Determination of Equine Cytochrome c Backbone Amide Hydrogen/Deuterium Exchange Rates by Mass Spectrometry Using a Wider Time Window and Isotope Envelope

NASA Astrophysics Data System (ADS)

Hamuro, Yoshitomo

2017-03-01

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

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.

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.

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.

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

PubMed

Hamuro, Yoshitomo

2017-03-01

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

H NMR studies of substrate hydrogen exchange reactions catalyzed by L-methionine gamma-lyase

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

Esaki, N.; Nakayama, T.; Sawada, S.

Hydrogen exchange reactions of various L-amino acids catalyzed by L-methionine gamma-lyase (EC 4.4.1.11) have been studied. The enzyme catalyzes the rapid exchange of the alpha- and beta-hydrogens of L-methionine and S-methyl-L-cysteine with deuterium from the solvent. The rate of alpha-hydrogen exchange was about 40 times faster than that of the enzymatic elimination reaction of the sulfur-containing amino acids. The enzyme also catalyzes the exchange reaction of alpha- and beta-hydrogens of the straight-chain L-amino acids which are not susceptible to elimination. The exchange rates of the alpha-hydrogen and the total beta-hydrogens of L-alanine and L-alpha-aminobutyrate with deuterium followed first-order kinetics. Formore » L-norvaline, L-norleucine, S-methyl-L-cysteine, and L-methionine, the rate of alpha-hydrogen exchange followed first-order kinetics, but the rate of total beta-hydrogen exchange decreased due to a primary isotope effect at the alpha-position. L-Phenylalanine and L-tryptophan slowly underwent alpha-hydrogen exchange. The pro-R hydrogen of glycine was deuterated stereospecifically.« less

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.

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).

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.

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

PubMed Central

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

2015-01-01

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

Measurement of backbone hydrogen-deuterium exchange in the type III secretion system needle protein PrgI by solid-state NMR

NASA Astrophysics Data System (ADS)

Chevelkov, Veniamin; Giller, Karin; Becker, Stefan; Lange, Adam

2017-10-01

In this report we present site-specific measurements of amide hydrogen-deuterium exchange rates in a protein in the solid state phase by MAS NMR. Employing perdeuteration, proton detection and a high external magnetic field we could adopt the highly efficient Relax-EXSY protocol previously developed for liquid state NMR. According to this method, we measured the contribution of hydrogen exchange on apparent 15N longitudinal relaxation rates in samples with differing D2O buffer content. Differences in the apparent T1 times allowed us to derive exchange rates for multiple residues in the type III secretion system needle protein.

Protein and Peptide Gas-phase Structure Investigation Using Collision Cross Section Measurements and Hydrogen Deuterium Exchange

NASA Astrophysics Data System (ADS)

Khakinejad, Mahdiar

Protein and peptide gas-phase structure analysis provides the opportunity to study these species outside of their explicit environment where the interaction network with surrounding molecules makes the analysis difficult [1]. Although gas-phase structure analysis offers a unique opportunity to study the intrinsic behavior of these biomolecules [2-4], proteins and peptides exhibit very low vapor pressures [2]. Peptide and protein ions can be rendered in the gas-phase using electrospray ionization (ESI) [5]. There is a growing body of literature that shows proteins and peptides can maintain solution structures during the process of ESI and these structures can persist for a few hundred milliseconds [6-9]. Techniques for monitoring gas-phase protein and peptide ion structures are categorized as physical probes and chemical probes. Collision cross section (CCS) measurement, being a physical probe, is a powerful method to investigate gas-phase structure size [3, 7, 10-15]; however, CCS values alone do not establish a one to one relation with structure(i.e., the CCS value is an orientationally averaged value [15-18]. Here we propose the utility of gas-phase hydrogen deuterium exchange (HDX) as a second criterion of structure elucidation. The proposed approach incudes extensive MD simulations to sample biomolecular ion conformation space with the production of numerous, random in-silico structures. Subsequently a CCS can be calculated for these structures and theoretical CCS values are compared with experimental values to produce a pool of candidate structures. Utilizing a chemical reaction model based on the gas-phase HDX mechanism, the HDX kinetics behavior of these candidate structures are predicted and compared to experimental results to nominate the best in-silico structures which match (chemically and physically) with experimental observations. For the predictive approach to succeed, an extensive technique and method development is essential. To combine CCS

Para-hydrogen induced polarization of amino acids, peptides and deuterium-hydrogen gas.

PubMed

Glöggler, Stefan; Müller, Rafael; Colell, Johannes; Emondts, Meike; Dabrowski, Martin; Blümich, Bernhard; Appelt, Stephan

2011-08-14

Signal Amplification by Reversible-Exchange (SABRE) is a method of hyperpolarizing substrates by polarization transfer from para-hydrogen without hydrogenation. Here, we demonstrate that this method can be applied to hyperpolarize small amounts of all proteinogenic amino acids and some chosen peptides down to the nanomole regime and can be detected in a single scan in low-magnetic fields down to 0.25 mT (10 kHz proton frequency). An outstanding feature is that depending on the chemical state of the used catalyst and the investigated amino acid or peptide, hyperpolarized hydrogen-deuterium gas is formed, which was detected with (1)H and (2)H NMR spectroscopy at low magnetic fields of B(0) = 3.9 mT (166 kHz proton frequency) and 3.2 mT (20 kHz deuterium frequency).

Comprehensive Gas-Phase Peptide Ion Structure Studies Using Ion Mobility Techniques: Part 2. Gas-Phase Hydrogen/Deuterium Exchange for Ion Population Estimation.

PubMed

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

2017-05-01

Gas-phase hydrogen/deuterium exchange (HDX) using D 2 O reagent and collision cross-section (CCS) measurements are utilized to monitor the ion conformers of the model peptide acetyl-PAAAAKAAAAKAAAAKAAAAK. The measurements are carried out on a home-built ion mobility instrument coupled to a linear ion trap mass spectrometer containing electron transfer dissociation (ETD) capabilities. ETD is utilized to obtain per-residue deuterium uptake data for select ion conformers, and a new algorithm is presented for interpreting the HDX data. Using molecular dynamics (MD) production data and a hydrogen accessibility scoring (HAS)-number of effective collisions (NEC) model, hypothetical HDX behavior is attributed to various in-silico candidate (CCS match) structures. The HAS-NEC model is applied to all candidate structures, and non-negative linear regression is employed to determine structure contributions resulting in the best match to deuterium uptake. The accuracy of the HAS-NEC model is tested with the comparison of predicted and experimental isotopic envelopes for several of the observed c-ions. It is proposed that gas-phase HDX can be utilized effectively as a second criterion (after CCS matching) for filtering suitable MD candidate structures. In this study, the second step of structure elucidation, 13 nominal structures were selected (from a pool of 300 candidate structures) and each with a population contribution proposed for these ions. Graphical Abstract ᅟ.

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.

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.

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.

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

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.

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

Characterization of Aggregation Propensity of a Human Fc-Fusion Protein Therapeutic by Hydrogen/Deuterium Exchange Mass Spectrometry

NASA Astrophysics Data System (ADS)

Huang, Richard Y.-C.; Iacob, Roxana E.; Krystek, Stanley R.; Jin, Mi; Wei, Hui; Tao, Li; Das, Tapan K.; Tymiak, Adrienne A.; Engen, John R.; Chen, Guodong

2017-05-01

Aggregation of protein therapeutics has long been a concern across different stages of manufacturing processes in the biopharmaceutical industry. It is often indicative of aberrant protein therapeutic higher-order structure. In this study, the aggregation propensity of a human Fc-fusion protein therapeutic was characterized. Hydrogen/deuterium exchange mass spectrometry (HDX-MS) was applied to examine the conformational dynamics of dimers collected from a bioreactor. HDX-MS data combined with spatial aggregation propensity calculations revealed a potential aggregation interface in the Fc domain. This study provides a general strategy for the characterization of the aggregation propensity of Fc-fusion proteins at the molecular level.

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.

Online Hydrogen-Deuterium Exchange Traveling Wave Ion Mobility Mass Spectrometry (HDX-IM-MS): a Systematic Evaluation

NASA Astrophysics Data System (ADS)

Cryar, Adam; Groves, Kate; Quaglia, Milena

2017-06-01

Hydrogen-deuterium exchange mass spectrometry (HDX-MS) is an important tool for measuring and monitoring protein structure. A bottom-up approach to HDX-MS provides peptide level deuterium uptake values and a more refined localization of deuterium incorporation compared with global HDX-MS measurements. The degree of localization provided by HDX-MS is proportional to the number of peptides that can be identified and monitored across an exchange experiment. Ion mobility spectrometry (IMS) has been shown to improve MS-based peptide analysis of biological samples through increased separation capacity. The integration of IMS within HDX-MS workflows has been commercialized but presently its adoption has not been widespread. The potential benefits of IMS, therefore, have not yet been fully explored. We herein describe a comprehensive evaluation of traveling wave ion mobility integrated within an online-HDX-MS system and present the first reported example of UDMSE acquisition for HDX analysis. Instrument settings required for optimal peptide identifications are described and the effects of detector saturation due to peak compression are discussed. A model system is utilized to confirm the comparability of HDX-IM-MS and HDX-MS uptake values prior to an evaluation of the benefits of IMS at increasing sample complexity. Interestingly, MS and IM-MS acquisitions were found to identify distinct populations of peptides that were unique to the respective methods, a property that can be utilized to increase the spatial resolution of HDX-MS experiments by >60%. [Figure not available: see fulltext.

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.

Probing Conformational Dynamics of Tau Protein by Hydrogen/Deuterium Exchange Mass Spectrometry

NASA Astrophysics Data System (ADS)

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

2018-01-01

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

Determination of Backbone Amide Hydrogen Exchange Rates of Cytochrome c Using Partially Scrambled Electron Transfer Dissociation Data

NASA Astrophysics Data System (ADS)

Hamuro, Yoshitomo; E, Sook Yen

2018-05-01

The technological goal of hydrogen/deuterium exchange-mass spectrometry (HDX-MS) is to determine backbone amide hydrogen exchange rates. The most critical challenge to achieve this goal is obtaining the deuterium incorporation in single-amide resolution, and gas-phase fragmentation may provide a universal solution. The gas-phase fragmentation may generate the daughter ions which differ by a single amino acid and the difference in deuterium incorporations in the two analogous ions can yield the deuterium incorporation at the sub-localized site. Following the pioneering works by Jørgensen and Rand, several papers utilized the electron transfer dissociation (ETD) to determine the location of deuterium in single-amide resolution. This paper demonstrates further advancement of the strategy by determining backbone amide hydrogen exchange rates, instead of just determining deuterium incorporation at a single time point, in combination with a wide time window monitoring. A method to evaluate the effects of scrambling and to determine the exchange rates from partially scrambled HDX-ETD-MS data is described. All parent ions for ETD fragmentation were regio-selectively scrambled: The deuterium in some regions of a peptide ion was scrambled while that in the other regions was not scrambled. The method determined 31 backbone amide hydrogen exchange rates of cytochrome c in the non-scrambled regions. Good fragmentation of a parent ion, a low degree of scrambling, and a low number of exchangeable hydrogens in the preceding side chain are the important factors to determine the exchange rate. The exchange rates determined by the HDX-MS are in good agreement with those determined by NMR. [Figure not available: see fulltext.

Determination of Backbone Amide Hydrogen Exchange Rates of Cytochrome c Using Partially Scrambled Electron Transfer Dissociation Data.

PubMed

Hamuro, Yoshitomo; E, Sook Yen

2018-05-01

The technological goal of hydrogen/deuterium exchange-mass spectrometry (HDX-MS) is to determine backbone amide hydrogen exchange rates. The most critical challenge to achieve this goal is obtaining the deuterium incorporation in single-amide resolution, and gas-phase fragmentation may provide a universal solution. The gas-phase fragmentation may generate the daughter ions which differ by a single amino acid and the difference in deuterium incorporations in the two analogous ions can yield the deuterium incorporation at the sub-localized site. Following the pioneering works by Jørgensen and Rand, several papers utilized the electron transfer dissociation (ETD) to determine the location of deuterium in single-amide resolution. This paper demonstrates further advancement of the strategy by determining backbone amide hydrogen exchange rates, instead of just determining deuterium incorporation at a single time point, in combination with a wide time window monitoring. A method to evaluate the effects of scrambling and to determine the exchange rates from partially scrambled HDX-ETD-MS data is described. All parent ions for ETD fragmentation were regio-selectively scrambled: The deuterium in some regions of a peptide ion was scrambled while that in the other regions was not scrambled. The method determined 31 backbone amide hydrogen exchange rates of cytochrome c in the non-scrambled regions. Good fragmentation of a parent ion, a low degree of scrambling, and a low number of exchangeable hydrogens in the preceding side chain are the important factors to determine the exchange rate. The exchange rates determined by the HDX-MS are in good agreement with those determined by NMR. Graphical Abstract ᅟ.

Determination of Backbone Amide Hydrogen Exchange Rates of Cytochrome c Using Partially Scrambled Electron Transfer Dissociation Data

NASA Astrophysics Data System (ADS)

Hamuro, Yoshitomo; E, Sook Yen

2018-03-01

The technological goal of hydrogen/deuterium exchange-mass spectrometry (HDX-MS) is to determine backbone amide hydrogen exchange rates. The most critical challenge to achieve this goal is obtaining the deuterium incorporation in single-amide resolution, and gas-phase fragmentation may provide a universal solution. The gas-phase fragmentation may generate the daughter ions which differ by a single amino acid and the difference in deuterium incorporations in the two analogous ions can yield the deuterium incorporation at the sub-localized site. Following the pioneering works by Jørgensen and Rand, several papers utilized the electron transfer dissociation (ETD) to determine the location of deuterium in single-amide resolution. This paper demonstrates further advancement of the strategy by determining backbone amide hydrogen exchange rates, instead of just determining deuterium incorporation at a single time point, in combination with a wide time window monitoring. A method to evaluate the effects of scrambling and to determine the exchange rates from partially scrambled HDX-ETD-MS data is described. All parent ions for ETD fragmentation were regio-selectively scrambled: The deuterium in some regions of a peptide ion was scrambled while that in the other regions was not scrambled. The method determined 31 backbone amide hydrogen exchange rates of cytochrome c in the non-scrambled regions. Good fragmentation of a parent ion, a low degree of scrambling, and a low number of exchangeable hydrogens in the preceding side chain are the important factors to determine the exchange rate. The exchange rates determined by the HDX-MS are in good agreement with those determined by NMR. [Figure not available: see fulltext.

Quantum molecular dynamics study on the proton exchange, ionic structures, and transport properties of warm dense hydrogen-deuterium mixtures

NASA Astrophysics Data System (ADS)

Liu, Lei; Li, Zhi-Guo; Dai, Jia-Yu; Chen, Qi-Feng; Chen, Xiang-Rong

2018-06-01

Comprehensive knowledge of physical properties such as equation of state (EOS), proton exchange, dynamic structures, diffusion coefficients, and viscosities of hydrogen-deuterium mixtures with densities from 0.1 to 5 g /cm3 and temperatures from 1 to 50 kK has been presented via quantum molecular dynamics (QMD) simulations. The existing multi-shock experimental EOS provides an important benchmark to evaluate exchange-correlation functionals. The comparison of simulations with experiments indicates that a nonlocal van der Waals density functional (vdW-DF1) produces excellent results. Fraction analysis of molecules using a weighted integral over pair distribution functions was performed. A dissociation diagram together with a boundary where the proton exchange (H2+D2⇌2 HD ) occurs was generated, which shows evidence that the HD molecules form as the H2 and D2 molecules are almost 50% dissociated. The mechanism of proton exchange can be interpreted as a process of dissociation followed by recombination. The ionic structures at extreme conditions were analyzed by the effective coordination number model. High-order cluster, circle, and chain structures can be founded in the strongly coupled warm dense regime. The present QMD diffusion coefficient and viscosity can be used to benchmark two analytical one-component plasma (OCP) models: the Coulomb and Yukawa OCP models.

Differential hydrogen/deuterium exchange mass spectrometry analysis of protein–ligand interactions

PubMed Central

Chalmers, Michael J; Busby, Scott A; Pascal, Bruce D; West, Graham M; Griffin, Patrick R

2011-01-01

Functional regulation of ligand-activated receptors is driven by alterations in the conformational dynamics of the protein upon ligand binding. Differential hydrogen/deuterium exchange (HDX) coupled with mass spectrometry has emerged as a rapid and sensitive approach for characterization of perturbations in conformational dynamics of proteins following ligand binding. While this technique is sensitive to detecting ligand interactions and alterations in receptor dynamics, it also can provide important mechanistic insights into ligand regulation. For example, HDX has been used to determine a novel mechanism of ligand activation of the nuclear receptor peroxisome proliferator activated receptor-γ, perform detailed analyses of binding modes of ligands within the ligand-binding pocket of two estrogen receptor isoforms, providing insight into selectivity, and helped classify different types of estrogen receptor-α ligands by correlating their pharmacology with the way they interact with the receptor based solely on hierarchical clustering of receptor HDX signatures. Beyond small-molecule–receptor interactions, this technique has also been applied to study protein–protein complexes, such as mapping antibody–antigen interactions. In this article, we summarize the current state of the differential HDX approaches and the future outlook. We summarize how HDX analysis of protein–ligand interactions has had an impact on biology and drug discovery. PMID:21329427

Energy Levels of Hydrogen and Deuterium

National Institute of Standards and Technology Data Gateway

SRD 142 NIST Energy Levels of Hydrogen and Deuterium (Web, free access)   This database provides theoretical values of energy levels of hydrogen and deuterium for principle quantum numbers n = 1 to 200 and all allowed orbital angular momenta l and total angular momenta j. The values are based on current knowledge of the revelant theoretical contributions including relativistic, quantum electrodynamic, recoil, and nuclear size effects.

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.

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).

Distribution of deuterium and hydrogen in Zr and Ti foil assemblies under the action of a pulsed deuterium high-temperature plasma

NASA Astrophysics Data System (ADS)

Bondarenko, G. G.; Volobuev, I. V.; Eriskin, A. A.; Kobzev, A. P.; Nikulin, V. Ya.; Peregudova, E. N.; Silin, P. V.; Borovitskaya, I. V.

2017-09-01

Deuteron and proton elastic recoil detection analysis is used to study the accumulation and redistribution of deuterium and hydrogen in assemblies of two high-pure zirconium or titanium foils upon pulsed action of high-temperature deuterium plasma (PHTDP) in a plasma-focus installation PF-4. It is noted that, under the action of PHTDP, an implanted deuterium and hydrogen gas impurity are redistributed in the irradiated foils in large depths, which are significantly larger than the deuterium ion free paths (at their maximum velocity to 108 cm/s). The observed phenomenon is attributed to the carrying out of implanted deuterium and hydrogen under the action of powerful shock waves formed in the metallic foils under the action of PHTDP and/or the acceleration of diffusion of deuterium and hydrogen atoms under the action of a compression-rarefaction shock wave at the shock wave front with the redistribution of deuterium and hydrogen to large depths.

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

Isotopic exchange of hydrogen in aromatic amino acids

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

Pshenichnikova, A.B.; Karnaukhova, E.N.; Mitsner, B.I.

The kinetics of the isotopic replacement of hydrogen in the aromatic amino acids L-tryptophan, L-tyrosine, and L-phenylalanine in solutions of deuterochloric and deuterosulfuric acids in deuterium oxide were investigated by PMR spectroscopy. The reactions were shown to be of first orders with respect both to the concentration of the substrate and to the activity of the deuterium ion. The isotopic effects of hydrogen and the values of the activation energy of H-D exchange in different positions of the aromatic ring in tryptophan and tyrosine were determined. The effect of properties of the medium on the rate of the isotopic exchangemore » of hydrogen is discussed. 17 refs., 2 figs., 2 tabs.« less

Ion Mobility Spectrometry-Mass Spectrometry Coupled with Gas-Phase Hydrogen/Deuterium Exchange for Metabolomics Analyses

NASA Astrophysics Data System (ADS)

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

2018-02-01

Ion mobility spectrometry-mass spectrometry (IMS-MS) in combination with gas-phase hydrogen/deuterium exchange (HDX) and collision-induced dissociation (CID) is evaluated as an analytical method for small-molecule standard and mixture characterization. Experiments show that compound ions exhibit unique HDX reactivities that can be used to distinguish different species. Additionally, it is shown that gas-phase HDX kinetics can be exploited to provide even further distinguishing capabilities by using different partial pressures of reagent gas. The relative HDX reactivity of a wide variety of molecules is discussed in light of the various molecular structures. Additionally, hydrogen accessibility scoring (HAS) and HDX kinetics modeling of candidate ( in silico) ion structures is utilized to estimate the relative ion conformer populations giving rise to specific HDX behavior. These data interpretation methods are discussed with a focus on developing predictive tools for HDX behavior. Finally, an example is provided in which ion mobility information is supplemented with HDX reactivity data to aid identification efforts of compounds in a metabolite extract.

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

The pion nucleon scattering lengths from pionic hydrogen and deuterium

NASA Astrophysics Data System (ADS)

Schröder, H.-Ch.; Badertscher, A.; Goudsmit, P. F. A.; Janousch, M.; Leisi, H. J.; Matsinos, E.; Sigg, D.; Zhao, Z. G.; Chatellard, D.; Egger, J.-P.; Gabathuler, K.; Hauser, P.; Simons, L. M.; Rusi El Hassani, A. J.

2001-07-01

This is the final publication of the ETH Zurich Neuchâtel PSI collaboration on the pionic hydrogen and deuterium precision X-ray experiments. We describe the recent hydrogen 3 p 1 s measurement, report on the determination of the Doppler effect correction to the transition line width, analyze the deuterium shift measurement and discuss implications of the combined hydrogen and deuterium results. From the pionic hydrogen 3 p 1 s transition experiments we obtain the strong-interaction energy level shift \\varepsilon_{1s} = -7.108±0.013 (stat.)±0.034 (syst.) eV and the total decay width Γ_{1s} = 0.868±0.040 (stat.)±0.038 (syst.) eV of the 1s state. Taking into account the electromagnetic corrections we find the hadronic π N s-wave scattering amplitude a_{π-prightarrowπ-p} = 0.0883±0.0008 m_{π}^{-1} for elastic scattering and a_{π-prightarrowπ0n} = -0.128±0.006 m_{π} ^{-1} for single charge exchange, respectively. We then combine the pionic hydrogen results with the 1 s level shift measurement on pionic deuterium and test isospin symmetry of the strong interaction: our data are still compatible with isospin symmetry. The isoscalar and isovector π N scattering lengths (within the framework of isospin symmetry) are found to be b_0 = -0.0001^{+0.0009}_{-0.0021} m_{π}^{-1} and b1 = -0.0885^{+0.0010}_{-0.0021} m_{π} ^{-1}, respectively. Using the GMO sum rule, we obtain from b_1 a new value of the π N coupling constant (g_{π N} = 13.21_{-0.05}^{+0.11}) from which follows the Goldberger Treiman discrepancy Δ_{{GT}} =0.027_{-0.008}^{+0.012}. The new values of b_0 and g_{π N} imply an increase of the nucleon sigma term by at least 9 MeV.

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.

Top-Down Hydrogen-Deuterium Exchange Analysis of Protein Structures Using Ultraviolet Photodissociation.

PubMed

Brodie, Nicholas I; Huguet, Romain; Zhang, Terry; Viner, Rosa; Zabrouskov, Vlad; Pan, Jingxi; Petrotchenko, Evgeniy V; Borchers, Christoph H

2018-03-06

Top-down hydrogen-deuterium exchange (HDX) analysis using electron capture or transfer dissociation Fourier transform mass spectrometry (FTMS) is a powerful method for the analysis of secondary structure of proteins in solution. The resolution of the method is a function of the degree of fragmentation of backbone bonds in the proteins. While fragmentation is usually extensive near the N- and C-termini, electron capture (ECD) or electron transfer dissociation (ETD) fragmentation methods sometimes lack good coverage of certain regions of the protein, most often in the middle of the sequence. Ultraviolet photodissociation (UVPD) is a recently developed fast-fragmentation technique, which provides extensive backbone fragmentation that can be complementary in sequence coverage to the aforementioned electron-based fragmentation techniques. Here, we explore the application of electrospray ionization (ESI)-UVPD FTMS on an Orbitrap Fusion Lumos Tribrid mass spectrometer to top-down HDX analysis of proteins. We have incorporated UVPD-specific fragment-ion types and fragment-ion mixtures into our isotopic envelope fitting software (HDX Match) for the top-down HDX analysis. We have shown that UVPD data is complementary to ETD, thus improving the overall resolution when used as a combined approach.

Supercritical fluid chromatography coupled with in-source atmospheric pressure ionization hydrogen/deuterium exchange mass spectrometry for compound speciation.

PubMed

Cho, Yunju; Choi, Man-Ho; Kim, Byungjoo; Kim, Sunghwan

2016-04-29

An experimental setup for the speciation of compounds by hydrogen/deuterium exchange (HDX) with atmospheric pressure ionization while performing chromatographic separation is presented. The proposed experimental setup combines the high performance supercritical fluid chromatography (SFC) system that can be readily used as an inlet for mass spectrometry (MS) and atmospheric pressure photo ionization (APPI) or atmospheric pressure chemical ionization (APCI) HDX. This combination overcomes the limitation of an approach using conventional liquid chromatography (LC) by minimizing the amount of deuterium solvents used for separation. In the SFC separation, supercritical CO2 was used as a major component of the mobile phase, and methanol was used as a minor co-solvent. By using deuterated methanol (CH3OD), AP HDX was achieved during SFC separation. To prove the concept, thirty one nitrogen- and/or oxygen-containing standard compounds were analyzed by SFC-AP HDX MS. The compounds were successfully speciated from the obtained SFC-MS spectra. The exchange ions were observed with as low as 1% of CH3OD in the mobile phase, and separation could be performed within approximately 20min using approximately 0.24 mL of CH3OD. The results showed that SFC separation and APPI/APCI HDX could be successfully performed using the suggested method. Copyright © 2016 Elsevier B.V. All rights reserved.

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…

ETD in a traveling wave ion guide at tuned Z-spray ion source conditions allows for site-specific hydrogen/deuterium exchange measurements.

PubMed

Rand, Kasper D; Pringle, Steven D; Morris, Michael; Engen, John R; Brown, Jeffery M

2011-10-01

The recent application of electron transfer dissociation (ETD) to measure the hydrogen exchange of proteins in solution at single-residue resolution (HX-ETD) paves the way for mass spectrometry-based analyses of biomolecular structure at an unprecedented level of detail. The approach requires that activation of polypeptide ions prior to ETD is minimal so as to prevent undesirable gas-phase randomization of the deuterium label from solution (i.e., hydrogen scrambling). Here we explore the use of ETD in a traveling wave ion guide of a quadrupole-time-of-flight (Q-TOF) mass spectrometer with a "Z-spray" type ion source, to measure the deuterium content of individual residues in peptides. We systematically identify key parameters of the Z-spray ion source that contribute to collisional activation and define conditions that allow ETD experiments to be performed in the traveling wave ion guide without gas-phase hydrogen scrambling. We show that ETD and supplemental collisional activation in a subsequent traveling wave ion guide allows for improved extraction of residue-specific deuterium contents in peptides with low charge. Our results demonstrate the feasibility, and illustrate the advantages of performing HX-ETD experiments on a high-resolution Q-TOF instrument equipped with traveling wave ion guides. Determination of parameters of the Z-spray ion source that contribute to ion heating are similarly pertinent to a growing number of MS applications that also rely on an energetically gentle transfer of ions into the gas-phase, such as the analysis of biomolecular structure by native mass spectrometry in combination with gas-phase ion-ion/ion-neutral reactions or ion mobility spectrometry. © American Society for Mass Spectrometry, 2011

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.

NMR Stratagems for the Study of Multiple Kinetic Hydrogen/Deuterium Isotope Effectsof Proton Exchange. Example: Di-p-fluorophenylformamidine/THF

NASA Astrophysics Data System (ADS)

Limbach, Hans-Heinrich; Meschede, Ludger; Scherer, Gerd

1989-05-01

Stratagems are presented for the determination of kinetic isotope effects of proton exchange reactions by dynamic NMR spectroscopy. In such experiments, lineshape analyses and/or polarization transfer experiments are performed on the exchanging protons or deuterons as well as on remote spins, as a function of the deuterium fraction in the mobile proton sites. These methods are NMR analogs of previous proton inventory techniques involving classical kinetic methods. A theory is developed in order to derive the kinetic isotope effects as well as the number of transferred protons from the experimental NMR spectra. The technique is then applied to the problem of proton exchange in the system 15N,15N'-di-p-fluorophenylibrmamidine, a nitrogen analog of formic acid, dissolved in tetrahydrofuran-d8 (THF). DFFA forms two conformers in THF to which s-trans and s-cis structures have been assigned. Only the s-trans conformer is able to dimerize and exchange protons. Lineshape simulations and magnetization transfer experiments were carried out at 189,2 K, at a concentration of 0.02 mol l-1, as a function of the deuterium fraction D in the 1H-15N sites. Using 1H NMR spectroscopy, a linear dependence of the inverse proton lifetimes on D was observed. From this it was concluded that two protons are transported in the rate limiting step of the proton exchange. This result is expected for a double proton transfer in an s-trans dimer with a cyclic structure. The full kinetic HH/HD/DD isotope effects of 233:11:1 at 189 K were determined through 19F NMR experiments on the same samples. The deviation from the rule of geometric mean, although substantial, is much smaller than found in previous studies of intramolecular HH transfer reactions. Possible causes of this effect are discussed.

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

ERIC Educational Resources Information Center

Nichols, Michael A.; Waner, Mark J.

2010-01-01

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

Polarized hydrogen/deuterium molecules

NASA Astrophysics Data System (ADS)

Shestakov, Yu V.; Nikolenko, D. M.; Rachek, I. A.; Sadykov, R. Sh; Toporkov, D. K.; Yurchenko, A. V.; Zevakov, S. A.

2017-12-01

The prototype of a polarized molecular hydrogen/deuterium source which is based on the classical Stern-Gerlach separation scheme has been tested at the Budker Institute of Nuclear Physics (BINP), Novosibirsk. It consists of the circular slit nozzle cooled down to 6.5 K and the two superconducting sextupole magnets. The flux of polarized hydrogen molecules of 3·1012 mol/s was measured for a total gas flow through the nozzle of 5·10-2 Torr·l/s. The obtained results will be used to develop a much more intense source of polarized molecules.

Use of pressure in reversed-phase liquid chromatography to study protein conformational changes by differential deuterium exchange.

PubMed

Makarov, Alexey A; Schafer, Wes A; Helmy, Roy

2015-02-17

The market of protein therapeutics is exploding, and characterization methods for proteins are being further developed to understand and explore conformational structures with regards to function and activity. There are several spectroscopic techniques that allow for analyzing protein secondary structure in solution. However, a majority of these techniques need to use purified protein, concentrated enough in the solution to produce a relevant spectrum. In this study, we describe a novel approach which uses ultrahigh pressure liquid chromatography (UHPLC) coupled with mass-spectrometry (MS) to explore compressibility of the secondary structure of proteins under increasing pressure detected by hydrogen-deuterium exchange (HDX). Several model proteins were used for these studies. The studies were conducted with UHPLC in isocratic mode at constant flow rate and temperature. The pressure was modified by a backpressure regulator up to about 1200 bar. It was found that the increase of retention factors upon pressure increase, at constant flow rate and temperature, was based on reduction of the proteins' molecular molar volume. The change in the proteins' molecular molar volume was caused by changes in protein folding, as was revealed by differential deuterium exchange. The degree of protein folding under certain UHPLC conditions can be controlled by pressure, at constant temperature and flow rate. By modifying pressure during UHPLC separation, it was possible to achieve changes in protein folding, which were manifested as changes in the number of labile protons exchanged to deuterons, or vice versa. Moreover, it was demonstrated with bovine insulin that a small difference in the number of protons exchanged to deuterons (based on protein folding under pressure) could be observed between batches obtained from different sources. The use of HDX during UHPLC separation allowed one to examine protein folding by pressure at constant flow rate and temperature in a mixture of

Observations of interstellar hydrogen and deuterium toward Alpha Centauri A

NASA Technical Reports Server (NTRS)

Landsman, W. B.; Henry, R. C.; Moos, H. W.; Linsky, J. L.

1984-01-01

A composite profile is presented of the Ly-alpha emission line of Alpha Cen A, obtained from 10 individual spectra with the high-resolution spectrograph aboard the International Ultraviolet Explorer (IUE) satellite. There is excellent overall agreement with two previous Copernicus observations. Interstellar deuterium is detected, and a lower limit is set on the deuterium to hydrogen ratio of nDI/nHI greater than 8 x 10 to the -6th. In addition, the deuterium bulk velocity appears blueshifted by 8 + or - 2 km/s with respect to interstellar hydrogen, suggesting a nonuniform medium along the line of sight.

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.

Effective Application of Bicelles for Conformational Analysis of G Protein-Coupled Receptors by Hydrogen/Deuterium Exchange Mass Spectrometry

NASA Astrophysics Data System (ADS)

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

2015-05-01

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

Hexicon 2: Automated Processing of Hydrogen-Deuterium Exchange Mass Spectrometry Data with Improved Deuteration Distribution Estimation

NASA Astrophysics Data System (ADS)

Lindner, Robert; Lou, Xinghua; Reinstein, Jochen; Shoeman, Robert L.; Hamprecht, Fred A.; Winkler, Andreas

2014-06-01

Hydrogen-deuterium exchange (HDX) experiments analyzed by mass spectrometry (MS) provide information about the dynamics and the solvent accessibility of protein backbone amide hydrogen atoms. Continuous improvement of MS instrumentation has contributed to the increasing popularity of this method; however, comprehensive automated data analysis is only beginning to mature. We present Hexicon 2, an automated pipeline for data analysis and visualization based on the previously published program Hexicon (Lou et al. 2010). Hexicon 2 employs the sensitive NITPICK peak detection algorithm of its predecessor in a divide-and-conquer strategy and adds new features, such as chromatogram alignment and improved peptide sequence assignment. The unique feature of deuteration distribution estimation was retained in Hexicon 2 and improved using an iterative deconvolution algorithm that is robust even to noisy data. In addition, Hexicon 2 provides a data browser that facilitates quality control and provides convenient access to common data visualization tasks. Analysis of a benchmark dataset demonstrates superior performance of Hexicon 2 compared with its predecessor in terms of deuteration centroid recovery and deuteration distribution estimation. Hexicon 2 greatly reduces data analysis time compared with manual analysis, whereas the increased number of peptides provides redundant coverage of the entire protein sequence. Hexicon 2 is a standalone application available free of charge under http://hx2.mpimf-heidelberg.mpg.de.

Hexicon 2: automated processing of hydrogen-deuterium exchange mass spectrometry data with improved deuteration distribution estimation.

PubMed

Lindner, Robert; Lou, Xinghua; Reinstein, Jochen; Shoeman, Robert L; Hamprecht, Fred A; Winkler, Andreas

2014-06-01

Hydrogen-deuterium exchange (HDX) experiments analyzed by mass spectrometry (MS) provide information about the dynamics and the solvent accessibility of protein backbone amide hydrogen atoms. Continuous improvement of MS instrumentation has contributed to the increasing popularity of this method; however, comprehensive automated data analysis is only beginning to mature. We present Hexicon 2, an automated pipeline for data analysis and visualization based on the previously published program Hexicon (Lou et al. 2010). Hexicon 2 employs the sensitive NITPICK peak detection algorithm of its predecessor in a divide-and-conquer strategy and adds new features, such as chromatogram alignment and improved peptide sequence assignment. The unique feature of deuteration distribution estimation was retained in Hexicon 2 and improved using an iterative deconvolution algorithm that is robust even to noisy data. In addition, Hexicon 2 provides a data browser that facilitates quality control and provides convenient access to common data visualization tasks. Analysis of a benchmark dataset demonstrates superior performance of Hexicon 2 compared with its predecessor in terms of deuteration centroid recovery and deuteration distribution estimation. Hexicon 2 greatly reduces data analysis time compared with manual analysis, whereas the increased number of peptides provides redundant coverage of the entire protein sequence. Hexicon 2 is a standalone application available free of charge under http://hx2.mpimf-heidelberg.mpg.de.

Allosteric Coupling of CARMIL and V-1 Binding to Capping Protein Revealed by Hydrogen-Deuterium Exchange.

PubMed

Johnson, Britney; McConnell, Patrick; Kozlov, Alex G; Mekel, Marlene; Lohman, Timothy M; Gross, Michael L; Amarasinghe, Gaya K; Cooper, John A

2018-05-29

Actin assembly is important for cell motility. The ability of actin subunits to join or leave filaments via the barbed end is critical to actin dynamics. Capping protein (CP) binds to barbed ends to prevent subunit gain and loss and is regulated by proteins that include V-1 and CARMIL. V-1 inhibits CP by sterically blocking one binding site for actin. CARMILs bind at a distal site and decrease the affinity of CP for actin, suggested to be caused by conformational changes. We used hydrogen-deuterium exchange with mass spectrometry (HDX-MS) to probe changes in structural dynamics induced by V-1 and CARMIL binding to CP. V-1 and CARMIL induce changes in both proteins' binding sites on the surface of CP, along with a set of internal residues. Both also affect the conformation of CP's ββ subunit "tentacle," a second distal actin-binding site. Concerted regulation of actin assembly by CP occurs through allosteric couplings between CP modulator and actin binding sites. Copyright © 2018 The Author(s). Published by Elsevier Inc. All rights reserved.

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.

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

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

Lu, Jia; Harrison, Rane A.; Li, Lianbo

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

A Hydrogen Exchange Method Using Tritium and Sephadex: Its Application to Ribonuclease*

PubMed Central

Englander, S. Walter

2012-01-01

A new method for measuring the hydrogen exchange of macromolecules in solution is described. The method uses tritium to trace the movement of hydrogen, and utilizes Sephadex columns to effect, in about 2 minutes, a separation between tritiated macromolecule and tritiated solvent great enough to allow the measurement of bound tritium. High sensitivity and freedom from artifact is demonstrated and the possible value of the technique for investigation of other kinds of colloid-small molecule interaction is indicated. Competition experiments involving tritium, hydrogen, and deuterium indicate the absence of any equilibrium isotope effect in the ribonuclease-hydrogen isotope system, though a secondary kinetic isotope effect is apparent when ribonuclease is largely deuterated. Ribonuclease shows four clearly distinguishable kinetic classes of exchangeable hydrogens. Evidence is marshaled to suggest the independently measurable classes II, III, and IV (in order of decreasing rate of exchange) to represent “random-chain” peptides, peptides involved in α-helix, and otherwise shielded side-chain and peptide hydrogens, respectively. PMID:14075117

A technique for determining the deuterium/hydrogen contrast map in neutron macromolecular crystallography.

PubMed

Chatake, Toshiyuki; Fujiwara, Satoru

2016-01-01

A difference in the neutron scattering length between hydrogen and deuterium leads to a high density contrast in neutron Fourier maps. In this study, a technique for determining the deuterium/hydrogen (D/H) contrast map in neutron macromolecular crystallography is developed and evaluated using ribonuclease A. The contrast map between the D2O-solvent and H2O-solvent crystals is calculated in real space, rather than in reciprocal space as performed in previous neutron D/H contrast crystallography. The present technique can thus utilize all of the amplitudes of the neutron structure factors for both D2O-solvent and H2O-solvent crystals. The neutron D/H contrast maps clearly demonstrate the powerful detectability of H/D exchange in proteins. In fact, alternative protonation states and alternative conformations of hydroxyl groups are observed at medium resolution (1.8 Å). Moreover, water molecules can be categorized into three types according to their tendency towards rotational disorder. These results directly indicate improvement in the neutron crystal structure analysis. This technique is suitable for incorporation into the standard structure-determination process used in neutron protein crystallography; consequently, more precise and efficient determination of the D-atom positions is possible using a combination of this D/H contrast technique and standard neutron structure-determination protocols.

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

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.

Comparative higher-order structure analysis of antibody biosimilars using combined bottom-up and top-down hydrogen-deuterium exchange mass spectrometry.

PubMed

Pan, Jingxi; Zhang, Suping; Borchers, Christoph H

2016-12-01

Hydrogen/deuterium exchange (HDX) coupled with mass spectrometry (MS) is a powerful technique for higher-order structural characterization of antibodies. Although the peptide-based bottom-up HDX approach and the protein-based top-down HDX approach have complementary advantages, the work done so far on biosimilars has involved only one or the other approach. Herein we have characterized the structures of two bevacizumab (BEV) biosimilars and compared them to the reference BEV using both methods. A sequence coverage of 87% was obtained for the heavy chain and 74% for the light chain in the bottom-up approach. The deuterium incorporation behavior of the peptic peptides from the three BEVs were compared side by side and showed no differences at various HDX time points. Top-down experiments were carried out using subzero temperature LC-MS, and the deuterium incorporation of the intact light chain and heavy chain were obtained. Top-down ETD was also performed to obtain amino acid-level HDX information that covered 100% of the light chain, but only 50% coverage is possible for the heavy chain. Consistent with the intact subunit level data, no differences were observed in the amino acid level HDX data. All these results indicate that there are no differences between the three BEV samples with respect to their high-order structures. The peptide level information from the bottom-up approach, and the residue level and intact subunit level information from the top-down approach were complementary and covered the entire antibody. Copyright © 2016 Elsevier B.V. All rights reserved.

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

PubMed

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

2014-06-02

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

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

PubMed Central

2015-01-01

Solid state amide hydrogen/deuterium exchange with mass spectrometric analysis (ssHDX-MS) was used to assess the conformation of myoglobin (Mb) in lyophilized formulations, and the results correlated with the extent of aggregation during storage. Mb was colyophilized with sucrose (1:1 or 1:8 w/w), mannitol (1:1 w/w), or NaCl (1:1 w/w) or in the absence of excipients. Immediately after lyophilization, samples of each formulation were analyzed by ssHDX-MS and Fourier transform infrared spectroscopy (FTIR) to assess Mb conformation, and by dynamic light scattering (DLS) and size exclusion chromatography (SEC) to determine the extent of aggregation. The remaining samples were then placed on stability at 25 °C and 60% RH or 40 °C and 75% RH for up to 1 year, withdrawn at intervals, and analyzed for aggregate content by SEC and DLS. In ssHDX-MS of samples immediately after lyophilization (t = 0), Mb was less deuterated in solids containing sucrose (1:1 and 1:8 w/w) than in those containing mannitol (1:1 w/w), NaCl (1:1 w/w), or Mb alone. Deuterium uptake kinetics and peptide mass envelopes also indicated greater Mb structural perturbation in mannitol, NaCl, or Mb-alone samples at t = 0. The extent of deuterium incorporation and kinetic parameters related to rapidly and slowly exchanging amide pools (Nfast, Nslow), measured at t = 0, were highly correlated with the extent of aggregation on storage as measured by SEC. In contrast, the extent of aggregation was weakly correlated with FTIR band intensity and peak position measured at t = 0. The results support the use of ssHDX-MS as a formulation screening tool in developing lyophilized protein drug products. PMID:24816133

Separation and identification of structural isomers by quadrupole collision-induced dissociation-hydrogen/deuterium exchange-infrared multiphoton dissociation (QCID-HDX-IRMPD).

PubMed

Gucinski, Ashley C; Somogyi, Arpád; Chamot-Rooke, Julia; Wysocki, Vicki H

2010-08-01

A new approach that uses a hybrid Q-FTICR instrument and combines quadrupole collision-induced dissociation, hydrogen-deuterium exchange, and infrared multiphoton dissociation (QCID-HDX-IRMPD) has been shown to effectively separate and differentiate isomeric fragment ion structures present at the same m/z. This method was used to study protonated YAGFL-OH (free acid), YAGFL-NH(2) (amide), cyclic YAGFL, and YAGFL-OCH(3) (methyl ester). QCID-HDX of m/z 552.28 (C(29)H(38)N(5)O(6)) from YAGFL-OH reveals at least two distributions of ions corresponding to the b(5) ion and a non-C-terminal water loss ion structure. Subsequent IRMPD fragmentation of each population shows distinct fragmentation patterns, reflecting the different structures from which they arise. This contrasts with data for YAGFL-NH(2) and YAGFL-OCH(3), which do not show two distinct H/D exchange populations for the C(29)H(38)N(5)O(6) structure formed by NH(3) and HOCH(3) loss, respectively. Relative extents of exchange for C(29)H(38)N(5)O(6) ions from six sequence isomers (YAGFL, AGFLY, GFLYA, FLYAG, LYAGF, and LFGAY) show a sequence dependence of relative isomer abundance. Supporting action IRMPD spectroscopy data are also presented herein and also show that multiple structures are present for the C(29)H(38)N(5)O(6) species from YAGFL-OH. Copyright 2010. Published by Elsevier Inc.

