends. An analytical method using a Fourier development of the current sheets is employed for an inductor in cylindrical sectors, and a direct method is used for a massive inductor. Numerical and analytical results are compared. Pour des raisons de discrétion, les champs de fuite doivent être minimisés en propulsion M.H.D. où les champs magnétiques doivent être intenses. Le calcul du champ magnétique d'un propulseur M.H.D. naval annulaire, constitué de secteurs inducteurs supraconducteurs est représenté. Dans la zone active, hors des têtes de bobines, une formulation analytique peut être utilisée. Une méthode analytique utilisant le développemment en série de Fourier du courant est adoptée pour les industeurs cylindriques, et une méthode directe pour les inducteurs massifs. Les résultats numériques sont comparés à ceux obtenus avec un logiciel d'éléments finis 2D.

  15. Laser Processed Heat Exchangers

    NASA Technical Reports Server (NTRS)

    Hansen, Scott

    2017-01-01

    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.

  16. Clinical expression of patients with the D1152H CFTR mutation.

    PubMed

    Terlizzi, Vito; Carnovale, Vincenzo; Castaldo, Giuseppe; Castellani, Carlo; Cirilli, Natalia; Colombo, Carla; Corti, Fabiola; Cresta, Federico; D'Adda, Alice; Lucarelli, Marco; Lucidi, Vincenzina; Macchiaroli, Annamaria; Madarena, Elisa; Padoan, Rita; Quattrucci, Serena; Salvatore, Donatello; Zarrilli, Federica; Raia, Valeria

    2015-07-01

    Discordant results were reported on the clinical expression of subjects bearing the D1152H CFTR mutation, and also for the small number of cases reported so far. A retrospective review of clinical, genetic and biochemical data was performed from individuals homozygous or compound heterozygous for the D1152H mutation followed in 12 Italian cystic fibrosis (CF) centers. 89 subjects carrying at least D1152H on one allele were identified. 7 homozygous patients had very mild clinical expression. Over half of the 74 subjects compound heterozygous for D1152H and a I-II-III class mutation had borderline or pathological sweat test and respiratory or gastrointestinal symptoms; one third had pulmonary bacteria colonization and 10/74 cases had complications (i.e. diabetes, allergic bronchopulmonary aspergillosis, and hemoptysis). However, their clinical expression was less severe as compared to a group of CF patients homozygous for the F508del mutation. Finally, 8 subjects compound heterozygous for D1152H and a IV-V class mutation showed very mild disease. The natural history of subjects bearing the D1152H mutation is widely heterogeneous and is influenced by the mutation in trans. Copyright © 2014 European Cystic Fibrosis Society. Published by Elsevier B.V. All rights reserved.

  17. Resonances at very low temperature for the reaction D2 + H

    NASA Astrophysics Data System (ADS)

    Simbotin, I.; Côté, R.

    2017-05-01

    We present numerical results for rate coefficients of reaction and vibrational quenching in the collision of H with {{{D}}}2(v,j) at cold and ultracold temperatures. We explore both ortho-D{}2(j=0) and para-D{}2(j=1) for several initial vibrational states (v≤slant 5), and find resonant structures in the energy range 0.01-10 K, which are sensitive to the initial rovibrational state (v, j). We compare the reaction rates for D2 + H with our previously obtained results for the isotopologue reaction H2 + D, and discuss the implications of our detailed study of this benchmark system for ultracold chemistry.

  18. Mass data graphics requirements for symbol generators: example 2D airport navagation and 3D terrain function

    NASA Astrophysics Data System (ADS)

    Schiefele, Jens; Bader, Joachim; Kastner, S.; Wiesemann, Thorsten; von Viebahn, Harro

    2002-07-01

    Next generation of cockpit display systems will display mass data. Mass data includes terrain, obstacle, and airport databases. Display formats will be two and eventually 3D. A prerequisite for the introduction of these new functions is the availability of certified graphics hardware. The paper describes functionality and required features of an aviation certified 2D/3D graphics board. This graphics board should be based on low-level and hi-level API calls. These graphic calls should be very similar to OpenGL. All software and the API must be aviation certified. As an example application, a 2D airport navigation function and a 3D terrain visualization is presented. The airport navigation format is based on highly precise airport database following EUROCAE ED-99/RTCA DO-272 specifications. Terrain resolution is based on EUROCAE ED-98/RTCA DO-276 requirements.

  19. Numerical investigation of band gaps in 3D printed cantilever-in-mass metamaterials

    NASA Astrophysics Data System (ADS)

    Qureshi, Awais; Li, Bing; Tan, K. T.

    2016-06-01

    In this research, the negative effective mass behavior of elastic/mechanical metamaterials is exhibited by a cantilever-in-mass structure as a proposed design for creating frequency stopping band gaps, based on local resonance of the internal structure. The mass-in-mass unit cell model is transformed into a cantilever-in-mass model using the Bernoulli-Euler beam theory. An analytical model of the cantilever-in-mass structure is derived and the effects of geometrical dimensions and material parameters to create frequency band gaps are examined. A two-dimensional finite element model is created to validate the analytical results, and excellent agreement is achieved. The analytical model establishes an easily tunable metamaterial design to realize wave attenuation based on locally resonant frequency. To demonstrate feasibility for 3D printing, the analytical model is employed to design and fabricate 3D printable mechanical metamaterial. A three-dimensional numerical experiment is performed using COMSOL Multiphysics to validate the wave attenuation performance. Results show that the cantilever-in-mass metamaterial is capable of mitigating stress waves at the desired resonance frequency. Our study successfully presents the use of one constituent material to create a 3D printed cantilever-in-mass metamaterial with negative effective mass density for stress wave mitigation purposes.

  20. Communication: Prediction of the rate constant of bimolecular hydrogen exchange in the water dimer using an ab initio potential energy surface.

    PubMed

    Wang, Yimin; Bowman, Joel M; Huang, Xinchuan

    2010-09-21

    We report the properties of two novel transition states of the bimolecular hydrogen exchange reaction in the water dimer, based on an ab initio water dimer potential [A. Shank et al., J. Chem. Phys. 130, 144314 (2009)]. The realism of the two transition states is assessed by comparing structures, energies, and harmonic frequencies obtained from the potential energy surface and new high-level ab initio calculations. The rate constant for the exchange is obtained using conventional transition state theory with a tunneling correction. We employ a one-dimensional approach for the tunneling calculations using a relaxed potential from the full-dimensional potential in the imaginary-frequency normal mode of the saddle point, Q(im). The accuracy of this one-dimensional approach has been shown for the ground-state tunneling splittings for H and D-transfer in malonaldehyde and for the D+H(2) reaction [Y. Wang and J. M. Bowman, J. Chem. Phys. 129, 121103 (2008)]. This approach is applied to calculate the rate constant for the H(2)O+H(2)O exchange and also for H(2)O+D(2)O→2HOD. The local zero-point energy is also obtained using diffusion Monte Carlo calculations in the space of real-frequency-saddle-point normal modes, as a function of Q(im).