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.

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.

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

PubMed

Wang, Guanbo; Kaltashov, Igor A

2014-08-05

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

Optimization and application of atmospheric pressure chemical and photoionization hydrogen-deuterium exchange mass spectrometry for speciation of oxygen-containing compounds.

PubMed

Acter, Thamina; Kim, Donghwi; Ahmed, Arif; Jin, Jang Mi; Yim, Un Hyuk; Shim, Won Joon; Kim, Young Hwan; Kim, Sunghwan

2016-05-01

This paper presents a detailed investigation of the feasibility of optimized positive and negative atmospheric pressure chemical ionization (APCI) mass spectrometry (MS) and atmospheric pressure photoionization (APPI) MS coupled to hydrogen-deuterium exchange (HDX) for structural assignment of diverse oxygen-containing compounds. The important parameters for optimization of HDX MS were characterized. The optimized techniques employed in the positive and negative modes showed satisfactory HDX product ions for the model compounds when dichloromethane and toluene were employed as a co-solvent in APCI- and APPI-HDX, respectively. The evaluation of the mass spectra obtained from 38 oxygen-containing compounds demonstrated that the extent of the HDX of the ions was structure-dependent. The combination of information provided by different ionization techniques could be used for better speciation of oxygen-containing compounds. For example, (+) APPI-HDX is sensitive to compounds with alcohol, ketone, or aldehyde substituents, while (-) APPI-HDX is sensitive to compounds with carboxylic functional groups. In addition, the compounds with alcohol can be distinguished from other compounds by the presence of exchanged peaks. The combined information was applied to study chemical compositions of degraded oils. The HDX pattern, double bond equivalent (DBE) distribution, and previously reported oxidation products were combined to predict structures of the compounds produced from oxidation of oil. Overall, this study shows that APCI- and APPI-HDX MS are useful experimental techniques that can be applied for the structural analysis of oxygen-containing compounds.

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.

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

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.

Conversion of deuterium gas to heavy water by catalytic isotopic exchange using wetproof catalyst

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

Quaiattini, R.J.; McGauley, M.P.; Burns, D.L.

The invention at Chalk River Nuclear Laboratories of a simple method of wetproofing platinum catalysts allows them to retain their activity in liquid water. High performance catalysts for the hydrogen-water isotope exchange reaction that remain active for years can now be routinely produced. The first commercial application using the ordered-bed-type wetproofed isotope exchange catalyst developed and patented by Atomic Energy of Canada Ltd. has been successfully completed. Approximately 9100 m/sup 3/ of deuterium gas stored at Brookhaven National Laboratory was converted to high grade heavy water. Conversion efficiency exceeded 99.8%. The product D/sub 2/O concentration was 6.7 percentage points highermore » than the feed D/sub 2/ gas.« less

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%.

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 %.

Ordered ground states of metallic hydrogen and deuterium

NASA Technical Reports Server (NTRS)

Ashcroft, N. W.

1981-01-01

The physical attributes of some of the more physically distinct ordered states of metallic hydrogen and metallic deuterium at T = 0 and nearby are discussed. The likelihood of superconductivity in both is considered with respect to the usual coupling via the density fluctuations of the ions.

Functional Dynamics of Hexameric Helicase Probed by Hydrogen Exchange and Simulation

PubMed Central

Radou, Gaël; Dreyer, Frauke N.; Tuma, Roman; Paci, Emanuele

2014-01-01

The biological function of large macromolecular assemblies depends on their structure and their dynamics over a broad range of timescales; for this reason, it is a significant challenge to investigate these assemblies using conventional experimental techniques. One of the most promising experimental techniques is hydrogen-deuterium exchange detected by mass spectrometry. Here, we describe to our knowledge a new computational method for quantitative interpretation of deuterium exchange kinetics and apply it to a hexameric viral helicase P4 that unwinds and translocates RNA into a virus capsid at the expense of ATP hydrolysis. Room-temperature dynamics probed by a hundred nanoseconds of all-atom molecular dynamics simulations is sufficient to predict the exchange kinetics of most sequence fragments and provide a residue-level interpretation of the low-resolution experimental results. The strategy presented here is also a valuable tool to validate experimental data, e.g., assignments, and to probe mechanisms that cannot be observed by x-ray crystallography, or that occur over timescales longer than those that can be realistically simulated, such as the opening of the hexameric ring. PMID:25140434

A centroid molecular dynamics study of liquid para-hydrogen and ortho-deuterium.

PubMed

Hone, Tyler D; Voth, Gregory A

2004-10-01

Centroid molecular dynamics (CMD) is applied to the study of collective and single-particle dynamics in liquid para-hydrogen at two state points and liquid ortho-deuterium at one state point. The CMD results are compared with the results of classical molecular dynamics, quantum mode coupling theory, a maximum entropy analytic continuation approach, pair-product forward- backward semiclassical dynamics, and available experimental results. The self-diffusion constants are in excellent agreement with the experimental measurements for all systems studied. Furthermore, it is shown that the method is able to adequately describe both the single-particle and collective dynamics of quantum liquids. (c) 2004 American Institute of Physics

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.

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

PubMed

Tanabe, Katsuaki

2016-01-01

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

Structural Insights of Glucan Phosphatase Dynamics using Amide Hydrogen/Deuterium Exchange Mass Spectrometry

PubMed Central

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

2009-01-01

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

Comment on "A centroid molecular dynamics study of liquid para hydrogen and ortho deuterium" [J. Chem. Phys. 121, 6412 (2004)].

PubMed

Miller, Thomas F; Manolopoulos, David E; Madden, Paul A; Konieczny, Martin; Oberhofer, Harald

2005-02-01

We show that the two phase points considered in the recent simulations of liquid para hydrogen by Hone and Voth lie in the liquid-vapor coexistence region of a purely classical molecular dynamics simulation. By contrast, their phase point for ortho deuterium was in the one-phase liquid region for both classical and quantum simulations. These observations are used to account for their report that quantum mechanical effects enhance the diffusion in liquid para hydrogen and decrease it in ortho deuterium.(c) 2005 American Institute of Physics.

Measurement of the ratio of hydrogen to deuterium at the KSTAR 2009 experimental campaign

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

Kwak, Jong-Gu; Wang, Son Jong; Kim, Sun Ho

The control of the ratio of hydrogen to the deuterium is one of the very important issues for ion cyclotron range of frequency (ICRF) minority heating as well as the plasma wall interaction in the tokamak. The ratio of hydrogen to deuterium during the tokamak shot was deduced from the emission spectroscopy measurements during the KSTAR 2009 experimental campaign. Graphite tiles were used for the plasma facing components (PFCs) at KSTAR and its surface area exposed to the plasma was about 11 m{sup 2}. The data showed that it remained as high as around 50% during the campaign period becausemore » graphite tiles were exposed to the air for about two months and the hydrogen contents at the tiles are not fully pumped out due to the lack of baking on the PFC in the 2009 campaign. The validation of the spectroscopy method was checked by using the Zeeman effects and the ratio of hydrogen to the deuterium is compared with results from the residual gas analysis. During the tokamak shot, the ratio is low below 10% initially and saturated after around 1 s. When there is a hydrogen injection to the vessel via ion cyclotron wall conditioning and the boronization process where the carbone is used, the ratio of the hydrogen to the deuterium is increased by up to 100% and it recovers to around 50% after one day of operation. However it does not decrease below 50% at the end of the experimental campaign. It was found that the full baking on the PFC (with a high temperature and sufficient vacuum pumping) is required for the ratio control which guarantees the efficient ICRF heating at the KSTAR 2010 experimental campaign.« less

Comparative Study of Hydrogen- and Deuterium-Induced Degradation of Ferroelectric (Pb,La)(Zr,Ti)O3 Capacitors Using Time-of-Flight Secondary Ion Measurement.

PubMed

Takada, Yoko; Okamoto, Naoki; Saito, Takeyasu; Yoshimura, Takeshi; Fujimura, Norifumi; Higuchi, Koji; Kitajima, Akira; Shishido, Rie

2016-10-01

Ferroelectric (Pb,La)(Zr,Ti)O 3 (PLZT) capacitors were fabricated with Pt, Al:ZnO (AZO), or Sn:In 2 O 3 (ITO) top electrodes. Hydrogen- or deuterium-induced degradation was investigated for the three capacitors by annealing in a 3% H 2 /balance N 2 or 3% D 2 /balance N 2 ambient environment at 200 °C and 1 torr. The remnant polarization of all capacitors decreased after annealing in both H 2 and D 2 ambient after 45 min, and the remnant polarization of the Pt/PLZT/Pt capacitor significantly decreased after 45-min annealing compared with that of the AZO/PLZT/Pt and ITO/PLZT/Pt capacitors, even though the initial remnant polarization for the Pt/PLZT/Pt capacitor was larger. Time-of-flight secondary ion mass spectrometry showed slight differences in hydrogen content for the three different capacitors after H 2 annealing. In contrast, the deuterium content of the Pt/PLZT/Pt and AZO/PLZT/Pt or ITO/PLZT/PT capacitors was significantly different after deuterium annealing. Deuterium depth profiles for the Pt/PLZT/Pt capacitor after annealing showed that deuterium conformally exists in the PLZT layer of the Pt/PLZT/Pt capacitor, and deuterium accumulation under the Pt bottom electrode was also observed. This result suggests that diffusion of deuterium in Pt was much higher than that in PLZT. AZO and ITO top electrodes could act as a hydrogen barrier layer for ferroelectric films.

Effects of lithium-implantation on the hydrogen retention in both a-C:H and a-SiC:H materials submitted to deuterium bombardment

NASA Astrophysics Data System (ADS)

Barbier, G.; Ross, G. G.; El Khakani, M. A.; Chevarier, N.; Chevarier, A.

1997-02-01

The hydrogen release in plasma facing materials is a challenging problem for the hydrogen recycling. The hydrogen desorption from the a-C:H and a-SiC:H materials induced by deuterium bombardment has been investigated. Prior to the deuterium bombardment, both materials were implanted with different fluences of lithium ions. Before and after each irradiation, depth profiles of H, Li and deuterium were determined by nuclear microanalysis. After deuterium bombardment, it is shown that the retention of the initial hydrogen in both materials was enhanced by increasing the total dose of the implanted Li. For the a-C:H samples, the hydrogen desorption under deuterium bombardment was strongly reduced by lithium implantation. This effect was also evidenced in a-SiC:H samples, even though it is less spectacular than in a-C:H. Also, nuclear analyses showed that the retained dose of deuterium decreases when the lithium concentration increases. This could be a result of the formation of LiH bonds which occurs to the detriment of deuterium retention in both a-C:H and a-SiC:H materials. Preliminary results of both materials exposed to TdeV tokamak discharges confirms the role of Li in hydrogen retention, already observed in deuterium bombardment exposure.

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.

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.

Ultraviolet observations of cool stars. VII - Local interstellar hydrogen and deuterium Lyman-alpha

NASA Technical Reports Server (NTRS)

Mcclintock, W.; Henry, R. C.; Linsky, J. L.; Moos, H. W.

1978-01-01

High-resolution Copernicus spectra of Epsilon Eri and Epsilon Ind containing interstellar hydrogen and deuterium L-alpha absorption lines are presented, reduced, and analyzed. Parameters of the interstellar hydrogen and deuterium toward these two stars are derived independently, without any assumptions concerning the D/H ratio. Copernicus spectra of Alpha Aur and Alpha Cen A are reanalyzed, and limits on the D/H number-density ratio consistent with the data for all four stars are considered. A comparison of the present estimates for the parameters of the local interstellar medium with those obtained by other techniques shows that there is no compelling evidence for significant variations in the hydrogen density and D/H ratio in the local interstellar medium. On this basis the hypothesis of an approaching local interstellar cloud proposed by Vidal-Madjar et al. (1978) is rejected

Hydrogen-deuterium substitution in solid ethanol by surface reactions at low temperatures

NASA Astrophysics Data System (ADS)

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

2016-10-01

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

High-resolution spectroscopy of the 1S-2S transition of atomic hydrogen and deuterium

NASA Astrophysics Data System (ADS)

Schmidt-Kaler, F.; Leibfried, D.; Seel, S.; Zimmermann, C.; König, W.; Weitz, M.; Hänsch, T. W.

1995-04-01

Two-photon spectroscopy of the hydrogen 1S-2S transition in a cold atomic beam has reached a resolution Δν/ν of 1 part in 1011 in hydrogen and 7 parts in 1012 in deuterium. The hydrogen and deuterium 1S-2S transition frequencies have been determined with a precision of 1 part in 1011. This leads to an accurate value for the Rydberg constant, while the 1S Lamb shift and the isotope shift are determined with order of magnitude improvements over previous measurements. We describe in detail the 1S-2S spectrometer, calculate the line shape of the resonance, and compare it to the experimental data.

Deuterium Enrichment in Stratospheric Molecular Hydrogen

NASA Astrophysics Data System (ADS)

Rahn, T.; Eiler, J.; McCarthy, M. C.; Boering, K. A.; Wennberg, P.; Atlas, E.; Donnelly, S.; Schauffler, S.

2002-12-01

Molecular hydrogen (H2) is the second most abundant reduced gas in the atmosphere (after methane) with a globally averaged mixing ratio of ~ 530 ppbv. Its largest source is believed to be photochemical oxidation of methane (C H4) and non-methane hydrocarbons (NMHCs); other recognized sources include biomass burning, fossil fuel burning, nitrogen fixation, and ocean degassing. As with other atmospheric trace gases, the stable isotopic content of H2 has the potential to help quantify various aspects of its production and destruction. The average deuterium content of H2 (expressed as δDH2) is enriched by ~110 ‰ relative to Vienna Standard Mean Ocean Water while CH4 in the troposphere, the precursor for photochemical H2 production, is depleted by ~ 90 ‰ relative to V-SMOW and similar values are expected for NMHCs. Both natural and anthropogenic combustion sources of H2 have been shown to be depleted in deuterium by 200 to 300 ‰ (Gerst and Quay, 2001; Rahn et al., 2002), and the ocean and N2 fixation sources are expected to be in near thermodynamic equilibrium with local H2O and should have deuterium levels of ~-700 ‰ (Rahn et al., 2002). In order to offset these deuterium depleted sources and account for the observed tropospheric δDH2, the balancing loss processes must discriminate against reaction with HD and/or the total fractionation associated with CH4 oxidation and the subsequent reactions leading to H2 must favor production of deuterated H2. We have analyzed a suite of stratospheric air samples in order to investigate the photochemical processes influencing the deuterium content of H2. While the mixing ratio of H2 is nearly constant, the deuterium content increases such that δD=440 ‰ in samples with a stratospheric mean age of ~6 years. The constant mixing ratio results from the fact that production due to CH4 oxidation and loss due to H2 oxidation are approximately equal. The observed trend in δD of stratospheric H2 can only be accounted for by an

Hydrogen and deuterium in the local interstellar medium

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

Murthy, J.N.

1987-01-01

This work reports on the results of a series of IUE observations of interstellar HI and DI Ly..cap alpha.. absorption against the chromospheric Ly..cap alpha.. emission of the nearby late-type stars ..cap alpha.. Cen B(1.3 pc), epsilon Eri (3.3 pc), Procyon (3.5 pc), Altair (5.1 pc), Capella (13.2 pc), and HR 1099 (33 pc). The density, velocity dispersion, and bulk velocity of the neutral hydrogen along the line of sight to each of these stars was derived. Lower limits were placed on the deuterium-to-hydrogen (D/H) ratio towards the same stars. These IUE results are generally consistent with previous observations ofmore » the same stars with the Copernicus satellite showing that this modeling procedure is independent of stellar variations over a period of several years. The HI absorption profile towards Altair shows a broad saturated core and steep line wings, consistent with a multicomponent interstellar medium in that direction. The bulk velocities towards the other stars are consistent with a bulk flow from the approximate direction of the galactic center but do show local variations from a uniform flow, possibly indicating a complicated velocity structure even in the solar neighborhood. Interstellar deuterium is detected towards every star except Altair and the derived values for the D/H ratio are consistent with those previously found with Copernicus.« less

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.

Submolecular regulation of cell transformation by deuterium depleting water exchange reactions in the tricarboxylic acid substrate cycle.

PubMed

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

2016-02-01

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

External reflection FTIR of peptide monolayer films in situ at the air/water interface: experimental design, spectra-structure correlations, and effects of hydrogen-deuterium exchange.

PubMed Central

Flach, C R; Brauner, J W; Taylor, J W; Baldwin, R C; Mendelsohn, R

1994-01-01

A Fourier transform infrared spectrometer has been interfaced with a surface balance and a new external reflection infrared sampling accessory, which permits the acquisition of spectra from protein monolayers in situ at the air/water interface. The accessory, a sample shuttle that permits the collection of spectra in alternating fashion from sample and background troughs, reduces interference from water vapor rotation-vibration bands in the amide I and amide II regions of protein spectra (1520-1690 cm-1) by nearly an order of magnitude. Residual interference from water vapor absorbance ranges from 50 to 200 microabsorbance units. The performance of the device is demonstrated through spectra of synthetic peptides designed to adopt alpha-helical, antiparallel beta-sheet, mixed beta-sheet/beta-turn, and unordered conformations at the air/water interface. The extent of exchange on the surface can be monitored from the relative intensities of the amide II and amide I modes. Hydrogen-deuterium exchange may lower the amide I frequency by as much as 11-12 cm-1 for helical secondary structures. This shifts the vibrational mode into a region normally associated with unordered structures and leads to uncertainties in the application of algorithms commonly used for determination of secondary structure from amide I contours of proteins in D2O solution. PMID:7919013

Deciphering the Mode of Action of the Processive Polysaccharide Modifying Enzyme Dermatan Sulfate Epimerase 1 by Hydrogen-Deuterium Exchange Mass Spectrometry.

PubMed

Tykesson, Emil; Mao, Yang; Maccarana, Marco; Pu, Yi; Gao, Jinshan; Lin, Cheng; Zaia, Joseph; Westergren-Thorsson, Gunilla; Ellervik, Ulf; Malmström, Lars; Malmström, Anders

2016-02-01

Distinct from template-directed biosynthesis of nucleic acids and proteins, the enzymatic synthesis of heterogeneous polysaccharides is a complex process that is difficult to study using common analytical tools. Therefore, the mode of action and processivity of those enzymes are largely unknown. Dermatan sulfate epimerase 1 (DS-epi1) is the predominant enzyme during the formation of iduronic acid residues in the glycosaminoglycan dermatan sulfate. Using recombinant DS-epi1 as a model enzyme, we describe a tandem mass spectrometry-based method to study the mode of action of polysaccharide processing enzymes. The enzyme action on the substrate was monitored by hydrogen-deuterium exchange mass spectrometry and the sequence information was then fed into mathematical models with two different assumptions of the mode of action for the enzyme: processive reducing end to non-reducing end, and processive non-reducing end to reducing end. Model data was scored by correlation to experimental data and it was found that DS-epi1 attacks its substrate on a random position, followed by a processive mode of modification towards the non-reducing end and that the substrate affinity of the enzyme is negatively affected by each additional epimerization event. It could also be shown that the smallest active substrate was the reducing end uronic acid in a tetrasaccharide and that octasaccharides and longer oligosaccharides were optimal substrates. The method of using tandem mass spectrometry to generate sequence information of the complex enzymatic products in combination with in silico modeling can be potentially applied to study the mode of action of other enzymes involved in polysaccharide biosynthesis.

Protein Internal Dynamics Associated With Pre-System Glass Transition Temperature Endothermic Events: Investigation of Insulin and Human Growth Hormone by Solid State Hydrogen/Deuterium Exchange.

PubMed

Fang, Rui; Grobelny, Pawel J; Bogner, Robin H; Pikal, Michael J

2016-11-01

Lyophilized proteins are generally stored below their glass transition temperature (T g ) to maintain long-term stability. Some proteins in the (pure) solid state showed a distinct endotherm at a temperature well below the glass transition, designated as a pre-T g endotherm. The pre-T g endothermic event has been linked with a transition in protein internal mobility. The aim of this study was to investigate the internal dynamics of 2 proteins, insulin and human growth hormone (hGH), both of which exhibit the pre-T g endothermic event with onsets at 50°C-60°C. Solid state hydrogen/deuterium (H/D) exchange of both proteins was characterized by Fourier transform infrared spectroscopy over a temperature range from 30°C to 80°C. A distinct sigmoidal transition in the extent of H/D exchange had a midpoint of 56.1 ± 1.2°C for insulin and 61.7 ± 0.9°C for hGH, suggesting a transition to greater mobility in the protein molecules at these temperatures. The data support the hypothesis that the pre-T g event is related to a transition in internal protein mobility associated with the protein dynamical temperature. Exceeding the protein dynamical temperature is expected to activate protein internal motion and therefore may have stability consequences. Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Comparison of hydrogen and deuterium adsorption on Pd(100).

PubMed

Gladys, M J; Kambali, I; Karolewski, M A; Soon, A; Stampfl, C; O'Connor, D J

2010-01-14

Low energy ion recoil spectroscopy is a powerful technique for the determination of adsorbate position on metal surfaces. In this study, this technique is employed to compare the adsorption sites of hydrogen and deuterium on Pd(100) by detection of either H or D recoil ions produced by Ne(+) bombardment. Comparisons of experimental and Kalypso simulated azimuthal yield distributions show that, at room temperature, both hydrogen isotopes are adsorbed in the fourfold hollow site of Pd(100), however, at different heights above the surface (H-0.20 A and D-0.25 A). The adsorbates remain in the hollow site at all temperatures up to 383 K even though they move up to 0.40-0.45 A above the surface. Density functional theory calculations show a similar coverage dependent adsorption height for both H and D and confirm a real difference between the H and D adsorption heights based on zero point energies.

Deuterium Enrichment of PAHs by VUV Irradiation of Interstellar Ices

NASA Technical Reports Server (NTRS)

Bernstein, Max P.; Sandford, Scott A.; Allamandola, Louis J.; Gillette, J. Seb; Zare, Richard N.; DeVincenzi, Donald (Technical Monitor)

1998-01-01

Laboratory results demonstrate that polycyclic aromatic hydrocarbons (PAHs) rapidly exchange their hydrogen atoms with those of nearby molecules when they are frozen into low-temperature ices and exposed to vacuum ultraviolet radiation. As a result, PAHs quickly become deuterium-enriched when VUV irradiated in D-containing ices. This mechanism has important consequences for several astrophysical issues owing to the ubiquitous nature of PAHs in the interstellar medium. For example, this process may explain the deuterium enrichments found in PAHs in meteorites and interplanetary dust particles. These results also provide general predictions about the molecular siting of the deuterium on aromatic materials in meteorites if this process produced a significant fraction of their D-enrichment.

Load-dependent destabilization of the γ-rotor shaft in FOF1 ATP synthase revealed by hydrogen/deuterium-exchange mass spectrometry

PubMed Central

Vahidi, Siavash; Bi, Yumin; Dunn, Stanley D.; Konermann, Lars

2016-01-01

FoF1 is a membrane-bound molecular motor that uses proton-motive force (PMF) to drive the synthesis of ATP from ADP and Pi. Reverse operation generates PMF via ATP hydrolysis. Catalysis in either direction involves rotation of the γε shaft that connects the α3β3 head and the membrane-anchored cn ring. X-ray crystallography and other techniques have provided insights into the structure and function of FoF1 subcomplexes. However, interrogating the conformational dynamics of intact membrane-bound FoF1 during rotational catalysis has proven to be difficult. Here, we use hydrogen/deuterium exchange mass spectrometry to probe the inner workings of FoF1 in its natural membrane-bound state. A pronounced destabilization of the γ C-terminal helix during hydrolysis-driven rotation was observed. This behavior is attributed to torsional stress in γ, arising from γ⋅⋅⋅α3β3 interactions that cause resistance during γ rotation within the apical bearing. Intriguingly, we find that destabilization of γ occurs only when FoF1 operates against a PMF-induced torque; the effect disappears when PMF is eliminated by an uncoupler. This behavior resembles the properties of automotive engines, where bearings inflict greater forces on the crankshaft when operated under load than during idling. PMID:26884184

Refinement of the experimental dynamic structure factor for liquid para-hydrogen and ortho-deuterium using semi-classical quantum simulation.

PubMed

Smith, Kyle K G; Poulsen, Jens Aage; Cunsolo, A; Rossky, Peter J

2014-01-21

The dynamic structure factor of liquid para-hydrogen and ortho-deuterium in corresponding thermodynamic states (T = 20.0 K, n = 21.24 nm(-3)) and (T = 23.0 K, n = 24.61 nm(-3)), respectively, has been computed by both the Feynman-Kleinert linearized path-integral (FK-LPI) and Ring-Polymer Molecular Dynamics (RPMD) methods and compared with Inelastic X Ray Scattering spectra. The combined use of computational and experimental methods enabled us to reduce experimental uncertainties in the determination of the true sample spectrum. Furthermore, the refined experimental spectrum of para-hydrogen and ortho-deuterium is consistently reproduced by both FK-LPI and RPMD results at momentum transfers lower than 12.8 nm(-1). At larger momentum transfers the FK-LPI results agree with experiment much better for ortho-deuterium than for para-hydrogen. More specifically we found that for k ∼ 20.0 nm(-1) para-hydrogen provides a test case for improved approximations to quantum dynamics.

The hydrogen isotope ratio in W7-AS during deuterium NBI heating

NASA Astrophysics Data System (ADS)

Zebisch, P.; Taglauer, E.; W7-AS Team; NBI Team

1999-04-01

With a so-called sniffer probe the fraction of hydrogen during discharges with deuterium NBI heating was studied in the plasma edge of the stellarator W7-AS. As expected, the ratios were significantly lower than in discharges with hydrogen NBI heating but were higher than those in discharges with only ECRH. An examination of the possible reasons for this increase concludes that it is not only partially caused by the direct influence of neutral injection but also depends on the energy content of the plasma determined by the heating power and the confinement time. Of course, the isotope ratio also depends on the starting conditions, i.e. the isotope ratio before the onset of NBI.

IUE observations of hydrogen and deuterium in the local interstellar medium

NASA Technical Reports Server (NTRS)

Murthy, J.; Henry, R. C.; Moos, H. W.; Landsman, W. B.; Linsky, J. L.

1987-01-01

High-resolution Ly-alpha spectra of the late-type stars Epsilon Eri, Procyon, Altair, Capella, and HR 1099 taken with the short-wavelength camera on IUE are presented. The density, velocity dispersion, and bulk velocity of the interstellar H I toward each of the stars is derived from the spectra. Lower limits on the deuterium-to-hydrogen ratio toward these stars are obtained.

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.

Palladium-catalyzed Br/D exchange of arenes: Selective deuterium incorporation with versatile functional group tolerance and high efficiency

DOE PAGES

Zhang, Honghai -Hai; Bonnesen, Peter V.; Hong, Kunlun

2015-07-13

There is a facile method for introducing one or more deuterium atoms onto an aromatic nucleus via Br/D exchange with high functional group tolerance and high incorporation efficiency is disclosed. Deuterium-labeled aryl chlorides and aryl borates which could be used as substrates in cross-coupling reactions to construct more complicated deuterium-labeled compounds can also be synthesized by this method.

Determination of hydrogen/deuterium ratio with neutron measurements on MAST

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

Klimek, I., E-mail: iwona.klimek@physics.uu.se; Cecconello, M.; Ericsson, G.

2014-11-15

On MAST, compressional Alfvén eigenmodes can be destabilized by the presence of a sufficiently large population of energetic particles in the plasma. This dependence was studied in a series of very similar discharges in which increasing amounts of hydrogen were puffed into a deuterium plasma. A simple method to estimate the isotopic ratio n{sub H}/n{sub D} using neutron emission measurements is here described. The inferred isotopic ratio ranged from 0.0 to 0.6 and no experimental indication of changes in radial profile of n{sub H}/n{sub D} were observed. These findings are confirmed by TRANSP/NUBEAM simulations of the neutron emission.

Refinement of the experimental dynamic structure factor for liquid para-hydrogen and ortho-deuterium using semi-classical quantum simulation

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

Smith, Kyle K. G., E-mail: kylesmith@utexas.edu; Rossky, Peter J., E-mail: peter.rossky@austin.utexas.edu; Poulsen, Jens Aage, E-mail: jens72@chem.gu.se

The dynamic structure factor of liquid para-hydrogen and ortho-deuterium in corresponding thermodynamic states (T = 20.0 K, n = 21.24 nm{sup −3}) and (T = 23.0 K, n = 24.61 nm{sup −3}), respectively, has been computed by both the Feynman-Kleinert linearized path-integral (FK-LPI) and Ring-Polymer Molecular Dynamics (RPMD) methods and compared with Inelastic X Ray Scattering spectra. The combined use of computational and experimental methods enabled us to reduce experimental uncertainties in the determination of the true sample spectrum. Furthermore, the refined experimental spectrum of para-hydrogen and ortho-deuterium is consistently reproduced by both FK-LPI and RPMD results at momentum transfers lower than 12.8 nm{sup −1}.more » At larger momentum transfers the FK-LPI results agree with experiment much better for ortho-deuterium than for para-hydrogen. More specifically we found that for k ∼ 20.0 nm{sup −1} para-hydrogen provides a test case for improved approximations to quantum dynamics.« less

Effects of hydrogen atom spin exchange collisions on atomic hydrogen maser oscillation frequency

NASA Technical Reports Server (NTRS)

Crampton, S. B.

1979-01-01

Frequency shifts due to collisions between hydrogen atoms in an atomic hydrogen maser frequency standard are studied. Investigations of frequency shifts proportional to the spin exchange frequency shift cross section and those proportional to the duration of exchange collisions are discussed. The feasibility of operating a hydrogen frequency standard at liquid helium temperatures is examined.

Electron spin resonance of an irradiated single crystal of potassium hydrogen maleate

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

Iwasaki, Machio; Itoh, Koichi

1963-09-15

Electron spin resonance absorptions of x-irradiated single crystals of potassium hydrogen maleate and potassium deuterium maleate were observed. Both compounds gave the same hyperfine structures, although the slightly sharper line widths were observed for the deuterium exchanged compound.

Hydrogen-Deuterium Exchange Mass Spectrometry Reveals Calcium Binding Properties and Allosteric Regulation of Downstream Regulatory Element Antagonist Modulator (DREAM).

PubMed

Zhang, Jun; Li, Jing; Craig, Theodore A; Kumar, Rajiv; Gross, Michael L

2017-07-18

Downstream regulatory element antagonist modulator (DREAM) is an EF-hand Ca 2+ -binding protein that also binds to a specific DNA sequence, downstream regulatory elements (DRE), and thereby regulates transcription in a calcium-dependent fashion. DREAM binds to DRE in the absence of Ca 2+ but detaches from DRE under Ca 2+ stimulation, allowing gene expression. The Ca 2+ binding properties of DREAM and the consequences of the binding on protein structure are key to understanding the function of DREAM. Here we describe the application of hydrogen-deuterium exchange mass spectrometry (HDX-MS) and site-directed mutagenesis to investigate the Ca 2+ binding properties and the subsequent conformational changes of full-length DREAM. We demonstrate that all EF-hands undergo large conformation changes upon calcium binding even though the EF-1 hand is not capable of binding to Ca 2+ . Moreover, EF-2 is a lower-affinity site compared to EF-3 and -4 hands. Comparison of HDX profiles between wild-type DREAM and two EF-1 mutated constructs illustrates that the conformational changes in the EF-1 hand are induced by long-range structural interactions. HDX analyses also reveal a conformational change in an N-terminal leucine-charged residue-rich domain (LCD) remote from Ca 2+ -binding EF-hands. This LCD domain is responsible for the direct interaction between DREAM and cAMP response element-binding protein (CREB) and regulates the recruitment of the co-activator, CREB-binding protein. These long-range interactions strongly suggest how conformational changes transmit the Ca 2+ signal to CREB-mediated gene transcription.

A Reexamination of Deuterium Fractionation on Mars

NASA Astrophysics Data System (ADS)

Pathare, A.; Paige, D. A.

1997-07-01

The ratio of deuterium to hydrogen in the Martian atmosphere is enhanced by a factor of 5 with respect to the terrestrial value, probably due to fractionation associated with thermal Jeans escape from the top of the atmosphere. Theoretical analyses of the relative efficiency of H and D escape have suggested that the deuterium enrichment implies Mars has outgassed the vast majority of its H2O and that the Martian atmosphere is presently not exchanging water with a juvenile reservoir. However, measurements of high and variable D/H values within hydrous minerals in SNC meteorites strongly suggest that mixing between the atmosphere and juvenile water has taken place. Furthermore, the lack of any observed enrichment of atmospheric (18) O with respect to (16) O, in spite of fractionating nonthermal escape mechanisms, indicates buffering by some juvenile source of oxygen, most probably in the form of a surface or subsurface reservoir of water. We propose that this apparent paradox in the interpretation of isotopic hydrogen and oxygen fractionation --or lack thereof-- can be resolved by re-examining the standard model of deuterium fractionation efficiency on Mars. Specifically, we demonstrate the importance of using upper atmospheric temperatures more representative of the range experienced by the Martian exosphere over the course of the solar cycle. Preliminary calculations involving changes in effusion velocity and diffusive separation as a function of exospheric temperature indicate that incorporating these more representative lower exospheric temperatures will reduce the relative efficiency of D escape, in which case the observed enrichment of deuterium can indeed result from exchange with a juvenile source of water. We are in the process of confirming these computations with a one-dimensional upper atmospheric photochemical model that considers the effects of changing solar activity and exospheric temperature on ionospheric composition. If our initial calculations are

IUE observations of neutral hydrogen and deuterium in the local interstellar medium

NASA Technical Reports Server (NTRS)

Landsman, W. B.; Murthy, J.; Henry, R. C.; Moos, H. W.; Linsky, J. L.

1986-01-01

Small-aperture, high-dispersion IUE spectra have been obtained of seven late-type stars that, in general, confirm previous Copernicus results concerning the distribution of hydrogen and deuterium in the local interstellar medium. In addition, the IUE Ly Alpha spectra of Altair, and of the Alpha Cen components, suggest that multiple velocity components exist in these two directions.

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

NASA Astrophysics Data System (ADS)

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

2018-01-01

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

Effects of Drying Process on an IgG1 Monoclonal Antibody Using Solid-State Hydrogen Deuterium Exchange with Mass Spectrometric Analysis (ssHDX-MS).

PubMed

Moussa, Ehab M; Wilson, Nathan E; Zhou, Qi Tony; Singh, Satish K; Nema, Sandeep; Topp, Elizabeth M

2018-01-03

Lyophilization and spray drying are widely used to manufacture solid forms of therapeutic proteins. Lyophilization is used to stabilize proteins vulnerable to degradation in solution, whereas spray drying is mainly used to prepare inhalation powders or as an alternative to freezing for storing bulk drug substance. Both processes impose stresses that may adversely affect protein structure, stability and bioactivity. Here, we compared lyophilization with and without controlled ice nucleation, and spray drying for their effects on the solid-state conformation and matrix interactions of a model IgG1 monoclonal antibody (mAb). Solid-state conformation and matrix interactions of the mAb were probed using solid-state hydrogen-deuterium exchange with mass spectrometric analysis (ssHDX-MS), and solid-state Fourier transform infrared (ssFTIR) and solid-state fluorescence spectroscopies. mAb conformation and/or matrix interactions were most perturbed in mannitol-containing samples and the distribution of states was more heterogeneous in sucrose and trehalose samples that were spray dried. The findings demonstrate the sensitivity of ssHDX-MS to changes weakly indicated by spectroscopic methods, and support the broader use of ssHDX-MS to probe formulation and process effects on proteins in solid samples.

Protein hydrogen exchange: Testing current models

PubMed Central

Skinner, John J; Lim, Woon K; Bédard, Sabrina; Black, Ben E; Englander, S Walter

2012-01-01

To investigate the determinants of protein hydrogen exchange (HX), HX rates of most of the backbone amide hydrogens of Staphylococcal nuclease were measured by NMR methods. A modified analysis was used to improve accuracy for the faster hydrogens. HX rates of both near surface and well buried hydrogens are spread over more than 7 orders of magnitude. These results were compared with previous hypotheses for HX rate determination. Contrary to a common assumption, proximity to the surface of the native protein does not usually produce fast exchange. The slow HX rates for unprotected surface hydrogens are not well explained by local electrostatic field. The ability of buried hydrogens to exchange is not explained by a solvent penetration mechanism. The exchange rates of structurally protected hydrogens are not well predicted by algorithms that depend only on local interactions or only on transient unfolding reactions. These observations identify some of the present difficulties of HX rate prediction and suggest the need for returning to a detailed hydrogen by hydrogen analysis to examine the bases of structure-rate relationships, as described in the companion paper (Skinner et al., Protein Sci 2012;21:996–1005). PMID:22544567

Polarized deuterium internal target at AmPS (NIKHEF)

NASA Astrophysics Data System (ADS)

Ferro-Luzzi, M.; Zhou, Z.-L.; van den Brand, J. F. J.; Bulten, H. J.; Alarcon, R.; van Bakel, N.; Botto, T.; Bouwhuis, M.; van Buuren, L.; Comfort, J.; Doets, M.; Dolfini, S.; Ent, R.; Geurts, D.; Heimberg, P.; Higinbotham, D. W.; de Jager, C. W.; Lang, J.; de Lange, D. J.; Norum, B.; Passchier, I.; Poolman, H. R.; Six, E.; Steijger, J.; Szczerba, D.; Unal, O.; de Vries, H.

1998-01-01

We describe the polarized deuterium target internal to the NIKHEF medium-energy electron storage ring. Tensor polarized deuterium was produced in an atomic beam source and injected into a storage cell target. A Breit-Rabi polarimeter was used to monitor the injected atomic beam intensity and polarization. An electrostatic ion-extraction system and a Wien filter were utilized to measure on-line the atomic fraction of the target gas in the storage cell. This device was supplemented with a tensor polarization analyzer using the neutron anisotropy of the 3H(d,n)α reaction at 60 keV. This method allows determining the density-averaged nuclear polarization of the target gas, independent of spatial and temporal variations. We address issues important for polarized hydrogen/deuterium internal targets, such as the effects of spin-exchange collisions and resonant transitions induced by the RF fields of the charged particle beam.

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.

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.

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

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

Yun, Youngjoo; Kim, Dong Kyun; Seo, Min-Duk

2015-01-30

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

Hydrogen and deuterium transport and inventory parameters through W and W-alloys for fusion reactor applications

NASA Astrophysics Data System (ADS)

Benamati, G.; Serra, E.; Wu, C. H.

2000-12-01

The aim of this work is to measure the hydrogen/deuterium transport and inventory parameters in relevant structural and/or armour materials for the International Thermonuclear Experimental Reactor (ITER) divertor such as W and W-alloys. The W-alloys: W, W + 1% La 2O 3 and W + 5% Re have been investigated. The materials were supplied from the Metallwerk Plansee GmbH (Austria). Measurements were conducted using a time-dependent permeation method over the temperature range 673-873 K with hydrogen and deuterium pressures in the range 10-100 kPa (100-1000 mbar). The samples were also characterized using optical microscopy, SEM and energy dispersive spectroscopy (EDS) in order to investigate the composition, microstructure and morphology of the surfaces and cross-sections through the samples.

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.

Temperature-induced conformational change at the catalytic site of Sulfolobus solfataricus alcohol dehydrogenase highlighted by Asn249Tyr substitution. A hydrogen/deuterium exchange, kinetic, and fluorescence quenching study.

PubMed

Secundo, Francesco; Russo, Consiglia; Giordano, Antonietta; Carrea, Giacomo; Rossi, Mosè; Raia, Carlo A

2005-08-23

A combination of hydrogen/deuterium exchange, fluorescence quenching, and kinetic studies was used to acquire experimental evidence for the crystallographically hypothesized increase in local flexibility which occurs in thermophilic NAD(+)-dependent Sulfolobus solfataricus alcohol dehydrogenase (SsADH) upon substitution Asn249Tyr. The substitution, located at the adenine-binding site, proved to decrease the affinity for both coenzyme and substrate, rendering the mutant enzyme 6-fold more active when compared to the wild-type enzyme [Esposito et al. (2003) FEBS Lett. 539, 14-18]. The amide H/D exchange data show that the wild-type and mutant enzymes have similar global flexibility at 22 and 60 degrees C. However, the temperature dependence of the Stern-Volmer constant determined by acrylamide quenching shows that the increase in temperature affects the local flexibility differently, since the K(SV) increment is significantly higher for the wild-type than for the mutant enzyme over the range 18-45 degrees C. Interestingly, the corresponding van't Hoff plot (log K(SV) vs 1/T) proves nonlinear for the apo and holo wild-type and apo mutant enzymes, with a break at approximately 45 degrees C in all three cases due to a conformational change affecting the tryptophan microenvironment experienced by the quencher molecules. The Arrhenius and van't Hoff plots derived from the k(cat) and K(M) thermodependence measured with cyclohexanol and NAD(+) at different temperatures display an abrupt change of slope at 45-50 degrees C. This proves more pronounced in the case of the mutant enzyme compared to the wild-type enzyme due to a conformational change in the structure rather than to an overlapping of two or more rate-limiting reaction steps with different temperature dependencies of their rate constants. Three-dimensional analysis indicates that the observed conformational change induced by temperature is associated with the flexible loops directly involved in the substrate and

Polarized deuterium internal target at AmPS (NIKHEF)

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

Norum, Blaine; De Jager, Cornelis; Geurts, D.

1997-08-01

We describe the polarized deuterium target internal to the NIKHEF medium-energy electron storage ring. Tensor polarized deuterium was produced in an atomic beam source and injected into a storage cell target. A Breit-Rabi polarimeter was used to monitor the injected atomic beam intensity and polarization. An electrostatic ion-extraction system and a Wien filter were utilized to measure on-line the atomic fraction of the target gas in the storage cell. This device was supplemented with a tensor polarization analyzer using the neutron anisotropy of the 3H(d,n)sigma reaction at 60 keV. This method allows determining the density-averaged nuclear polarization of the targetmore » gas, independent of spatial and temporal variations. We address issues important for polarized hydrogen/deuterium internal targets, such as the effects of spin-exchange collisions and resonant transitions induced by the RF fields of the charged particle beam.« less

Polarized deuterium internal target at AmPS (NIKHEF)

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

Ferro-Luzzi, M.; NIKHEF, P.O. Box 41882, 1009 DB Amsterdam; Zhou, Z.-L.

1998-01-20

We describe the polarized deuterium target internal to the NIKHEF medium-energy electron storage ring. Tensor polarized deuterium was produced in an atomic beam source and injected into a storage cell target. A Breit-Rabi polarimeter was used to monitor the injected atomic beam intensity and polarization. An electrostatic ion-extraction system and a Wien filter were utilized to measure on-line the atomic fraction of the target gas in the storage cell. This device was supplemented with a tensor polarization analyzer using the neutron anisotropy of the {sup 3}H(d,n){alpha} reaction at 60 keV. This method allows determining the density-averaged nuclear polarization of themore » target gas, independent of spatial and temporal variations. We address issues important for polarized hydrogen/deuterium internal targets, such as the effects of spin-exchange collisions and resonant transitions induced by the RF fields of the charged particle beam.« less

Detection of lipid-induced structural changes of the Marburg virus matrix protein VP40 using hydrogen/deuterium exchange-mass spectrometry

PubMed Central

Wijesinghe, Kaveesha J.; Urata, Sarah; Bhattarai, Nisha; Kooijman, Edgar E.; Gerstman, Bernard S.; Chapagain, Prem P.; Li, Sheng; Stahelin, Robert V.

2017-01-01

Marburg virus (MARV) is a lipid-enveloped virus from the Filoviridae family containing a negative sense RNA genome. One of the seven MARV genes encodes the matrix protein VP40, which forms a matrix layer beneath the plasma membrane inner leaflet to facilitate budding from the host cell. MARV VP40 (mVP40) has been shown to be a dimeric peripheral protein with a broad and flat basic surface that can associate with anionic phospholipids such as phosphatidylserine. Although a number of mVP40 cationic residues have been shown to facilitate binding to membranes containing anionic lipids, much less is known on how mVP40 assembles to form the matrix layer following membrane binding. Here we have used hydrogen/deuterium exchange (HDX) mass spectrometry to determine the solvent accessibility of mVP40 residues in the absence and presence of phosphatidylserine and phosphatidylinositol 4,5-bisphosphate. HDX analysis demonstrates that two basic loops in the mVP40 C-terminal domain make important contributions to anionic membrane binding and also reveals a potential oligomerization interface in the C-terminal domain as well as a conserved oligomerization interface in the mVP40 N-terminal domain. Lipid binding assays confirm the role of the two basic patches elucidated with HD/X measurements, whereas molecular dynamics simulations and membrane insertion measurements complement these studies to demonstrate that mVP40 does not appreciably insert into the hydrocarbon region of anionic membranes in contrast to the matrix protein from Ebola virus. Taken together, we propose a model by which association of the mVP40 dimer with the anionic plasma membrane facilitates assembly of mVP40 oligomers. PMID:28167534

Detection of lipid-induced structural changes of the Marburg virus matrix protein VP40 using hydrogen/deuterium exchange-mass spectrometry.

PubMed

Wijesinghe, Kaveesha J; Urata, Sarah; Bhattarai, Nisha; Kooijman, Edgar E; Gerstman, Bernard S; Chapagain, Prem P; Li, Sheng; Stahelin, Robert V

2017-04-14

Marburg virus (MARV) is a lipid-enveloped virus from the Filoviridae family containing a negative sense RNA genome. One of the seven MARV genes encodes the matrix protein VP40, which forms a matrix layer beneath the plasma membrane inner leaflet to facilitate budding from the host cell. MARV VP40 (mVP40) has been shown to be a dimeric peripheral protein with a broad and flat basic surface that can associate with anionic phospholipids such as phosphatidylserine. Although a number of mVP40 cationic residues have been shown to facilitate binding to membranes containing anionic lipids, much less is known on how mVP40 assembles to form the matrix layer following membrane binding. Here we have used hydrogen/deuterium exchange (HDX) mass spectrometry to determine the solvent accessibility of mVP40 residues in the absence and presence of phosphatidylserine and phosphatidylinositol 4,5-bisphosphate. HDX analysis demonstrates that two basic loops in the mVP40 C-terminal domain make important contributions to anionic membrane binding and also reveals a potential oligomerization interface in the C-terminal domain as well as a conserved oligomerization interface in the mVP40 N-terminal domain. Lipid binding assays confirm the role of the two basic patches elucidated with HD/X measurements, whereas molecular dynamics simulations and membrane insertion measurements complement these studies to demonstrate that mVP40 does not appreciably insert into the hydrocarbon region of anionic membranes in contrast to the matrix protein from Ebola virus. Taken together, we propose a model by which association of the mVP40 dimer with the anionic plasma membrane facilitates assembly of mVP40 oligomers. © 2017 by The American Society for Biochemistry and Molecular Biology, Inc.

D0 production in deep inelastic muon scattering on hydrogen and deuterium

NASA Astrophysics Data System (ADS)

Aubert, J. J.; Bassompierre, G.; Becks, K. H.; Benchouk, C.; Best, C.; Böhm, E.; de Bouard, X.; Brasse, F. W.; Broll, C.; Brown, S.; Carr, J.; Clifft, R. W.; 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.; Minssieux, H.; 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.; Schneider, A.; Sloan, T.; Stier, H. E.; Stockhausen, W.; Thénard, J. M.; Thompson, J. C.; Urban, L.; Villers, M.; Wahlen, H.; Whalley, M.; Williams, D.; Williams, W. S. C.; Williamson, J.; Wimpenny, S. J.

1986-01-01

Inclusive D0(D0) production in deep inelastic scattering of 280 GeV and 240 GeV muons on hydrogen and deuterium targets has been measured; differential cross sections are given and the total cross sections extrapolated to Q2 = 0. They are compared with the results of photoproduction experiments and with measurements of the muoproduction of charm detected indirectly by multimuon events.

Structural phase transition at high temperatures in solid molecular hydrogen and deuterium

NASA Astrophysics Data System (ADS)

Cui, T.; Takada, Y.; Cui, Q.; Ma, Y.; Zou, G.

2001-07-01

We study the effect of temperature up to 1000 K on the structure of dense molecular para-hydrogen (p-H2) and ortho-deuterium (o-D2), using the path-integral Monte Carlo method. We find a structural phase transition from orientationally disordered hexagonal close packed (hcp) to an orthorhombic structure of Cmca symmetry before melting. The transition is basically induced by thermal fluctuations, but quantum fluctuations of protons (deuterons) are important in determining the transition temperature through effectively hardening the intermolecular interaction. We estimate the phase line between hcp and Cmca phases as well as the melting line of the Cmca solid.

First measurements of deuterium-tritium and deuterium-deuterium fusion reaction yields in ignition-scalable direct-drive implosions

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

Forrest, C. J.; Radha, P. B.; Knauer, J. P.

In this study, the deuterium-tritium (D-T) and deuterium-deuterium neutron yield ratio in cryogenic inertial confinement fusion (ICF) experiments is used to examine multifluid effects, traditionally not included in ICF modeling. This ratio has been measured for ignition-scalable direct-drive cryogenic DT implosions at the Omega Laser Facility using a high-dynamic-range neutron time-of-flight spectrometer. The experimentally inferred yield ratio is consistent with both the calculated values of the nuclear reaction rates and the measured preshot target-fuel composition. These observations indicate that the physical mechanisms that have been proposed to alter the fuel composition, such as species separation of the hydrogen isotopes, aremore » not significant during the period of peak neutron production in ignition-scalable cryogenic direct-drive DT implosions.« less

First measurements of deuterium-tritium and deuterium-deuterium fusion reaction yields in ignition-scalable direct-drive implosions

DOE PAGES

Forrest, C. J.; Radha, P. B.; Knauer, J. P.; ...

2017-03-03

In this study, the deuterium-tritium (D-T) and deuterium-deuterium neutron yield ratio in cryogenic inertial confinement fusion (ICF) experiments is used to examine multifluid effects, traditionally not included in ICF modeling. This ratio has been measured for ignition-scalable direct-drive cryogenic DT implosions at the Omega Laser Facility using a high-dynamic-range neutron time-of-flight spectrometer. The experimentally inferred yield ratio is consistent with both the calculated values of the nuclear reaction rates and the measured preshot target-fuel composition. These observations indicate that the physical mechanisms that have been proposed to alter the fuel composition, such as species separation of the hydrogen isotopes, aremore » not significant during the period of peak neutron production in ignition-scalable cryogenic direct-drive DT implosions.« less

Nickel-Catalyzed Proton-Deuterium Exchange (HDX) Procedures for Glycosidic Linkage Analysis of Complex Carbohydrates.

PubMed

Price, Neil P J; Hartman, Trina M; Vermillion, Karl E

2015-07-21

The structural analysis of complex carbohydrates typically requires the assignment of three parameters: monosaccharide composition, the position of glycosidic linkages between monosaccharides, and the position and nature of noncarbohydrate substituents. The glycosidic linkage positions are often determined by permethylation analysis, but this can be complicated by high viscosity or poor solubility, resulting in under-methylation. This is a drawback because an under-methylated position may be misinterpreted as the erroneous site of a linkage or substituent. Here, we describe an alternative approach to linkage analysis that makes use of a nonreversible deuterium exchange of C-H protons on the carbohydrate backbone. The exchange reaction is conducted in deuterated water catalyzed by Raney nickel, and results in the selective exchange of C-H protons adjacent to free hydroxyl groups. Hence, the position of the residual C-H protons is indicative of the position of glycosidic linkages or other substituents and can be readily assigned by heteronuclear single quantum coherence-nuclear magnetic resonance (HSQC-NMR) or, following suitable derivatization, by gas chromatography-mass spectroscopy (GC/MS) analysis. Moreover, because the only changes to the parent sugar are proton/deuterium exchanges, the composition and linkage analysis can be determined in a single step.

Determination of diffusion coefficients of hydrogen and deuterium in Zr-2.5%Nb pressure tube material using hot vacuum extraction-quadrupole mass spectrometry

NASA Astrophysics Data System (ADS)

Shrivastava, Komal Chandra; Kulkarni, A. S.; Ramanjaneyulu, P. S.; Sunil, Saurav; Saxena, M. K.; Singh, R. N.; Tomar, B. S.; Ramakumar, K. L.

2015-06-01

The diffusion coefficients of hydrogen and deuterium in Zr-2.5%Nb alloy were measured in the temperature range 523 to 673 K, employing hot vacuum extraction-quadrupole mass spectrometry (HVE-QMS). One end of the Zr-2.5%Nb alloy specimens was charged electrolytically with the desired hydrogen isotope. After annealing at different temperatures for a predetermined time, the specimens were cut into thin slices, which were analyzed for their H2/D2 content using the HVE-QMS technique. The depth profile data were fitted into the equation representing the solution of Fick's second law of diffusion. The activation energy of hydrogen/deuterium diffusion was obtained from the Arrhenius relation between the diffusion coefficient and temperature. The temperature dependent diffusion coefficient can be represented as DH = 1.41 × 10-7 exp(-36,000/RT) and DD = 6.16 × 10-8 exp(-35,262/RT) for hydrogen and deuterium, respectively.

Local Conformational Stability of HIV-1 gp120 in Unliganded and CD4-Bound States as Defined by Amide Hydrogen/Deuterium Exchange▿ †

PubMed Central

Kong, Leopold; Huang, Chih-chin; Coales, Stephen J.; Molnar, Kathleen S.; Skinner, Jeff; Hamuro, Yoshitomo; Kwong, Peter D.

2010-01-01

The binding reaction of the HIV-1 gp120 envelope glycoprotein to the CD4 receptor involves exceptional changes in enthalpy and entropy. Crystal structures of gp120 in unliganded and various ligand-bound states, meanwhile, reveal an inner domain able to fold into diverse conformations, a structurally invariant outer domain, and, in the CD4-bound state, a bridging sheet minidomain. These studies, however, provide only hints as to the flexibility of each state. Here we use amide hydrogen/deuterium exchange coupled to mass spectrometry to provide quantifications of local conformational stability for HIV-1 gp120 in unliganded and CD4-bound states. On average, unliganded core gp120 displayed >10,000-fold slower exchange of backbone-amide hydrogens than a theoretically unstructured protein of the same composition, with binding by CD4 reducing the rate of gp120 amide exchange a further 10-fold. For the structurally constant CD4, alterations in exchange correlated well with alterations in binding surface (P value = 0.0004). For the structurally variable gp120, however, reductions in flexibility extended outside the binding surface, and regions of expected high structural diversity (inner domain/bridging sheet) displayed roughly 20-fold more rapid exchange in the unliganded state than regions of low diversity (outer domain). Thus, despite an extraordinary reduction in entropy, neither unliganded gp120 nor free CD4 was substantially unstructured, suggesting that most of the diverse conformations that make up the gp120 unliganded state are reasonably ordered. The results provide a framework for understanding how local conformational stability influences entropic change, conformational diversity, and structural rearrangements in the gp120-CD4 binding reaction. PMID:20660185

Chemical shift and electric field gradient tensors for the amide and carboxyl hydrogens in the model peptide N-acetyl-D,L-valine. Single-crystal deuterium NMR study.

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

Gerald, R. E., II; Bernhard, T.; Haeberlen, U.

1993-01-01

Solid-state NMR spectroscopy is well established as a method for describing molecular structure with resolution on the atomic scale. Many of the NMR observables result from anisotropic interactions between the nuclear spin and its environment. These observables can be described by second-rank tensors. For example, the eigenvalues of the traceless symmetric part of the hydrogen chemical shift (CS) tensor provide information about the strength of inter- or intramolecular hydrogen bonding. On the other hand, the eigenvectors of the deuterium electric field gradient (EFG) tensor give deuteron/proton bond directions with an accuracy rivalled only by neutron diffraction. In this paper themore » authors report structural information of this type for the amide and carboxyl hydrogen sites in a single crystal of the model peptide N-acetyl-D,L-valine (NAV). They use deuterium NMR to infer both the EFG and CS tensors at the amide and carboxyl hydrogen sites in NAV. Advantages of this technique over multiple-pulse proton NMR are that it works in the presence of {sup 14}N spins which are very hard to decouple from protons and that additional information in form of the EFG tensors can be derived. The change in the CS and EFG tensors upon exchange of a deuteron for a proton (the isotope effect) is anticipated to be very small; the effect on the CS tensors is certainly smaller than the experimental errors. NAV has served as a model peptide before in a variety of NMR studies, including those concerned with developing solid-state NMR spectroscopy as a method for determining the structure of proteins. NMR experiments on peptide or protein samples which are oriented in at least one dimension can provide important information about the three-dimensional structure of the peptide or the protein. In order to interpret the NMR data in terms of the structure of the polypeptide, the relationship of the CS and EFG tensors to the local symmetry elements of an amino acide, e.g., the peptide

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.

Deuterium enrichment by selective photo-induced dissociation of an organic carbonyl compound

DOEpatents

Marling, John B.

1981-01-01

A method for producing a deuterium enriched material by photoinduced dissociation which uses as the working material a gas phase photolytically dissociable organic carbonyl compound containing at least one hydrogen atom bonded to an atom which is adjacent to a carbonyl group and consisting of molecules wherein said hydrogen atom is present as deuterium and molecules wherein said hydrogen atom is present as another isotope of hydrogen. The organic carbonyl compound is subjected to intense infrared radiation at a preselected wavelength to selectively excite and thereby induce dissociation of the deuterium containing species to yield a deuterium enriched stable molecular product. Undissociated carbonyl compound, depleted in deuterium, is preferably redeuterated for reuse.

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.

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.

Process for exchanging hydrogen isotopes between gaseous hydrogen and water

DOEpatents

Hindin, Saul G.; Roberts, George W.

1980-08-12

A process for exchanging isotopes of hydrogen, particularly tritium, between gaseous hydrogen and water is provided whereby gaseous hydrogen depeleted in tritium and liquid or gaseous water containing tritium are reacted in the presence of a metallic catalyst.

Water drives the deuterium content of the methane emitted from plants

NASA Astrophysics Data System (ADS)

Vigano, I.; Holzinger, R.; Keppler, F.; Greule, M.; Brand, W. A.; Geilmann, H.; van Weelden, H.; Röckmann, T.

2010-07-01

The spatial distribution of the deuterium content of precipitation has a well-established latitudinal variation that is reflected in organic molecules in plants growing at different locations. Some laboratory and field studies have already shown that the deuterium content of methane emitted from methanogens can be partially related to δD variations of the water in the surrounding environment. Here we present a similar relation for the methane emitted from plant biomass under UV radiation. To show this relation, we determined the hydrogen isotopic composition of methane released from leaves of a range of plants grown with water of different deuterium content (δD = -130‰ to +115‰). The plant leaves were irradiated with UV light and the CH 4 isotopic composition was measured by continuous flow isotope ratio mass spectrometry (CF-IRMS). Furthermore, the deuterium content of bulk biomass and of the methoxyl (OCH 3) groups of the biomass was measured. The D/H ratio successively decreases from bulk biomass (δD = -106‰ to -50‰) via methoxyl groups (δD = -310‰ to -115‰) to the CH 4 emitted (δD = -581‰ to -196‰). The range of isotope ratios in bulk biomass and OCH 3 groups is smaller than in the water used to grow the plants. Methoxyl groups, which contain only non-exchangeable hydrogen, can be used to assess the fraction of external water that was incorporated before OCH 3 groups were formed. Surprisingly, the CH 4 formed under UV irradiation has a wider isotopic range than the OCH 3 groups. Although the precise production pathway cannot be fully determined, the presented experiments indicate that methoxyl groups are not the only source substrate for CH 4, but that other sources, including very depleted ones, must contribute. The main limitation to the interpretation of the data is the possible influence of exchangeable water, which could not be quantified. Future studies should include measurements of leaf water and avoid interaction between different

A General Method for Predicting Amino Acid Residues Experiencing Hydrogen Exchange

PubMed Central

Wang, Boshen; Perez-Rathke, Alan; Li, Renhao; Liang, Jie

2018-01-01

Information on protein hydrogen exchange can help delineate key regions involved in protein-protein interactions and provides important insight towards determining functional roles of genetic variants and their possible mechanisms in disease processes. Previous studies have shown that the degree of hydrogen exchange is affected by hydrogen bond formations, solvent accessibility, proximity to other residues, and experimental conditions. However, a general predictive method for identifying residues capable of hydrogen exchange transferable to a broad set of proteins is lacking. We have developed a machine learning method based on random forest that can predict whether a residue experiences hydrogen exchange. Using data from the Start2Fold database, which contains information on 13,306 residues (3,790 of which experience hydrogen exchange and 9,516 which do not exchange), our method achieves good performance. Specifically, we achieve an overall out-of-bag (OOB) error, an unbiased estimate of the test set error, of 20.3 percent. Using a randomly selected test data set consisting of 500 residues experiencing hydrogen exchange and 500 which do not, our method achieves an accuracy of 0.79, a recall of 0.74, a precision of 0.82, and an F1 score of 0.78.

Determination of the deuterium/hydrogen ratio in gas reaction products by laser-induced breakdown spectroscopy

NASA Astrophysics Data System (ADS)

D'Ulivo, A.; Onor, M.; Pitzalis, E.; Spiniello, R.; Lampugnani, L.; Cristoforetti, G.; Legnaioli, S.; Palleschi, V.; Salvetti, A.; Tognoni, E.

2006-07-01

This paper reports the first application of laser-induced breakdown spectroscopy technique (LIBS) to the determination of deuterium/hydrogen numeric ratio ( β) in the headspace gases, essentially HD + H 2, that are generated by the hydrolysis of NaBD 4-NaBH 4 mixtures (molar fraction of NaBD 4, x = 50-100%) in acidic H 2O media (0 < pH < 1). The LIBS measurement of β can be easily achieved with a coefficient of variation better than 5% (over four replicates). The value of β allowed the calculation of the molar fraction of NaBD 4, xLIBS, with a coefficient of variation better than 2.5%. The comparison of x vs. xLIBS gives results that are in good agreement, within an average deviation of 3%, for x in the range of 50-100%. The best performances are obtained for β close to unit, which makes LIBS perfectly suited for the detection of H-D exchange taking place during aqueous hydrolysis of NaBD 4 or NaBH 4.

Individual Basepair Stability of DNA and RNA Studied by NMR-Detected Solvent Exchange

PubMed Central

Steinert, Hannah S.; Rinnenthal, Jörg; Schwalbe, Harald

2012-01-01

In this study, we have optimized NMR methodology to determine the thermodynamic parameters of basepair opening in DNA and RNA duplexes by characterizing the temperature dependence of imino proton exchange rates of individual basepairs. Contributions of the nuclear Overhauser effect to exchange rates measured with inversion recovery experiments are quantified, and the influence of intrinsic and external catalysis exchange mechanisms on the imino proton exchange rates is analyzed. Basepairs in DNA and RNA have an approximately equal stability, and the enthalpy and entropy values of their basepair dissociation are correlated linearly. Furthermore, the compensation temperature, Tc, which is derived from the slope of the correlation, coincides with the melting temperature, and duplex unfolding occurs at that temperature where all basepairs are equally thermodynamically stable. The impact of protium-deuterium exchange of the imino hydrogen on the free energy of RNA basepair opening is investigated, and it is found that two A·U basepairs show distinct fractionation factors. PMID:22713572

THE BIOLOGY OF DEUTERIUM

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

Katz, J.J.; Crespi, H.L.; Finkel, A.J.

1958-10-31

g been noted, but the full scope and nature of these effects still remain largely unexplored. Early work was greatly hampered by the difficulties of obtaining deuterium but the development of a vast nuclear energy technology has made deuterium available on a larghe scale. It has now become opportune to undertake comprehensive reports work undertaken on algae, fungi, bacteria, and mammals. Mice will tolerate up to about 40 per cent D/sub 2/O in the drinking water for at least four months; of about 30 per cent heavy water. When deuteration is into various tissues and organs to the amount ofmore » from 40 to 50 per cent of the deuterium in the body fluids. 25 atom per cent, for as long as 12 months without obcal effects of deuterium is the kinetic isotpe effect. In general, bonds to deuterium react less readily than bonds to hydrogen; in consequence, reaction reates are decreased, and a depression in tissue metabolism should result. At concentrations about 30 atom per cen deuterium mice and rats show weakness, neutrmuscular por and death Since neoplastic cells metabolize rapidly, presumably these should be particularly sensitive to the effects of deuteration. Deuteration of host mice resulted in reduced growth rates of injected Krebs-2 ascites tumors and of inoculated P-1534 lymphatic leukemia. The general effects of deuterium on growth has been Chlorella vulgaris and Scenedesmus obliquus, have been have been harvested that yield water of combustion containing more than 90 atom per cent deuterium. The e were altered by deuteration. The fungi Penicillium notatum and Aspergillus fonsecaeus have been grown in media containing various concentrations of D/sub 2/O up to 99.6 per cent, and here, too, morphology, sporulation, pigment production, and growth rate were all affected by deuteration. The results obtained with algae clearly indicate the feasibility of producing fully deuterated compounds of biological significance by biosynthetic procedures. Bacterial studies on

Diffusion of hydrogen in a hydrogen-saturated tungsten

NASA Astrophysics Data System (ADS)

Krstic, Predrag; Kaganovich, Igor

2015-11-01

Hydrogen diffusion in monoscrystalline tungsten is studied by molecular dynamics with BOP potential in function of hydrogen concentration and temperature. Tungsten surface is prepared by cumulative irradiation of the 25 eV deuterium atoms at various fluences. The diffusion coefficients for T>500K and various D concentrations were calculated from the average slope of the mean square displacements of deuterium as functions of time. The accumulation of deuterium suppresses its diffusion at all temperatures. The results are in a reasonable agreement with the existing experiments. Supported by the LDRD of PPPL.

Hydrogen And Deuterium In The Local Interstellar Medium.

NASA Astrophysics Data System (ADS)

Murthy, Jayant

2016-03-01

In this work we report on the results of a series of IUE observations of interstellar HI and DI Ly alpha absorption against the chromospheric Lyalpha emission of the nearby late -type stars alpha Cen B(1.3 pc), epsilon Eri (3.3 pc), Procyon (3.5 pc), Altair (5.1 pc), Capella (13.2 pc), and HR 1099 (33 pc). From these observations we have derived the density, velocity dispersion, and bulk velocity of the neutral hydrogen along the line of sight to each of these stars. We have also placed lower limits on the deuterium to hydrogen (D/H) ratio towards the same stars. Our IUE results are generally consistent with previous observations of the same stars with the Copernicus satellite showing that our modelling procedure is independent of stellar variations over a period of several years. The HI absorption profile towards Altair shows a broad saturated core and steep line wings, consistent with a multicomponent interstellar medium in that direction. The bulk velocities towards the other stars are consistent with a bulk flow from the approximate direction of the galactic center but do show local variations from a uniform flow, possibly indicating a complicated velocity structure even in the solar neighbourhood. Interstellar deuterium is detected towards every star except Altair and the derived values for the D/H ratio are consistent with those previously found with Copernicus. In particular, we confirm the strong lower limit of 1.9 times 10^{-5} on the D/H ratio found towards Capella and we also place a lower limit of 1.5 times 10 ^{-5} on the D/H ratio towards alpha Cen B. Although an interstellar D/H ratio of 2 times 10^ {-5} is consistent with all the observations of late-type stars, the lower D/H ratios found towards several hot stars may indicate real variations in the D/H ratio in the local interstellar medium. Finally, we discuss the reality of a step in the cosmic background and of several galactic emission lines found by Auriemma et al. (1984) and show that, in

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

Deuterium separation by infrared-induced addition reaction

DOEpatents

Marling, John B.

1977-01-01

A method for deuterium enrichment by the infrared-induced addition reaction of a deuterium halide with an unsaturated aliphatic compound. A gaseous mixture of a hydrogen halide feedstock and an unsaturated aliphatic compound, particularly an olefin, is irradiated to selectively vibrationally excite the deuterium halide contained therein. The excited deuterium halide preferentially reacts with the unsaturated aliphatic compound to produce a deuterated addition product which is removed from the reaction mixture.

Microwave-assisted deuterium exchange: the convenient preparation of isotopically labelled analogues for stable isotope dilution analysis of volatile wine phenols.

PubMed

Crump, Anna M; Sefton, Mark A; Wilkinson, Kerry L

2014-11-01

This study reports the convenient, low cost, one-step synthesis of labelled analogues of six volatile phenols, guaiacol, 4-methylguaiacol, 4-ethylguaiacol, 4-ethylphenol, eugenol and vanillin, using microwave-assisted deuterium exchange, for use as internal standards for stable isotope dilution analysis. The current method improves on previous strategies in that it enables incorporation of deuterium atoms on the aromatic ring, thereby ensuring retention of the isotope label during mass spectrometry fragmentation. When used as standards for SIDA, these labelled volatile phenols will improve the accuracy and reproducibility of quantitative food and beverage analysis. Copyright © 2014 Elsevier Ltd. All rights reserved.

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

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

An examination of dynamics crosstalk between SH2 and SH3 domains by hydrogen/deuterium exchange and mass spectrometry

PubMed Central

Hochrein, James M.; Lerner, Edwina C.; Schiavone, Anthony P.; Smithgall, Thomas E.; Engen, John R.

2006-01-01

The ability of proteins to regulate their own enzymatic activity can be facilitated by changes in structure or protein dynamics in response to external regulators. Because many proteins contain SH2 and SH3 domains, transmission of information between the domains is a potential method of allosteric regulation. To determine if ligand binding to one modular domain may alter structural dynamics in an adjacent domain, allowing potential transmission of information through the protein, we used hydrogen exchange and mass spectrometry to measure changes in protein dynamics in the SH3 and SH2 domains of hematopoietic cell kinase (Hck). Ligand binding to either domain had little or no effect on hydrogen exchange in the adjacent domain, suggesting that changes in protein structure or dynamics are not a means of SH2/SH3 crosstalk. Furthermore, ligands of varying affinity covalently attached to SH3/SH2 altered dynamics only in the domain to which they bind. Such results demonstrate that ligand binding may not structurally alter adjacent SH3/SH2 domains and implies that other aspects of protein architecture contribute to the multiple levels of regulation in proteins containing SH3 and SH2 domains. PMID:16322569

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

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

Meezan, N. B., E-mail: meezan1@llnl.gov; Hopkins, L. F. Berzak; Pape, S. Le

2015-06-15

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

Field emission energy distributions of hydrogen and deuterium on the /100/ and /110/ planes of tungsten.

NASA Technical Reports Server (NTRS)

Plummer, E. W.; Bell, A. E.

1972-01-01

Total energy distributions of field emitted electrons from the tungsten (110) and (100) planes as a function of coverage by hydrogen and deuterium have been recorded utilizing a spherical deflection energy analyzer. The elastic tunneling resonance spectrum gives a plot of the 'local density of states' in the adsorbate. The inelastic tunneling spectrum reveals those discrete excitation energies available in the adsorbate-substrate complex. These spectroscopic data have been used to infer the chemical nature of the binding states which have been observed in the flash desorption spectrum of hydrogen from tungsten.

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

A Deuterium NMR Study of Bent-Core Liquid Crystals. 1; Synthesis and Characterization of Deuterium-Labeled Oxadiazole-Containing Liquid Crystals

NASA Technical Reports Server (NTRS)

Dingemans, Theo J.; Madsen, Louis A.; Samulski, Edward T.; Bushnell, Dennis M. (Technical Monitor)

2002-01-01

We have synthesized two deuterated boomerang-shaped liquid crystals based on 2,5-bis(4-hydroxyphenyl)-1,3,4-oxadiazole (ODBP). Deuterium was introduced in the rigid 2,5-diphenyl-1,3,4-oxadiazole core and in the aromatic ring of the terminal 4-dodecyloxyphenyl moiety using standard acid catalyzed deuterium exchange conditions. Both compounds, ([4,4'(1,3,4-oxadiazole-2,5-diyl-d4)] di-4-dodecyloxybenzoate: ODBP-d4-Ph-O-C12) and ([4,4'(1,3,4-oxadiazole-2,5-diyl)] di-4-dodecyloxy-benzoate-d4; ODBP-Ph-d4-O-C12) were investigated by nuclear magnetic resonance, optical microscopy and differential scanning calorimetry. The optical textures and thermal behavior of both compounds were found to be identical to the non-deuterated analog [4,4(1,3,4-oxadiazole-2,5-diyl)] di-4-dodecyloxybenzoate (ODBP-Ph-O-C12) which we reported earlier. These compounds exhibit behavior indicative of a biaxial nematic liquid crystal phase, which we hope to confirm using deuterium NMR spectroscopy in the next phase of this study.

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.

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.

Site occupancy of interstitial deuterium atoms in face-centred cubic iron

PubMed Central

Machida, Akihiko; Saitoh, Hiroyuki; Sugimoto, Hidehiko; Hattori, Takanori; Sano-Furukawa, Asami; Endo, Naruki; Katayama, Yoshinori; Iizuka, Riko; Sato, Toyoto; Matsuo, Motoaki; Orimo, Shin-ichi; Aoki, Katsutoshi

2014-01-01

Hydrogen composition and occupation state provide basic information for understanding various properties of the metal–hydrogen system, ranging from microscopic properties such as hydrogen diffusion to macroscopic properties such as phase stability. Here the deuterization process of face-centred cubic Fe to form solid-solution face-centred cubic FeDx is investigated using in situ neutron diffraction at high temperature and pressure. In a completely deuterized specimen at 988 K and 6.3 GPa, deuterium atoms occupy octahedral and tetrahedral interstitial sites with an occupancy of 0.532(9) and 0.056(5), respectively, giving a deuterium composition x of 0.64(1). During deuterization, the metal lattice expands approximately linearly with deuterium composition at a rate of 2.21 Å3 per deuterium atom. The minor occupation of the tetrahedral site is thermally driven by the intersite movement of deuterium atoms along the ‹111› direction in the face-centred cubic metal lattice. PMID:25256789

Enhancement of deuterium retention in damaged tungsten by plasma-induced defect clustering

NASA Astrophysics Data System (ADS)

Jin, Younggil; Roh, Ki-Baek; Sheen, Mi-Hyang; Kim, Nam-Kyun; Song, Jaemin; Kim, Young-Woon; Kim, Gon-Ho

2017-12-01

The enhancement of deuterium retention was investigated for tungsten in the presence of both 2.8 MeV self-ion induced cascade damage and fuel hydrogen isotope plasma. Vacancy clustering in cascade damaged polycrystalline tungsten occurred due to deuterium irradiation and was observed near the grain boundary by using all-step transmission electron microscopy analysis. Analysis of the highest desorption temperature peak using thermal desorption spectroscopy supports reasonable evidence of defect clustering in the damaged polycrystalline tungsten. The defect clustering was neither observed on the damaged polycrystalline tungsten without deuterium irradiation nor on the damaged single-crystalline tungsten with deuterium irradiation. This result implies the synergetic role of deuterium and grain boundary on defect clustering. This study proposes a path for the defect transform from point defect to defect cluster, by the agglomeration between irradiated deuterium and cascade damage-induced defect. This agglomeration may induce more severe damage on the tungsten divertor at which the high fuel hydrogen ions, fast neutrons, and self-ions are irradiated simultaneously and it would increase the in-vessel tritium inventory.

Measurements of the separated longitudinal structure function FL from hydrogen and deuterium targets at low Q2

NASA Astrophysics Data System (ADS)

Tvaskis, V.; Tvaskis, A.; Niculescu, I.; Abbott, D.; Adams, G. S.; Afanasev, A.; Ahmidouch, A.; Angelescu, T.; Arrington, J.; Asaturyan, R.; Avery, S.; Baker, O. K.; Benmouna, N.; Berman, B. L.; Biselli, A.; Blok, H. P.; Boeglin, W. U.; Bosted, P. E.; Brash, E.; Breuer, H.; Chang, G.; Chant, N.; Christy, M. E.; Connell, S. H.; Dalton, M. M.; Danagoulian, S.; Day, D.; Dodario, T.; Dunne, J. A.; Dutta, D.; El Khayari, N.; Ent, R.; Fenker, H. C.; Frolov, V. V.; Gaskell, D.; Garrow, K.; Gilman, R.; Gueye, P.; Hafidi, K.; Hinton, W.; Holt, R. J.; Horn, T.; Huber, G. M.; Jackson, H.; Jiang, X.; Jones, M. K.; Joo, K.; Kelly, J. J.; Keppel, C. E.; Kuhn, J.; Kinney, E.; Klein, A.; Kubarovsky, V.; Liang, Y.; Lolos, G.; Lung, A.; Mack, D.; Malace, S.; Markowitz, P.; Mbianda, G.; McGrath, E.; Mckee, D.; Meekins, D. G.; Mkrtchyan, H.; Napolitano, J.; Navasardyan, T.; Niculescu, G.; Nozar, M.; Ostapenko, T.; Papandreou, Z.; Potterveld, D.; Reimer, P. E.; Reinhold, J.; Roche, J.; Rock, S. E.; Schulte, E.; Segbefia, E.; Smith, C.; Smith, G. R.; Stoler, P.; Tadevosyan, V.; Tang, L.; Telfeyan, J.; Todor, L.; Ungaro, M.; Uzzle, A.; Vidakovic, S.; Villano, A.; Vulcan, W. F.; Warren, G.; Wesselmann, F.; Wojtsekhowski, B.; Wood, S. A.; Yan, C.; Zihlmann, B.

2018-04-01

Structure functions, as measured in lepton-nucleon scattering, have proven to be very useful in studying the partonic dynamics within the nucleon. However, it is experimentally difficult to separately determine the longitudinal and transverse structure functions, and consequently there are substantially less data available in particular for the longitudinal structure function. Here, we present separated structure functions for hydrogen and deuterium at low four-momentum transfer squared, Q2<1 GeV2 , and compare them with parton distribution parametrization and kT factorization approaches. While differences are found, the parametrizations generally agree with the data, even at the very low-Q2 scale of the data. The deuterium data show a smaller longitudinal structure function and a smaller ratio of longitudinal to transverse cross section, R , than the proton. This suggests either an unexpected difference in R for the proton and the neutron or a suppression of the gluonic distribution in nuclei.

Tunneling in hydrogen and deuterium atom addition to CO at low temperatures

NASA Astrophysics Data System (ADS)

Andersson, Stefan; Goumans, T. P. M.; Arnaldsson, Andri

2011-09-01

The hydrogen and deuterium atom addition reactions of CO to form HCO and DCO are addressed by Harmonic Quantum Transition State Theory calculations. Special attention is paid to the reactions at very low temperatures (5-20 K) where it is found that quantum tunneling leads to substantial rates of reaction. This supports experiments in the solid phase, which conclude that these reactions are driven by tunneling at low temperatures. The calculated kinetic isotope effect of kD/ kH = 1/250 is found to be lower than the experimentally deduced value of 0.08 for the surface reaction. Possible reasons for this discrepancy are discussed.

Development of Approaches for Deuterium Incorporation in Plants

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

Evans, Barbara R

2015-01-01

Soon after the discovery of deuterium, efforts to utilize this stable isotope of hydrogen for labeling of plants began and have proven successful for natural abundance to 20% enrichment. However, isotopic labeling with deuterium (2H) in higher plants at the level of 40% and higher is complicated by both physiological responses, particularly water exchange through transpiration, and inhibitory effects of D2O on germination, rooting, and growth. The highest incorporation of 40 50% had been reported for photoheterotrophic cultivation of the duckweed Lemna. Higher substitution is desirable for certain applications using neutron scattering and nuclear magnetic resonance (NMR) techniques. 1H2H-NMR andmore » mass spectroscopy are standard methods frequently used for determination of location and amount of deuterium substitution. The changes in infrared (IR) absorption observed for H to D substitution in hydroxyl and alkyl groups provide rapid initial evaluation of incorporation. Short-term experiments with cold-tolerant annual grasses can be carried out in enclosed growth containers to evaluate incorporation. Growth in individual chambers under continuous air perfusion with dried sterile-filtered air enables long-term cultivation of multiple plants at different D2O concentrations. Vegetative propagation from cuttings extends capabilities to species with low germination rates. Cultivation in 50% D2O of annual ryegrass and switchgrass following establishment of roots by growth in H2O produces samples with normal morphology and 30 40 % deuterium incorporation in the biomass. Winter grain rye (Secale cereale) was found to efficiently incorporate deuterium by photosynthetic fixation from 50% D2O but did not incorporate deuterated phenylalanine-d8 from the growth medium.« less

Molecular Identification of the Deuterium-Rich Carrier in Insoluble Organic Matter in Carbonaceous Chondrites

NASA Astrophysics Data System (ADS)

Remusat, L.; Robert, F.; Meibom, A.; Mostefaoui, S.; Delpoux, O.; Binet, L.; Gourier, D.; Derenne, S.

2007-12-01

Insoluble organic matter (IOM) in primitive carbonaceous chondrites is known to be enriched in deuterium, with D/H ratios > 300×10 -6. It is also characterized by a high degree of isotopic heterogeneity, as demonstrated by the observation of D-rich "hot spots" in NanoSIMS ion microprobe images [1] and by GC-irMS studies [2]. Understanding the origin of this heterogeneity represents a fundamental challenge with implications for the origin and distribution of organics in the interstellar medium and in the protoplanetary disk from which our planetary system formed. We have determined the carrier of the isotopically anomalous hydrogen in IOM isolated from the carbonaceous chondrite Orgueil. Electron Paramagnetic Resonance spectroscopy has shown that hydrogen in the benzylic bond of organic radicals has a deuterium to hydrogen (D/H) ratio of 1.5±0.5×10-2 in Orgueil IOM, which is the highest solar system D/H ratio ever reported [3]. By combining these data with quantitative image analysis recorded at a high spatial resolution with the NanoSIMS, we are able to prove that the organic radicals can account for the deuterium excess in the IOM D-rich "hot spots". Furthermore, the radicals fall on a well-defined trend between D/H ratio and C-H bond energy [2], consistent with a new interpretation of the hydrogen isotopic variations in solar system organics according to which pre-existing organics exchange their D with highly deuterated gaseous molecules, such as H2D+ or HD2+. The distributions of these deuterated species has been theoritically mapped in protostellar disks [4]. This conclusion runs contrary to previous interpretations, according to which the IOM is an interstellar product reprocessed in the protosolar gas and deuterium-rich "hot spot" relics of pristine interstellar organic matter, which escaped solar nebula or parent body processes. [1] Busemann et al (2006) Science 312, 727-730; [2] Remusat L. et al. (2006) Earth Planet. Sci. Let. 243, 15-25 ; [3] Delpoux O

Evidence of 9Be  +  p nuclear reactions during 2ω CH and hydrogen minority ICRH in JET-ILW hydrogen and deuterium plasmas

NASA Astrophysics Data System (ADS)

Krasilnikov, A. V.; Kiptily, V.; Lerche, E.; Van Eester, D.; Afanasyev, V. I.; Giroud, C.; Goloborodko, V.; Hellesen, C.; Popovichev, S. V.; Mironov, M. I.; contributors, JET

2018-02-01

The intensity of 9Be  +  p nuclear fusion reactions was experimentally studied during second harmonic (2ω CH) ion-cyclotron resonance heating (ICRH) and further analyzed during fundamental hydrogen minority ICRH of JET-ILW hydrogen and deuterium plasmas. In relatively low-density plasmas with a high ICRH power, a population of fast H+ ions was created and measured by neutral particle analyzers. Primary and secondary nuclear reaction products, due to 9Be  +  p interaction, were observed with fast ion loss detectors, γ-ray spectrometers and neutron flux monitors and spectrometers. The possibility of using 9Be(p, d)2α and 9Be(p, α)6Li nuclear reactions to create a population of fast alpha particles and study their behaviour in non-active stage of ITER operation is discussed in the paper.

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

PubMed

Cho, Kyu Taek; Mench, Matthew M

2012-03-28

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

DNA Interactions Probed by Hydrogen-Deuterium Exchange (HDX) Fourier Transform Ion Cyclotron Resonance Mass Spectrometry Confirm External Binding Sites on the Minichromosomal Maintenance (MCM) Helicase*

PubMed Central

Graham, Brian W.; Tao, Yeqing; Dodge, Katie L.; Thaxton, Carly T.; Olaso, Danae; Young, Nicolas L.; Marshall, Alan G.

2016-01-01

The archaeal minichromosomal maintenance (MCM) helicase from Sulfolobus solfataricus (SsoMCM) is a model for understanding structural and mechanistic aspects of DNA unwinding. Although interactions of the encircled DNA strand within the central channel provide an accepted mode for translocation, interactions with the excluded strand on the exterior surface have mostly been ignored with regard to DNA unwinding. We have previously proposed an extension of the traditional steric exclusion model of unwinding to also include significant contributions with the excluded strand during unwinding, termed steric exclusion and wrapping (SEW). The SEW model hypothesizes that the displaced single strand tracks along paths on the exterior surface of hexameric helicases to protect single-stranded DNA (ssDNA) and stabilize the complex in a forward unwinding mode. Using hydrogen/deuterium exchange monitored by Fourier transform ion cyclotron resonance MS, we have probed the binding sites for ssDNA, using multiple substrates targeting both the encircled and excluded strand interactions. In each experiment, we have obtained >98.7% sequence coverage of SsoMCM from >650 peptides (5–30 residues in length) and are able to identify interacting residues on both the interior and exterior of SsoMCM. Based on identified contacts, positively charged residues within the external waist region were mutated and shown to generally lower DNA unwinding without negatively affecting the ATP hydrolysis. The combined data globally identify binding sites for ssDNA during SsoMCM unwinding as well as validating the importance of the SEW model for hexameric helicase unwinding. PMID:27044751

DNA Interactions Probed by Hydrogen-Deuterium Exchange (HDX) Fourier Transform Ion Cyclotron Resonance Mass Spectrometry Confirm External Binding Sites on the Minichromosomal Maintenance (MCM) Helicase.

PubMed

Graham, Brian W; Tao, Yeqing; Dodge, Katie L; Thaxton, Carly T; Olaso, Danae; Young, Nicolas L; Marshall, Alan G; Trakselis, Michael A

2016-06-10

The archaeal minichromosomal maintenance (MCM) helicase from Sulfolobus solfataricus (SsoMCM) is a model for understanding structural and mechanistic aspects of DNA unwinding. Although interactions of the encircled DNA strand within the central channel provide an accepted mode for translocation, interactions with the excluded strand on the exterior surface have mostly been ignored with regard to DNA unwinding. We have previously proposed an extension of the traditional steric exclusion model of unwinding to also include significant contributions with the excluded strand during unwinding, termed steric exclusion and wrapping (SEW). The SEW model hypothesizes that the displaced single strand tracks along paths on the exterior surface of hexameric helicases to protect single-stranded DNA (ssDNA) and stabilize the complex in a forward unwinding mode. Using hydrogen/deuterium exchange monitored by Fourier transform ion cyclotron resonance MS, we have probed the binding sites for ssDNA, using multiple substrates targeting both the encircled and excluded strand interactions. In each experiment, we have obtained >98.7% sequence coverage of SsoMCM from >650 peptides (5-30 residues in length) and are able to identify interacting residues on both the interior and exterior of SsoMCM. Based on identified contacts, positively charged residues within the external waist region were mutated and shown to generally lower DNA unwinding without negatively affecting the ATP hydrolysis. The combined data globally identify binding sites for ssDNA during SsoMCM unwinding as well as validating the importance of the SEW model for hexameric helicase unwinding. © 2016 by The American Society for Biochemistry and Molecular Biology, Inc.

First Measurements of Deuterium-Tritium and Deuterium-Deuterium Fusion Reaction Yields in Ignition-Scalable Direct-Drive Implosions

NASA Astrophysics Data System (ADS)

Forrest, C. J.; Radha, P. B.; Knauer, J. P.; Glebov, V. Yu.; Goncharov, V. N.; Regan, S. P.; Rosenberg, M. J.; Sangster, T. C.; Shmayda, W. T.; Stoeckl, C.; Gatu Johnson, M.

2017-03-01

The deuterium-tritium (D-T) and deuterium-deuterium neutron yield ratio in cryogenic inertial confinement fusion (ICF) experiments is used to examine multifluid effects, traditionally not included in ICF modeling. This ratio has been measured for ignition-scalable direct-drive cryogenic DT implosions at the Omega Laser Facility [T. R. Boehly et al., Opt. Commun. 133, 495 (1997), 10.1016/S0030-4018(96)00325-2] using a high-dynamic-range neutron time-of-flight spectrometer. The experimentally inferred yield ratio is consistent with both the calculated values of the nuclear reaction rates and the measured preshot target-fuel composition. These observations indicate that the physical mechanisms that have been proposed to alter the fuel composition, such as species separation of the hydrogen isotopes [D. T. Casey et al., Phys. Rev. Lett. 108, 075002 (2012), 10.1103/PhysRevLett.108.075002], are not significant during the period of peak neutron production in ignition-scalable cryogenic direct-drive DT implosions.

Hydrogen Exchange During Cell-Free Incorporation of Deuterated Amino Acids and an Approach to its Inhibition

PubMed Central

Tonelli, M.; Singarapu, K. K.; Markley, J. L.; Makino, S.; Sahu, S .C.; Matsubara, Y.; Endo, Y.; Kainosho, M.

2012-01-01

Perdeuteration, selective deuteration, and stereo array isotope labeling (SAIL) are valuable strategies for NMR studies of larger proteins and membrane proteins. To minimize scrambling of the label, it is best to use cell-free methods to prepare selectively labeled proteins. However, when proteins are prepared from deuterated amino acids by cell-free translation in H2O, exchange reactions can lead to contamination of 2H sites by 1H from the solvent. Examination of a sample of SAIL-chlorella ubiquitin prepared by Escherichia coli cell-free synthesis revealed that exchange had occurred at several residues (mainly at Gly, Ala, Asp, Asn, Glu, and Gln). We present results from a study aimed at identifying the exchanging sites and level of exchange and at testing a strategy for minimizing 1H contamination during wheat germ cell-free translation of proteins produced from deuterated amino acids by adding known inhibitors of transaminases (1 mM aminooxyacetic acid) and glutamate synthetase (0.1 mM L-methionine sulfoximine). By using a wheat germ cell-free expression system, we produced [U-2H,15N]-chlorella ubiquitin without and with added inhibitors, and [U-15N]-chlorella ubiquitin as a reference to determine the extent of deuterium incorporation. We also prepared a sample of [U-13C,15N]-chlorella ubiquitin, for use in assigning the sites of exchange. The added inhibitors did not reduce the protein yield and were successful in blocking hydrogen exchange at Cα sites with the exception of Gly. We discovered, in addition, that partial exchange occurred with or without the inhibitors at certain side-chain methyl and methylene groups: Ala-Hβ, Asn-Hβ, Asp-Hβ, Gln-Hγ, Glu-Hγ, and Lys-Hε. The side-chain labeling pattern, in particular the mixed chiral labeling resulting from partial exchange at certain sites, should be of interest in studies of large proteins, protein complexes, and membrane proteins. PMID:21984356

Measurements of the separated longitudinal structure function F L from hydrogen and deuterium targets at low Q 2

DOE PAGES

Tvaskis, V.; Tvaskis, A.; Niculescu, I.; ...

2018-04-26

Structure functions, as measured in lepton-nucleon scattering, have proven to be very useful in studying the partonic dynamics within the nucleon. Furthermore, it is experimentally difficult to separately determine the longitudinal and transverse structure functions, and consequently there are substantially less data available in particular for the longitudinal structure function. Here, we present separated structure functions for hydrogen and deuterium at low four-momentum transfer squared, Q 2 < 1 GeV 2, and compare them with parton distribution parametrization and k T factorization approaches. While differences are found, the parametrizations generally agree with the data, even at the very low-Q 2more » scale of the data. The deuterium data show a smaller longitudinal structure function and a smaller ratio of longitudinal to transverse cross section, R, than the proton. This suggests either an unexpected difference in R for the proton and the neutron or a suppression of the gluonic distribution in nuclei.« less

Measurements of the separated longitudinal structure function F L from hydrogen and deuterium targets at low Q 2

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

Tvaskis, V.; Tvaskis, A.; Niculescu, I.

Structure functions, as measured in lepton-nucleon scattering, have proven to be very useful in studying the partonic dynamics within the nucleon. Furthermore, it is experimentally difficult to separately determine the longitudinal and transverse structure functions, and consequently there are substantially less data available in particular for the longitudinal structure function. Here, we present separated structure functions for hydrogen and deuterium at low four-momentum transfer squared, Q 2 < 1 GeV 2, and compare them with parton distribution parametrization and k T factorization approaches. While differences are found, the parametrizations generally agree with the data, even at the very low-Q 2more » scale of the data. The deuterium data show a smaller longitudinal structure function and a smaller ratio of longitudinal to transverse cross section, R, than the proton. This suggests either an unexpected difference in R for the proton and the neutron or a suppression of the gluonic distribution in nuclei.« less

Hydrogen diffusion in Zircon

NASA Astrophysics Data System (ADS)

Ingrin, Jannick; Zhang, Peipei

2016-04-01

Hydrogen mobility in gem quality zircon single crystals from Madagascar was investigated through H-D exchange experiments. Thin slices were annealed in a horizontal furnace flushed with a gas mixture of Ar/D2(10%) under ambient pressure between 900 ° C to 1150 ° C. FTIR analyses were performed on oriented slices before and after each annealing run. H diffusion along [100] and [010] follow the same diffusion law D = D0exp[-E /RT], with log D0 = 2.24 ± 1.57 (in m2/s) and E = 374 ± 39 kJ/mol. H diffusion along [001] follows a slightly more rapid diffusion law, with log D0 = 1.11 ± 0.22 (in m2/s) and E = 334 ± 49 kJ/mol. H diffusion in zircon has much higher activation energy and slower diffusivity than other NAMs below 1150 ° C even iron-poor garnets which are known to be among the slowest (Blanchard and Ingrin, 2004; Kurka et al. 2005). During H-D exchange zircon incorporates also deuterium. This hydration reaction involves uranium reduction as it is shown from the exchange of U5+ and U4+ characteristic bands in the near infrared region during annealing. It is the first time that a hydration reaction U5+ + OH- = U4+ + O2- + 1/2H2, is experimentally reported. The kinetics of deuterium incorporation is slightly slower than hydrogen diffusion, suggesting that the reaction is limited by hydrogen mobility. Hydrogen isotopic memory of zircon is higher than other NAMs. Zircons will be moderately retentive of H signatures at mid-crustal metamorphic temperatures. At 500 ° C, a zircon with a radius of 300 μm would retain its H isotopic signature over more than a million years. However, a zircon is unable to retain this information for geologically significant times under high-grade metamorphism unless the grain size is large enough. Refrences Blanchard, M. and Ingrin, J. (2004) Hydrogen diffusion in Dora Maira pyrope. Physics and Chemistry of Minerals, 31, 593-605. Kurka, A., Blanchard, M. and Ingrin, J. (2005) Kinetics of hydrogen extraction and deuteration in

Hydrogen and oxygen isotope exchange reactions between clay minerals and water

USGS Publications Warehouse

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

1976-01-01

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

[Determination of deuterium concentration in foods and influence of water with modified isotopic composition on oxidation parameters and heavy hydrogen isotopes content in experimental animals].

PubMed

Basov, A A; Bykov, I M; Baryshev, M G; Dzhimak, S S; Bykov, M I

2014-01-01

The article presents the results of the study of the deuterium (D) content in food products as well as the influence of deuterium depleted water (DDW) on the concentration of heavy hydrogen isotopes in the blood and lyophilized tissues of rats. The most significant difference in the content of D was found between potato and pork fat, which indexes the standard delta notation (δ) D in promille, related to the international standard SMOW (Standard Mean Ocean of Water) amounted to -83,2 per thousand and -250,7 per thousand, respectively (p<0,05). Among the investigated samples of water deuterium concentration ranged from -75,5 per thousand (Narzan) to +72,1 per thousand (Kubai), that indicates the ability of some food products to increase the concentration of heavy hydrogen atoms in the body. The data obtained in the experimental modeling of the diet of male Wistar rats in the age of 5-6 mo (weight 235 ± 16 g) using DDW (δD = -743,2 per thousand) instead of drinking water (δD = -37,0 per thousand) with identical mineral composition showed that after 2 weeks significant (p <0,05) formation of isotopic (deuterium-protium, D/H) gradient in the body is possible. Changing the direction of isotopic D/H gradient in laboratory animals in comparison with its physiological indicators (72-127 per thousand, "plasma>tissue") is due to different rates ofisotopic exchange reactions in plasma and tissues (liver, kidney, heart), which can be explained by entering into the composition of a modified diet of organic substrates with more than DDW concentration D, which are involved in the construction of cellular structures and eventually lead to a redistribution of D and change direction of D/H gradient "plasma

Dynamic Compression Experiments on Hydrogen and Deuterium in the Warm Dense Liquid.

NASA Astrophysics Data System (ADS)

Desjarlais, Michael; McCoy, Chad; Cochrane, Kyle; Mattsson, Thomas; Knudson, Marcus; Redmer, Ronald

2017-06-01

Recently a shock-ramp platform has been developed on the Z Accelerator to access off-Hugoniot states in liquids. The accelerator delivers a two-step current pulse; the first accelerates the electrode to a constant velocity, which upon impact with the sample cell creates a well-defined shock, the subsequent current rise produces ramp compression from the initially shocked state producing relatively cool (1-2 kK), high pressure (>300 GPa), high compression (10 to 15-fold compression) states. This technique allows experimental access to the region of phase space where hydrogen is predicted to undergo a first-order phase transition from an insulating molecular-like to a conducting atomic-like liquid. Here we discuss the experimental platform, survey various theoretical predictions for the liquid-liquid, insulator-to-metal transition in hydrogen, and present results of experiments on both deuterium and hydrogen that clearly show an abrupt transition to a metallic state. We also present results from recent experiments at higher temperatures (3-4 kK) and compare the observations to both first-principles theory and previous step-wise loading experiments that exhibited a minimum metallic conductivity. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

Enzymatic preparation of. cap alpha. - and. beta. -deuterated or tritiated amino acids with l-methionine. gamma. -lyase

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

Esaki, N.; Sawada, S.; Tanaka, H.

L-Methionine ..gamma..-lyase catalyzes the exchange of ..cap alpha..- and ..beta..-hydrogens of L-methionine and S-methyl-L-cysteine with deuterium or tritium of solvents. The rate of ..cap alpha..-hydrogen exchange with deuterium was about 40 times faster than that of the elimination reactions. The deuterium and tritium were exchanged also with the ..cap alpha..- and ..beta..-hydrogens of the straight-chain amino acids which do not undergo the elimination: L-alanine, L-..cap alpha..-aminobutyrate, L-norvaline, and L-norleucine. No exchange occurs for the D-isomers, acidic L-amino acids, basic L-amino acids, and branched-chain L-amino acids, although ..cap alpha..-hydrogen of glycine, L-trypotophan, and L-phenylalanine is exchanged slowly. These enzymatic hydrogen-exchange reactionsmore » facilitate specific labeling of the L-amino acids with deuterium and tritium.« less

Deuterium-rich Water in Meteorites

NASA Astrophysics Data System (ADS)

Deloule, E.; Robert, F.

1995-09-01

D/H ratios of 2 meteorites (Renazzo CR and Semarkona LL3), which are known to exhibit the largest departures from the terrestrial hydrogen isotopic ratios, have been determined with the CRPG Nancy ion-microprobe. Correlations between the D/H ratios and the chemical compositions (H2O, K, Si, C/H) of plausible hydrogen carriers were observed. From these correlations, it is possible to show that, contrary to previous interpretations, phyllosilicates are the carriers of the deuterium-rich hydrogen in Semarkona and Renazzo : 870 x10-6 D/H 670 x106 (+4600 dD 3300) and 320 x10-6 (dD 1050), respectively. Hydrogen is also present in the chondrules of these two deuterium-rich meteorites. Isotopic equilibrium between the deuterium depleted phases and the deuterium-rich phyllosilicates was never attained. This is illustrated at a micron scale by the D/H ratios obtained continuously during a 3 hours measurement on a same position (see figure below). It can be seen that water-rich mineral(s) having D/H up to 550 x10-6 (dD = +2500) are in contact with a mineral having D/H = 234 x10-6 (dD = +500). The thickness of the boundary where the diffusion of hydrogen took place is restricted to less than 0.2 mm. Such isotopic heterogeneity is quite spectacular if one remembers that the isotopic variations that we can see within these 0.2 mm are an order of magnitude larger than the total observed variations on Earth. The large differences in D/H ratios between matrix (up to 700 x 10-6, dD up to +3500) and chondrules (from 120 x10-6 (dD = -230) to 230 x10-6 (dD = +475)) show that hydrogen in chondrules cannot originate from the matrix by simple contamination or diffusion processes. The high D/H ratios measured in water bearing minerals could not have been produced thermally within a dense solar nebula. Chemical reactions (i.e. involving ions or radicals), taking place in interstellar space or in the outer regions of the nebula at 110-140K are presently the only conceivable mechanisms

First Measurements of Deuterium-Tritium and Deuterium-Deuterium Fusion Reaction Yields in Ignition-Scalable Direct-Drive Implosions.

PubMed

Forrest, C J; Radha, P B; Knauer, J P; Glebov, V Yu; Goncharov, V N; Regan, S P; Rosenberg, M J; Sangster, T C; Shmayda, W T; Stoeckl, C; Gatu Johnson, M

2017-03-03

The deuterium-tritium (D-T) and deuterium-deuterium neutron yield ratio in cryogenic inertial confinement fusion (ICF) experiments is used to examine multifluid effects, traditionally not included in ICF modeling. This ratio has been measured for ignition-scalable direct-drive cryogenic DT implosions at the Omega Laser Facility [T. R. Boehly et al., Opt. Commun. 133, 495 (1997)OPCOB80030-401810.1016/S0030-4018(96)00325-2] using a high-dynamic-range neutron time-of-flight spectrometer. The experimentally inferred yield ratio is consistent with both the calculated values of the nuclear reaction rates and the measured preshot target-fuel composition. These observations indicate that the physical mechanisms that have been proposed to alter the fuel composition, such as species separation of the hydrogen isotopes [D. T. Casey et al., Phys. Rev. Lett. 108, 075002 (2012)PRLTAO0031-900710.1103/PhysRevLett.108.075002], are not significant during the period of peak neutron production in ignition-scalable cryogenic direct-drive DT implosions.

Hydrogen passivation of poly-Si/SiOx contacts for Si solar cells using Al2O3 studied with deuterium

NASA Astrophysics Data System (ADS)

Schnabel, Manuel; van de Loo, Bas W. H.; Nemeth, William; Macco, Bart; Stradins, Paul; Kessels, W. M. M.; Young, David L.

2018-05-01

The interplay between hydrogenation and passivation of poly-Si/SiOx contacts to n-type Si wafers is studied using atomic layer deposited Al2O3 and anneals in forming gas and nitrogen. The poly-Si/SiOx stacks are prepared by thermal oxidation followed by thermal crystallization of a-Si:H films deposited by plasma-enhanced chemical vapor deposition. Implied open-circuit voltages as high as 710 mV are achieved for p-type poly-Si/SiOx contacts to n-type Si after hydrogenation. Correlating minority carrier lifetime data and secondary ion mass spectrometry profiles reveals that the main benefit of Al2O3 is derived from its role as a hydrogen source for chemically passivating defects at SiOx; Al2O3 layers are found to hydrogenate poly-Si/SiOx much better than a forming gas anneal. By labelling Al2O3 and the subsequent anneal with different hydrogen isotopes, it is found that Al2O3 exchanges most of its hydrogen with the ambient upon annealing at 400 °C for 1 h even though there is no significant net change in its total hydrogen content.

The Effect of Ion Energy and Substrate Temperature on Deuterium Trapping in Tungsten

NASA Astrophysics Data System (ADS)

Roszell, John Patrick Town

Tungsten is a candidate plasma facing material for next generation magnetic fusion devices such as ITER and there are major operational and safety issues associated with hydrogen (tritium) retention in plasma facing components. An ion gun was used to simulate plasma-material interactions under various conditions in order to study hydrogen retention characteristics of tungsten thus enabling better predictions of hydrogen retention in ITER. Thermal Desorption Spectroscopy (TDS) was used to measure deuterium retention from ion irradiation while modelling of TDS spectra with the Tritium Migration Analysis Program (TMAP) was used to provide information about the trapping mechanisms involved in deuterium retention in tungsten. X-ray Photoelectron Spectroscopy (XPS) and Secondary Ion Mass Spectrometry (SIMS) were used to determine the depth resolved composition of specimens used for irradiation experiments. Carbon and oxygen atoms will be among the most common contaminants within ITER. C and O contamination in polycrystalline tungsten (PCW) specimens even at low levels (˜0.1%) was shown to reduce deuterium retention by preventing diffusion of deuterium into the bulk of the specimen. This diffusion barrier was also responsible for the inhibition of blister formation during irradiations at 500 K. These observations may provide possible mitigation techniques for problems associated with tritium retention and mechanical damage to plasma facing components caused by hydrogen implantation. Deuterium trapping in PCW and single crystal tungsten (SCW) was studied as a function of ion energy and substrate temperature. Deuterium retention was shown to decrease with decreasing ion energy below 100 eV/D+. Irradiation of tungsten specimens with 10 eV/D+ ions was shown to retain up to an order of magnitude less deuterium than irradiation with 500 eV/D+ ions. Furthermore, the retention mechanism for deuterium was shown to be consistent across the entire energy range studied (10-500 e

Estimation of Hydrogen-Exchange Protection Factors from MD Simulation Based on Amide Hydrogen Bonding Analysis.

PubMed

Park, In-Hee; Venable, John D; Steckler, Caitlin; Cellitti, Susan E; Lesley, Scott A; Spraggon, Glen; Brock, Ansgar

2015-09-28

Hydrogen exchange (HX) studies have provided critical insight into our understanding of protein folding, structure, and dynamics. More recently, hydrogen exchange mass spectrometry (HX-MS) has become a widely applicable tool for HX studies. The interpretation of the wealth of data generated by HX-MS experiments as well as other HX methods would greatly benefit from the availability of exchange predictions derived from structures or models for comparison with experiment. Most reported computational HX modeling studies have employed solvent-accessible-surface-area based metrics in attempts to interpret HX data on the basis of structures or models. In this study, a computational HX-MS prediction method based on classification of the amide hydrogen bonding modes mimicking the local unfolding model is demonstrated. Analysis of the NH bonding configurations from molecular dynamics (MD) simulation snapshots is used to determine partitioning over bonded and nonbonded NH states and is directly mapped into a protection factor (PF) using a logistics growth function. Predicted PFs are then used for calculating deuteration values of peptides and compared with experimental data. Hydrogen exchange MS data for fatty acid synthase thioesterase (FAS-TE) collected for a range of pHs and temperatures was used for detailed evaluation of the approach. High correlation between prediction and experiment for observable fragment peptides is observed in the FAS-TE and additional benchmarking systems that included various apo/holo proteins for which literature data were available. In addition, it is shown that HX modeling can improve experimental resolution through decomposition of in-exchange curves into rate classes, which correlate with prediction from MD. Successful rate class decompositions provide further evidence that the presented approach captures the underlying physical processes correctly at the single residue level. This assessment is further strengthened in a comparison of

Estimation of Hydrogen-Exchange Protection Factors from MD Simulation Based on Amide Hydrogen Bonding Analysis

PubMed Central

Park, In-Hee; Venable, John D.; Steckler, Caitlin; Cellitti, Susan E.; Lesley, Scott A.; Spraggon, Glen; Brock, Ansgar

2015-01-01

Hydrogen exchange (HX) studies have provided critical insight into our understanding of protein folding, structure and dynamics. More recently, Hydrogen Exchange Mass Spectrometry (HX-MS) has become a widely applicable tool for HX studies. The interpretation of the wealth of data generated by HX-MS experiments as well as other HX methods would greatly benefit from the availability of exchange predictions derived from structures or models for comparison with experiment. Most reported computational HX modeling studies have employed solvent-accessible-surface-area based metrics in attempts to interpret HX data on the basis of structures or models. In this study, a computational HX-MS prediction method based on classification of the amide hydrogen bonding modes mimicking the local unfolding model is demonstrated. Analysis of the NH bonding configurations from Molecular Dynamics (MD) simulation snapshots is used to determine partitioning over bonded and non-bonded NH states and is directly mapped into a protection factor (PF) using a logistics growth function. Predicted PFs are then used for calculating deuteration values of peptides and compared with experimental data. Hydrogen exchange MS data for Fatty acid synthase thioesterase (FAS-TE) collected for a range of pHs and temperatures was used for detailed evaluation of the approach. High correlation between prediction and experiment for observable fragment peptides is observed in the FAS-TE and additional benchmarking systems that included various apo/holo proteins for which literature data were available. In addition, it is shown that HX modeling can improve experimental resolution through decomposition of in-exchange curves into rate classes, which correlate with prediction from MD. Successful rate class decompositions provide further evidence that the presented approach captures the underlying physical processes correctly at the single residue level. This assessment is further strengthened in a comparison of

Individual breathing reactions measured in hemoglobin by hydrogen exchange methods.

PubMed Central

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

1980-01-01

Protein hydrogen exchange is generally believed to register some aspects of internal protein dynamics, but the kind of motion at work is not clear. Experiments are being done to identify the determinants of protein hydrogen exchange and to distinguish between local unfolding and accessibility-penetration mechanisms. Results with small molecules, polynucleotides, and proteins demonstrate that solvent accessibility is by no means sufficient for fast exchange. H-exchange slowing is quite generally connected with intramolecular H-bonding, and the exchange process depends pivotally on transient H-bond cleavage. At least in alpha-helical structures, the cooperative aspect of H-bond cleavage must be expressed in local unfolding reactions. Results obtained by use of a difference hydrogen exchange method appear to provide a direct measurement of transient, cooperative, local unfolding reactions in hemoglobin. The reality of these supposed coherent breathing units is being tested by using the difference H-exchange approach to tritium label the units one at a time and then attempting to locate the tritium by fragmenting the protein, separating the fragments, and testing them for label. Early results demonstrate the feasibility of this approach. PMID:7248462

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

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.

Is Deuterium Nuclear Fusion Catalyzed by Antineutrinos?

NASA Astrophysics Data System (ADS)

Shomer, Isaac

2010-02-01

The hypothesis of Fischbach and Jenkins that neutrinos emitted from the sun accelerate radioactive decay is noted. It is thought that neutrinos accelerate beta decay by reacting with neutron-rich nuclides to form a beta particle and a daughter product, with no antineutrino emitted. Conversely, it is proposed that antineutrinos can react with proton-rich nuclides to cause positron decay, with no neutrino emitted. It is also proposed that the nuclear fusion of the hydrogen bomb is triggered not only by the energy of the igniting fission bomb, but by the antineutrinos created by the rapid beta decay of the daughter products in the fission process. The contemplated mechanism for antineutrino initiated fusion is the following: 1. The antineutrinos from the fission daughter products cause positron decay of deuterium by the process outlined above. 2. In a later fusion step, these positrons subsequently react with neutrons in deuterium to create antineutrinos. Electrons are unavailable to annihilate positrons in the plasma of the hydrogen bomb. 3. These antineutrinos thereafter react with more deuterium to form positrons, thereby propagating a chain reaction. )

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

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.

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

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.

Deuterium Retention and Physical Sputtering of Low Activation Ferritic Steel

NASA Astrophysics Data System (ADS)

T, Hino; K, Yamaguchi; Y, Yamauchi; Y, Hirohata; K, Tsuzuki; Y, Kusama

2005-04-01

Low activation materials have to be developed toward fusion demonstration reactors. Ferritic steel, vanadium alloy and SiC/SiC composite are candidate materials of the first wall, vacuum vessel and blanket components, respectively. Although changes of mechanical-thermal properties owing to neutron irradiation have been investigated so far, there is little data for the plasma material interactions, such as fuel hydrogen retention and erosion. In the present study, deuterium retention and physical sputtering of low activation ferritic steel, F82H, were investigated by using deuterium ion irradiation apparatus. After a ferritic steel sample was irradiated by 1.7 keV D+ ions, the weight loss was measured to obtain the physical sputtering yield. The sputtering yield was 0.04, comparable to that of stainless steel. In order to obtain the retained amount of deuterium, technique of thermal desorption spectroscopy (TDS) was employed to the irradiated sample. The retained deuterium desorbed at temperature ranging from 450 K to 700 K, in the forms of DHO, D2, D2O and hydrocarbons. Hence, the deuterium retained can be reduced by baking with a relatively low temperature. The fluence dependence of retained amount of deuterium was measured by changing the ion fluence. In the ferritic steel without mechanical polish, the retained amount was large even when the fluence was low. In such a case, a large amount of deuterium was trapped in the surface oxide layer containing O and C. When the fluence was large, the thickness of surface oxide layer was reduced by the ion sputtering, and then the retained amount in the oxide layer decreased. In the case of a high fluence, the retained amount of deuterium became comparable to that of ferritic steel with mechanical polish or SS 316L, and one order of magnitude smaller than that of graphite. When the ferritic steel is used, it is required to remove the surface oxide layer for reduction of fuel hydrogen retention. Ferritic steel sample was

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

The structure of an integral membrane peptide: a deuterium NMR study of gramicidin.

PubMed Central

Prosser, R S; Daleman, S I; Davis, J H

1994-01-01

Solid state deuterium NMR was employed on oriented multilamellar dispersions consisting of 1,2-dilauryl-sn-glycero-3-phosphatidylcholine and deuterium (2H) exchange-labeled gramicidin D, at a lipid to protein molar ratio (L/P) of 15:1, in order to study the dynamic structure of the channel conformation of gramicidin in a liquid crystalline phase. The corresponding spectra were used to discriminate between several structural models for the channel structure of gramicidin (based on the left- and right-handed beta 6.3 LD helix) and other models based on a structure obtained from high resolution NMR. The oriented spectrum is complicated by the fact that many of the doublets, corresponding to the 20 exchangeable sites, partially overlap. Furthermore, the asymmetry parameter, eta, of the electric field gradient tensor of the amide deuterons is large (approximately 0.2) and many of the amide groups are involved in hydrogen bonding, which is known to affect the quadrupole coupling constant. In order to account for these complications in simulating the spectra in the fast motional regime, an ab initio program called Gaussian 90 was employed, which permitted us to calculate, by quantum mechanical means, the complete electric field gradient tensor for each residue in gramicidin (using two structural models). Our results indicated that the left-handed helical models were inconsistent with our observed spectra, whereas a model based on the high-resolution structure derived by Arseniev and coworkers, but relaxed by a simple energy minimization procedure, was consistent with our observed spectra. The molecular order parameter was then estimated from the motional narrowing assuming the relaxed (right-handed) Arseniev structure. Our resultant order parameter of SZZ = 0.91 translates into an rms angle of 14 degrees, formed by the helix axis and the local bilayer normal. The strong resemblance between our spectra (and also those reported for gramicidin in 1,2-dipalmitoyl-sn-glycero-3

Theoretical modeling of infrared spectra of the hydrogen and deuterium bond in aspirin crystal

NASA Astrophysics Data System (ADS)

Ghalla, Houcine; Rekik, Najeh; Michta, Anna; Oujia, Brahim; Flakus, Henryk T.

2010-01-01

An extended quantum theoretical approach of the ν IR lineshape of cyclic dimers of weakly H-bonded species is proposed. We have extended a previous approach [M.E.-A. Benmalti, P. Blaise, H.T. Flakus, O. Henri-Rousseau, Chem. Phys. 320 (2006) 267] by accounting for the anharmonicity of the slow mode which is described by a "Morse" potential in order to reproduce the polarized infrared spectra of the hydrogen and deuterium bond in acetylsalicylic acid (aspirin) crystals. From comparison of polarized IR spectra of isotopically neat and isotopically diluted aspirin crystals it resulted that centrosymmetric aspirin dimer was the bearer of the crystal main spectral properties. In this approach, the adiabatic approximation is performed for each separate H-bond bridge of the dimer and a strong non-adiabatic correction is introduced into the model via the resonant exchange between the fast mode excited states of the two moieties. Within the strong anharmonic coupling theory, according to which the X-H→⋯Y high-frequency mode is anharmonically coupled to the H-bond bridge, this model incorporated the Davydov coupling between the excited states of the two moieties, the quantum direct and indirect dampings and the anharmonicity for the H-bond bridge. The spectral density is obtained within the linear response theory by Fourier transform of the damped autocorrelation functions. The evaluated spectra are in fairly good agreement with the experimental ones by using a minimum number of independent parameters. The effect of deuteration has been well reproduced by reducing simply the angular frequency of the fast mode and the anharmonic coupling parameter.

Acidity and hydrogen exchange dynamics of iron(II)-bound nitroxyl in aqueous solution.

PubMed

Gao, Yin; Toubaei, Abouzar; Kong, Xianqi; Wu, Gang

2014-10-20

Nitroxyl-iron(II) (HNO-Fe(II)) complexes are often unstable in aqueous solution, thus making them very difficult to study. Consequently, many fundamental chemical properties of Fe(II)-bound HNO have remained unknown. Using a comprehensive multinuclear ((1)H, (15)N, (17)O) NMR approach, the acidity of the Fe(II)-bound HNO in [Fe(CN)5(HNO)](3-) was investigated and its pK(a) value was determined to be greater than 11. Additionally, HNO undergoes rapid hydrogen exchange with water in aqueous solution and this exchange process is catalyzed by both acid and base. The hydrogen exchange dynamics for the Fe(II)-bound HNO have been characterized and the obtained benchmark values, when combined with the literature data on proteins, reveal that the rate of hydrogen exchange for the Fe(II)-bound HNO in the interior of globin proteins is reduced by a factor of 10(6). © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrogen passivation of poly-Si/SiO x contacts for Si solar cells using Al 2O 3 studied with deuterium

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

Schnabel, Manuel; van de Loo, Bas W. H.; Nemeth, William

Here, the interplay between hydrogenation and passivation of poly-Si/SiO x contacts to n-type Si wafers is studied using atomic layer deposited Al 2O 3 and anneals in forming gas and nitrogen. The poly-Si/SiO x stacks are prepared by thermal oxidation followed by thermal crystallization of a-Si:H films deposited by plasma-enhanced chemical vapor deposition. Implied open-circuit voltages as high as 710 mV are achieved for p-type poly-Si/SiO x contacts to n-type Si after hydrogenation. Correlating minority carrier lifetime data and secondary ion mass spectrometry profiles reveals that the main benefit of Al 2O 3 is derived from its role as amore » hydrogen source for chemically passivating defects at SiO x; Al 2O 3 layers are found to hydrogenate poly-Si/SiO x much better than a forming gas anneal. By labelling Al 2O 3 and the subsequent anneal with different hydrogen isotopes, it is found that Al 2O 3 exchanges most of its hydrogen with the ambient upon annealing at 400 °C for 1 h even though there is no significant net change in its total hydrogen content.« less

Hydrogen passivation of poly-Si/SiO x contacts for Si solar cells using Al 2O 3 studied with deuterium

DOE PAGES

Schnabel, Manuel; van de Loo, Bas W. H.; Nemeth, William; ...

2018-05-14

Here, the interplay between hydrogenation and passivation of poly-Si/SiO x contacts to n-type Si wafers is studied using atomic layer deposited Al 2O 3 and anneals in forming gas and nitrogen. The poly-Si/SiO x stacks are prepared by thermal oxidation followed by thermal crystallization of a-Si:H films deposited by plasma-enhanced chemical vapor deposition. Implied open-circuit voltages as high as 710 mV are achieved for p-type poly-Si/SiO x contacts to n-type Si after hydrogenation. Correlating minority carrier lifetime data and secondary ion mass spectrometry profiles reveals that the main benefit of Al 2O 3 is derived from its role as amore » hydrogen source for chemically passivating defects at SiO x; Al 2O 3 layers are found to hydrogenate poly-Si/SiO x much better than a forming gas anneal. By labelling Al 2O 3 and the subsequent anneal with different hydrogen isotopes, it is found that Al 2O 3 exchanges most of its hydrogen with the ambient upon annealing at 400 °C for 1 h even though there is no significant net change in its total hydrogen content.« less

The Variability of Atmospheric Deuterium Brightness at Mars: Evidence for Seasonal Dependence

NASA Astrophysics Data System (ADS)

Mayyasi, Majd; Clarke, John; Bhattacharyya, Dolon; Deighan, Justin; Jain, Sonal; Chaffin, Michael; Thiemann, Edward; Schneider, Nick; Jakosky, Bruce

2017-10-01

The enhanced ratio of deuterium to hydrogen on Mars has been widely interpreted as indicating the loss of a large column of water into space, and the hydrogen content of the upper atmosphere is now known to be highly variable. The variation in the properties of both deuterium and hydrogen in the upper atmosphere of Mars is indicative of the dynamical processes that produce these species and propagate them to altitudes where they can escape the planet. Understanding the seasonal variability of D is key to understanding the variability of the escape rate of water from Mars. Data from a 15 month observing campaign, made by the Mars Atmosphere and Volatile Evolution Imaging Ultraviolet Spectrograph high-resolution echelle channel, are used to determine the brightness of deuterium as observed at the limb of Mars. The D emission is highly variable, with a peak in brightness just after southern summer solstice. The trends of D brightness are examined against extrinsic as well as intrinsic sources. It is found that the fluctuations in deuterium brightness in the upper atmosphere of Mars (up to 400 km), corrected for periodic solar variations, vary on timescales that are similar to those of water vapor fluctuations lower in the atmosphere (20-80 km). The observed variability in deuterium may be attributed to seasonal factors such as regional dust storm activity and subsequent circulation lower in the atmosphere.

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

Eight-Liter Hydrogen-Deuterium Bubble Chamber in Magnetic Field; VOS MILITROVAYA VODORODNO-DEITERIEVAYA PUZYR'KOVAYA KAMERA V MAGNITNOM POLE

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

Blokhintseva, T.D.; Vasilenko, A.T.; Grebinnik, V.G.

1961-01-01

A design of an 8-liter hydrogen-deuterium bubble chamber is described, and its operating characteristics are given. The chamber is a metal-glass device with the vertical location of its working volume. The chamber is illuminated by means of a lens. In the expansion system the bellows are used. The magnetic field is 12000 oersted in the working volume. The operating cycle of the chamber does not exceed 2 secs. (auth)

Deuterium isotope effects on 13C and 15N chemical shifts of intramolecularly hydrogen-bonded enaminocarbonyl derivatives of Meldrum’s and Tetronic acid

NASA Astrophysics Data System (ADS)

Ullah, Saif; Zhang, Wei; Hansen, Poul Erik

2010-07-01

Secondary deuterium isotope effects on 13C and 15N nuclear shieldings in a series of cyclic enamino-diesters and enamino-esters and acyclic enaminones and enamino-esters have been examined and analysed using NMR and DFT (B3LYP/6-31G(d,p)) methods. One-dimensional and two-dimensional NMR spectra of enaminocarbonyl and their deuterated analogues were recorded in CDCl 3 and CD 2Cl 2 at variable temperatures and assigned. 1JNH coupling constants for the derivatives of Meldrum's and tetronic acids reveal that they exist at the NH-form. It was demonstrated that deuterium isotope effects, for the hydrogen bonded compounds, due to the deuterium substitution at the nitrogen nucleus lead to large one-bond isotope effects at nitrogen, 1Δ 15N(D), and two-bond isotope effects on carbon nuclei, 2ΔC(ND), respectively. A linear correlations exist between 2ΔC(ND) and 1Δ 15N(D) whereas the correlation with δNH is divided into two. A good agreement between the experimentally observed 2ΔC(ND) and calculated dσ 13C/dR NH was obtained. A very good correlation between calculated NH bond lengths and observed NH chemical shifts is found. The observed isotope effects are shown to depend strongly on Resonance Assisted Hydrogen bonding.

Deuterium-tritium pulse propulsion with hydrogen as propellant and the entire space-craft as a gigavolt capacitor for ignition

NASA Astrophysics Data System (ADS)

Winterberg, F.

2013-08-01

A deuterium-tritium (DT) nuclear pulse propulsion concept for fast interplanetary transport is proposed utilizing almost all the energy for thrust and without the need for a large radiator: By letting the thermonuclear micro-explosion take place in the center of a liquid hydrogen sphere with the radius of the sphere large enough to slow down and absorb the neutrons of the DT fusion reaction, heating the hydrogen to a fully ionized plasma at a temperature of ∼105 K. By using the entire spacecraft as a magnetically insulated gigavolt capacitor, igniting the DT micro-explosion with an intense GeV ion beam discharging the gigavolt capacitor, possible if the space craft has the topology of a torus.

Isotopically exchangeable organic hydrogen in coal relates to thermal maturity and maceral composition

USGS Publications Warehouse

Mastalerz, Maria; Schimmelmann, A.

2002-01-01

Hydrogen isotopic exchangeability (Hex) and ??Dn values of non-exchangeable organic hydrogen were investigated in coal kerogens ranging in rank from lignite to graphite. The relative abundance of Hex is highest in lignite with about 18% of total hydrogen being exchangeable, and decreases to around 2.5% in coals with Ro of 1.7 to ca. 5.7%. At Still higher rank (Ro > 6%), Hex increases slightly, although the abundance of total hydrogen decreases. ??Dn is influenced by original biochemical D/H ratios and by thermal maturation in contact with water. Therefore, ??Dn does not show an overall consistent trend with maturity. ?? 2002 Elsevier Science Ltd. All rights reserved.

Determination of the ratio r v = d v u v of the valence quark distributions in the proton from neutrino and antineutrino reactions on hydrogen and deuterium

NASA Astrophysics Data System (ADS)

Jones, G. T.; Jones, R. W. L.; Kennedy, B. W.; Klein, H.; Morrison, D. R. O.; Wachsmuth, H.; Miller, D. B.; Mobayyen, M. M.; Wainstein, S.; Aderholz, M.; Hantke, D.; Katz, U. F.; Kern, J.; Schmitz, N.; Wittek, W.; Borner, H. P.; Myatt, G.; Cooper-Sarkar, A. M.; Guy, J.; Venus, W.; Bullock, F. W.; Burke, S.

1994-12-01

Based on a QCD analysis of the parton momentum distributions in the proton, the ratio r v = d v / u v of the d and u valence quark distributions is determined as function of x in the range 0.01< x<0.7. The analysis uses data from neutrino and antineutrino charged current interactions on hydrogen and deuterium, obtained with BEBC in the (anti)neutrino wideband beam of the CERN SPS. Since v mainly depends on the deuterium/hydrogen ratios of the normalised x-y-Q 2-distributions many systematic effects cancel. It is found that r v decreases with increasing x, and drops below the naive SU(6) expectation of 0.5 for x≳0.3. An extrapolation of r v to x=1 is consistent with the hypothesis r v (1)=0.

Deuterium diffusion and retention in tungsten coated with barrier layer during ion irradiation

NASA Astrophysics Data System (ADS)

Begrambekov, L. B.; Kaplevsky, A. S.; Dovganyuk, S. S.; Evsin, A. E.; Baryshnikova, I. E.

2017-12-01

The results of the comparative analysis of low-temperature desorption of deuterium from tungsten coated with aluminum and yttrium films under the irradiation by hydrogen plasma with oxygen impurity are presented. The irradiation of aluminum or yttrium coating by H2+1%O2 plasma leads to the desorption of implanted deuterium from the samples. It was shown that the number of atoms desorbed depends on the sign of enthalpy of hydrogen solution in the metal film.

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.

Backbone dynamics of a model membrane protein: measurement of individual amide hydrogen-exchange rates in detergent-solubilized M13 coat protein using /sup 13/C NMR hydrogen/deuterium isotope shifts

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

Henry, G.D.; Weiner, J.H.; Sykes, B.D.

Hydrogen-exchange rates have been measured for individual assigned amide protons in M13 coat protein, a 50-residue integral membrane protein, using a /sup 13/C nuclear magnetic resonance (NMR) equilibrium isotope shift technique. The locations of the more rapidly exchanging amides have been determined. In D/sub 2/O solutions, a peptide carbonyl resonance undergoes a small upfield isotope shift (0.08-0.09 ppm) from its position in H/sub 2/O solutions; in 1:1 H/sub 2/O/D/sub 2/O mixtures, the carbonyl line shape is determined by the exchange rate at the adjacent nitrogen atom. M13 coat protein was labeled biosynthetically with /sup 13/C at the peptide carbonyls ofmore » alanine, glycine, phenylalanine, proline, and lysine, and the exchange rates of 12 assigned amide protons in the hydrophilic regions were measured as a function of pH by using the isotope shift method. This equilibrium technique is sensitive to the more rapidly exchanging protons which are difficult to measure by classical exchange-out experiments. In proteins, structural factors, notably H bonding, can decrease the exchange rate of an amide proton by many orders of magnitude from that observed in the freely exposed amides of model peptides such as poly(DL-alanine). With corrections for sequence-related inductive effects, the retardation of amide exchange in sodium dodecyl sulfate solubilized coat protein has been calculated with respect to poly(DL-alanine). The most rapidly exchanging protons, which are retarded very little or not at all, are shown to occur at the N- and C-termini of the molecule. A model of the detergent-solubilized coat protein is constructed from these H-exchange data which is consistent with circular dichroism and other NMR results.« less

The temperature and ion energy dependence of deuterium retention in lithium films

NASA Astrophysics Data System (ADS)

Buzi, Luxherta; Koel, Bruce E.; Skinner, Charles H.

2016-10-01

Lithium conditioning of plasma facing components in magnetic fusion devices has improved plasma performance and lowered hydrogen recycling. For applications of lithium in future high heat flux and long pulse duration machines it is important to understand and parameterize deuterium retention in lithium. This work presents surface science studies of deuterium retention in lithium films as a function of surface temperature, incident deuterium ion energy and flux. Initial experiments are performed on thin (3-30 ML) lithium films deposited on a single crystal molybdenum substrate to avoid effects due to grain boundaries, intrinsic defects and impurities. A monoenergetic and mass-filtered deuterium ion beam was generated in a differentially pumped Colutron ion gun. Auger electron spectroscopy and X-ray photoelectron spectroscopy were used to identify the elemental composition and temperature programmed desorption was used to measure the deuterium retention under the different conditions. Support was provided through DOE Contract Number DE-AC02-09CH11466.

Characterization of an atomic hydrogen source for charge exchange experiments

DOE PAGES

Leutenegger, M. A.; Beiersdorfer, P.; Betancourt-Martinez, G. L.; ...

2016-07-02

Here, we characterized the dissociation fraction of a thermal dissociation atomic hydrogen source by injecting the mixed atomic and molecular output of the source into an electron beam ion trap containing highly charged ions and recording the x-ray spectrum generated by charge exchange using a high-resolution x-ray calorimeter spectrometer. We exploit the fact that the charge exchange state-selective capture cross sections are very different for atomic and molecular hydrogen incident on the same ions, enabling a clear spectroscopic diagnostic of the neutral species.

Hydrogen desorption using honeycomb finned heat exchangers integrated in adsorbent storage systems

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

Corgnale, Claudio; Hardy, Bruce; Chahine, Richard

One of the main technical hurdles associated with adsorbent based hydrogen storage systems is relative to their ability to discharge hydrogen effectively, as dictated by fuel cell requirements. In this study, a new honeycomb finned heat exchanger concept was examined to evaluate its potential as a heat transfer system for hydrogen desorption. A bench scale 0.5 L vessel was equipped with the proposed heat exchanger, filled with MOF-5® adsorbent material. The heating power, required to desorb hydrogen, was provided by a 100 W electric heater placed in the center of the honeycomb structure. Two desorption tests, at room temperature andmore » under cryogenic temperatures, were carried out to evaluate the hydrogen desorption performance of the proposed system under different operating conditions. The bench scale vessel performance was verified from both an experimental and a modeling point of view, demonstrating the ability to desorb about 45% of the adsorbed hydrogen in reduced time and applying low heating power. Further modeling analyses were also carried out showing the potential of the proposed system to reach high hydrogen discharging rates at cryogenic temperature conditions and operating pressures between 100 bar and 5 bar. The proposed adsorption system also demonstrated to be able to discharge all the available hydrogen in less than 500 s operating at cryogenic conditions and with a nominal heating power of 100 W.« less

Hydrogen desorption using honeycomb finned heat exchangers integrated in adsorbent storage systems

DOE PAGES

Corgnale, Claudio; Hardy, Bruce; Chahine, Richard; ...

2018-03-01

One of the main technical hurdles associated with adsorbent based hydrogen storage systems is relative to their ability to discharge hydrogen effectively, as dictated by fuel cell requirements. In this study, a new honeycomb finned heat exchanger concept was examined to evaluate its potential as a heat transfer system for hydrogen desorption. A bench scale 0.5 L vessel was equipped with the proposed heat exchanger, filled with MOF-5® adsorbent material. The heating power, required to desorb hydrogen, was provided by a 100 W electric heater placed in the center of the honeycomb structure. Two desorption tests, at room temperature andmore » under cryogenic temperatures, were carried out to evaluate the hydrogen desorption performance of the proposed system under different operating conditions. The bench scale vessel performance was verified from both an experimental and a modeling point of view, demonstrating the ability to desorb about 45% of the adsorbed hydrogen in reduced time and applying low heating power. Further modeling analyses were also carried out showing the potential of the proposed system to reach high hydrogen discharging rates at cryogenic temperature conditions and operating pressures between 100 bar and 5 bar. The proposed adsorption system also demonstrated to be able to discharge all the available hydrogen in less than 500 s operating at cryogenic conditions and with a nominal heating power of 100 W.« less

Molecular Beam Studies of Hot Atom Chemical Reactions: Reactive Scattering of Energetic Deuterium Atoms

DOE R&D Accomplishments Database

Continetti, R. E.; Balko, B. A.; Lee, Y. T.

1989-02-01

A brief review of the application of the crossed molecular beams technique to the study of hot atom chemical reactions in the last twenty years is given. Specific emphasis is placed on recent advances in the use of photolytically produced energetic deuterium atoms in the study of the fundamental elementary reactions D + H{sub 2} -> DH + H and the substitution reaction D + C{sub 2}H{sub 2} -> C{sub 2}HD + H. Recent advances in uv laser and pulsed molecular beam techniques have made the detailed study of hydrogen atom reactions under single collision conditions possible.

Properties of thick GEM in low-pressure deuterium

NASA Astrophysics Data System (ADS)

Lee, C. S.; Ota, S.; Tokieda, H.; Kojima, R.; Watanabe, Y. N.; Uesaka, T.

2014-05-01

Deuteron inelastic scattering (d, d') provides a promising spectroscopic tool to study nuclear incompressibility. In studies of deuteron inelastic scattering of unstable nuclei, measurements of low-energy recoiled particles is very important. In order to perform these measurements, we are developing a GEM-TPC based gaseous active target, called CAT (Center for nuclear study Active Target), operated with pure deuterium gas. The CAT has been tested with deuterium gas at 1 atm and 100-μm-thick GEMs. The low-pressure operation of CAT is planned in order to improve the detection capability for lower-energy recoil particles. A 400 μm-thick gas electron multiplier (THGEM) was chosen for the low-pressure operation of CAT. However, the properties of THGEM in low-pressure deuterium are currently undocumented. In this work, the performance of THGEM with low-pressure pure deuterium gas has been investigated. The effective gas gain of THGEM has been measured in various conditions using a 5.5-MeV 241Am alpha source. The effective gas gain was measured for 0.2-, 0.3- and 0.4-atm deuterium gas and a gas gain of about 103 was achieved by a double THGEM structure at 0.2 atm. The maximum achieved gain decreased with increasing gas pressure. The dependences of the effective gas gain on the electric field strengths of the drift, transfer and induction regions were investigated. The gain stability as a function of time in hydrogen gas was also tested and a relaxation time of THGEM of about 60 hours was observed with a continuous irradiation of alpha particles, which is significantly longer than previous studies have reported. We have tried to evaluate the gas gain of THGEM in deuterium gas by considering only the Townsend ionization process; however, it turned out that more phenomenological aspects, such as transfer efficiency, should be included in the evaluation. The basic properties of THGEM in low-pressure deuterium have been investigated for the first time.

A mini-type hydrogen generator from aluminum for proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Wang, Er-Dong; Shi, Peng-Fei; Du, Chun-Yu; Wang, Xiao-Rui

A safe and simple hydrogen generator, which produced hydrogen by chemical reaction of aluminum and sodium hydroxide solution, was proposed for proton exchange membrane fuel cells. The effects of concentration, dropping rate and initial temperature of sodium hydroxide solution on hydrogen generation rate were investigated. The results showed that about 38 ml min -1 of hydrogen generation rate was obtained with 25 wt.% concentration and 0.01 ml s -1 dropping rate of sodium hydroxide solution. The cell fueled by hydrogen from the generator exhibited performance improvement at low current densities, which was mainly due to the humidified hydrogen reduced the protonic resistivity of the proton exchange membrane. The hydrogen generator could stably operate a single cell under 500 mA for nearly 5 h with about 77% hydrogen utilization ratio.

Apparatus for separating and recovering hydrogen isotopes

DOEpatents

Heung, Leung K.

1994-01-01

An apparatus for recovering hydrogen and separating its isotopes. The apparatus includes a housing bearing at least a fluid inlet and a fluid outlet. A baffle is disposed within the housing, attached thereto by a bracket. A hollow conduit is coiled about the baffle, in spaced relation to the baffle and the housing. The coiled conduit is at least partially filled with a hydride. The hydride can be heated to a high temperature and cooled to a low temperature quickly by circulating a heat transfer fluid in the housing. The spacing between the baffle and the housing maximizes the heat exchange rate between the fluid in the housing and the hydride in the conduit. The apparatus can be used to recover hydrogen isotopes (protium, deuterium and tritium) from gaseous mixtures, or to separate hydrogen isotopes from each other.

Displacement damage dose and implantation temperature effects on the trapping and release of deuterium implanted into SiC

NASA Astrophysics Data System (ADS)

Muñoz, P.; García-Cortés, I.; Sánchez, F. J.; Moroño, A.; Malo, M.; Hodgson, E. R.

2017-09-01

Radiation damage to flow channel insert (FCI) materials is an important issue for the concept of dual-coolant blanket development in future fusion devices. Silicon Carbide (SiC) is one of the most suitable materials for FCI. Because of the severe radiation environment and exposure to tritium during operation it is of fundamental importance to study hydrogen isotope trapping and release in these materials. Here the trapping, detrapping, and diffusion of deuterium implanted into SiC is studied in correlation with pre- and post-damage induced under different conditions. For this, SiC samples are pre-damaged with 50 keV Ne+ ions at different temperatures (20, 200, 450, 700 °C) to different damage doses (1, 3.6, 7 dpa). Next, deuterium is introduced into the samples at 450 °C by ion implantation at 7 keV. The implanted deuterium retained in the sample is analysed using secondary ion mass spectrometry (SIMS) and thermo-stimulated desorption (TSD) measurements. The results indicate that with increasing neon damage dose, the maximum deuterium desorption occurs at higher temperatures. In contrast, when increasing neon implantation temperature for a fixed dose, the maximum deuterium desorption release temperature decreases. It is interpreted that the neon bombardment produces thermally stable traps for hydrogen isotopes and the stability of this damage increases with neon pre-implantation dose. A decrease of the trapping of implanted deuterium is also observed to occur due to damage recovery by thermal annealing during pre-implantation at the higher temperatures. Finally, direct particle bombardment induced deuterium release is also observed.

NMR Analysis of Amide Hydrogen Exchange Rates in a Pentapeptide-Repeat Protein from A. thaliana.

PubMed

Xu, Shenyuan; Ni, Shuisong; Kennedy, Michael A

2017-05-23

At2g44920 from Arabidopsis thaliana is a pentapeptide-repeat protein (PRP) composed of 25 repeats capped by N- and C-terminal α-helices. PRP structures are dominated by four-sided right-handed β-helices typically consisting of mixtures of type II and type IV β-turns. PRPs adopt repeated five-residue (Rfr) folds with an Rfr consensus sequence (STAV)(D/N)(L/F)(S/T/R)(X). Unlike other PRPs, At2g44920 consists exclusively of type II β-turns. At2g44920 is predicted to be located in the thylakoid lumen although its biochemical function remains unknown. Given its unusual structure, we investigated the biophysical properties of At2g44920 as a representative of the β-helix family to determine if it had exceptional global stability, backbone dynamics, or amide hydrogen exchange rates. Circular dichroism measurements yielded a melting point of 62.8°C, indicating unexceptional global thermal stability. Nuclear spin relaxation measurements indicated that the Rfr-fold core was rigid with order parameters ranging from 0.7 to 0.9. At2g44920 exhibited a striking range of amide hydrogen exchange rates spanning 10 orders of magnitude, with lifetimes ranging from minutes to several months. A weak correlation was found among hydrogen exchange rates, hydrogen bonding energies, and amino acid solvent-accessible areas. Analysis of contributions from fast (approximately picosecond to nanosecond) backbone dynamics to amide hydrogen exchange rates revealed that the average order parameter of amides undergoing fast exchange was significantly smaller compared to those undergoing slow exchange. Importantly, the activation energies for amide hydrogen exchange were found to be generally higher for the slowest exchanging amides in the central Rfr coil and decreased toward the terminal coils. This could be explained by assuming that the concerted motions of two preceding or following coils required for hydrogen bond disruption and amide hydrogen exchange have a higher activation energy

An Experimental Investigation of the Process of Isotope Exchange that Takes Place when Heavy Water Is Exposed to the Atmosphere

ERIC Educational Resources Information Center

Deeney, F. A.; O'Leary, J. P.

2009-01-01

We have used the recently developed method for rapid measurement of maximum density temperature to determine the rate at which hydrogen and deuterium isotope exchange takes place when a sample of heavy water is exposed to the atmosphere. We also provide a simple explanation for the observed linear rate of transition. (Contains 2 figures.)

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.

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

Study of ion-irradiated tungsten in deuterium plasma

NASA Astrophysics Data System (ADS)

Khripunov, B. I.; Gureev, V. M.; Koidan, V. S.; Kornienko, S. N.; Latushkin, S. T.; Petrov, V. B.; Ryazanov, A. I.; Semenov, E. V.; Stolyarova, V. G.; Danelyan, L. S.; Kulikauskas, V. S.; Zatekin, V. V.; Unezhev, V. N.

2013-07-01

Experimental study aimed at investigation of neutron induced damage influence on fusion reactor plasma facing materials is reported. Displacement damage was produced in tungsten by high-energy helium and carbon ions at 3-10 MeV. The reached level of displacement damage ranged from several dpa to 600 dpa. The properties of the irradiated tungsten were studied in steady-state deuterium plasma on the LENTA linear divertor simulator. Plasma exposures were made at 250 eV of ion energy to fluence 1021-1022 ion/сm2. Erosion dynamics of the damaged layer and deuterium retention were observed. Surface microstructure modifications and important damage of the 5 μm layer shown. Deuterium retention in helium-damaged tungsten (ERD) showed its complex behavior (increase or decrease) depending on implanted helium quantity and the structure of the surface layer.

The deuterium content of water in some volcanic glasses

USGS Publications Warehouse

Friedman, I.; Smith, R.L.

1958-01-01

The deuterium-hydrogen composition (relative to Lake Michigan water = 0.0) of water extractsd from coexisting perlite and obsidian from eleven different localities was determined. The water content of the obsidians is generally from 0.09 to 0.29 per cent by weight, though two samples from near Olancha, California, contain about 0.92 per cent. The relative deuterium concentration is from -4.6 to -12.3 per cent. The coexisting perlite contains from 2.0 to 3.8 per cent of water with a relative deuterium concentration of -3.1 to -16.6 per cent. The deuterium concentration in the perlites is not related to that in the enclosed obsidian. The deuterium concentration in the perlite water is related to the deuterium concentration of the modern meteoric water and the perlite water contains approximately 4 per cent less deuterium than does the groundwater of the area in which the perlites occur. The above relations hold true for perlites from northern New Mexico, east slope of the Sierra Nevada. California Coast Range, Yellowstone Park, Wyoming, and New Zealand. As the water in the obsidian is unrelated to meteoric water, but the enclosing perlite water is related, we believe that this is evidence for the secondary hydration of obsidian to form high water content perlitic glass. ?? 1958.

Method and source for producing a high concentration of positively charged molecular hydrogen or deuterium ions

DOEpatents

Ehlers, Kenneth W.; Leung, Ka-Ngo

1988-01-01

A high concentration of positive molecular ions of hydrogen or deuterium gas is extracted from a positive ion source having a short path length of extracted ions, relative to the mean free path of the gas molecules, to minimize the production of other ion species by collision between the positive ions and gas molecules. The ion source has arrays of permanent magnets to produce a multi-cusp magnetic field in regions remote from the plasma grid and the electron emitters, for largely confining the plasma to the space therebetween. The ion source has a chamber which is short in length, relative to its transverse dimensions, and the electron emitters are at an even shorter distance from the plasma grid, which contains one or more extraction apertures.

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

Exchanging partially hydrogenated fat for palmitic acid in the diet increases LDL-cholesterol and endogenous cholesterol synthesis in normocholesterolemic women.

PubMed

Sundram, Kalyana; French, Margaret A; Clandinin, M Thomas

2003-08-01

Partial hydrogenation of oil results in fats containing unusual isomeric fatty acids characterized by cis and trans configurations. Hydrogenated fats containing trans fatty acids increase plasma total cholesterol (TC) and LDL-cholesterol while depressing HDL-cholesterol levels. Identifying the content of trans fatty acids by food labeling is overshadowed by a reluctance of health authorities to label saturates and trans fatty acids separately. Thus, it is pertinent to compare the effects of trans to saturated fatty acids using stable isotope methodology to establish if the mechanism of increase in TC and LDL-cholesterol is due to the increase in the rate of endogenous synthesis of cholesterol. Ten healthy normocholesterolemic female subjects consumed each of two diets containing approximately 30% of energy as fat for a fourweek period. One diet was high in palmitic acid (10.6% of energy) from palm olein and the other diet exchanged 5.6% of energy as partially hydrogenated fat for palmitic acid. This fat blend resulted in monounsaturated fatty acids decreasing by 4.9 % and polyunsaturated fats increasing by 2.7%. The hydrogenated fat diet treatment provided 3.1% of energy as elaidic acid. For each dietary treatment, the fractional synthesis rates for cholesterol were measured using deuterium-labeling procedures and blood samples were obtained for blood lipid and lipoprotein measurements. Subjects exhibited a higher total cholesterol and LDL-cholesterol level when consuming the diet containing trans fatty acids while also depressing the HDL-cholesterol level. Consuming the partially hydrogenated fat diet treatment increased the fractional synthesis rate of free cholesterol. Consumption of hydrogenated fats containing trans fatty acids in comparison to a mixtur e of palmitic and oleic acids increase plasma cholesterol levels apparently by increasing endogenous synthesis of cholesterol.

Intracrystalline site preference of hydrogen isotopes in borax

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

Pradhananga, T.M.; Matsuo, S.

1985-01-03

The total hydrogen involved in borax synthesized at 25/sup 0/C in aqueous solution is enriched in deuterium by 5.3% compared with the mother liquor. There is no change in the value of the D/H fractionation factor between the hydrogen in borax and those in the mother liquor with changes in the degree of supersaturation. The fractionation factor changes slightly with a change in the crystallization temperature of borax in the range from 5 to 25/sup 0/C. The D/H ratio in the different sites of borax was estimated by a fractional dehydration technique. The results show that hydrogen atoms of themore » polyanionic group (B/sub 4/O/sub 5/(OH)/sub 4/) are much more enriched in deuterium than those of the cationic group (Na/sub 2/ x 8H/sub 2/O). The delta D values, referred to the mother liquor from which the borax was crystallized, for the cationic group (site A) and the polyanionic group (site B) are -35 +/- 3 and 167 +/- 13%, respectively based on the fractional dehydration results obtained at -21/sup 0/C. At -21/sup 0/C, isotopic exchange between different sites during dehydration is assumed not to occur. The mechanism for dehydration of borax is discussed. 48 references, 8 figures, 3 tables.« less

Deuterium retention in tungsten in dependence of the surface conditions

NASA Astrophysics Data System (ADS)

Ogorodnikova, O. V.; Roth, J.; Mayer, M.

2003-03-01

The paper reviews hydrogen isotope retention and migration in tungsten (W). Due to a large scatter of the deuterium (D) retention database, new measurements of ion-driven D retention in polycrystalline W foil have been performed to clarify the mechanism of hydrogen isotope inventory in W. Deuterium retention has been investigated as a function of ion fluence, implantation temperature, incident energy and surface conditions. Special attention has been given on the investigation of D retention in thin films of tungsten carbide and tungsten oxide which can be formed on W surface in a fusion device. Such kinds of films increase the D retention in W. Several points are reviewed: (i) inventory in pure W, (ii) inventory in W pre-implanted by carbon ions and (iii) inventory in tungsten oxide.

An Isotope Study of Hydrogenation of poly-Si/SiOx Passivated Contacts for Si Solar Cells: Preprint

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

Schnabel, Manuel; Nemeth, William; van de Loo, Bas, W.H.

2017-06-26

For many years, the record Si solar cell efficiency stood at 25.0%. Only recently have several companies and institutes managed to produce more efficient cells, using passivated contacts of made doped poly-Si or a-Si:H and a passivating intrinsic interlayer in all cases. Common to these designs is the need to passivate the layer stack with hydrogen. In this contribution, we perform a systematic study of passivated contact passivation by hydrogen, using poly-Si/SiOx passivated contacts on n-Cz-Si, and ALD Al2O3 followed by a forming gas anneal (FGA) as the hydrogen source. We study p-type and n-type passivated contacts with implied Vocmore » exceeding 690 and 720 mV, respectively, and perform either the ALD step or the FGA with deuterium instead of hydrogen in order to separate the two processes via SIMS. By examining the deuterium concentration at the SiOx in both types of samples, we demonstrate that the FGA supplies negligible hydrogen species to the SiOx, regardless of whether the FGA is hydrogenated or deuterated. Instead, it supplies the thermal energy needed for hydrogen species in the Al2O3 to diffuse there. Furthermore, the concentration of hydrogen species at the SiOx can saturate while implied Voc continues to increase, showing that the energy from the FGA is also required for hydrogen species already at the SiOx to find recombination-active defects to passivate.« less

Thermally induced hydrosilylation at deuterium-terminated silicon nanoparticles: an investigation of the radical chain propagation mechanism.

PubMed

Holm, Jason; Roberts, Jeffrey T

2009-06-16

Isotopic labeling techniques were employed to study alkene addition to hydrogen- and deuterium-terminated silicon nanoparticles. Deuterium-terminated silicon nanoparticle synthesis is described, as is the characterization of fresh deuterium-terminated particles by transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and in situ Fourier transform infrared spectroscopy (FTIR). Particles were refluxed in pure 1-dodecene and subsequently characterized by FTIR and nuclear magnetic resonance (NMR) spectroscopy. (1)H NMR results showed features consistent with dodecyl-terminated nanoparticles. Infrared absorption spectra of refluxed particles showed strong evidence of new C-D bond formation, which is consistent with a radical chain mechanism for alkene addition by hydrosilylation.

Measurement of trace impurities in ultra pure hydrogen and deuterium at the parts-per-billion level using gas chromatography

NASA Astrophysics Data System (ADS)

Ganzha, V.; Ivshin, K.; Kammel, P.; Kravchenko, P.; Kravtsov, P.; Petitjean, C.; Trofimov, V.; Vasilyev, A.; Vorobyov, A.; Vznuzdaev, M.; Wauters, F.

2018-02-01

A series of muon experiments at the Paul Scherrer Institute in Switzerland deploy ultra-pure hydrogen active targets. A new gas impurity analysis technique was developed, based on conventional gas chromatography, with the capability to measure part-per-billion (ppb) traces of nitrogen and oxygen in hydrogen and deuterium. Key ingredients are a cryogenic admixture accumulation, a directly connected sampling system and a dedicated calibration setup. The dependence of the measured concentration on the sample volume was investigated, confirming that all impurities from the sample gas are collected in the accumulation column and measured with the gas chromatograph. The system was calibrated utilizing dynamic dilution of admixtures into the gas flow down to sub-ppb level concentrations. The total amount of impurities accumulated in the purification system during a three month long experimental run was measured and agreed well with the calculated amount based on the measured concentrations in the flow.

Hydrogen/Chlorine exchange reactions of gaseous carbanions.

PubMed

Chen, Hao; Cooks, R Graham; Meurer, Eduardo C; Eberlin, Marcos N

2005-12-01

Gas-phase reactions of three typical carbanions CH(2)NO(2)(-), CH(2)CN(-), and CH(2)S(O)CH(3)(-) with the chloromethanes CH(2)Cl(2), CHCl(3), and CCl(4), examined by tandem mass spectrometry, show a novel hydrogen/chlorine exchange reaction. For example, reaction between the nitromethyl anion CH(2)NO(2)(-) and carbon tetrachloride CCl(4) forms the ion CHClNO(2)(-). The suggested reaction mechanism involves nucleophilic attack by CH(2)NO(2)(-) at the chlorine of CCl(4) followed by proton transfer within the resulting complex [CH(2)ClNO(2) + CCl(3)(-)] to form CHClNO(2)(-) and CHCl(3). Two other carbanions CH(2)CN(-) and CH(2)S(O)CH(3)(-) also undergo the novel hydrogen/chlorine exchange reactions with CCl(4) but to a much smaller extent, their higher nucleophilicities favoring competitive nucleophilic attack reactions. Proton abstraction is the exclusive pathway in the reactions of these carbanions with CHCl(3). While CH(2)CN(-) and CH(2)S(O)CH(3)(-) promote mainly proton abstraction and nucleophilic displacement in reactions with CH(2)Cl(2), CH(2)NO(2)(-) does not react.

NMR studies of structure, hydrogen exchange, and main-chain dynamics in a disrupted-core mutant of thioredoxin.

PubMed Central

De Lorimier, R.; Hellinga, H. W.; Spicer, L. D.

1996-01-01

Core-packing mutants of proteins often approach molten globule states, and hence may have attributes of folding intermediates. We have studied a core-packing mutant of thioredoxin, L78K, in which a leucine residue is substituted by lysine, using 15N heteronuclear two- and three-dimensional NMR. Chemical shift differences between the mutant and wild-type main-chain resonances reveal that structural changes caused by the mutation are localized within 12 A of the altered side chain. The majority of resonances are unchanged, as are many 1H-1H NOEs indicative of the main-chain fold, suggesting that the structure of L78K is largely similar to wild type. Hydrogen exchange studies reveal that residues comprising the central beta-sheet of both mutant and wild-type proteins constitute a local unfolding unit, but with the unfolding/folding equilibrium approximately 12 times larger in L78K. The dynamics of main-chain NH bonds in L78K were studied by 15N spin relaxation and compared with a previous study of wild type. Order parameters for angular motion of NH bonds in the mutant are on average lower than in wild type, suggesting greater spatial freedom on a rapid time scale, but may also be related to different rotational correlation times in the two proteins. There is also evidence of greater conformational exchange in the mutant. Differences between mutant and wild type in hydrogen exchange and main-chain dynamics are not confined to the vicinity of the mutation. We infer that mispacking of the protein core in one location affects local dynamics and stability throughout. PMID:8976564

Hydrogen exchange differences between chemoreceptor signaling complexes localize to functionally important subdomains.

PubMed

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

2014-12-16

The goal of understanding mechanisms of transmembrane signaling, one of many key life processes mediated by membrane proteins, has motivated numerous studies of bacterial chemotaxis receptors. Ligand binding to the receptor causes a piston motion of an α helix in the periplasmic and transmembrane domains, but it is unclear how the signal is then propagated through the cytoplasmic domain to control the activity of the associated kinase CheA. Recent proposals suggest that signaling in the cytoplasmic domain involves opposing changes in dynamics in different subdomains. However, it has been difficult to measure dynamics within the functional system, consisting of extended arrays of receptor complexes with two other proteins, CheA and CheW. We have combined hydrogen exchange mass spectrometry with vesicle template assembly of functional complexes of the receptor cytoplasmic domain to reveal that there are significant signaling-associated changes in exchange, and these changes localize to key regions of the receptor involved in the excitation and adaptation responses. The methylation subdomain exhibits complex changes that include slower hydrogen exchange in complexes in a kinase-activating state, which may be partially consistent with proposals that this subdomain is stabilized in this state. The signaling subdomain exhibits significant protection from hydrogen exchange in complexes in a kinase-activating state, suggesting a tighter and/or larger interaction interface with CheA and CheW in this state. These first measurements of the stability of protein subdomains within functional signaling complexes demonstrate the promise of this approach for measuring functionally important protein dynamics within the various physiologically relevant states of multiprotein complexes.

Hydrogen Exchange Differences between Chemoreceptor Signaling Complexes Localize to Functionally Important Subdomains

PubMed Central

2015-01-01

The goal of understanding mechanisms of transmembrane signaling, one of many key life processes mediated by membrane proteins, has motivated numerous studies of bacterial chemotaxis receptors. Ligand binding to the receptor causes a piston motion of an α helix in the periplasmic and transmembrane domains, but it is unclear how the signal is then propagated through the cytoplasmic domain to control the activity of the associated kinase CheA. Recent proposals suggest that signaling in the cytoplasmic domain involves opposing changes in dynamics in different subdomains. However, it has been difficult to measure dynamics within the functional system, consisting of extended arrays of receptor complexes with two other proteins, CheA and CheW. We have combined hydrogen exchange mass spectrometry with vesicle template assembly of functional complexes of the receptor cytoplasmic domain to reveal that there are significant signaling-associated changes in exchange, and these changes localize to key regions of the receptor involved in the excitation and adaptation responses. The methylation subdomain exhibits complex changes that include slower hydrogen exchange in complexes in a kinase-activating state, which may be partially consistent with proposals that this subdomain is stabilized in this state. The signaling subdomain exhibits significant protection from hydrogen exchange in complexes in a kinase-activating state, suggesting a tighter and/or larger interaction interface with CheA and CheW in this state. These first measurements of the stability of protein subdomains within functional signaling complexes demonstrate the promise of this approach for measuring functionally important protein dynamics within the various physiologically relevant states of multiprotein complexes. PMID:25420045

Deuterium retention and release behaviours of tungsten and deuterium co-deposited layers

NASA Astrophysics Data System (ADS)

Qiao, L.; Zhang, H. W.; Xu, J.; Chai, L. Q.; Hu, M.; Wang, P.

2018-04-01

Tungsten (W) layer deposited in argon and deuterium atmosphere by magnetron sputtering was used as a model system to study the deuterium (D) retention and release behavior in co-deposited W layer. After deposition several selected samples were exposed in deuterium plasma at 370 K with a flux of 4.0 × 1021 D/(m2 s) up to a fluence of 1.1 × 1025 D/m2. Structures of co-deposited W layers are investigated by field-emission scanning electron microscopy (FESEM) and X-ray diffraction (XRD), and the corresponding D retention and release behaviors are studied as functions of deposition and exposure parameters using thermal desorption spectroscopy (TDS). Two main D release peaks were detected from TDS spectra located near 600 and 800 K in these W and D co-deposited layers, and total deuterium retention increased linearly as a function of W layer's thickness. After deuterium plasma exposure, the total D retention amount in W layer increases significantly and D release peak shifts to lower temperature. Clearly, despite the high density of defects expected in co-deposited W layers, the initial deuterium retention before exposure to the deuterium plasma is low even for the samples with a W&D layer. But due to the high densities of defects, during the deuterium plasma exposure the deuterium retention increases faster for co-deposited layer than for the bulk W sample.

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.

Reversible Inter- and Intramolecular Carbon-Hydrogen Activation, Hydrogen Addition, and Catalysis by the Unsaturated Complex Pt(IPr)(SnBu(t)3)(H).

PubMed

Koppaka, Anjaneyulu; Captain, Burjor

2016-03-21

The complex Pt(IPr)(SnBu(t)3)(H) (1) was obtained from the reaction of Pt(COD)2 with Bu(t)3SnH and IPr [IPr = N,N'-bis(2,6-diisopropylphenyl)imidazol-2-ylidene]. Complex 1 undergoes exchange reactions with deuterated solvents (C6D6, toluene-d8, and CD2Cl2), where the hydride ligand and the methyl hydrogen atoms on the isopropyl group of the IPr ligand have been replaced by deuterium atoms. Complex 1 reacts with H2 gas reversibly at room temperature to yield the complex Pt(IPr)(SnBu(t)3)(H)3 (2). Complex 2 also undergoes exchange reactions with deuterated solvents as in 1 to deuterate the hydride ligands and the methyl hydrogen atoms on the isopropyl group of the IPr ligand. Complex 1 catalyzes the hydrogenation of styrene to ethylbenzene at room temperature. The reaction of 1 with 1 equiv of styrene at -20 °C yields the η(2)-coordinated product Pt(IPr)(SnBu(t)3)(η(2)-CH2CHPh)(H) (3), and with 2 equiv of styrene, it forms Pt(IPr)(η(2)-CH2CHPh)2 (4).

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.

Analysis and test of a breadboard cryogenic hydrogen/Freon heat exchanger

NASA Technical Reports Server (NTRS)

Desjardins, L. F.; Hooper, J.

1973-01-01

System studies required to verify a tube-in-tube cryogenic heat exchanger as optimum for the space shuttle mission are described. Design of the optimum configuration, which could be fabricated from commercially available hardware, is discussed. Finally, testing of the proposed configuration with supercritical hydrogen and Freon 21 is discussed and results are compared with thermal and dynamic analysis.

[Consideration of the deuterium-free water supply to an expedition to Mars].

PubMed

Siniak, Iu E; Turusov, V S; Grigor'ev, A I; Zaridze, D G; Gaĭdadymov, V B; Gus'kova, E I; Antoshina, E E; Gor'kova, T G; Trukhanova, L S

2003-01-01

Interplanetary missions, including to Mars, will put crews into severe radiation conditions. Search for methods of reducing the risk of radiation-induced cancer is of the top priority in preparation for the mission to Mars. One of the options is designing life support systems that will generate water with low content of the stable hydrogen isotope (deuterium) to be consumed by crewmembers. Preliminary investigations have shown that a decrease of the deuterium fraction by 65% does impart to water certain anti-cancer properties. Therefore, drinking deuterium-free water has the potential to reduce the risk of cancer consequent to the extreme radiation exposure of the Martian crew.

Role of deuterium desorption kinetics on the thermionic emission properties of polycrystalline diamond films with respect to kinetic isotope effects

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

Paxton, W. F., E-mail: william.f.paxton@vanderbilt.edu; Howell, M.; Kang, W. P.

2014-06-21

The desorption kinetics of deuterium from polycrystalline chemical vapor deposited diamond films were characterized by monitoring the isothermal thermionic emission current behavior. The reaction was observed to follow a first-order trend as evidenced by the decay rate of the thermionic emission current over time which is in agreement with previously reported studies. However, an Arrhenius plot of the reaction rates at each tested temperature did not exhibit the typical linear behavior which appears to contradict past observations of the hydrogen (or deuterium) desorption reaction from diamond. This observed deviation from linearity, specifically at lower temperatures, has been attributed to non-classicalmore » processes. Though no known previous studies reported similar deviations, a reanalysis of the data obtained in the present study was performed to account for tunneling which appeared to add merit to this hypothesis. Additional investigations were performed by reevaluating previously reported data involving the desorption of hydrogen (as opposed to deuterium) from diamond which further indicated this reaction to be dominated by tunneling at the temperatures tested in this study (<775 °C). An activation energy of 3.19 eV and a pre-exponential constant of 2.3 × 10{sup 12} s{sup −1} were determined for the desorption reaction of deuterium from diamond which is in agreement with previously reported studies.« less

Application of Gas Chromatography-Tandem Mass Spectrometry (GC/MS/MS) for the Analysis of Deuterium Enrichment of Water

PubMed Central

Walker, Dillon K.; Thaden, John J.; Deutz, Nicolaas E.P.

2015-01-01

Incorporation of deuterium from deuterium oxide (2H2O) into biological components is a commonly used approach in metabolic studies. Determining the dilution of deuterium in the body water pool (BW) can be used to estimate body composition. We describe three sensitive GC-MS/MS methods to measure water enrichment in BW . Samples were reacted with NaOH and U-13C3-acetone in an autosampler vial to promote deuterium exchange with U-13C3-acetone hydrogens. Headspace injections were made of U-13C3-acetone-saturated air onto a 30m DB-1MS column in EI-mode. Subjects ingested 30ml 2H2O and plasma samples were collected. BW was determined by standard equation. DXA scans were performed to calculate body mass, body volume and bone mineral content. A 4 compartmental model was used to estimate body composition (fat and fat free mass). Full scan experiments generated a m/z 45 peak and to a lesser extent a m/z 61 peak. Product fragment ions further monitored included 45 and 46 using selected ion monitoring (SIM;Method1), the 61>45 and 62>46 transition using multiple reaction monitoring (MRM;Method2) and the Neutral Loss, 62>45, transition (Method3). MRM methods were optimized for collision energy (CE) and collision-induced dissociation (CID) argon gas pressure with 6eV CE and 1.5 mTorr CID gas being optimal. Method2 was used for finally determination of 2H2O enrichment of subjects due to lower natural background. We have developed a sensitive method to determine 2H2O enrichment in body water to enable measurement of FM and FFM. PMID:26169138

The biophysical effects of deuterium oxide on biomolecules and living cells through open notebook science

NASA Astrophysics Data System (ADS)

Salvagno, Anthony L.

not possible. Molecular effects were examined using a variety of tools including: dynamic light spectroscopy, Fourier transform-infrared spectroscopy, cavity ring-down spectroscopy, and optical tweezers. Heat induced protein aggregation was possible in H2O, but prevented in the presence of D2O and analyzed via DLS. Deuterium exchange and replacement was observed and quantified using both FT-IR and CRDS. With FT-IR it was possible to identify differences between solvents, while the time-scale of hydrogen-deuterium exchange was quantified for bulk water with CRDS. Using optical tweezers, DNA was overstretched in both H2O and D2O. The average force for DNA overstretching was found to be ~2.5pN higher in D2O compared to H2O. Deuterium oxide has a stabilizing force on biomolecules, which prevents protein denaturing and can affect the timing for cellular processes. It is because of this molecular property that D2O is observed to affect organisms grown with D2O instead of H2O. Despite this, there seems to be an optimal concentration of deuterium which is above the natural concentration of 155.6ppm. In the presence of deuterium depleted water, cells exhibit signs of stress, further demonstrating that deuterium isn't merely tolerated in solution, but actually required as hypothesized by Gilbert N. Lewis in 1934.

Multi-MBar studies of Oxygen and Hydrogen

NASA Astrophysics Data System (ADS)

Dalladay-Simpson, Philip

2013-06-01

The study of simple archetypal molecular systems having an electronic structure heavily altered by ultra-high compression holds the promise of major breakthroughs in our understanding of matter. Among these systems, oxygen and deuterium are of particular interest due to their abundance in the Universe. We have used optical and synchrotron x-ray diffraction techniques to probe O2 and H2 (D2) to above 300 GPa. Our study on dense oxygen more than doubles the pressure range at which it had been investigated before; the picture we observe is quite different from what was experimentally reported and predicted by theory. Our experiments on dense hydrogen (deuterium) reveal the appearance of a new semiconducting phase at above 220 GPa which persists up to 320 GPa - the highest pressure reached in our studies. This phase is characterized by emergence of intense, well defined low frequency Raman bands, together with the unprecedented softening of the vibron, ν1, and appearance of a secondary vibron, ν2 and slowly closing band-gap. Analysis of the Raman spectra suggests a peculiar graphene-like structure consisting of both atomic and molecular layers. For both systems we will discuss the differences in results and interpretations which currently present in the literature.

Carbon impurities behavior and its impact on ion thermal confinement in high-ion-temperature deuterium discharges on the Large Helical Device

NASA Astrophysics Data System (ADS)

Mukai, K.; Nagaoka, K.; Takahashi, H.; Yokoyama, M.; Murakami, S.; Nakano, H.; Ida, K.; Yoshinuma, M.; Seki, R.; Kamio, S.; Fujiwara, Y.; Oishi, T.; Goto, M.; Morita, S.; Morisaki, T.; Osakabe, M.; LHD Experiment Group1, the

2018-07-01

The behavior of carbon impurities in deuterium plasmas and its impact on thermal confinement were investigated in comparison with hydrogen plasmas in the Large Helical Device (LHD). Deuterium plasma experiments have been started in the LHD and high-ion-temperature plasmas with central ion temperature (T i) of 10 keV were successfully obtained. The thermal confinement improvement could be sustained for a longer time compared with hydrogen plasmas. An isotope effect was observed in the time evolution of the carbon density profiles. A transiently peaked profile was observed in the deuterium plasmas due to the smaller carbon convection velocity and diffusivity in the deuterium plasmas compared with the hydrogen plasmas. The peaked carbon density profile was strongly correlated to the ion thermal confinement improvement. The peaking of the carbon density profile will be one of the clues to clarify the unexplained mechanisms for the formations of ion internal transport barrier and impurity hole on LHD. These results could also lead to a better understanding of the isotope effect in the thermal confinement in torus plasma.

Study of the potential for improving the economics of hydrogen liquefaction through the use of centrifugal compressors and the addition of a heavy water plant

NASA Technical Reports Server (NTRS)

Baker, C. R.

1977-01-01

An approach to the liquefaction of hydrogen was developed which permits the application of standard centrifugal compressors in place of reciprocating machines. A second fluid, such as propane, is added to the hydrogen prior to compression to form a mixture having a molecular weight much greater than that of hydrogen alone, so that a standard centrifugal compressor can be used. After compression, the mixture is cooled to cryogenic temperature levels where the propane condenses out of the mixture and is separated as a liquid. Since a small amount of deuterium is produced during hydrogen liquefaction, the potential of recovering deuterium and selling it as a co-product was investigated. Deuterium, in the form of heavy water, can be used in certain nuclear reactors as a neutron moderator to reduce the neutron velocity and enhance the probability of neutron collision with uranium nucleii.

Gas-phase fragmentation of peptides by MALDI in-source decay with limited amide hydrogen (1H/2H) scrambling.

PubMed

Bache, Nicolai; Rand, Kasper D; Roepstorff, Peter; Jørgensen, Thomas J D

2008-08-15

To achieve a fundamental understanding of the function of proteins and protein complexes at the molecular level, it is crucial to obtain a detailed knowledge about their dynamic and structural properties. The kinetics of backbone amide hydrogen exchange is intimately linked to the structural dynamics of the protein, and in recent years, the monitoring of the isotopic exchange of these hydrogens by mass spectrometry has become a recognized method. At present, the resolution of this method is, however, limited and single-residue resolution is typically only obtained for a few residues in a protein. It would therefore be desirable if gas-phase fragmentation could be used to localize incorporated deuterons as this would ultimately lead to single-residue resolution. A central obstacle for this approach is, however, the occurrence of intramolecular migration of amide hydrogens upon activation of the gaseous protein (i.e., hydrogen scrambling). Here we investigate the occurrence of scrambling in selectively labeled peptides upon fragmentation by matrix-assisted laser desorption/ionization in-source decay (MALDI ISD). We have utilized peptides with a unique regioselective deuterium incorporation that allows us to accurately determine the extent of scrambling upon fragmentation. Our results show that the level of scrambling upon MALDI ISD is so low that the solution deuteration pattern is readily apparent in the gas-phase fragment ions. These results suggest that MALDI ISD may prove useful for hydrogen exchange studies of purified peptides and small proteins.

Protein structural dynamics at the gas/water interface examined by hydrogen exchange mass spectrometry.

PubMed

Xiao, Yiming; Konermann, Lars

2015-08-01

Gas/water interfaces (such as air bubbles or foam) are detrimental to the stability of proteins, often causing aggregation. This represents a potential problem for industrial processes, for example, the production and handling of protein drugs. Proteins possess surfactant-like properties, resulting in a high affinity for gas/water interfaces. The tendency of previously buried nonpolar residues to maximize contact with the gas phase can cause significant structural distortion. Most earlier studies in this area employed spectroscopic tools that could only provide limited information. Here we use hydrogen/deuterium exchange (HDX) mass spectrometry (MS) for probing the conformational dynamics of the model protein myoglobin (Mb) in the presence of N(2) bubbles. HDX/MS relies on the principle that unfolded and/or highly dynamic regions undergo faster deuteration than tightly folded segments. In bubble-free solution Mb displays EX2 behavior, reflecting the occurrence of short-lived excursions to partially unfolded conformers. A dramatically different behavior is seen in the presence of N(2) bubbles; EX2 dynamics still take place, but in addition the protein shows EX1 behavior. The latter results from interconversion of the native state with conformers that are globally unfolded and long-lived. These unfolded species likely correspond to Mb that is adsorbed to the surface of gas bubbles. N(2) sparging also induces aggregation. To explain the observed behavior we propose a simple model, that is, "semi-unfolded" ↔ "native" ↔ "globally unfolded" → "aggregated". This model quantitatively reproduces the experimentally observed kinetics. To the best of our knowledge, the current study marks the first exploration of surface denaturation phenomena by HDX/MS. © 2015 The Protein Society.

Effect of second-order exchange in electron-hydrogen scattering

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

Madison, D.H.; Bray, I.; McCarthy, I.

1990-05-07

The electron-hydrogen scattering problem has been a nemesis to theoretical atomic physicists due to the fact that even the most sophisticated of theoretical calculations, both perturbative and nonperturbative, do not agree with experiment. The current opinion is that the perturbative approach cannot be used for this problem since recent second-order calculations are not in agreement with the experimental data and higher-order calculations are deemed impractical. However, these second-order calculations neglected second-order exchange. We have now added exchange to the second-order calculation and have found that the primary source of disagreement between experiment and theory for intermediate energies is attributable notmore » to higher-order terms but to second-order exchange.« less

Gas phase recombination of hydrogen and deuterium atoms. Ph.D. Thesis

NASA Technical Reports Server (NTRS)

Trainor, D. W.; Ham, D. O.; Kaufman, F.

1973-01-01

Rate constants for the reaction H + H + M - H2 + M, with M = H2, He, and Ar were measured over the temperature range 77 to 298 K. Hydrogen atoms were produced by thermal dissociation and absolute atom concentrations were measured through use of self-balancing, isothermal catalytic probe detector. The specific rate constants were 8.1 + or - 0.4 x 10 to the minus 33rd power, 7.0 + or - 0.4 x 10 to the minus 33rd power, and 9.2 + or - 0.6 x at 298 K for M = H2, He, and Ar respectively; these values rising to 18.5 + or - 2.2 x 10 to the minus 33rd power, 12.0 + or - 1.5 x 10 to the minus 33rd power, and 27.4 + or - 4.6 x 10 to the minus 33rd power cm to the 6th power/molecules sq/sec at 77 K. for the equivalent deuterium atom process with D2 as the third body, the rate constants are 6.1 + or - 0.3 x 10 to the minus 33rd power cm to the 6th power/molecules sq/sec at 298 K and 15.1 + or - 1.0 x 10 to the minus 33rd power cm to the 6th power/molecules sq/sec at 77 K. These values are compared with previous experimental measurements and with recent theoretical calculations.

Deuterium used as artificial tracer in column studies under saturated water flow conditions

NASA Astrophysics Data System (ADS)

Koeniger, P.; Geiges, M.; Leibundgut, Ch.

2003-04-01

In contrast to numerous investigations using deuterium as an environmental tracer, hydrological investigations with deuterium-labelled water are rather rare. Currently applications in groundwater studies are restricted due to increasing costs of spiking large water quantities but an application as intelligent tracer might be of advantage especially in combination with other tracers and under distinct environmental conditions. Therefore deuterium was applied as artificial tracer in column experiments that are well proved as a tool to characterise tracer behaviour in recent studies. Deuterium was tested in comparison to the more familiar conservative tracer fluorescein. Varying experimental conditions, e.g. column length (0.5, 1.0, 1.5 m), initial tracer concentration (0.01, 0.02, 0.2 mg) and flow velocity (1.5 to 6.0 m/d) were used to investigate tracer behaviour under saturated water flow conditions. Deuterium was analysed using an H/Device with chrome reduction connected to an isotope ratio mass spectrometer and expressed in relative concentrations [per mill V-SMOW]. Theoretical tracer breakthrough curves were calculated using a one dimensional dispersion model. The results indicate higher mean transport velocities and smaller dispersion for deuterium in all experiments. Due to different molecule properties that also determine the interaction of soil substrate and tracer, deuterium indicates a more conservative transport behaviour. Deuterium is non-toxic, completely soluble, chemically and biologically stable and not subject to light-influenced decay. Furthermore, it shows promise for investigations of water flow in the unsaturated zone, and of interactions of water in soil-plant-atmosphere systems. A further discussion of problems, together with possibilities for applying deuterium as an artificial tracer, will be presented.

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.

Two-photon exchange correction to the hyperfine splitting in muonic hydrogen

NASA Astrophysics Data System (ADS)

Tomalak, Oleksandr

2017-12-01

We reevaluate the Zemach, recoil and polarizability corrections to the hyperfine splitting in muonic hydrogen expressing them through the low-energy proton structure constants and obtain the precise values of the Zemach radius and two-photon exchange (TPE) contribution. The uncertainty of TPE correction to S energy levels in muonic hydrogen of 105 ppm exceeds the ppm accuracy level of the forthcoming 1S hyperfine splitting measurements at PSI, J-PARC and RIKEN-RAL.

Interaction of toluene with two-color asymmetric laser fields: Controlling the directional emission of molecular hydrogen fragments

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

Kaziannis, S.; Kotsina, N.; Kosmidis, C.

The interaction of toluene with strong asymmetric two-color laser irradiation of 40 fs duration is studied by means of Time of flight mass spectrometry. Highly energetic H{sub 2}{sup +} and H{sub 3}{sup +} fragment ions are produced through an isomerization process taking place within transient multiply charged parent ions. Comparative study of deuterium labeled toluene isotopes enables the discrimination between molecular hydrogen fragments formed exclusively within the CH{sub 3}- part from those that require hydrogen atom exchange between the former and the phenyl moiety. It is demonstrated that by manipulating the relative phase of the ω/2ω field components the selectivemore » ionization of oriented toluene molecules can be used as a tool to control the directional emission of the H{sub 2}{sup +}, H{sub 3}{sup +} species.« less

Influence of displacement damage on deuterium and helium retention in austenitic and ferritic-martensitic alloys considered for ADS service

NASA Astrophysics Data System (ADS)

Voyevodin, V. N.; Karpov, S. A.; Kopanets, I. E.; Ruzhytskyi, V. V.; Tolstolutskaya, G. D.; Garner, F. A.

2016-01-01

The behavior of ion-implanted hydrogen (deuterium) and helium in austenitic 18Cr10NiTi stainless steel, EI-852 ferritic steel and ferritic/martensitic steel EP-450 and their interaction with displacement damage were investigated. Energetic argon irradiation was used to produce displacement damage and bubble formation to simulate nuclear power environments. The influence of damage morphology and the features of radiation-induced defects on deuterium and helium trapping in structural alloys was studied using ion implantation, the nuclear reaction D(3He,p)4He, thermal desorption spectrometry and transmission electron microscopy. It was found in the case of helium irradiation that various kinds of helium-radiation defect complexes are formed in the implanted layer that lead to a more complicated spectra of thermal desorption. Additional small changes in the helium spectra after irradiation with argon ions to a dose of ≤25 dpa show that the binding energy of helium with these traps is weakly dependent on the displacement damage. It was established that retention of deuterium in ferritic and ferritic-martensitic alloys is three times less than in austenitic steel at damage of ∼1 dpa. The retention of deuterium in steels is strongly enhanced by presence of radiation damages created by argon ion irradiation, with a shift in the hydrogen release temperature interval of 200 K to higher temperature. At elevated temperatures of irradiation the efficiency of deuterium trapping is reduced by two orders of magnitude.

A Infrared Absorption Study of Dopant-Hydrogen Complexes in Semiconductors

NASA Astrophysics Data System (ADS)

Kozuch, David Michael

1992-01-01

Hydrogen passivation of shallow electrical dopants in semiconductors has been investigated. In particular, the passivation of the shallow dopants tin, carbon, and silicon in gallium arsenide has been studied via Fourier transform infrared spectroscopy, thermal annealing, Hall effect, secondary ion mass spectroscopy, and uniaxial stress. The bond-stretching and bond-wagging vibrational modes of the rm Sn_{Ga} - H complex in GaAs have been identified at 1327.8 cm^{-1} and 967.7 cm ^{-1}, respectively. The presence of hydrogen in the defect pair is confirmed by the deuterium -shifted bond-stretching signal at 746.6 cm^ {-1}. Infrared and Hall data correlated the passivation of Sn_{rm Ga } donors with the formation of the rm Sn_{Ga} - H complexes. A series of isochronal anneals probed the thermal stability of the complex. Arguments supporting an antibonding configuration for the rm Sn_{Ga} - H complex are presented. Infrared measurements on highly carbon doped epi -layers reveal new absorption signals at 2643, 2651, and 2688 cm^{-1} in addition to the previously identified rm C_ {As} - H stretching vibration at 2636 cm^{-1}. These new signals are related to a family of carbon-hydrogen complexes: rm C_{x} - H. Deuterium -shifted counterparts for all these signals have been observed for the first time. Sources of hydrogen have been traced to the metalorganic precursors and carrier gas used during epi-layer growth. Hydrogen-containing annealing ambients were surprisingly effective for introducing hydrogen into the epi-layers. Several atomic arrangements for the new rm C_{x} - H complexes have been considered with the most likely candidate being a rm C_{As} - H complex perturbed by another C_{rm As} acceptor in a second nearest neighbor position. The first uniaxial stress measurements have been performed on the rm Si_{As} - H complex in GaAs. The stress-induced frequency shifts and the intensity ratios of the stress-split components of the 2094.45 cm^{-1} stretching

Investigation of Kp- and Kd-atom formation and their collisional processes with hydrogen and deuterium targets by the classical-trajectory Monte Carlo method

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

Raeisi, G. M.; Department of Physics, Shahrekord University, Shahrekord 115; Kalantari, S. Z.

The classical-trajectory Monte Carlo method has been used to study the capture of negative kaons by hydrogen and deuterium atoms; subsequently, the elastic scattering, Stark mixing, and Coulomb deexcitation cross sections of Kp and Kd atoms have been determined. The results for kaonic atom formation confirm the initial conditions that have been parametrically applied by most atomic cascade models. Our results show that Coulomb deexcitation in Kp and Kd atoms with {Delta}n>1 is important in addition to n=1. We have shown that the contribution of molecular structure effects to the cross sections of the collisional processes is larger than themore » isotopic effects of the targets. We have also compared our results with the semiclassical approaches.« less

How amide hydrogens exchange in native proteins.

PubMed

Persson, Filip; Halle, Bertil

2015-08-18

Amide hydrogen exchange (HX) is widely used in protein biophysics even though our ignorance about the HX mechanism makes data interpretation imprecise. Notably, the open exchange-competent conformational state has not been identified. Based on analysis of an ultralong molecular dynamics trajectory of the protein BPTI, we propose that the open (O) states for amides that exchange by subglobal fluctuations are locally distorted conformations with two water molecules directly coordinated to the N-H group. The HX protection factors computed from the relative O-state populations agree well with experiment. The O states of different amides show little or no temporal correlation, even if adjacent residues unfold cooperatively. The mean residence time of the O state is ∼100 ps for all examined amides, so the large variation in measured HX rate must be attributed to the opening frequency. A few amides gain solvent access via tunnels or pores penetrated by water chains including native internal water molecules, but most amides access solvent by more local structural distortions. In either case, we argue that an overcoordinated N-H group is necessary for efficient proton transfer by Grotthuss-type structural diffusion.

How amide hydrogens exchange in native proteins

PubMed Central

Persson, Filip; Halle, Bertil

2015-01-01

Amide hydrogen exchange (HX) is widely used in protein biophysics even though our ignorance about the HX mechanism makes data interpretation imprecise. Notably, the open exchange-competent conformational state has not been identified. Based on analysis of an ultralong molecular dynamics trajectory of the protein BPTI, we propose that the open (O) states for amides that exchange by subglobal fluctuations are locally distorted conformations with two water molecules directly coordinated to the N–H group. The HX protection factors computed from the relative O-state populations agree well with experiment. The O states of different amides show little or no temporal correlation, even if adjacent residues unfold cooperatively. The mean residence time of the O state is ∼100 ps for all examined amides, so the large variation in measured HX rate must be attributed to the opening frequency. A few amides gain solvent access via tunnels or pores penetrated by water chains including native internal water molecules, but most amides access solvent by more local structural distortions. In either case, we argue that an overcoordinated N–H group is necessary for efficient proton transfer by Grotthuss-type structural diffusion. PMID:26195754

Determination of the parton distributions and structure functions of the proton from neutrino and antineutrino reactions on hydrogen and deuterium

NASA Astrophysics Data System (ADS)

Jones, G. T.; Jones, R. W. L.; Kennedy, B. W.; Klein, H.; Morrison, D. R. O.; Wachsmuth, H.; Miller, D. B.; Mobayyen, M. M.; Wainstein, S.; Aderholz, M.; Hantke, D.; Katz, U. F.; Kern, J.; Schmitz, N.; Wittek, W.; Borner, H. P.; Myatt, G.; Cooper-Sarkar, A. M.; Guy, J.; Venus, W.; Bullock, F. W.; Burke, S.

1994-12-01

This analysis is based on data from neutrino and antineutrino scattering on hydrogen and deuterium, obtained with BEBC in the (anti) neutrino wideband beam of the CERN SPS. The parton momentum distributions in the proton and the proton structure functions are determined in the range 0.01

A comparison of the energy distributions of hadrons produced in deep inelastic scattering of muons on hydrogen and deuterium targets

NASA Astrophysics Data System (ADS)

Aubert, J. J.; Bassompierre, G.; Becks, K. H.; Benchouk, C.; Best, C.; 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.; Eszes, G.; 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.; Korzen, B.; 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.; Pavel, N.; Payre, P.; Peroni, C.; Peschel, H.; Pessard, H.; Pietrzyk, U.; Ribarics, P.; Rith, K.; Schneegans, M.; Schneider, A.; Sloan, T.; Stier, H. E.; Stockhausen, W.; Thénard, J. M.; Thompson, J. C.; Urban, L.; Villers, M.; Wahlen, H.; Whalley, M.; Williams, D.; Williams, W. S. C.; Williamson, J.; Wimpenny, S. J.

1986-06-01

The energy distribution of inclusive hadrons produced by 280 GeV muons on hydrogen and deuterium targets are compared. The sum of the scaled energy distributions of the positive and negative hadrons is found to be the same for the two targets. The difference of these distributions is observed to factorise in x and z and the z-dependence is found to be independent of the target type and have a form (1- z)2.1±0.2. The net charge of the hadronic jet is positive at high x even in the case when the scattering takes place on the neutron. These results are in good agreement with the expectations of the Quark Parton Model.

HYDROGEN ISOTOPE TARGETS

DOEpatents

Ashley, R.W.

1958-08-12

The design of targets for use in the investigation of nuclear reactions of hydrogen isotopes by bombardment with accelerated particles is described. The target con struction eomprises a backing disc of a metal selected from the group consisting of molybdenunn and tungsten, a eoating of condensed titaniunn on the dise, and a hydrogen isotope selected from the group consisting of deuterium and tritium absorbed in the coatiag. The proeess for preparing these hydrogen isotope targets is described.

Adsorption of iodine on hydrogen-reduced silver-exchanged mordenite: Experiments and modeling

DOE PAGES

Nan, Yue; Tavlarides, Lawrence L.; DePaoli, David W.

2016-08-03

The adsorption process of iodine, a major volatile radionuclide in the off-gas streams of spent nuclear fuel reprocessing, on hydrogen-reduced silver-exchanged mordenite (Ag 0Z) was studied at the micro-scale. The gas-solid mass transfer and reaction involved in the adsorption process were investigated and evaluated with appropriate models. Optimal conditions for reducing the silver-exchanged mordenite (AgZ) in a hydrogen stream were determined. Kinetic and equilibrium data of iodine adsorption on Ag 0Z were obtained by performing single-layer adsorption experiments with experimental systems of high precision at 373–473 K over various iodine concentrations. Results indicate approximately 91% to 97% of the iodinemore » adsorption was through the silver-iodine reaction. The effect of temperature on the iodine loading capacity of Ag 0Z was discussed. In conclusion, the Shrinking Core model describes the data well, and the primary rate controlling mechanisms were macro-pore diffusion and silver-iodine reaction. © 2016 American Institute of Chemical Engineers AIChE J, 2016« less

Phosphoglucoisomerase-catalyzed interconversion of hexose phosphates: isotopic discrimination between hydrogen and deuterium.

PubMed

Malaisse, W J; Malaisse-Lagae, F; Liemans, V; Ottinger, R; Willem, R

1990-03-27

The discrimination between the isotopes of hydrogen in the reaction catalyzed by yeast phosphoglucoisomerase is examined by NMR, as well as by spectrofluorometric or radioisotopic methods. The monodirectional conversion of D-glucose 6-phosphate to D-fructose 6-phosphate displays a lower maximal velocity with D-[2-2H]glucose 6-phosphate than unlabelled D-glucose 6-phosphate, with little difference in the affinity of the enzyme for these two substrates. About 72% of the deuterium located on the C2 of D-[1-13C,2-2H]glucose 6-phosphate is transferred intramolecularly to the C1 of D-[1-13C,1-2H]fructose 6-phosphate. The velocity of the monodirectional conversion of D-[U-14C]glucose 6-phosphate (or D-[2-3H]glucose 6-phosphate) to D-fructose 6-phosphate is virtually identical in H2O and D2O, respectively, but is four times lower with the tritiated than 14C-labelled ester. In the monodirectional reaction, the intramolecular transfer from the C2 of D-[2-3H]glucose 6-phosphate is higher in the presence of D2O than H2O. Whereas prolonged exposure of D-[1-13C]glucose 6-phosphate to D2O, in the presence of phosphoglucoisomerase, leads to the formation of both D-[1-13C,2-2H]glucose 6-phosphate and D-[1-13C,1-2H]fructose 6-phosphate, no sizeable incorporation of dueterium from D2O on the C1 of D-[1-13C]fructose 1,6-bisphosphate is observed when the monodirectional conversion of D-[1-13C]glucose 6-phosphate occurs in the concomitant presence of phosphoglucoisomerase and phosphofructokinase. The latter finding contrasts with the incorporation of hydrogen from 1H2O or tritium from 3H2O in the monodirectional conversion of D-[2-3H]glucose 6-phosphate and unlabelled D-glucose 6-phosphate, respectively, to their corresponding ketohexose esters.

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.

8-Hydroxy-5-deazaflavin-reducing hydrogenase from Methanobacterium thermoautotrophicum: 2. Kinetic and hydrogen-transfer studies.

PubMed

Livingston, D J; Fox, J A; Orme-Johnson, W H; Walsh, C T

1987-07-14

Steady-state kinetic parameters have been obtained for the pure 8-hydroxy-5-deazaflavin-reducing hydrogenase. With H2 and 8-hydroxy-5-deazariboflavin (F0) as substrates, Km (H2) = 12 microM, Km (F0) = 26 microM, and Kcat = 225 s-1. In the back-direction, F0H2 is reoxidized (anaerobically) at 225 s-1. Initial velocity patterns, product inhibition patterns, dead-end inhibition by carbon monoxide, and transhydrogenation to Procion Red HE-3B suggest a two-site hybrid ping-pong mechanism. A kinetic derivation for the rate equation is provided in the Appendix. Studies with D2 and with D2O reveal that no steps involving D transfer are substantially rate determining. Further, D2 yields F0H2 with no deuterium at C5 while in D2O a 5-monodeuterio F0H2 product is formed, indicating complete exchange of hydrogens from H2 with solvent before final transfer of a hydride ion out from reduced enzyme to C5 of F0.

In-vivo NMR studies of deuterium-labeled photosensitizers in mice tumor model

NASA Astrophysics Data System (ADS)

Ramaprasad, Subbaraya; Liu, Y. H.; Pandey, R. K.; Shiau, Fuu-Yau; Smith, Kevin M.

1993-06-01

Photodynamic therapy (PDT) has emerged as a promising modality for the treatment of cancer. We are using newly synthesized and chemically defined and characterized porphyrin photosensitizers that are specifically labeled with deuterium to perform in vivo NMR studies in a murine tumor model. In vivo magnetic resonance offers the potential for repetitive, safe, noninvasive evaluation of photosensitizers, tumor metabolism, and the effect of PDT on the tumor metabolism. In an effort to monitor noninvasively the photosensitizers in an in vivo tumor model, we are synthesizing several deuterium labeled photosensitizers which absorb red light at or above 630 nm. Development of methods to test these photosensitizers directly in humans is not feasible at this time, since these photosensitizers are new and we do not yet understand the side effects. In addition, we do not understand the potential benefits compared with Photofrin II, the widely used photosensitizer. To perform our in vivo deuterium NMR studies on mouse foot tumors, we have constructed a solenoid coil which operates at 30.7 MHz for the deuterium nucleus. We have been able to detect the deuterium labeled photosensitizer in the tumor after a direct intra-tumor injection. The use of 31P NMR to predict the possible outcome of PDT in these tumors is also discussed.

Hydrogen isotope separation utilizing bulk getters

DOEpatents

Knize, R.J.; Cecchi, J.L.

1991-08-20

Tritium and deuterium are separated from a gaseous mixture thereof, derived from a nuclear fusion reactor or some other source, by providing a casing with a bulk getter therein for absorbing the gaseous mixture to produce an initial loading of the getter, partially desorbing the getter to produce a desorbed mixture which is tritium-enriched, pumping the desorbed mixture into a separate container, the remaining gaseous loading in the getter being deuterium-enriched, desorbing the getter to a substantially greater extent to produce a deuterium-enriched gaseous mixture, and removing the deuterium-enriched mixture into another container. The bulk getter may comprise a zirconium-aluminum alloy, or a zirconium-vanadium-iron alloy. The partial desorption may reduce the loading by approximately fifty percent. The basic procedure may be extended to produce a multistage isotope separator, including at least one additional bulk getter into which the tritium-enriched mixture is absorbed. The second getter is then partially desorbed to produce a desorbed mixture which is further tritium-enriched. The last-mentioned mixture is then removed from the container for the second getter, which is then desorbed to a substantially greater extent to produce a desorbed mixture which is deuterium-enriched. The last-mentioned mixture is then removed so that the cycle can be continued and repeated. The method of isotope separation is also applicable to other hydrogen isotopes, in that the method can be employed for separating either deuterium or tritium from normal hydrogen. 4 figures.

Hydrogen isotope separation utilizing bulk getters

DOEpatents

Knize, Randall J.; Cecchi, Joseph L.

1991-01-01

Tritium and deuterium are separated from a gaseous mixture thereof, derived from a nuclear fusion reactor or some other source, by providing a casing with a bulk getter therein for absorbing the gaseous mixture to produce an initial loading of the getter, partially desorbing the getter to produce a desorbed mixture which is tritium-enriched, pumping the desorbed mixture into a separate container, the remaining gaseous loading in the getter being deuterium-enriched, desorbing the getter to a substantially greater extent to produce a deuterium-enriched gaseous mixture, and removing the deuterium-enriched mixture into another container. The bulk getter may comprise a zirconium-aluminum alloy, or a zirconium-vanadium-iron alloy. The partial desorption may reduce the loading by approximately fifty percent. The basic procedure may be extended to produce a multistage isotope separator, including at least one additional bulk getter into which the tritium-enriched mixture is absorbed. The second getter is then partially desorbed to produce a desorbed mixture which is further tritium-enriched. The last-mentioned mixture is then removed from the container for the second getter, which is then desorbed to a substantially greater extent to produce a desorbed mixture which is deuterium-enriched. The last-mentioned mixture is then removed so that the cycle can be continued and repeated. The method of isotope separation is also applicable to other hydrogen isotopes, in that the method can be employed for separating either deuterium or tritium from normal hydrogen.

Hydrogen isotope separation utilizing bulk getters

DOEpatents

Knize, Randall J.; Cecchi, Joseph L.

1990-01-01

Tritium and deuterium are separated from a gaseous mixture thereof, derived from a nuclear fusion reactor or some other source, by providing a casing with a bulk getter therein for absorbing the gaseous mixture to produce an initial loading of the getter, partially desorbing the getter to produce a desorbed mixture which is tritium-enriched, pumping the desorbed mixture into a separate container, the remaining gaseous loading in the getter being deuterium-enriched, desorbing the getter to a substantially greater extent to produce a deuterium-enriched gaseous mixture, and removing the deuterium-enriched mixture into another container. The bulk getter may comprise a zirconium-aluminum alloy, or a zirconium-vanadium-iron alloy. The partial desorption may reduce the loading by approximately fifty percent. The basic procedure may be extended to produce a multistage isotope separator, including at least one additional bulk getter into which the tritium-enriched mixture is absorbed. The second getter is then partially desorbed to produce a desorbed mixture which is further tritium-enriched. The last-mentioned mixture is then removed from the container for the second getter, which is then desorbed to a substantially greater extent to produce a desorbed mixture which is deuterium-enriched. The last-mentioned mixture is then removed so that the cycle can be continued and repeated. The method of isotope separation is also applicable to other hydrogen isotopes, in that the method can be employed for separating either deuterium or tritium from normal hydrogen.

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

Preparation and analysis of deuterium-labeled aspirin: application to pharmacokinetic studies

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

Pedersen, A.K.; FitzGerald, G.A.

Inhibition of endogenous prostacyclin and thromboxane biosynthesis by aspirin is critically dose-dependent in humans. Gastrointestinal and hepatic hydrolysis may limit systemic availability of aspirin, especially in low doses, perhaps contributing to the biochemical selectivity of aspirin. Existing analytical methods do not permit determination of systemic bioavailability when low (less than 100 mg) doses of aspirin are administered. Deuterium-labeled aspirin (2-acetoxy(3,4,5,6-/sup 2/H4)benzoic acid) was synthesized from salicylic acid by catalytic exchange and subsequent acetylation. Analysis of the compounds as benzyl esters by GC-MS followed extractive alkylation from plasma. Heptadeuterated compounds were used as internal standards. Simultaneous administration of tetradeuterated aspirin intravenouslymore » with native aspirin orally to anesthetized dogs permitted kinetic studies of both aspirin and salicylic acid. The sensitivity of the method is superior to published methods using HPLC and, thus, more applicable to studies of low dose aspirin. Pulse administration of stable isotope-labeled aspirin permits detailed and repeated studies of dose-related aspirin pharmacokinetics in humans.« less

Significant Quantum Effects in Hydrogen Activation

DOE PAGES

Kyriakou, Georgios; Davidson, Erlend R. M.; Peng, Guowen; ...

2014-03-31

Dissociation of molecular hydrogen is an important step in a wide variety of chemical, biological, and physical processes. Due to the light mass of hydrogen, it is recognized that quantum effects are often important to its reactivity. However, understanding how quantum effects impact the reactivity of hydrogen is still in its infancy. Here, we examine this issue using a well-defined Pd/Cu(111) alloy that allows the activation of hydrogen and deuterium molecules to be examined at individual Pd atom surface sites over a wide range of temperatures. Experiments comparing the uptake of hydrogen and deuterium as a function of temperature revealmore » completely different behavior of the two species. The rate of hydrogen activation increases at lower sample temperature, whereas deuterium activation slows as the temperature is lowered. Density functional theory simulations in which quantum nuclear effects are accounted for reveal that tunneling through the dissociation barrier is prevalent for H 2 up to ~190 K and for D 2 up to ~140 K. Kinetic Monte Carlo simulations indicate that the effective barrier to H 2 dissociation is so low that hydrogen uptake on the surface is limited merely by thermodynamics, whereas the D 2 dissociation process is controlled by kinetics. These data illustrate the complexity and inherent quantum nature of this ubiquitous and seemingly simple chemical process. Here, examining these effects in other systems with a similar range of approaches may uncover temperature regimes where quantum effects can be harnessed, yielding greater control of bond-breaking processes at surfaces and uncovering useful chemistries such as selective bond activation or isotope separation.« less

Water Behavior in Bacterial Spores by Deuterium NMR Spectroscopy

PubMed Central

2015-01-01

Dormant bacterial spores are able to survive long periods of time without nutrients, withstand harsh environmental conditions, and germinate into metabolically active bacteria when conditions are favorable. Numerous factors influence this hardiness, including the spore structure and the presence of compounds to protect DNA from damage. It is known that the water content of the spore core plays a role in resistance to degradation, but the exact state of water inside the core is a subject of discussion. Two main theories present themselves: either the water in the spore core is mostly immobile and the core and its components are in a glassy state, or the core is a gel with mobile water around components which themselves have limited mobility. Using deuterium solid-state NMR experiments, we examine the nature of the water in the spore core. Our data show the presence of unbound water, bound water, and deuterated biomolecules that also contain labile deuterons. Deuterium–hydrogen exchange experiments show that most of these deuterons are inaccessible by external water. We believe that these unreachable deuterons are in a chemical bonding state that prevents exchange. Variable-temperature NMR results suggest that the spore core is more rigid than would be expected for a gel-like state. However, our rigid core interpretation may only apply to dried spores whereas a gel core may exist in aqueous suspension. Nonetheless, the gel core, if present, is inaccessible to external water. PMID:24950158

Iridium-Catalysed ortho-Directed Deuterium Labelling of Aromatic Esters--An Experimental and Theoretical Study on Directing Group Chemoselectivity.

PubMed

Devlin, Jennifer; Kerr, William J; Lindsay, David M; McCabe, Timothy J D; Reid, Marc; Tuttle, Tell

2015-06-25

Herein we report a combined experimental and theoretical study on the deuterium labelling of benzoate ester derivatives, utilizing our developed iridium N-heterocyclic carbene/phosphine catalysts. A range of benzoate esters were screened, including derivatives with electron-donating and -withdrawing groups in the para- position. The substrate scope, in terms of the alkoxy group, was studied and the nature of the catalyst counter-ion was shown to have a profound effect on the efficiency of isotope exchange. Finally, the observed chemoselectivity was rationalized by rate studies and theoretical calculations, and this insight was applied to the selective labelling of benzoate esters bearing a second directing group.

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

[Influence of deuterium depleted water on freeze-dried tissue isotopic composition and morphofunctional body performance in rats of different generations].

PubMed

Dzhimak, S S; Baryshev, M G; Basov, A A; Timakov, A A

2014-01-01

The influence of deuterium depleted water on the body of different rats generations was investigated in physiological conditions. As a result of this study it was established that the most significant and rapid reduction in D/H equilibrium was observed in plasma (by 36.2%), and lyophilized kidney tissues (by 15.8%). Less pronounced deuterium decrease was characteristic of liver tissue (9.3%) and heart (8.5%). Stabilization of the isotopic exchange reaction rate was fixed in the blood and tissues of rats, starting from the second generation. At the same time when deuterium depleted water (40 ppm) was used in dietary intake, the change in morphological and functional parameters in laboratory animals associated with the processes of adaptation to the effects of substress isotopic D/H gradient was also noted. The study shows that modification of:only drinking water intake regime can't significantly change the deuterium content in tissues of metabolically active organs, because of the concurrent deuterium receipt in food substances of plant and animal origin.

Study of hydrogen bond polarized IR spectra of cinnamic acid crystals

NASA Astrophysics Data System (ADS)

Flakus, Henryk T.; Jabłońska, Magdalena

2004-11-01

This paper presents the results of investigation of the polarized IR spectra of cinnamic acid and of its deuterium derivative crystals. The spectra were measured by a transmission method, using polarized light, at the room temperature and at 77 K, for two different crystalline faces. Theoretical analysis of the results concerned linear dichroic effects, H/D isotopic and temperature effects, observed in the spectra of the hydrogen and of the deuterium bonds in cinnamic acid crystals, at the frequency ranges of the νO-H and the νO-D bands. The basic crystal spectral properties could be satisfactorily interpreted in a quantitative way for a centrosymmetric cyclic hydrogen bond dimer model. Such a model explains not only a two-branch structure of the νO-H and νO-D bands in crystalline spectra, but also some essential linear dichroic effects in the band frequency ranges, measured for isotopically diluted crystals. Model calculations, performed within the limits of the 'strong-coupling' model, allowed for quantitative interpretation and for understanding of the basic properties of the hydrogen bond IR spectra of cinnamic acid crystals, H/D isotopic, temperature and dichroic effects included. In the scope of our studies the mechanism of H/D isotopic 'self-organization' processes, taking place in the crystal hydrogen bond lattices, was also recognized. It was proved that for isotopically diluted crystalline samples of cinnamic acid, a non-random distribution of protons and deuterons occurs exclusively in the hydrogen bond dimers. Nevertheless, these co-operative interactions between the hydrogen bonds do not involve the adjacent hydrogen bond dimers in each unit cell. The two-branch fine structure pattern of the νO-H and νO-D bands was ascribed to the vibronic mechanism of vibrational dipole selection rule breaking in centrosymmetric hydrogen bond dimers. The observed in the spectra very high intensity of the forbidden transition sub-band in the analyzed νO-H and �

Characterization of a deuterium-deuterium plasma fusion neutron generator

NASA Astrophysics Data System (ADS)

Lang, R. F.; Pienaar, J.; Hogenbirk, E.; Masson, D.; Nolte, R.; Zimbal, A.; Röttger, S.; Benabderrahmane, M. L.; Bruno, G.

2018-01-01

We characterize the neutron output of a deuterium-deuterium plasma fusion neutron generator, model 35-DD-W-S, manufactured by NSD/Gradel-Fusion. The measured energy spectrum is found to be dominated by neutron peaks at 2.2 MeV and 2.7 MeV. A detailed GEANT4 simulation accurately reproduces the measured energy spectrum and confirms our understanding of the fusion process in this generator. Additionally, a contribution of 14 . 1 MeV neutrons from deuterium-tritium fusion is found at a level of 3 . 5%, from tritium produced in previous deuterium-deuterium reactions. We have measured both the absolute neutron flux as well as its relative variation on the operational parameters of the generator. We find the flux to be proportional to voltage V 3 . 32 ± 0 . 14 and current I 0 . 97 ± 0 . 01. Further, we have measured the angular dependence of the neutron emission with respect to the polar angle. We conclude that it is well described by isotropic production of neutrons within the cathode field cage.

Hydrogen molecules and hydrogen-related defects in crystalline silicon

NASA Astrophysics Data System (ADS)

Fukata, N.; Sasaki, S.; Murakami, K.; Ishioka, K.; Nakamura, K. G.; Kitajima, M.; Fujimura, S.; Kikuchi, J.; Haneda, H.

1997-09-01

We have found that hydrogen exists in molecular form in crystalline silicon treated with hydrogen atoms in the downstream of a hydrogen plasma. The vibrational Raman line of hydrogen molecules is observed at 4158 cm-1 for silicon samples hydrogenated between 180 and 500 °C. The assignment of the Raman line is confirmed by its isotope shift to 2990 cm-1 for silicon treated with deuterium atoms. The Raman intensity has a maximum for hydrogenation at 400 °C. The vibrational Raman line of the hydrogen molecules is broad and asymmetric. It consists of at least two components, possibly arising from hydrogen molecules in different occupation sites in crystalline silicon. The rotational Raman line of hydrogen molecules is observed at 590 cm-1. The Raman band of Si-H stretching is observed for hydrogenation temperatures between 100 and 500 °C and the intensity has a maximum for hydrogenation at 250 °C.

Hydrogen-oxygen proton-exchange membrane fuel cells and electrolyzers

NASA Technical Reports Server (NTRS)

Baldwin, R.; Pham, M.; Leonida, A.; Mcelroy, J.; Nalette, T.

1989-01-01

Hydrogen-oxygen solid polymer electrolyte (SPE) fuel cells and SPE electrolyzers (products of Hamilton Standard) both use a Proton-Exchange Membrane (PEM) as the sole electrolyte. These solid electrolyte devices have been under continuous development for over 30 years. This experience has resulted in a demonstrated ten-year SPE cell life capability under load conditions. Ultimate life of PEM fuel cells and electrolyzers is primarily related to the chemical stability of the membrane. For perfluorocarbon proton exchange membranes an accurate measure of the membrane stability is the fluoride loss rate. Millions of cell hours have contributed to establishing a relationship between fluoride loss rates and average expected ultimate cell life. This relationship is shown. Several features have been introduced into SPE fuel cells and SPE electrolyzers such that applications requiring greater than or equal to 100,000 hours of life can be considered. Equally important as the ultimate life is the voltage stability of hydrogen-oxygen fuel cells and electrolyzers. Here again the features of SPE fuel cells and SPE electrolyzers have shown a cell voltage stability in the order of 1 microvolt per hour. That level of stability has been demonstrated for tens of thousands of hours in SPE fuel cells at up to 500 amps per square foot (ASF) current density.

Single charge exchange between hydrogen-like projectiles and hydrogen atom: the post version of the BDW-4B approximation

NASA Astrophysics Data System (ADS)

Azizan, Sh; Shojaei, F.; Fathi, R.

2016-04-01

The post version of the four-body Born distorted wave method (BDW-4B) is applied to calculate the total cross section for single electron exchange in the collision of hydrogen-like projectiles with hydrogen atom. The post form of transition amplitude is obtained in terms of two-dimensional real integrals which can be computed numerically. This second-order theory which satisfies the correct boundary conditions is used for the collision of {{H}}, {{H}}{{{e}}}+, {{L}}{{{i}}}2+, {{{B}}}4+, {{{C}}}5+ with hydrogen atoms at intermediate and high impact energies. The validity of our results is assessed in comparison with available experimental data and other theories.

Variability of Deuterium Fractionation Associated With Soil Uptake of Atmospheric Molecular Hydrogen

NASA Astrophysics Data System (ADS)

Rahn, T.; Randerson, J. T.; Eiler, J.

2005-12-01

Molecular hydrogen (H2) is the second most abundant reduced gas in the atmosphere (after methane) with a globally averaged mixing ratio of ~530 nmol/mol. Its largest sources are photochemical oxidation of methane and non-methane hydrocarbons with other recognized sources that include biomass burning, fossil fuel burning, nitrogen fixation, and ocean degassing. These sources are balanced by reaction of H2 with hydroxyl radicals (~25%) in the atmosphere and by deposition at the terrestrial soil surface (~75%). As with other atmospheric trace gases, the stable isotopic content of H2 has the potential to help quantify the various aspects of its production and destruction. The average deuterium content of H2 is dDH2 = ~130 ‰ relative to Standard Mean Ocean Water. While recent studies have begun to elucidate the deuterium content of the individual sources of H2 and the fractionation associated with hydroxyl oxidation has been well established in the laboratory, there are still few data documenting the fractionation associated with soil uptake. We measured the fractionation associated with soil uptake in May, June and August of 2002 in three upland ecosystems that were part of an Alaskan fire chronosequence. Fire occurred at these sites in 1999, 1987, and ~1920. Grasses and herbaceous vegetation establish initially after fire and are gradually replaced by deciduous trees and finally by evergreen trees and moss. All three sites were in interior Alaska near the town of Delta Junction (63° 54'N, 145° 40'W). Fluxes were measured with a Plexiglas flux chamber (8 liter volume) with a manifold of four ~400 ml double-valved glass flasks in parallel and a diaphragm pump for circulation (5 SLPM). Flasks were continuously flushed by the circulating system and isolated sequentially; they were then returned to the laboratory at Caltech for subsequent analysis. In the field, the chamber was seated on Plexiglas collars that were installed prior to initiating the study and left in

Infrared Spectroscopy and Born-Oppenheimer Molecular Dynamics Simulation Study on Deuterium Substitution in the Crystalline Benzoic Acid.

PubMed

Gług, Maciej; Brela, Mateusz Z; Boczar, Marek; Turek, Andrzej M; Boda, Łukasz; Wójcik, Marek J; Nakajima, Takahito; Ozaki, Yukihiro

2017-01-26

In this study we present complementary computational and experimental studies of hydrogen bond interaction in crystalline benzoic acid and its deuterated and partially deuterated derivatives. The experimental part of the presented work includes preparation of partially deuterated samples and measurement of attenuated total reflection (ATR)-FTIR spectra. Analysis of the geometrical parameters and time course of dipole moment of crystalline benzoic acid and its deuterated and partially deuterated derivatives by Born-Oppenheimer molecular dynamics (BOMD) enabled us to deeply analyze the IR spectra. Presented simulations based on BOMD gave us opportunity to investigate individual motion and its contribution to the IR spectra. The band contours calculated using Fourier transform of autocorrelation function are in quantitative agreement with the experimental spectra. Characterization of single bands was carried out by "normal coordinate analysis". The salient point of our study is a comparison of the spectra of the deuterated and partially deuterated crystalline benzoic acid with that of the nondeuterated one. Furthermore, we have applied the principal component analysis for analysis of the number of components in partially deuterated systems. In this study, we reveal that the arrangements of hydrogen and deuterium atoms in partially deuterated samples are random.

Reprint of: Effects of cold deformation, electron irradiation and extrusion on deuterium desorption behavior in Zr-1%Nb alloy

NASA Astrophysics Data System (ADS)

Morozov, O.; Mats, O.; Mats, V.; Zhurba, V.; Khaimovich, P.

2018-01-01

The present article introduces the data of analysis of ranges of ion-implanted deuterium desorption from Zr-1% Nb alloy. The samples studied underwent plastic deformation, low temperature extrusion and electron irradiation. Plastic rolling of the samples at temperature ∼300 K resulted in plastic deformation with the degree of ε = 3.9 and the formation of nanostructural state with the average grain size of d = 61 nm. The high degree of defectiveness is shown in thermodesorption spectrum as an additional area of the deuterium desorption in the temperature ranges 650-850 K. The further processing of the sample (that had undergone plastic deformation by plastic rolling) with electron irradiation resulted in the reduction of the average grain size (58 nm) and an increase in borders concentration. As a result the amount of deuterium desorpted increased in the temperature ranges 650-900 K. In case of Zr-1% Nb samples deformed by extrusion the extension of desorption area is observed towards the temperature reduction down to 420 K. The formation of the phase state of deuterium solid solution in zirconium was not observed. The structural state behavior is a control factor in the process of deuterium thermodesorption spectrum structure formation with a fixed implanted deuterium dose (hydrogen diagnostics). It appears as additional temperature ranges of deuterium desorption depending on the type, character and defect content.

Efficient Neutron Production from a Novel Configuration of Deuterium Gas-Puff Z-Pinch

NASA Astrophysics Data System (ADS)

Klir, D.; Kubes, P.; Rezac, K.; Cikhardt, J.; Kravarik, J.; Sila, O.; Shishlov, A. V.; Kovalchuk, B. M.; Ratakhin, N. A.; Kokshenev, V. A.; Labetsky, A. Yu.; Cherdizov, R. K.; Fursov, F. I.; Kurmaev, N. E.; Dudkin, G. N.; Nechaev, B. A.; Padalko, V. N.; Orcikova, H.; Turek, K.

2014-03-01

A novel configuration of a deuterium z pinch has been used to generate fusion neutrons. Injecting an outer hollow cylindrical plasma shell around an inner deuterium gas puff, neutron yields from DD reactions reached Yn=(2.9±0.3)×1012 at 700 ns implosion time and 2.7 MA current. Such a neutron yield means a tenfold increase in comparison with previous deuterium gas puff experiments at the same current generator. The increase of beam-target yields was obtained by a larger amount of current assembled on the z-pinch axis, and subsequently by higher induced voltage and higher energies of deuterons. A stack of CR-39 track detectors on the z-pinch axis showed hydrogen ions up to 38 MeV. Maximum neutron energies of 15 and 22 MeV were observed by radial and axial time-of-flight detectors, respectively. The number of DD neutrons per one joule of stored plasma energy approached 5×107. This implies that deuterium gas puff z pinches belong to the most efficient plasma-based sources of DD neutrons.

Single crystal diamond detector measurements of deuterium-deuterium and deuterium-tritium neutrons in Joint European Torus fusion plasmas.

PubMed

Cazzaniga, C; Sundén, E Andersson; Binda, F; Croci, G; Ericsson, G; Giacomelli, L; Gorini, G; Griesmayer, E; Grosso, G; Kaveney, G; Nocente, M; Perelli Cippo, E; Rebai, M; Syme, B; Tardocchi, M

2014-04-01

First simultaneous measurements of deuterium-deuterium (DD) and deuterium-tritium neutrons from deuterium plasmas using a Single crystal Diamond Detector are presented in this paper. The measurements were performed at JET with a dedicated electronic chain that combined high count rate capabilities and high energy resolution. The deposited energy spectrum from DD neutrons was successfully reproduced by means of Monte Carlo calculations of the detector response function and simulations of neutron emission from the plasma, including background contributions. The reported results are of relevance for the development of compact neutron detectors with spectroscopy capabilities for installation in camera systems of present and future high power fusion experiments.

Resonance Raman studies of the HOOP modes in octopus bathorhodopsin with deuterium-labeled retinal chromophores

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

Deng, H.; Manor, D.; Weng, G.

1991-05-07

Resonance Raman spectra of the hydrogen out-of-plane (HOOP) vibrational modes in the retinal chromophore of octopus bathorhodopsin with deuterium label(s) along the polyene chain have been obtained. In clear contrast with bovine bathorhodopsin's HOOP modes, there are only two major HOOP bands at 887 and 940 cm{sup {minus}1} for octopus bathorhodopsin. On the basis of their isotopic shifts upon deuterium labeling, the authors have assigned the band at 887 cm{sup {minus}1} to C{sub 10}H and C{sub 14}H HOOP modes, and the band at 940 cm{sup {minus}1} to C{sub 11}H{double bond}C{sub 12}H A{sub u}-like HOOP mode. They found also that themore » C{sub 10}H and C{sub 14}H HOOP wags are also similar to those in the model-compound studies. However, they have found that the interaction between the C{sub 7}H and C{sub 8}H HOOP internal coordinates of the chromophore in octopus bathorhodopsin is different from that of the chromophore in solution. The twisted nature of the chromophore, semiquantitatively discussed here, likely affects the {lambda}{sub max} of the chromophore and its enthalpy. The nature of the HOOP modes of octopus bathorhodopsin differs substantially from those found in bovine bathorhodopsin.« less

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

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.

Destabilizing Mutations Alter the Hydrogen Exchange Mechanism in Ribonuclease A

PubMed Central

Bruix, Marta; Ribó, Marc; Benito, Antoni; Laurents, Douglas V.; Rico, Manuel; Vilanova, Maria

2008-01-01

The effect of strongly destabilizing mutations, I106A and V108G of Ribonuclease A (RNase A), on its structure and stability has been determined by NMR. The solution structures of these variants are essentially equivalent to RNase A. The exchange rates of the most protected amide protons in RNase A (35°C), the I106A variant (35°C), and the V108G variant (10°C) yield stability values of 9.9, 6.0, and 6.8 kcal/mol, respectively, when analyzed assuming an EX2 exchange mechanism. Thus, the destabilization induced by these mutations is propagated throughout the protein. Simulation of RNase A hydrogen exchange indicates that the most protected protons in RNase A and the V108G variant exchange via the EX2 regime, whereas those of I106A exchange through a mixed EX1 + EX2 process. It is striking that a single point mutation can alter the overall exchange mechanism. Thus, destabilizing mutations joins high temperatures, high pH and the presence of denaturating agents as a factor that induces EX1 exchange in proteins. The calculations also indicate a shift from the EX2 to the EX1 mechanism for less protected groups within the same protein. This should be borne in mind when interpreting exchange data as a measure of local stability in less protected regions. PMID:18192347

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.

Near-infrared spectroscopic observation of the ageing process in archaeological wood using a deuterium exchange method.

PubMed

Tsuchikawa, Satoru; Yonenobu, Hitoshi; Siesler, H W

2005-03-01

The ageing degradation of the fine wood structure of dry-exposed archaeological wood was investigated by Fourier transform near-infrared spectroscopy with the aid of a deuterium exchange method. The archaeological wood sample was taken from an old wooden temple in Japan (late 7th century), which has been designated as a UNESCO world heritage site. Comparing the analytical results with those of a modern wood sample of the same species, the ageing process of archaeological wood was clarified as a change in the state of order on a macromolecular structural level. It can be concluded from NIR spectra that the amorphous region, and partially semi-crystalline region, in cellulose, hemicellulose, and lignin decreased by the ageing degradation, whereas the crystalline region in cellulose was not affected by the ageing. The accessibility of the diffusant to effect H/D-exchange was monitored by an OH-related absorption band obtained from FT-NIR transmission spectroscopy and characteristically varied with the ageing process of the wood samples, the absorption bands characteristic of a specific state of order and the diffusion agent. Finally, we proposed a morphological model to describe the variation of the fine structure of the microfibrils in the cell wall with ageing degradation. The state of microfibrils changed loosely by ageing, so that elementary fibrils were arranged loosely under 5 A, whereas several elementary fibrils in the modern wood were arranged in very close proximity under 3 A to each other.

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

Detection of a deuterium isotope effect in di- and trisubstituted alkylphenylnitrosoureas. An SCE study in Chinese hamster V79-E cells.

PubMed

Thust, R; Mendel, J; Bach, B; Schwarz, H

1985-06-01

The genotoxicity of 1-methyl-3-phenyl-1-nitrosourea (MPNU), 1-methyl-3-(p-chlorophenyl)-1-nitrosourea (C1-MPNU), 1-ethyl-3-phenyl-1-nitrosourea (EPNU), 1,3-dimethyl-3-phenyl-1-nitrosourea (DMPNU) and their derivatives substituted by deuterium in different positions was studied using sister chromatid exchange (SCE) induction in Chinese hamster V79-E cells. Deuterium substitution in the 1-methyl group of MPNU (MPNU-d3) and C1-MPNU (C1-MPNU-d3) diminished the SCE-inducing capacity by 20-30% and by 30-40% in DMPNU (DMPNU-d3B). There was no altered SCE activity detected when the phenyl group of MPNU (MPNU-d5) or the 3-methyl group of DMPNU (DMPNU-d3A) was deuterium labeled. No isotope effect was detected in deuterated EPNU derivatives, presumably due to the instability of these compounds. It is surmised that the easier delocalization of the positive charge in the deuterated alkyl diazonium ion causes a diminished reactivity and therefore influences the type and amount of DNA alkylation. Furthermore, the experiments with DMPNU and its derivatives revealed that, in contrast to mono- and disubstituted nitrosoureas, the biological activities of these very stable trisubstituted nitrosoureas are strongly influenced by a serum factor in the culture fluid.

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.

Intracellular sodium hydrogen exchange inhibition and clinical myocardial protection.

PubMed

Mentzer, Robert M; Lasley, Robert D; Jessel, Andreas; Karmazyn, Morris

2003-02-01

Although the mechanisms underlying ischemia/reperfusion injury remain elusive, evidence supports the etiologic role of intracellular calcium overload and oxidative stress induced by reactive oxygen species. Activation of the sodium hydrogen exchanger (NHE) is associated with intracellular calcium accumulation. Inhibition of the NHE-1 isoform may attenuate the consequences of this injury. Although there is strong preclinical and early clinical evidence that NHE inhibitors may be cardioprotective, definitive proof of this concept in humans awaits the results of ongoing clinical trials.

Effects of molecular dissociation on the hydrogen equation of state

NASA Astrophysics Data System (ADS)

Bonev, Stanimir; Schwegler, Eric; Galli, Giulia; Gygi, Francois

2002-03-01

It has been suggested recently(François Gygi and G. Galli, submitted to Phys. Rev. Lett.) that the physical mechanism behind the larger compressibility of liquid deuterium observed in laser shock experiments as compared to ab initio simulations may be related to shock-induced electronic excitations. A possible result of such non-adiabatic processes is hindering of the molecular dissociation. This has motivated us to study the importance of molecular dissociation on the hydrogen equation of state. To this end, we have carried out ab initio molecular dynamics simulations of liquid deuterium where intramolecular dissociation is prevented by the use of bond length contraints. Simulations at both fixed thermodynamic conditions and dynamical simulations of shocked deuterium will be discussed.

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

Qualitative and quantitative analysis of mixtures of compounds containing both hydrogen and deuterium

NASA Technical Reports Server (NTRS)

Crespi, H. L.; Harkness, L.; Katz, J. J.; Norman, G.; Saur, W.

1969-01-01

Method allows qualitative and quantitative analysis of mixtures of partially deuterated compounds. Nuclear magnetic resonance spectroscopy determines location and amount of deuterium in organic compounds but not fully deuterated compounds. Mass spectroscopy can detect fully deuterated species but not the location.

Application of a New Ensemble Conserving Quantum Dynamics Simulation Algorithm to Liquid para-Hydrogen and ortho-Deuterium

DOE PAGES

Smith, Kyle K.G.; Poulsen, Jens Aage; Nyman, Gunnar; ...

2015-06-30

Here, we apply the Feynman-Kleinert Quasi-Classical Wigner (FK-QCW) method developed in our previous work [Smith et al., J. Chem. Phys. 142, 244112 (2015)] for the determination of the dynamic structure factor of liquid para-hydrogen and ortho-deuterium at state points of (T = 20.0 K, n = 21.24 nm -3) and (T = 23.0 K, n = 24.61 nm -3), respectively. When applied to this challenging system, it is shown that this new FK-QCW method consistently reproduces the experimental dynamic structure factor reported by Smith et al. [J. Chem. Phys. 140, 034501 (2014)] for all momentum transfers considered. Moreover, this showsmore » that FK-QCW provides a substantial improvement over the Feynman-Kleinert linearized path-integral method, in which purely classical dynamics are used. Furthermore, for small momentum transfers, it is shown that FK-QCW provides nearly the same results as ring-polymer molecular dynamics (RPMD), thus suggesting that FK-QCW provides a potentially more appealing algorithm than RPMD since it is not formally limited to correlation functions involving linear operators.« less

Application of a new ensemble conserving quantum dynamics simulation algorithm to liquid para-hydrogen and ortho-deuterium.

PubMed

Smith, Kyle K G; Poulsen, Jens Aage; Nyman, Gunnar; Cunsolo, Alessandro; Rossky, Peter J

2015-06-28

We apply the Feynman-Kleinert Quasi-Classical Wigner (FK-QCW) method developed in our previous work [Smith et al., J. Chem. Phys. 142, 244112 (2015)] for the determination of the dynamic structure factor of liquid para-hydrogen and ortho-deuterium at state points of (T = 20.0 K, n = 21.24 nm(-3)) and (T = 23.0 K, n = 24.61 nm(-3)), respectively. When applied to this challenging system, it is shown that this new FK-QCW method consistently reproduces the experimental dynamic structure factor reported by Smith et al. [J. Chem. Phys. 140, 034501 (2014)] for all momentum transfers considered. This shows that FK-QCW provides a substantial improvement over the Feynman-Kleinert linearized path-integral method, in which purely classical dynamics are used. Furthermore, for small momentum transfers, it is shown that FK-QCW provides nearly the same results as ring-polymer molecular dynamics (RPMD), thus suggesting that FK-QCW provides a potentially more appealing algorithm than RPMD since it is not formally limited to correlation functions involving linear operators.

Application of a New Ensemble Conserving Quantum Dynamics Simulation Algorithm to Liquid para-Hydrogen and ortho-Deuterium

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

Smith, Kyle K.G.; Poulsen, Jens Aage; Nyman, Gunnar

Here, we apply the Feynman-Kleinert Quasi-Classical Wigner (FK-QCW) method developed in our previous work [Smith et al., J. Chem. Phys. 142, 244112 (2015)] for the determination of the dynamic structure factor of liquid para-hydrogen and ortho-deuterium at state points of (T = 20.0 K, n = 21.24 nm -3) and (T = 23.0 K, n = 24.61 nm -3), respectively. When applied to this challenging system, it is shown that this new FK-QCW method consistently reproduces the experimental dynamic structure factor reported by Smith et al. [J. Chem. Phys. 140, 034501 (2014)] for all momentum transfers considered. Moreover, this showsmore » that FK-QCW provides a substantial improvement over the Feynman-Kleinert linearized path-integral method, in which purely classical dynamics are used. Furthermore, for small momentum transfers, it is shown that FK-QCW provides nearly the same results as ring-polymer molecular dynamics (RPMD), thus suggesting that FK-QCW provides a potentially more appealing algorithm than RPMD since it is not formally limited to correlation functions involving linear operators.« less

Application of a new ensemble conserving quantum dynamics simulation algorithm to liquid para-hydrogen and ortho-deuterium

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

Smith, Kyle K. G., E-mail: kylesmith@utexas.edu; Poulsen, Jens Aage, E-mail: jens72@chem.gu.se; Nyman, Gunnar, E-mail: nyman@chem.gu.se

We apply the Feynman-Kleinert Quasi-Classical Wigner (FK-QCW) method developed in our previous work [Smith et al., J. Chem. Phys. 142, 244112 (2015)] for the determination of the dynamic structure factor of liquid para-hydrogen and ortho-deuterium at state points of (T = 20.0 K, n = 21.24 nm{sup −3}) and (T = 23.0 K, n = 24.61 nm{sup −3}), respectively. When applied to this challenging system, it is shown that this new FK-QCW method consistently reproduces the experimental dynamic structure factor reported by Smith et al. [J. Chem. Phys. 140, 034501 (2014)] for all momentum transfers considered. This shows that FK-QCWmore » provides a substantial improvement over the Feynman-Kleinert linearized path-integral method, in which purely classical dynamics are used. Furthermore, for small momentum transfers, it is shown that FK-QCW provides nearly the same results as ring-polymer molecular dynamics (RPMD), thus suggesting that FK-QCW provides a potentially more appealing algorithm than RPMD since it is not formally limited to correlation functions involving linear operators.« less

Sulfur and Hydrogen Isotope Anomalies in Meteorite Sulfonic Acids

NASA Technical Reports Server (NTRS)

Cooper, George W.; Thiemens, Mark H.; Jackson, Teresa L.; Chang, Sherwood

1997-01-01

Intramolecular carbon, hydrogen, and sulfur isotope ratios were measured on a homologous series of organic sulfonic acids discovered in the Murchison meteorite. Mass-independent sulfur isotope fractionations were observed along with high deuterium/hydrogen ratios. The deuterium enrichments indicate formation of the hydrocarbon portion of these compounds in a low-temperature environment that is consistent with that of interstellar clouds. Sulfur-33 enrichments observed in methanesulfonic acid could have resulted from gas-phase ultraviolet irradiation of a precursor, carbon disulfide. The source of the sulfonic acid precursors may have been the reactive interstellar molecule carbon monosulfide.

Deuterium velocity and temperature measurements on the DIII-D tokamak.

PubMed

Grierson, B A; Burrell, K H; Solomon, W M; Pablant, N A

2010-10-01

Newly installed diagnostic capabilities on the DIII-D tokamak [J. L. Luxon, Nucl. Fusion 46, 6114 (2002)] enable the measurement of main ion (deuterium) velocity and temperature by charge exchange recombination spectroscopy. The uncertainty in atomic physics corrections for determining the velocity is overcome by exploiting the geometrical dependence of the apparent velocity on the viewing angle with respect to the neutral beam.

Cryogenic distillation facility for isotopic purification of protium and deuterium

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

Alekseev, I.; Arkhipov, Ev.; Bondarenko, S.

Isotopic purification of the protium and deuterium is an important requirement of many physics experiments. A cryogenic facility for high-efficiency separation of hydrogen isotopes with a cryogenic distillation column as the main element is described. The instrument is portable, so that it can be used at the experimental site. It was designed and built at the Petersburg Nuclear Physics Institute, Gatchina, Russia. Fundamental operating parameters have been measured including a liquid holdup in the column packing, the pressure drops across the column and the purity of the product at different operating modes. A mathematical model describes expected profiles of hydrogenmore » isotope concentration along the distillation column. An analysis of ortho-parahydrogen isomeric composition by gas chromatography was used for evaluation of the column performance during the tuning operations. The protium content during deuterium purification (≤100 ppb) was measured using gas chromatography with accumulation of the protium in the distillation column. A high precision isotopic measurement at the Institute of Particle Physics, ETH-Zurich, Switzerland, provided an upper bound of the deuterium content in protium (≤6 ppb), which exceeds all commercially available products.« less

Equations of state for hydrogen and deuterium.

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

Kerley, Gerald Irwin

2003-12-01

This report describes the complete revision of a deuterium equation of state (EOS) model published in 1972. It uses the same general approach as the 1972 EOS, i.e., the so-called 'chemical model,' but incorporates a number of theoretical advances that have taken place during the past thirty years. Three phases are included: a molecular solid, an atomic solid, and a fluid phase consisting of both molecular and atomic species. Ionization and the insulator-metal transition are also included. The most important improvements are in the liquid perturbation theory, the treatment of molecular vibrations and rotations, and the ionization equilibrium and mixturemore » models. In addition, new experimental data and theoretical calculations are used to calibrate certain model parameters, notably the zero-Kelvin isotherms for the molecular and atomic solids, and the quantum corrections to the liquid phase. The report gives a general overview of the model, followed by detailed discussions of the most important theoretical issues and extensive comparisons with the many experimental data that have been obtained during the last thirty years. Questions about the validity of the chemical model are also considered. Implications for modeling the 'giant planets' are also discussed.« less

Feature Based Retention Time Alignment for Improved HDX MS Analysis

NASA Astrophysics Data System (ADS)

Venable, John D.; Scuba, William; Brock, Ansgar

2013-04-01

An algorithm for retention time alignment of mass shifted hydrogen-deuterium exchange (HDX) data based on an iterative distance minimization procedure is described. The algorithm performs pairwise comparisons in an iterative fashion between a list of features from a reference file and a file to be time aligned to calculate a retention time mapping function. Features are characterized by their charge, retention time and mass of the monoisotopic peak. The algorithm is able to align datasets with mass shifted features, which is a prerequisite for aligning hydrogen-deuterium exchange mass spectrometry datasets. Confidence assignments from the fully automated processing of a commercial HDX software package are shown to benefit significantly from retention time alignment prior to extraction of deuterium incorporation values.

Ion temperatures in HIP-1 and SUMMA from charge-exchange neutral optical emission spectra

NASA Technical Reports Server (NTRS)

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

1976-01-01

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

On the habitability of universes without stable deuterium

NASA Astrophysics Data System (ADS)

Adams, Fred C.; Grohs, Evan

2017-05-01

In both stars and in the early universe, the production of deuterium is the first step on the way to producing heavier nuclei. If the strong force were slightly weaker, then deuterium would not be stable, and many authors have noted that nuclesynthesis would be compromised so that helium production could not proceed through standard reaction chains. Motivated by the possibility that other regions of space-time could have different values for the fundamental constants, this paper considers stellar evolution in universes without stable deuterium and argues that such universes can remain habitable. Even in universes with no stellar nucleosynthesis, stars can form and will generate energy through gravitational contraction. Using both analytic estimates and a state-of-the-art stellar evolution code, we show that such stars can be sufficiently luminous and long-lived to support life. Stars with initial masses that exceed the Chandrasekhar mass cannot be supported by degeneracy pressure and will explode at the end of their contraction phase. The resulting explosive nucleosynthesis can thus provide the universe with some heavy elements. We also explore the possibility that helium can be produced in stellar cores through a triple-nucleon reaction that is roughly analogous to the triple-alpha reaction that operates in our universe. Stars burning hydrogen through this process are somewhat hotter than those in our universe, but otherwise play the same role. Next we show that with even trace amounts (metallicity Z ∼10-10) of heavy elements - produced through the triple-nucleon process or by explosive nucleosynthesis - the CNO cycle can operate and allow stars to function. Finally, we consider Big Bang Nucleosynthesis without stable deuterium and find that only trace amounts of helium are produced, with even smaller abundances of other nuclei. With stars evolving through gravitational contraction, explosive nucleosynthesis, the triple-nucleon reaction, and the CNO cycle

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.

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

Ryan, John James

The E665 spectrometer at Fermila.b measured Deep-Inelastic Scattering of 490 GeV /c muons off several targets: Hydrogen, Deuterium, and Xenon. Events were selected from the Xenon and Deuterium targets, with a range of energy exchange,more » $$\

Compact determination of hydrogen isotopes

DOE PAGES

Robinson, David

2017-04-06

Scanning calorimetry of a confined, reversible hydrogen sorbent material has been previously proposed as a method to determine compositions of unknown mixtures of diatomic hydrogen isotopologues and helium. Application of this concept could result in greater process knowledge during the handling of these gases. Previously published studies have focused on mixtures that do not include tritium. This paper focuses on modeling to predict the effect of tritium in mixtures of the isotopologues on a calorimetry scan. Furthermore, the model predicts that tritium can be measured with a sensitivity comparable to that observed for hydrogen-deuterium mixtures, and that under so memore » conditions, it may be possible to determine the atomic fractions of all three isotopes in a gas mixture.« less

76 FR 52994 - Application for a License To Export Heavy Water

Federal Register 2010, 2011, 2012, 2013, 2014

2011-08-24

... NUCLEAR REGULATORY COMMISSION Application for a License To Export Heavy Water Pursuant to 10 CFR... (liters). producing an active water). pharmaceutical ingredient known as CTP-499, which incorporates heavy water as the source of deuterium to achieve the hydrogen-deuterium exchange. November 30, 2010 December...

Symmetry and the geometric phase in ultracold hydrogen-exchange reactions

NASA Astrophysics Data System (ADS)

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

2017-08-01

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

Deuterium permeation through EPDM rubber compounds

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

Zapp, P.E.

1988-01-01

The permeation of deuterium through a specially formulated compound of ethylene propylene diene rubber was measured in the temperature range of 26/degree/C to 120/degree/C. The results were similar to permeation through two commercial compounds of this elastomer. Permeation was reduced after gamma irradiation (in the presence of hydrogen gas to simulate a tritium exposure). However the reduction was smaller than that experienced by the two commercial compounds. Radiation damage is apparently less severe in the special compound. It is possible that mechanical properties such as compression set may be influenced less by ionizing radiation in this compound as compared withmore » the commercial compounds. 4 figs., 1 tab.« less

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

Comprehensive physicochemical studies of a new hybrid material: 2-Amino-4-methyl-3-nitropyridinium hydrogen oxalate

NASA Astrophysics Data System (ADS)

Bryndal, I.; Kucharska, E.; Wandas, M.; Lorenc, J.; Hermanowicz, K.; Mączka, M.; Lis, T.; Marchewka, M.; Hanuza, J.

2014-01-01

A new organic-organic salt, 2-amino-4-methyl-3-nitropyridinium hydrogen oxalate (AMNPO), and its deuterium analogue have been synthesized and characterized by means of FT-IR, FT-Raman, DSC and single crystal X-ray studies. The DSC measurements and temperature dependence of the IR and Raman spectra in the range 4-295 K show that it undergoes a reversible phase transition at ∼240 K. At room temperature it crystallizes in noncentrosymmetric space group P21. The unit-cell is built of the 2-amino-4-methyl-3-nitropyridinium cations and oxalate monoanions which are connected via the Nsbnd H⋯O and Osbnd H⋯O hydrogen bonds. The geometrical and hydrogen bond parameters are similar for non-deuterated (at 120 and 293 K) and deuterated compounds (at 90 K). The phase transition is probably a consequence of order-disorder transition inside of hydrogen network. The 6-311G(2d,2p) basis set with B3LYP functional have been used to discuss the structure and vibrational spectra of the studied compound.

Solar Wind Charge Exchange Studies Of Highly Charged Ions On Atomic Hydrogen

NASA Astrophysics Data System (ADS)

Draganić, I. N.; Seely, D. G.; McCammon, D.; Havener, C. C.

2011-06-01

Accurate studies of low-energy charge exchange (CX) are critical to understanding underlying soft X-ray radiation processes in the interaction of highly charged ions from the solar wind with the neutral atoms and molecules in the heliosphere, cometary comas, planetary atmospheres, interstellar winds, etc.. Particularly important are the CX cross sections for bare, H-like, and He-like ions of C, N, O and Ne, which are the dominant charge states for these heavier elements in the solar wind. Absolute total cross sections for single electron capture by H-like ions of C, N, O and fully-stripped O ions from atomic hydrogen have been measured in an expanded range of relative collision energies (5 eV/u-20 keV/u) and compared to previous H-oven measurements. The present measurements are performed using a merged-beams technique with intense highly charged ion beams extracted from a 14.5 GHz ECR ion source installed on a high voltage platform at the Oak Ridge National Laboratory. For the collision energy range of 0.3 keV/u-3.3 keV/u, which corresponds to typical ion velocities in the solar wind, the new measurements are in good agreement with previous H-oven measurements. The experimental results are discussed in detail and compared with theoretical calculations where available.

Hydrogen atom distribution and hydrogen induced site depopulation for the La{sub 2-x}Mg{sub x}Ni{sub 7}-H system

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

Guzik, Matylda N., E-mail: Matylda.Guzik@ife.no; Physics Department, Institute for Energy Technology, P.O. Box 40, NO-2027 Kjeller; Hauback, Bjorn C.

2012-02-15

La{sub 2-x}Mg{sub x}Ni{sub 7} and its hydrides/deuterides were investigated by high resolution synchrotron powder X-ray and neutron diffraction. Upon deuteration the single phase sample of the intermetallic compound with the refined composition La{sub 1.63}Mg{sub 0.37}Ni{sub 7} (space group: P6{sub 3}/mmc) expands isotropically, in contrast to the Mg free phase. The hydrogen uptake, {approx}9 D/f.u., is higher than in La{sub 2}Ni{sub 7}D{sub 6.5}. The refined composition accounts for La{sub 1.63}Mg{sub 0.37}Ni{sub 7}D{sub 8.8} (beta-phase). Rietveld refinements using the neutron and synchrotron diffraction data suggest that deuterium atoms occupy 5 different interstitial sites within both AB{sub 2} and AB{sub 5} slabs, eithermore » in an ordered or a disordered way. All determined D sites have an occupancy >50% and the shortest D-D contact is 1.96(3) A. It is supposed that a competition between the tendency to form directional bonds and repulsive D-D (H-H) interactions is the most important factor that influences the distribution of deuterium atoms in this structure. A hitherto unknown second, alpha-phase with composition La{sub 1.63}Mg{sub 0.37}Ni{sub 7}D{sub 0.56}, crystallizing with the same hexagonal symmetry as La{sub 1.63}Mg{sub 0.37}Ni{sub 7}D{sub 8.8}, has been discovered. The unit cell parameters for this D-poor phase differ slightly from those of the intermetallic. Alpha-phase displays only one D site (4f, space group: P6{sub 3}/mmc) occupied >50%, which is not populated in the D-rich beta-phase. This hydrogen/deuterium induced site depopulation can be explained by repulsive D-D (H-H) interactions that are likely to influence non-occupancy of certain interstices in metal lattice when absorbing hydrogen. - Graphical abstract: The detailed D atoms arrangement in La{sub 1.63}Mg{sub 0.37}Ni{sub 7}D{sub 8.8} differs significantly from the previously reported La{sub 1.5}Mg{sub 0.5}Ni{sub 7}D{sub 8.9(9.1)}. The present model consists of only five deuterium

Highly tritiated water processing by isotopic exchange

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

Shu, W.M.; Willms, R.S.; Glugla, M.

2015-03-15

Highly tritiated water (HTW) is produced in fusion machines and one of the promising technologies to process it is isotopic exchange. 3 kinds of Pt-catalyzed zeolite (13X-APG, CBV-100-CY and HiSiv-1000) were tested as candidates for isotopic exchange of highly tritiated water (HTW), and CBV-100-CY (Na-Y type with a SiO{sub 2}/Al{sub 2}O{sub 3} ratio of ∼ 5.0) shows the best performance. Small-scale tritium testing indicates that this method is efficient for reaching an exchange factor (EF) of 100. Full-scale non-tritium testing implies that an EF of 300 can be achieved in 24 hours of operation if a temperature gradient is appliedmore » along the column. For the isotopic exchange, deuterium recycled from the Isotope Separation System (deuterium with 1% T and/or 200 ppm T) should be employed, and the tritiated water regenerated from the Pt-catalyzed zeolite bed after isotopic exchange should be transferred to Water Detritiation System (WDS) for further processing.« less

Meridional distribution of molecular hydrogen and its deuterium content in the atmosphere

NASA Astrophysics Data System (ADS)

Rice, Andrew; Quay, Paul; Stutsman, Johnny; Gammon, Richard; Price, Heather; Jaeglé, Lyatt

2010-06-01

The atmospheric molecular hydrogen concentration and its deuterium abundance were measured in remote air samples collected onboard six Pacific Ocean ship transects between 37°N and 77°S during years 2001 through 2005. The data reveal a year-round interhemispheric gradient in H2 concentration and isotopic composition with the extratropical Northern Hemisphere lower in H2 concentration by 17 ± 11 ppb and δD of H2 by 16 ± 12‰ than the Southern Hemisphere (95% confidence). On the basis of these snapshots, the interhemispheric gradient in δD was observed to be smallest in September through November, a time that experiences the largest gradient in concentration, and the largest in April, a time that has a small gradient in concentration. A simple hemispheric box model of the atmosphere indicates that, while the hemispheric asymmetry in soil sink of H2 is primarily responsible for the observed interhemispheric gradient in H2 concentration, the hemispheric difference in the δD of the H2 sources and sinks are equally responsible for the observed interhemispheric gradient in δD. Both the inverse correlation between interhemispheric H2 and δD gradients and their seasonal changes point to the importance of the H2 produced by photochemical sources. Comparisons with a three-dimensional chemical transport model shows reasonable agreement with mean behavior in both variables and provides an accounting for H2 sources and sinks within ±15% without a dramatic change in the H2 budget. Anomalous H2 concentrations and δD in tropics and low-latitude regions observed during the November-December 2001 meridional H2 and δD snapshot is thought to be a result of H2 emissions from biomass burning, possibly from continental Africa.

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.

Hydrogen exchange mass spectrometry of bacteriorhodopsin reveals light-induced changes in the structural dynamics of a biomolecular machine.

PubMed

Pan, Yan; Brown, Leonid; Konermann, Lars

2011-12-21

Many proteins act as molecular machines that are fuelled by a nonthermal energy source. Examples include transmembrane pumps and stator-rotor complexes. These systems undergo cyclic motions (CMs) that are being driven along a well-defined conformational trajectory. Superimposed on these CMs are thermal fluctuations (TFs) that are coupled to stochastic motions of the solvent. Here we explore whether the TFs of a molecular machine are affected by the occurrence of CMs. Bacteriorhodopsin (BR) is a light-driven proton pump that serves as a model system in this study. The function of BR is based on a photocycle that involves trans/cis isomerization of a retinal chromophore, as well as motions of transmembrane helices. Hydrogen/deuterium exchange (HDX) mass spectrometry was used to monitor the TFs of BR, focusing on the monomeric form of the protein. Comparative HDX studies were conducted under illumination and in the dark. The HDX kinetics of BR are dramatically accelerated in the presence of light. The isotope exchange rates and the number of backbone amides involved in EX2 opening transitions increase roughly 2-fold upon illumination. In contrast, light/dark control experiments on retinal-free protein produced no discernible differences. It can be concluded that the extent of TFs in BR strongly depends on photon-driven CMs. The light-induced differences in HDX behavior are ascribed to protein destabilization. Specifically, the thermodynamic stability of the dark-adapted protein is estimated to be 5.5 kJ mol(-1) under the conditions of our work. This value represents the free energy difference between the folded state F and a significantly unfolded conformer U. Illumination reduces the stability of F by 2.2 kJ mol(-1). Mechanical agitation caused by isomerization of the chromophore is transferred to the surrounding protein scaffold, and subsequently, the energy dissipates into the solvent. Light-induced retinal motions therefore act analogously to an internal heat

Optimization of Feasibility Stage for Hydrogen/Deuterium Exchange Mass Spectrometry

NASA Astrophysics Data System (ADS)

Hamuro, Yoshitomo; Coales, Stephen J.

2018-03-01

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

Deuterium trapping in tungsten

NASA Astrophysics Data System (ADS)

Poon, Michael

Tungsten is one of the primary material candidates being investigated for use in the first-wall of a magnetic confinement fusion reactor. An ion accelerator was used to simulate the type of ion interaction that may occur at a plasma-facing material. Thermal desorption spectroscopy (TDS) was the primary tool used to analyze the effects of the irradiation. Secondary ion mass spectroscopy (SIMS) was used to determine the distribution of trapped D in the tungsten specimen. The tritium migration analysis program (TMAP) was used to simulate thermal desorption profiles from the D depth distributions. Fitting of the simulated thermal desorption profiles with the measured TDS results provided values of the D trap energies. Deuterium trapping in single crystal tungsten was studied as a function of the incident ion fluence, ion flux, irradiation temperature, irradiation history, and surface impurity levels during irradiation. The results show that deuterium was trapped at vacancies and voids. Two deuterium atoms could be trapped at a tungsten vacancy, with trapping energies of 1.4 eV and 1.2 eV for the first and second D atoms, respectively. In a tungsten void, D is trapped as atoms adsorbed on the inner walls of the void with a trap energy of 2.1 eV, or as D2 molecules inside the void with a trap energy of 1.2 eV. Deuterium trapping in polycrystalline tungsten was also studied as a function of the incident fluence, irradiation temperature, and irradiation history. Deuterium trapping in polycrystalline tungsten also occurs primarily at vacancies and voids with the same trap energies as in single crystal tungsten; however, the presence of grain boundaries promotes the formation of large surface blisters with high fluence irradiations at 500 K. In general, D trapping is greater in polycrystalline tungsten than in single crystal tungsten. To simulate mixed materials comprising of carbon (C) and tungsten, tungsten specimens were pre-irradiated with carbon ions prior to D

Erosion and deuterium retention of CLF-1 steel exposed to deuterium plasma

NASA Astrophysics Data System (ADS)

Qiao, L.; Wang, P.; Hu, M.; Gao, L.; Jacob, W.; Fu, E. G.; Luo, G. N.

2017-12-01

In recent years reduced activation ferritic martensitic steel has been proposed as the plasma-facing material in remote regions of the first wall. This study reports the erosion and deuterium retention behaviours in CLF-1 steel exposed to deuterium (D) plasma in a linear experimental plasma system as function of incident ion energy and fluence. The incident D ion energy ranges from 30 to 180 eV at a flux of 4 × 1021 D m-2 s-1 up to a fluence of 1025 D m-2. SEM images revealed a clear change of the surface morphology as functions of incident fluence and impinging energy. The mass loss results showed a decrease of the total sputtering yield of CLF-1 steel with increasing incident fluence by up to one order of magnitude. The total sputtering yield of CLF-1 steel after 7.2 × 1024 D m-2 deuterium plasma exposure reduced by a factor of 4 compared with that of pure iron, which can be attributed to the enrichment of W at the surface due to preferential sputtering of iron and chromium. After D plasma exposure, the total deuterium retention in CLF-1 steel samples measured by TDS decreased with increasing incident fluence and energy, and a clear saturation tendency as function of incident fluence or energy was also observed.

Deuterium supersaturation in low-energy plasma-loaded tungsten surfaces

NASA Astrophysics Data System (ADS)

Gao, L.; Jacob, W.; von Toussaint, U.; Manhard, A.; Balden, M.; Schmid, K.; Schwarz-Selinger, T.

2017-01-01

Fundamental understanding of hydrogen-metal interactions is challenging due to a lack of knowledge on defect production and/or evolution upon hydrogen ingression, especially for metals undergoing hydrogen irradiation with ion energy below the displacement thresholds reported in literature. Here, applying a novel low-energy argon-sputter depth profiling method with significantly improved depth resolution for tungsten (W) surfaces exposed to deuterium (D) plasma at 300 K, we show the existence of a 10 nm thick D-supersaturated surface layer (DSSL) with an unexpectedly high D concentration of ~10 at.% after irradiation with ion energy of 215 eV. Electron back-scatter diffraction reveals that the W lattice within this DSSL is highly distorted, thus strongly blurring the Kikuchi pattern. We explain this strong damage by the synergistic interaction of energetic D ions and solute D atoms with the W lattice. Solute D atoms prevent the recombination of vacancies with interstitial W atoms, which are produced by collisions of energetic D ions with W lattice atoms (Frenkel pairs). This proposed damaging mechanism could also be active on other hydrogen-irradiated metal surfaces. The present work provides deep insight into hydrogen-induced lattice distortion at plasma-metal interfaces and sheds light on its modelling work.

The formation of excited atoms during charge exchange between hydrogen ions and alkali atoms. Ph.D. Thesis

NASA Technical Reports Server (NTRS)

Nieman, R. A.

1971-01-01

The charge exchange cross sections for protons and various alkali atoms are calculated using the classical approximation of Gryzinski. It is assumed that the hydrogen atoms resulting from charge exchange exist in all possible excited states. Charge transfer collisions between protons and potassium as well as protons and sodium atoms are studied. The energy range investigated is between 4 and 30 keV. The theoretical calculations of the capture cross section and the cross section for the creation of metastable 2S hydrogen are compared to experimental values. Good quantitative agreement is found for the capture cross section but only qualitative agreement for the metastable cross section. Analysis of the Lyman alpha window in molecular oxygen suggests that measured values of the metastable cross section may be in error. Thick alkali target data are also presented. This allows the determination of the total electron loss cross section. Finally, some work was done with H2(+).

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

Hydrogen and methanol exchange processes for (TMP)Rh-OCH3(CH3OH) in binary solutions of methanol and benzene.

PubMed

Sarkar, Sounak; Li, Shan; Wayland, Bradford B

2011-04-18

Tetramesityl porphinato rhodium(III) methoxide ((TMP)Rh-OCH(3)) binds with methanol in benzene to form a 1:1 methanol complex ((TMP)Rh-OCH(3)(CH(3)OH)) (1). Dynamic processes are observed to occur for the rhodium(III) methoxide methanol complex (1) that involve both hydrogen and methanol exchange. Hydrogen exchange between coordinated methanol and methoxide through methanol in solution results in an interchange of the environments for the non-equivalent porphyrin faces that contain methoxide and methanol ligands. Interchange of the environments of the coordinated methanol and methoxide sites in 1 produces interchange of the inequivalent mesityl o-CH(3) groups, but methanol ligand exchange occurs on one face of the porphyrin and the mesityl o-CH(3) groups remain inequivalent. Rate constants for dynamic processes are evaluated by full line shape analysis for the (1)H NMR of the mesityl o-CH(3) and high field methyl resonances of coordinated methanol and methoxide groups in 1. The rate constant for interchange of the inequivalent porphyrin faces is associated with hydrogen exchange between 1 and methanol in solution and is observed to increase regularly with the increase in the mole fraction of methanol. The rate constant for methanol ligand exchange between 1 and the solution varies with the solution composition and fluctuates in a manner that parallels the change in the activation energy for methanol diffusion which is a consequence of solution non-ideality from hydrogen bonded clusters.

Study of polarized IR spectra of the hydrogen bond system in crystals of styrylacetic acid

NASA Astrophysics Data System (ADS)

Flakus, Henryk T.; Jabłońska, Magdalena; Jones, Peter G.

2006-10-01

We have investigated the polarized IR spectra of the hydrogen bond system in crystals of trans-styrylacetic acid C 6H 5sbnd CH dbnd CH sbnd CH 2sbnd COOH, and also in crystals of the following three deuterium isotopomers of the compound: C 6H 5sbnd CH dbnd CH sbnd CH 2sbnd COOD, C 6H 5sbnd CH dbnd CH sbnd CD 2sbnd COOH and C 6H 5sbnd CH dbnd CH sbnd CD 2sbnd COOD. The spectra were measured at room temperature and at 77 K by a transmission method. The spectral studies were preceded by determination of the X-ray crystal structure. Theoretical analysis of the results concerned linear dichroic effects, the H/D isotopic and temperature effects, observed in the solid-state IR spectra of the hydrogen and of the deuterium bond, at the frequency ranges of the νO sbnd H and the νO sbnd D bands, respectively. Basic spectral properties of the crystals can be interpreted satisfactorily in terms of the " strong-coupling" theory, when based on a hydrogen bond dimer model. This model sufficiently explained not only a two-branch structure of the νO sbnd H and the νO sbnd D bands, and temperature-induced evolution of the crystalline spectra, but also the linear dichroic effects observed in the band frequency ranges. A vibronic mechanism was analyzed, responsible for promotion of the symmetry-forbidden transition in the IR for the totally symmetric proton stretching vibrations in centrosymmetric hydrogen bond dimers. It was found to be of minor importance, when compared with analogous spectral properties of arylcarboxylic acid, or of cinnamic acid crystals. These effects were ascribed to a substantial weakening of electronic couplings between the hydrogen bonds of the associated carboxyl groups and the styryl radicals, associated with the separation of these groups in styrylacetic acid molecules by methylene groups in the molecules.

X-ray scattering measurements of dissociation-induced metallization of dynamically compressed deuterium

DOE PAGES

Davis, P.; Döppner, T.; Rygg, J. R.; ...

2016-04-18

Hydrogen, the simplest element in the universe, has a surprisingly complex phase diagram. Because of applications to planetary science, inertial confinement fusion and fundamental physics, its high-pressure properties have been the subject of intense study over the past two decades. While sophisticated static experiments have probed hydrogen’s structure at ever higher pressures, studies examining the higher-temperature regime using dynamic compression have mostly been limited to optical measurement techniques. Here we present spectrally resolved x-ray scattering measurements from plasmons in dynamically compressed deuterium. Combined with Compton scattering, and velocity interferometry to determine shock pressure and mass density, this allows us tomore » extract ionization state as a function of compression. Furthermore, the onset of ionization occurs close in pressure to where density functional theory-molecular dynamics (DFT-MD) simulations show molecular dissociation, suggesting hydrogen transitions from a molecular and insulating fluid to a conducting state without passing through an intermediate atomic phase.« less

Process for hydrogen isotope concentration between liquid water and hydrogen gas

DOEpatents

Stevens, William H.

1976-09-21

A process for hydrogen isotope exchange and concentration between liquid water and hydrogen gas, wherein liquid water and hydrogen gas are contacted, in an exchange section, with one another and with at least one catalyst body comprising at least one metal selected from Group VIII of the Periodic Table and preferably a support therefor, the catalyst body has a liquid-water-repellent, gas permeable polymer or organic resin coating, preferably a fluorinated olefin polymer or silicone coating, so that the isotope concentration takes place by two simultaneously occurring steps, namely, ##EQU1## WHILE THE HYDROGEN GAS FED TO THE EXCHANGE SECTION IS DERIVED IN A REACTOR VESSEL FROM LIQUID WATER THAT HAS PASSED THROUGH THE EXCHANGE SECTION.

Creatine Supplementation Increases Total Body Water in Soccer Players: a Deuterium Oxide Dilution Study.

PubMed

Deminice, R; Rosa, F T; Pfrimer, K; Ferrioli, E; Jordao, A A; Freitas, E

2016-02-01

This study aimed to evaluate changes in total body water (TBW) in soccer athletes using a deuterium oxide dilution method and bioelectrical impedance (BIA) formulas after 7 days of creatine supplementation. In a double-blind controlled manner, 13 healthy (under-20) soccer players were divided randomly in 2 supplementation groups: Placebo (Pla, n=6) and creatine supplementation (CR, n=7). Before and after the supplementation period (0.3 g/kg/d during 7 days), TBW was determined by deuterium oxide dilution and BIA methods. 7 days of creatine supplementation lead to a large increase in TBW (2.3±1.0 L) determined by deuterium oxide dilution, and a small but significant increase in total body weight (1.0±0.4 kg) in Cr group compared to Pla. The Pla group did not experience any significant changes in TBW or body weight. Although 5 of 6 BIA equations were sensitive to determine TBW changes induced by creatine supplementation, the Kushner et al. 16 method presented the best concordance levels when compared to deuterium dilution method. In conclusion, 7-days of creatine supplementation increased TBW determined by deuterium oxide dilution or BIA formulas. BIA can be useful to determine TBW changes promoted by creatine supplementation in soccer athletes, with special concern for formula choice. © Georg Thieme Verlag KG Stuttgart · New York.

The effect of relativistic Compton scattering on thermonuclear burn of pure deuterium fuel

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

Ghasemizad, A.; Nazirzadeh, M.; Khanbabaei, B.

The relativistic effects of the Compton scattering on the thermonuclear burn-up of pure deuterium fuel in non-equilibrium plasma have been studied by four temperature (4T) theory. In the limit of low electron temperatures and photon energies, the nonrelativistic Compton scattering is valid and a convenient approximation, but in the high energy exchange rates between electrons and photons, is seen to break down. The deficiencies of the nonrelativistic approximation can be overcome by using the relativistic correction in the photons kinetic equation. In this research, we have utilized the four temperature (4T) theory to calculate the critical burn-up parameter for puremore » deuterium fuel, while the Compton scattering is considered as a relativistic phenomenon. It was shown that the measured critical burn-up parameter in ignition with relativistic Compton scattering is smaller than that of the parameter in the ignition with the nonrelativistic Compton scattering.« less

Deep levels due to hydrogen in ZnO single crystals

NASA Astrophysics Data System (ADS)

Parmar, Narendra; Weber, Marc; Lynn, Kelvin

2009-05-01

Hydrogen impurities and oxygen vacancies are involved in the ˜0.7 eV shift of the optical absorption edge of ZnO. Deuterium causes a smaller shift. Titanium metal is used to bind hydrogen as it diffuses out of ZnO. Positron annihilation spectroscopy coupled with other techniques point to the presence of oxygen vacancies. Removing hydrogen followed by annealing in oxygen reduces the carrier concentration.

DYNAMIC DEUTERIUM ENRICHMENT IN COMETARY WATER VIA ELEY–RIDEAL REACTIONS

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

Yao, Yunxi; Giapis, Konstantinos P., E-mail: giapis@cheme.caltech.edu

2017-01-20

The deuterium-to-hydrogen ratio (D/H) in water found in the coma of Jupiter family comet (JFC) 67P/Churyumov–Gerasimenko was reported to be (5.3 ± 0.7) × 10{sup −4}, the highest among comets and three times the value for other JFCs with an ocean-like ratio. This discrepancy suggests the diverse origins of JFCs and clouds the issue of the origin of Earth’s oceanic water. Here we demonstrate that Eley–Rideal reactions between accelerated water ions and deuterated cometary surface analogs can lead to instantaneous deuterium enrichment in water scattered from the surface. The reaction proceeds with H{sub 2}O{sup +} abstracting adsorbed D atoms, formingmore » an excited H{sub 2}DO* state, which dissociates subsequently to produce energetic HDO. Hydronium ions are also produced readily by the abstraction of H atoms, consistent with H{sub 3}O{sup +} detection and abundance in various comets. Experiments with water isotopologs and kinematic analysis on deuterated platinum surfaces confirmed the dynamic abstraction mechanism. The instantaneous fractionation process is independent of the surface temperature and may operate on the surface of cometary nuclei or dust grains, composed of deuterium-rich silicates and carbonaceous chondrites. The requisite energetic water ions have been detected in the coma of 67P in two populations. This dynamic fractionation process may temporarily increase the water D/H ratio, especially as the comet gets closer to the Sun. The magnitude of the effect depends on the water ion energy-flux and the deuterium content of the exposed cometary surfaces.« less

Comprehensive physicochemical studies of a new hybrid material: 2-amino-4-methyl-3-nitropyridinium hydrogen oxalate.

PubMed

Bryndal, I; Kucharska, E; Wandas, M; Lorenc, J; Hermanowicz, K; Mączka, M; Lis, T; Marchewka, M; Hanuza, J

2014-01-03

A new organic-organic salt, 2-amino-4-methyl-3-nitropyridinium hydrogen oxalate (AMNPO), and its deuterium analogue have been synthesized and characterized by means of FT-IR, FT-Raman, DSC and single crystal X-ray studies. The DSC measurements and temperature dependence of the IR and Raman spectra in the range 4-295 K show that it undergoes a reversible phase transition at ~240 K. At room temperature it crystallizes in noncentrosymmetric space group P21. The unit-cell is built of the 2-amino-4-methyl-3-nitropyridinium cations and oxalate monoanions which are connected via the N-H···O and O-H···O hydrogen bonds. The geometrical and hydrogen bond parameters are similar for non-deuterated (at 120 and 293 K) and deuterated compounds (at 90K). The phase transition is probably a consequence of order-disorder transition inside of hydrogen network. The 6-311G(2d,2p) basis set with B3LYP functional have been used to discuss the structure and vibrational spectra of the studied compound. Copyright © 2013 Elsevier B.V. All rights reserved.

A small portable proton exchange membrane fuel cell and hydrogen generator for medical applications.

PubMed

Adlhart, O J; Rohonyi, P; Modroukas, D; Driller, J

1997-01-01

Small, lightweight power sources for total artificial hearts (TAH), left ventricular assist devices (LVAD), and other medical products are under development. The new power source will provide 2 to 3 times the capacity of conventional batteries. The implications of this new power source are profound. For example, for the Heartmate LVAD, 5 to 8 hours of operation are obtained with 3 lb of lead acid batteries (Personal Communication Mr. Craig Sherman, Thermo Cardiosystems, Inc TCI 11/29/96). With the same weight, as much as 14 hours of operation appear achievable with the proton exchange membrane (PEM) fuel cell power source. Energy densities near 135 watt-hour/L are achievable. These values significantly exceed those of most conventional and advanced primary and secondary batteries. The improvement is mission dependent and even applies for the short deployment cited above. The comparison to batteries becomes even more favorable if the mission length is increased. The higher capacity requires only replacement of lightweight hydride cartridges and logistically available water. Therefore, when one spare 50 L hydride cartridge weighing 115 g is added to the reactant supply the energy density of the total system increases to 230 watt-hour/kg. This new power source is comprised of a hydrogen fueled, air-breathing PEM fuel cell and a miniature hydrogen generator (US Patent No 5,514,353). The fuel cell is of novel construction and differs from conventional bipolar PEM fuel cells by the arrangement of cells on a single sheet of ion-exchange membrane. The construction avoids the weight and volume penalty of conventional bipolar stacks. The hydrogen consumed by the fuel cell is generated load-responsively in the miniature hydrogen generator, by reacting calcium hydride with water, forming in the process hydrogen and lime. The generator is cartridge rechargeable and available in capacities providing up to several hundred watt-hours of electric power.

Concept study of a hydrogen containment process during nuclear thermal engine ground testing

NASA Astrophysics Data System (ADS)

Wang, Ten-See; Stewart, Eric T.; Canabal, Francisco

A new hydrogen containment process was proposed for ground testing of a nuclear thermal engine. It utilizes two thermophysical steps to contain the hydrogen exhaust. First, the decomposition of hydrogen through oxygen-rich combustion at higher temperature; second, the recombination of remaining hydrogen with radicals at low temperature. This is achieved with two unit operations: an oxygen-rich burner and a tubular heat exchanger. A computational fluid dynamics methodology was used to analyze the entire process on a three-dimensional domain. The computed flammability at the exit of the heat exchanger was less than the lower flammability limit, confirming the hydrogen containment capability of the proposed process.

Excited configurations of hydrogen in the BaTiO3 -xHx perovskite lattice associated with hydrogen exchange and transport

NASA Astrophysics Data System (ADS)

Ito, T. U.; Koda, A.; Shimomura, K.; Higemoto, W.; Matsuzaki, T.; Kobayashi, Y.; Kageyama, H.

2017-01-01

Excited configurations of hydrogen in the oxyhydride BaTiO3 -xHx (x =0.1 -0.5 ), which are considered to be involved in its hydrogen transport and exchange processes, were investigated by positive muon spin relaxation spectroscopy using muonium (Mu) as a pseudoisotope of hydrogen. Muons implanted into the BaTiO3 -xHx perovskite lattice were mainly found in two qualitatively different metastable states. One was assigned to a highly mobile interstitial protonic state, which is commonly observed in perovskite oxides. The other was found to form an entangled two spin-1/2 system with the nuclear spin of an H- ion at the anion site. The structure of the (H,Mu) complex agrees well with that of a neutralized center containing two H- ions at a doubly charged oxygen vacancy, which was predicted to form in the SrTiO3 -δ perovskite lattice by a computational study [Y. Iwazaki et al., APL Mater. 2, 012103 (2014), 10.1063/1.4854355]. Above 100 K, interstitial Mu+ diffusion and retrapping to a deep defect were observed, which could be a rate-limiting step of macroscopic Mu/H transport in the BaTiO3 -xHx lattice.

Investigation of the hydrogen fluxes in the plasma edge of W7-AS during H-mode discharges

NASA Astrophysics Data System (ADS)

Langer, U.; Taglauer, E.; Fischer, R.; W7-AS Team

2001-03-01

In the stellarator W7-AS the H-mode is characterized by an edge transport barrier which is localized within a few centimeters inside the separatrix. The corresponding L-H transition shows well-known features such as the steepening of the temperature and density profiles in the region of the separatrix. With a so-called sniffer probe the temporal development of the hydrogen and deuterium fluxes has been studied in the plasma edge during different H-mode discharges with deuterium gas puffing. Prior to the transition a significant reduction of the deuterium and also the hydrogen fluxes can be observed. This fact confirms the assumption that the steepening of the density profiles starts at the outermost edge of the plasma. Moreover, sniffer probe measurements in the plasma edge could therefore identify a precursor for the L-H transition. The analysis of the hydrogen neutral gases shows a distinct change of the hydrogen isotope ratio during the transition. This observation is in agreement with the change in the particle fluxes onto the targets and can also be seen in the reduced H α signals from the limiters. It is further demonstrated that significant improvement in the time resolution of the measured data can be obtained by deconvolution of the data with the apparatus function using Bayesian probability theory and the Maximum Entropy method with adaptive kernels.

Investigation of Helicon discharges as RF coupling concept of negative hydrogen ion sources

NASA Astrophysics Data System (ADS)

Briefi, S.; Fantz, U.

2013-02-01

The ITER reference source for H- and D- requires a high RF input power (up to 90 kW per driver). To reduce the demands on the RF circuit, it is highly desirable to reduce the power consumption while retaining the values of the relevant plasma parameters namely the positive ion density and the atomic hydrogen density. Helicon plasmas are a promising alternative RF coupling concept but they are typically generated in long thin discharge tubes using rare gases and an RF frequency of 13.56 MHz. Hence the applicability to the ITER reference source geometry, frequency and the utilization of hydrogen/deuterium has to be proved. In this paper the strategy of the approach for using Helicon discharges for ITER reference source parameters is introduced and the first promising measurements which were carried out at a small laboratory experiment are presented. With increasing RF power a mode transition to the Helicon regime was observed for argon and argon/hydrogen mixtures. In pure hydrogen/deuterium the mode transition could not yet be achieved as the available RF power is too low. In deuterium a special feature of Helicon discharges, the socalled low field peak, could be observed at a moderate B-field of 3 mT.

Hydrogen-fluorine exchange in NaBH4-NaBF4.

PubMed

Rude, L H; Filsø, U; D'Anna, V; Spyratou, A; Richter, B; Hino, S; Zavorotynska, O; Baricco, M; Sørby, M H; Hauback, B C; Hagemann, H; Besenbacher, F; Skibsted, J; Jensen, T R

2013-11-07

Hydrogen-fluorine exchange in the NaBH4-NaBF4 system is investigated using a range of experimental methods combined with DFT calculations and a possible mechanism for the reactions is proposed. Fluorine substitution is observed using in situ synchrotron radiation powder X-ray diffraction (SR-PXD) as a new Rock salt type compound with idealized composition NaBF2H2 in the temperature range T = 200 to 215 °C. Combined use of solid-state (19)F MAS NMR, FT-IR and DFT calculations supports the formation of a BF2H2(-) complex ion, reproducing the observation of a (19)F chemical shift at -144.2 ppm, which is different from that of NaBF4 at -159.2 ppm, along with the new absorption bands observed in the IR spectra. After further heating, the fluorine substituted compound becomes X-ray amorphous and decomposes to NaF at ~310 °C. This work shows that fluorine-substituted borohydrides tend to decompose to more stable compounds, e.g. NaF and BF3 or amorphous products such as closo-boranes, e.g. Na2B12H12. The NaBH4-NaBF4 composite decomposes at lower temperatures (300 °C) compared to NaBH4 (476 °C), as observed by thermogravimetric analysis. NaBH4-NaBF4 (1:0.5) preserves 30% of the hydrogen storage capacity after three hydrogen release and uptake cycles compared to 8% for NaBH4 as measured using Sievert's method under identical conditions, but more than 50% using prolonged hydrogen absorption time. The reversible hydrogen storage capacity tends to decrease possibly due to the formation of NaF and Na2B12H12. On the other hand, the additive sodium fluoride appears to facilitate hydrogen uptake, prevent foaming, phase segregation and loss of material from the sample container for samples of NaBH4-NaF.

Infrared Spectroscopy of Deuterated Compounds.

ERIC Educational Resources Information Center

MacCarthy, Patrick

1985-01-01

Background information, procedures used, and typical results obtained are provided for an experiment (based on the potassium bromide pressed-pellet method) involving the infrared spectroscopy of deuterated compounds. Deuteration refers to deuterium-hydrogen exchange at active hydrogen sites in the molecule. (JN)

Hydrogen-oxygen proton-exchange membrane fuel cells and electrolyzers

NASA Technical Reports Server (NTRS)

Baldwin, R.; Pham, M.; Leonida, A.; Mcelroy, J.; Nalette, T.

1989-01-01

Hydrogen-oxygen SPE fuel cells and SPE electrolyzers (products of Hamilton Standard) both use a Proton-Exchange Membrane (PEM) as the sole electrolyte. The SPE cells have demonstrated a ten year life capability under load conditions. Ultimate life of PEM fuel cells and electrolyzers is primarily related to the chemical stability of the membrane. For perfluorocarbon proton-exchange membranes an accurate measure of the membrane stability is the fluoride loss rate. Millions of cell hours have contributed to establishing a relationship between fluroride loss rates and average expected ultimate cell life. Several features were introduced into SPE fuel cells and SPE electrolyzers such that applications requiring greater than or equal to 100,000 hours of life can be considered. Equally important as the ultimate life is the voltage stability of hydrogen-oxygen fuel cells and electrolyzers. Here again the features of SPE fuel cells and SPE electrolyzers have shown a cell voltage stability in the order of 1 microvolt per hour. That level of stability were demonstrated for tens of thousands of hours in SPE fuel cells at up to 500 amps per square foot (ASF) current density. The SPE electrolyzers have demonstrated the same at 1000 ASF. Many future extraterrestrial applications for fuel cells require that they be self recharged. To translate the proven SPE cell life and stability into a highly reliable extraterrestrial electrical energy storage system, a simplification of supporting equipment is required. Static phase separation, static fluid transport and static thermal control will be most useful in producting required system reliability. Although some 200,000 SPE fuel cell hours were recorded in earth orbit with static fluid phase separation, no SPE electrolyzer has, as yet, operated in space.

Deuterium retention and release from molybdenum exposed to a Penning discharge

NASA Astrophysics Data System (ADS)

Causey, R. A.; Kunz, C. L.; Cowgill, D. F.

2005-03-01

Both molybdenum and tungsten are candidate materials for plasma-facing applications in fusion reactors. While tungsten has a higher melting point and a higher threshold for sputtering, it is a brittle material that is difficult to machine into shapes required for fusion applications. For this reason, molybdenum is now receiving serious consideration as an alternative for tungsten. If molybdenum is to be used as a plasma-facing material, the hydrogen retention and recycling characteristics must be known. In this report, we present experimental results on deuterium retention in molybdenum after exposure to a Penning discharge at temperatures from 573 to 773 K. D2+ ions with energies of 1.2 keV were implanted into the 50 mm diameter molybdenum samples at fluxes of 10 20 D/m 2 s. Thermal desorption spectroscopy was used to determine both the amount of retained deuterium and the release kinetics. Low retention values similar to those measured previously for tungsten were observed.

Isotope effect in quasi-two-dimensional metal-organic antiferromagnets

NASA Astrophysics Data System (ADS)

Goddard, P. A.; Singleton, J.; Maitland, C.; Blundell, S. J.; Lancaster, T.; Baker, P. J.; McDonald, R. D.; Cox, S.; Sengupta, P.; Manson, J. L.; Funk, K. A.; Schlueter, J. A.

2008-08-01

Although the isotope effect in superconducting materials is well documented, changes in the magnetic properties of antiferromagnets due to isotopic substitution are seldom discussed and remain poorly understood. This is perhaps surprising given the possible link between the quasi-two-dimensional (Q2D) antiferromagnetic and superconducting phases of the layered cuprates. Here we report the experimental observation of shifts in the Néel temperature and critical magnetic fields (ΔTN/TN≈4%;ΔBc/Bc≈4%) in a Q2D organic molecular antiferromagnet on substitution of hydrogen for deuterium. These compounds are characterized by strong hydrogen bonds through which the dominant superexchange is mediated. We evaluate how the in-plane and interplane exchange energies evolve as the atoms of hydrogen on different ligands are substituted, and suggest a possible mechanism for this effect in terms of the relative exchange efficiency of hydrogen and deuterium bonds.

Sodium–hydrogen exchanger NHA1 and NHA2 control sperm motility and male fertility

PubMed Central

Chen, Su-Ren; Chen, M; Deng, S-L; Hao, X-X; Wang, X-X; Liu, Y-X

2016-01-01

Our previous work identified NHA1, a testis-specific sodium–hydrogen exchanger, is specifically localized on the principal piece of mouse sperm flagellum. Our subsequent study suggested that the number of newborns and fertility rate of NHA1-vaccinated female mice are significantly stepped down. In order to define the physiological function of NHA1 in spermatozoa, we generated Nha1Fx/Fx, Zp3-Cre (hereafter called Nha1 cKO) mice and found that Nha1 cKO males were viable and subfertile with reduced sperm motility. Notably, cyclic AMP (cAMP) synthesis by soluble adenylyl cyclase (sAC) was attenuated in Nha1 cKO spermatozoa and cAMP analogs restored sperm motility. Similar to Nha1 cKO males, Nha2Fx/Fx, Zp3-Cre (hereafter called Nha2 cKO) male mice were subfertile, indicating these two Nha genes may be functionally redundant. Furthermore, we demonstrated that male mice lacking Nha1 and Nha2 genes (hereafter called Nha1/2 dKO mice) were completely infertile, with severely diminished sperm motility owing to attenuated sAC-cAMP signaling. Importantly, principal piece distribution of NHA1 in spermatozoa are phylogenetically conserved in spermatogenesis. Collectively, our data revealed that NHA1 and NHA2 function as a key sodium–hydrogen exchanger responsible for sperm motility after leaving the cauda epididymidis. PMID:27010853

Signatures of the electron saddle swaps mechanism in the photon spectra following charge-exchange collisions

NASA Astrophysics Data System (ADS)

Otranto, Sebastian

2014-10-01

During the last few years, several experimental and theoretical studies have focused on state selective charge exchange processes between charged ions and alkali metals. These data are of particular importance for the tokamak nuclear fusion reactor program, since diagnostics on the plasma usually rely on charge-exchange spectroscopy. In this sense, alkali metals, have been proposed as potential alternatives to excited hydrogen/deuterium for which laboratory experiments are not feasible at present. In this talk, we present our recent work involving ion collisions with alkali metals. Oscillatory structures in the angular differential charge-exchange cross sections obtained using the MOTRIMS technique are correctly described by classical trajectory Monte Carlo simulations. These oscillations are found to originate from the number of swaps the electron undergoes around the projectile-target potential saddle before capture takes place and are very prominent at impact energies below 10 keV/amu. Moreover, cross sections of higher order of differentiability also indicate that the swaps leave distinctive signatures in the (n,l)-state selective cross sections and in the photon line emission cross sections. Oscillatory structures for the x-ray hardness ratio parameter are also predicted. In collaboration with Ronnie Hoekstra, Zernike Institute for Advanced Materials, University of Groningen and Ronald Olson, Department of Physics, Missouri University of Science and Technology.

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.

Extending the application of deuterium excess as a tracer in surface and groundwaters

NASA Astrophysics Data System (ADS)

Hurst, S.; Krishnamurthy, R. V.

2017-12-01

Stable isotopes of surface and ground waters provide invaluable information on the processes involved in their genesis. A starting point in these applications is the relationship between hydrogen (δ2H) and oxygen (δ18O), exemplified in the so-called Global Meteoric Water Line where δ2H=8δ18O+10 [1]. From this line Dansgaard [2] defined the parameter deuterium excess where d=δ2H-8δ18O. Generally, the d-excess value is fixed at the source, predominantly the equatorial oceans and retained. At an average humidity of about 85% the expected d-excess value is 10. Deviations indicate secondary changes in the air mass or a water body thus making d-excess a useful geophysical tracer. For instance, evaporation results in a higher d-excess in the vapor. Mixing of this water vapor with overhead air mass results in precipitation exhibiting d-excess values higher than Global Meteoric Water Line [3]. Alternatively, the fraction of liquid remaining will have low d-excess and in extreme cases negative d-excess. In this case a plot of d-excess-δ2H will give a straight line with a negative slope. This can be demonstrated from pan evaporation experiments [4]. Deviation from a perfect straight line on the d-excess-δ2H plot indicates a combination of mixing from various source waters and evaporation. This study will discuss various case studies from multiple environments applying this approach using d-excess. References [1] Craig, H. Standard for Reporting Concentrations of Deuterium and Oxygen-18 in Natural Waters. Science 133, 1833-1834 (1961). [2] Dansgaard, W. Stable isotopes in precipitation. Tellus A 16: 436-468 (1964). [3] Machavaram, M. &, Krishnamurthy, R.V. Earth surface evaporative process: a case study from the Great Lakes region of the United States based on deuterium excess in precipitation. Geochim. et Cosmochem. Acta 59, 4279-4283 (1995). [4] Simpson, H.J., Hamza, M.S., & White, J.W.C. Evaporative enrichment of deuterium and 18O in arid zone irrigation. IAEA, 241

Studies of Atomic Free Radicals Stored in a Cryogenic Environment

NASA Technical Reports Server (NTRS)

Lee, David M.; Hubbard, Dorthy (Technical Monitor); Alexander, Glen (Technical Monitor)

2003-01-01

Impurity-Helium Solids are porous gel-like solids consisting of impurity atoms and molecules surrounded by thin layers of solid helium. They provide an ideal medium for matrix isolation of free radicals to prevent recombination and store chemical energy. In this work electron spin resonance, nuclear magnetic resonance, X-ray diffraction, and ultrasound techniques have all been employed to study the properties of these substances. Detailed studies via electron spin resonance of exchange tunneling chemical reactions involving hydrogen and deuterium molecular and atomic impurities in these solids have been performed and compared with theory. Concentrations of hydrogen approaching the quantum solid criterion have been produced. Structured studies involving X ray diffraction, ultrasound, and electron spin resonance have shown that the impurities in impurity helium solids are predominantly contained in impurity clusters, with each cluster being surrounded by thin layers of solid helium.

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

Direct measurements and comparisons between deuterium and impurity rotation and density profiles in the H-mode steep gradient region on DIII-D

NASA Astrophysics Data System (ADS)

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

2016-10-01

The recently commissioned edge deuterium charge exchange recombination (CER) spectroscopy diagnostic on DIII-D is providing direct measurements of the deuterium rotation, temperature, and density in H-mode pedestals. The deuterium temperature and temperature scale length can be 50 % lower than the carbon measurement in the gradient region of the pedestal, indicating that the ion pedestal pressure can deviate significantly from that inferred from carbon CER. In addition, deuterium exhibits a larger toroidal rotation in the co-Ip direction near the separatrix compared with the carbon. These differences are qualitatively consistent with theory-based models that identify thermal ion orbit loss across the separatrix as a source of intrinsic angular momentum. The first direct measurements of the deuterium density pedestal profile show an inward shift of the impurity pedestal compared with the main ions, validating neoclassical predictions from the XGC0 code. Work supported by the U.S. DOE under DE-FC02-04ER54698 and DE-AC02-09CH11466.

Another Unprecedented Wieland Mechanism Confirmed: Hydrogen Formation from Hydrogen Peroxide, Formaldehyde, and Sodium Hydroxide.

PubMed

Czochara, Robert; Litwinienko, Grzegorz; Korth, Hans-Gert; Ingold, Keith U

2018-03-26

In 1923, Wieland and Wingler reported that in the molecular hydrogen producing reaction of hydrogen peroxide with formaldehyde in basic solution, free hydrogen atoms (H . ) are not involved. They postulated that bis(hydroxymethyl)peroxide, HOCH 2 OOCH 2 OH, is the intermediate, which decomposes to yield H 2 and formate, proposing a mechanism that would nowadays be considered as a "concerted process". Since then, several other (conflicting) "mechanisms" have been suggested. Our NMR and Raman spectroscopic and kinetic studies, particularly the determination of the deuterium kinetic isotope effect (DKIE), now confirm that in this base-dependent reaction, both H atoms of H 2 derive from the CH 2 hydrogen atoms of formaldehyde, and not from the OH groups of HOCH 2 OOCH 2 OH or from water. Quantum-chemical CBS-QB3 and W1BD computations show that H 2 release proceeds through a concerted process, which is strongly accelerated by double deprotonation of HOCH 2 OOCH 2 OH, thereby ruling out a free radical pathway. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ab initio studies of hydrogen adatoms on bilayer graphene

NASA Astrophysics Data System (ADS)

Mapasha, R. E.; Ukpong, A. M.; Chetty, N.

2012-05-01

We present a comparative density functional study of the adsorption of hydrogen on bilayer graphene. Six different exchange-correlation functionals are employed to explore the possible configurations of hydrogen adsorption at 50% coverage. Using the four variants of the nonlocal van der Waals density functional, we identify three distinct competing configurations that retain the coupled bilayer structure at 0 K. One of the configurations undergoes a spontaneous transformation from hexagonal to tetrahedral structure, under hydrogenation, with heat of formation ranging between -0.03 eV (vdW-DF) and -0.37 eV (vdW-DFC09x). This configuration has a finite band gap of around 3 eV, whereas all other competing configurations are either semimetallic or metallic. We also find two unique low-energy competing configurations of decoupled bilayer graphene, and therefore suggest the possibility of graphene exfoliation by hydrogen intercalation.

EFFECT OF DEUTERIUM OXIDE ON THE REPRODUCTIVE POTENTIAL OF MICE

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

Czajka, D.M.; Finkel, A.J.

1960-11-25

Replacement of hydrogen with deuterium by the administration of 25% D/ sub 2/O in the drinkng water resulted in certain alterations in the reproductive potential of female mice, These changes included an apparent decrease in the number of pregnancies carried close to term, an increase in the incidence of wholly nonviable litters, and a decrease in the survival of newborn mice. Examination of uterine contents late in pregnancy, however, revealed that neither the incidence of pregnancy nor the mean number of implanted embryos per pregnant female was correlated with the duration of deuteration. Reduction of the incidence of viable newbornmore » mice in part reflected the increase in nonviability of fetuses examined in utero late in gestation and in part may have been the result of maternal cannibalism. Reduction of fetal viability was greatest when the dams had been substantially deuterated at the time of implantation of the fetus, which occurred at about the fifth day after mating. When the administration of deuterium to female mice preceded mating by 1 week, the higher the level of deuteration, the lower was the total fetal viability. A critical level appeared to exist here between 25 and 30 at.% deuterium in the drinking water, above which fetal viability ceased. The reduction of mean litter size and of viability of the newbern was at least partly reversible by restoring the dams to ordinary drinking water. (auth)« less

A counter-intuitive approach to calculating non-exchangeable 2H isotopic composition of hair: treating the molar exchange fraction fE as a process-related rather than compound-specific variable

USGS Publications Warehouse

Landwehr, J.M.; Meier-Augenstein, W.; Kemp, H.F.

2011-01-01

Hair is a keratinous tissue that incorporates hydrogen from material that an animal consumes but it is metabolically inert following synthesis. The stable hydrogen isotope composition of hair has been used in ecological studies to track migrations of mammals as well as for forensic and archaeological purposes to determine the provenance of human remains or the recent geographic life trajectory of living people. Measurement of the total hydrogen isotopic composition of a hair sample yields a composite value comprised of both metabolically informative, non-exchangeable hydrogen and exchangeable hydrogen, with the latter reflecting ambient or sample preparation conditions. Neither of these attributes is directly measurable, and the non-exchangeable hydrogen composition is obtained by estimation using a commonly applied mathematical expression incorporating sample measurements obtained from two distinct equilibration procedures. This commonly used approach treats the fraction of exchangeable hydrogen as a mixing ratio, with a minimal procedural fractionation factor assumed to be close or equal to 1. Instead, we propose to use full molar ratios to derive an expression for the non-exchangeable hydrogen composition explicitly as a function of both the procedural fractionation factor α and the molar hydrogen exchange fraction fE. We apply these derivations in a longitudinal study of a hair sample and demonstrate that the molar hydrogen exchange fraction fE should, like the procedural fractionation factor α, be treated as a process-dependent parameter, i.e. a reaction-specific constant. This is a counter-intuitive notion given that maximum theoretical values for the molar hydrogen exchange fraction fE can be calculated that are arguably protein-type specific and, as such, fE could be regarded as a compound-specific constant. We also make some additional suggestions for future approaches to determine the non-exchangeable hydrogen composition of hair and the use of

Pressure-induced orientational glass phase in molecular para-hydrogen.

PubMed

Schelkacheva, T I; Tareyeva, E E; Chtchelkatchev, N M

2009-02-01

We propose a theoretical description of a possible orientational glass transition in solid molecular para-hydrogen and ortho-deuterium under pressure supposing that they are mixtures of J=0 and J=2 states of molecules. The theory uses the basic concepts and methods of standard spin-glass theory. We expect our orientational glass to correspond to the II' phase of the high-pressure hydrogen phase diagram.

Liquid-solid phase transition of hydrogen and deuterium in silica aerogel

NASA Astrophysics Data System (ADS)

Van Cleve, E.; Worsley, M. A.; Kucheyev, S. O.

2014-10-01

Behavior of hydrogen isotopes confined in disordered low-density nanoporous solids remains essentially unknown. Here, we use relaxation calorimetry to study freezing and melting of H2 and D2 in an ˜85%-porous base-catalyzed silica aerogel. We find that liquid-solid transition temperatures of both isotopes inside the aerogel are depressed. The phase transition takes place over a wide temperature range of ˜4 K and non-trivially depends on the liquid filling fraction, reflecting the broad pore size distribution in the aerogel. Undercooling is observed for both H2 and D2 confined inside the aerogel monolith. Results for H2 and D2 are extrapolated to tritium-containing hydrogens with the quantum law of corresponding states.

Cosmic Deuterium and Social Networking Software

NASA Astrophysics Data System (ADS)

Pasachoff, J. M.; Suer, T.-A.; Lubowich, D. A.; Glaisyer, T.

2006-08-01

For the education of newcomers to a scientific field and for the convenience of students and workers in the field, it is helpful to have all the basic scientific papers gathered. For the study of deuterium in the Universe, in 2004-5 we set up http://www.cosmicdeuterium.info with clickable links to all the historic and basic papers in the field and to many of the current papers. Cosmic deuterium is especially important because all deuterium in the Universe was formed in the epoch of nucleosynthesis in the first 1000 seconds after the Big Bang, so study of its relative abundance (D:H~1:100,000) gives us information about those first minutes of the Universe's life. Thus the understanding of cosmic deuterium is one of the pillars of modern cosmology, joining the cosmic expansion, the 3 degree cosmic background radiation, and the ripples in that background radiation. Studies of deuterium are also important for understanding Galactic chemical evolution, astrochemistry, interstellar processes, and planetary formation. Some papers had to be scanned while others are available at the Astrophysical Data System, adswww.harvard.edu, or to publishers' Websites. By 2006, social networking software (http:tinyurl.com/ zx5hk) had advanced with popular sites like facebook.com and MySpace.com; the Astrophysical Data System had even set up MyADS. Social tagging software sites like http://del.icio.us have made it easy to share sets of links to papers already available online. We have set up http://del.icio.us/deuterium to provide links to many of the papers on cosmicdeuterium.info, furthering previous del.icio.us work on /eclipses and /plutocharon. It is easy for the site owner to add links to a del.icio.us site; it takes merely clicking on a button on the browser screen once the site is opened and the desired link is viewed in a browser. Categorizing different topics by keywords allows subsets to be easily displayed. The opportunity to expose knowledge and build an ecosystem of web

Deuterium-lithium plasma as a source of fusion neutrons

NASA Astrophysics Data System (ADS)

Chirkov, A. Yu; Vesnin, V. R.

2017-11-01

The concepts of deuterium-tritium (D-T) fusion neutron source are currently developed for hybrid fusion-fission systems and the waste transmutation ones. The need to use tritium technologies is a deterrent factor in this promising direction of energy production. Potential possibilities of using systems that do not require tritium developments are of a significant interest. A deuterium-deuterium (D-D) reaction is considered for the use in demonstration fusion neutron sources. The product of this reaction is tritium, which will burn in the plasma with the emission of fast neutrons. D-D reaction is significantly slower then D-T reaction. Present study shows an increase in neutron yield using a powerful injection of the beam of deuterium atoms. The reactions of the deuterium with lithium isotopes are considered. In some of these reactions, fast neutrons can be obtained. The results of the calculation of the neutron yield from the deuterium lithium plasma are discussed. The estimates of the parameters needed for the realization of a source of fusion neutrons are presented.

CATALYTIC PROPERTIES OF SEMICONDUCTORS.

DTIC Science & Technology

SEMICONDUCTORS, CATALYSTS), (*CATALYSIS, REACTION KINETICS), (* SODIUM COMPOUNDS, TUNGSTATES), (*GALLIUM ALLOYS, ARSENIC ALLOYS), (*YTTERBIUM...COMPOUNDS, SILICIDES ), (*GERMANIUM, CATALYSIS), INTERNAL CONVERSION, EXCHANGE REACTIONS, HEAT OF ACTIVATION, THERMODYNAMICS, DEUTERIUM, POWDERS, SURFACES, HYDROGEN

Cytology is advanced by studying effects of deuterium environment

NASA Technical Reports Server (NTRS)

Bose, S.; Crespi, H. L.; Flaumenhaft, E.; Katz, J. J.

1967-01-01

Research of deuterium effects on biological systems shows deuteriation is not incompatible with life. With the successful cultivation of deuteriated bacteria, work is now being done on extraction of deuterio-compounds from bacteria.

Gas-driven permeation of deuterium through tungsten and tungsten alloys

DOE PAGES

Buchenauer, Dean A.; Karnesky, Richard A.; Fang, Zhigang Zak; ...

2016-03-25

Here, to address the transport and trapping of hydrogen isotopes, several permeation experiments are being pursued at both Sandia National Laboratories (deuterium gas-driven permeation) and Idaho National Laboratories (tritium gas- and plasma-driven tritium permeation). These experiments are in part a collaboration between the US and Japan to study the performance of tungsten at divertor relevant temperatures (PHENIX). Here we report on the development of a high temperature (≤1150 °C) gas-driven permeation cell and initial measurements of deuterium permeation in several types of tungsten: high purity tungsten foil, ITER-grade tungsten (grains oriented through the membrane), and dispersoid-strengthened ultra-fine grain (UFG) tungstenmore » being developed in the US. Experiments were performed at 500–1000 °C and 0.1–1.0 atm D 2 pressure. Permeation through ITER-grade tungsten was similar to earlier W experiments by Frauenfelder (1968–69) and Zaharakov (1973). Data from the UFG alloy indicates marginally higher permeability (< 10×) at lower temperatures, but the permeability converges to that of the ITER tungsten at 1000 °C. The permeation cell uses only ceramic and graphite materials in the hot zone to reduce the possibility for oxidation of the sample membrane. Sealing pressure is applied externally, thereby allowing for elevation of the temperature for brittle membranes above the ductile-to-brittle transition temperature.« less

Composition and evolution of the atmosphere of Venus

NASA Technical Reports Server (NTRS)

Donahue, Thomas (Principal Investigator)

1996-01-01

The contract year started by analyzing Jovian atmospheric data acquired by the Galileo Probe Mass Spectrometer (GPMS). Two Venus hydrogen projects got underway as well. The first study strives to understand how to reconcile the standard treatment of the evolution of the H2O and HDO resevoirs on Venus over 4.5 Gyr in the presence of H and D escape and injection by comets. The second study is calculating the charge exchange contribution to hydrogen loss rates, using realistic models for exospheric H, H(+), D, D(+), and ion temperature from PV data. This report includes the following papers as attachments and supporting data: 'The Galileo Probe Mass Spectrometer: Composition of Jupiter's Atmosphere'; 'Chemical Composition Measurements of the Atmosphere of Jupiter with the Galileo Probe Mass Spectrometer'; 'Ion/Neutral Escape of Hydrogen and Deuterium: Evolution of Water'; 'Hydrogen and Deuterium in the Thermosphere of Venus: Solar Cycle Variations and Escape'; and 'Solar Cycle Variations in H(+) and D(+) Densities in the Venus Ionosphere: Implications for Escape'.

Liquid–solid phase transition of hydrogen and deuterium in silica aerogel

DOE PAGES

Van Cleve, E.; Worsley, M. A.; Kucheyev, S. O.

2014-10-30

Behavior of hydrogen isotopes confined in disordered low-density nanoporous solids remains essentially unknown. Here, we use relaxation calorimetry to study freezing and melting of H 2 and D 2 in an ~85%-porous base-catalyzed silica aerogel. In this work, we find that liquid–solid transition temperatures of both isotopes inside the aerogel are depressed. The phase transition takes place over a wide temperature range of ~4 K and non-trivially depends on the liquid filling fraction, reflecting the broad pore size distribution in the aerogel. Undercooling is observed for both H 2 and D 2 confined inside the aerogel monolith. Lastly, results formore » H 2 and D 2 are extrapolated to tritium-containing hydrogens with the quantum law of corresponding states.« less

Liquid–solid phase transition of hydrogen and deuterium in silica aerogel

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

Van Cleve, E.; Worsley, M. A.; Kucheyev, S. O., E-mail: kucheyev@llnl.gov

2014-10-28

Behavior of hydrogen isotopes confined in disordered low-density nanoporous solids remains essentially unknown. Here, we use relaxation calorimetry to study freezing and melting of H{sub 2} and D{sub 2} in an ∼85%-porous base-catalyzed silica aerogel. We find that liquid–solid transition temperatures of both isotopes inside the aerogel are depressed. The phase transition takes place over a wide temperature range of ∼4 K and non-trivially depends on the liquid filling fraction, reflecting the broad pore size distribution in the aerogel. Undercooling is observed for both H{sub 2} and D{sub 2} confined inside the aerogel monolith. Results for H{sub 2} and D{sub 2}more » are extrapolated to tritium-containing hydrogens with the quantum law of corresponding states.« less

The solubility of hydrogen and deuterium in alloyed, unalloyed and impure plutonium metal

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

Richmond, Scott; Bridgewater, Jon S; Ward, John W

2010-01-01

Hydrogen is exothermically absorbed in many transition metals, all rare earths and the actinides. The hydrogen gas adsorbs, dissociates and diffuses into these metals as atomic hydrogen. Absorbed hydrogen is generally detrimental to Pu, altering its properties and greatly enhancing corrosion. Measuring the heat of solution of hydrogen in Pu and its alloys provides significant insight into the thermodynamics driving these changes. Hydrogen is present in all Pu metal unless great care is taken to avoid it. Heats of solution and formation are provided along with evidence for spinodal decomposition.

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

A Dosimetry Study of Deuterium-Deuterium Neutron Generator-based In Vivo Neutron Activation Analysis.

PubMed

Sowers, Daniel; Liu, Yingzi; Mostafaei, Farshad; Blake, Scott; Nie, Linda H

2015-12-01

A neutron irradiation cavity for in vivo neutron activation analysis (IVNAA) to detect manganese, aluminum, and other potentially toxic elements in human hand bone has been designed and its dosimetric specifications measured. The neutron source is a customized deuterium-deuterium neutron generator that produces neutrons at 2.45 MeV by the fusion reaction 2H(d, n)3He at a calculated flux of 7 × 10(8) ± 30% s(-1). A moderator/reflector/shielding [5 cm high density polyethylene (HDPE), 5.3 cm graphite and 5.7 cm borated (HDPE)] assembly has been designed and built to maximize the thermal neutron flux inside the hand irradiation cavity and to reduce the extremity dose and effective dose to the human subject. Lead sheets are used to attenuate bremsstrahlung x rays and activation gammas. A Monte Carlo simulation (MCNP6) was used to model the system and calculate extremity dose. The extremity dose was measured with neutron and photon sensitive film badges and Fuji electronic pocket dosimeters (EPD). The neutron ambient dose outside the shielding was measured by Fuji NSN3, and the photon dose was measured by a Bicron MicroREM scintillator. Neutron extremity dose was calculated to be 32.3 mSv using MCNP6 simulations given a 10-min IVNAA measurement of manganese. Measurements by EPD and film badge indicate hand dose to be 31.7 ± 0.8 mSv for neutrons and 4.2 ± 0.2 mSv for photons for 10 min; whole body effective dose was calculated conservatively to be 0.052 mSv. Experimental values closely match values obtained from MCNP6 simulations. These are acceptable doses to apply the technology for a manganese toxicity study in a human population.

Molecular processes in astrophysics: Calculations of hydrogen + hydrogen gas excitation, de-excitation, and cooling

NASA Astrophysics Data System (ADS)

Kelley, Matthew Thomas

The implications of H+H2 cooling in astrophysics is important to several applications. One of the most significant and pure applications is its role in cooling in the early universe. Other applications would include molecular dynamics in nebulae and their collapse into stars and astrophysical shocks. Shortly after the big bang, the universe was a hot primordial gas of photons, electrons, and nuclei among other ingredients. By far the most dominant nuclei in the early universe was hydrogen. In fact, in the early universe the matter density was 90 percent hydrogen and only 10 percent helium with small amounts of lithium and deuterium. In order for structure to form in the universe, this primordial gas must form atoms and cool. One of the significant cooling mechanisms is the collision of neutral atomic hydrogen with a neutral diatomic hydrogen molecule. This work performs calculations to determine collisional cooling rates of hydrogen using two potential surfaces.

Molecular dynamics simulations of interactions between hydrogen and fusion-relevant materials

NASA Astrophysics Data System (ADS)

de Rooij, E. D.

2010-02-01

sticking probability of small hydrocarbons is highest on material previously subjected to the highest hydrogen flux. This result suggests that redeposition is more effective under high than under low hydrogen fluxes, partly explaining the experimentally observed reduction in the carbon erosion yield. Lastly, we studied amorphous tungsten carbide. Amorphous material with three different carbon percentages (15, 50 and 95%) was subjected to deuterium bombardment and the resulting erosion and deuterium retention was analysed. The 95% carbon sample behaves like doped carbon, the carbon erosion yield is reduced and no tungsten is eroded. Segregation of the materials was observed, resulting in an accumulation of tungsten at the surface. The hydrogen retention was similar to a-C:H. The 15% carbon sample showed no significant erosion or retention. The most interesting was the 50% sample. Here deuterium bubbles formed that burst open after sufficiently long bombardment, thereby removing both carbon and tungsten from the surface. In the context of ITER our MD simulations suggest that tungsten is the better suited material since both the erosion and the hydrogen retention are significantly lower than for carbon.

EFFECTS OF DEUTERIUM OXIDE UPON POLIOVIRUS MULTIPLICATION

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

Carp, R.I.; Kritchevsky, D.; Koprowski, H.

1960-09-01

The effects of deuterium oxide on the multiplication of CHAT, an attenuated type of poliomyeliths virus, was studied in cells of HeLa and of monkey kidney cells in primary cultures. Yields of virus obtained from deuterated cells were consistently higher than those obtained from controls. The incorporation of deuterium oxide in the growth media resulted in an increase in the average plague size of polio virus. (C.H.)

Possibility of deuterium free water using as antitumoral means with reference to conditions of Martian expedition

NASA Astrophysics Data System (ADS)

Sinyak, Y.; Turusov, V.; Grigroriev, A.; Yaridze, D.; Gaidadimov, V.; Antoshina, E.; Gorkova, T.; Truhanova, L.

The interplanetary space flights, Martian program as an example, will take place under conditions of increasing radiation level on crew. The search of methods for a decrease of oncologic risk produced by irradiation of astronauts, is one of the major factors of a successful implementation of a flight program. One of such methods is a usage by crew of potable water with the reduced concentrations of a heavy stable isotope of hydrogen - deuterium, which can be obtained in the regenerative life support systems. The heavy water (D2O) has toxic properties, distorting biochemical reactions in the cell, inhibiting process of DNA replication. It can be presumed that the replacement of deuterium in the water for protium will result in normalization of cell metabolism, reparation will take place and this will lead to the inhibition of tumour development. In this study the water with a decreased by 65% of deuterium was used. Antitumour properties of D 2-free water were studied with transplantable Lewis lung carcinoma in BDF1 strain of mice. First results show that average time of appearance of the first nodules at the site of transplantation was 14 % longer in mice fed D 2-free water as compared to control. The tumour volume in the experimental group (decreased content of D2 ) was always lower than in the control. Statistically significant differences in the tumour volume were registered at the 13, 15, 23, 26 and 28 -th days after transplantation. Inhibition of tumour growth was equal to 100% and 51% at the 5 th and 15-th days after- transplantation respectively. Increase of life span in the experimental group was 10%. The results indicate that the use by astronauts of water with decreased content of deuterium may decrease the risk of oncological diseases under conditions of high radiation level in the flight to Mars.

Hydrogen-transfer and charge-transfer in photochemical and radiation induced reactions. Progress report, November 1, 1975--October 31, 1976

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

Cohen, S.G.

The relative importance of light absorption, quenching of triplet, and hydrogen transfer repair has been examined in retardation by mercaptans of photoreduction of aromatic ketones by alcohols. In the reduction of benzophenone by 2-propanol, retardation is efficient and, after correction for the first two effects, is due entirely to hydrogen-transfer repair, as indicated by deuterium labeling. In reduction of acetophenone by ..cap alpha..-methylbenzyl alcohol, repair by hydrogen transfer is also operative. In reduction of benzophenone by benzhydrol, retardation is less efficient and is due to quenching, as the ketyl radical does not abstract hydrogen from mercaptan rapidly in competition withmore » coupling. Deuterium isotope effects are discussed in terms of competitive reactions. Photoreduction of benzophenone by 2-butylamine and by triethylamine is retarded by aromatic mercaptans and disulfides. Of the retardation not due to light absorption and triplet quenching by the sulfur compounds, half is due to hydrogen-transfer repair, as indicated by racemization and deuterium labeling. The remainder is attributed to quenching by the sulfur compound of the charge-transfer-complex intermediate. Photoreduction by primary and secondary amines, but not by tertiary amines, is accelerated by aliphatic mercaptans. The acceleration is attributed to catalysis of hydrogen transfer by the mercaptan in the charge-transfer complex. The effect is large in hydrocarbon solvent, less in polar organic solvents and absent in water.« less

Modelling third harmonic ion cyclotron acceleration of deuterium beams for JET fusion product studies experiments

NASA Astrophysics Data System (ADS)

Schneider, M.; Johnson, T.; Dumont, R.; Eriksson, J.; Eriksson, L.-G.; Giacomelli, L.; Girardo, J.-B.; Hellsten, T.; Khilkevitch, E.; Kiptily, V. G.; Koskela, T.; Mantsinen, M.; Nocente, M.; Salewski, M.; Sharapov, S. E.; Shevelev, A. E.; Contributors, JET

2016-11-01

Recent JET experiments have been dedicated to the studies of fusion reactions between deuterium (D) and Helium-3 (3He) ions using neutral beam injection (NBI) in synergy with third harmonic ion cyclotron radio-frequency heating (ICRH) of the beam. This scenario generates a fast ion deuterium tail enhancing DD and D3He fusion reactions. Modelling and measuring the fast deuterium tail accurately is essential for quantifying the fusion products. This paper presents the modelling of the D distribution function resulting from the NBI+ICRF heating scheme, reinforced by a comparison with dedicated JET fast ion diagnostics, showing an overall good agreement. Finally, a sawtooth activity for these experiments has been observed and interpreted using SPOT/RFOF simulations in the framework of Porcelli’s theoretical model, where NBI+ICRH accelerated ions are found to have a strong stabilizing effect, leading to monster sawteeth.

Identification of trapped and boundary lipid binding sites in M13 coat protein/lipid complexes by deuterium NMR spectroscopy

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

Van Gorkom, L.C.; Horvath, L.I.; Hemminga, M.A.

The major coat protein of M13 bacteriophage has been incorporated into bilayers of 1,2-dimyristoyl-sn-glycero-3-phosphocholine, deuterated in the trimethyl segments of the choline headgroup (DMPC-d9). Two-component deuterium and phosphorus-31 NMR spectra have been observed from bilayer complexes containing the coat protein, indicating slow exchange (on the deuterium quadrupole anisotropy and phosphorus-31 chemical shift averaging time scales) of lipid molecules of less than 10(3) Hz between two motionally distinct environments in the complexes. The fraction of the isotropic spectral component increases with increasing M13 protein concentration, and this component is attributed to lipid headgroups, which are disordered relative to their order inmore » protein-free bilayers. The activation energy of the fast local motions of the trimethyl groups of the choline residue in the headgroup decreases from 23 kJ mol-1 in the pure lipid bilayers to 20 kJ mol-1 for the protein-associated lipid headgroups. The chemical exchange rate of lipid molecules between the two motionally distinct environments has been estimated to be 20-50 Hz by steady-state line-shape simulations of the deuterium spectra of DMPC-d9/M13 coat protein complexes using exchange-coupled modified Bloch equations. The off-rate was, as expected from one-to-one exchange, independent of the L/P ratio; tau off -1 = 0.23 kHz. It is suggested that the protein-associated lipid may be trapped between closely packed parallel aggregates of M13 coat protein and that the high local concentration of protein in a one-dimensional arrangement in lipid bilayers may be required for the fast reassembly of phage particles before release from an infected cell.« less

Diffusion of helium, hydrogen and deuterium in diamond: Experiment, theory and geochemical applications

NASA Astrophysics Data System (ADS)

Cherniak, D. J.; Watson, E. B.; Meunier, V.; Kharche, N.

2018-07-01

Diffusivities of helium, deuterium and hydrogen have been characterized in diamond. Polished CVD diamond was implanted with either 3He, 2H, or 1H. Implanted samples were sealed under vacuum in silica glass capsules, and annealed in 1-atm furnaces. 3He, 2H and 1H distributions were measured with Nuclear Reaction Analysis. We obtain these Arrhenius relations: DHe = 4.00 × 10-15 exp(-138 ± 14 kJ mol-1/RT) m2 s-1. D2H = 1.02 × 10-4 exp(-262 ± 17 kJ mol-1/RT) m2 s-1. D1H = 2.60 × 10-4 exp(-267 ± 15 kJ mol-1/RT) m2 s-1. Diffusivities of 1H and 2H agree within experimental uncertainties, indicating little diffusive mass fractionation of hydrogen in diamond. To complement the experimental measurements, we performed calculations using a first-principles quantum mechanical description of diffusion in diamond within the Density Functional Theory (DFT). Differences in 1H and 2H diffusivities from calculations are found to be ∼4.5%, reflected in differences in the pre-exponential factor. This small difference in diffusivities, despite the large relative mass difference between these isotopes, is due to the fact that the atomistic process involved in the transition along the diffusion pathway is dictated by local changes to the diamond structures rather than to vibrations involving 1H/2H. This finding is consistent with the experimental results given experimental uncertainties. In contrast, calculations for helium diffusion in diamond indicate a difference of 15% between diffusivities of 3He and 4He. Calculations of diffusion distances for hydrogen using our data yield a distance of 50 μm in diamond in 300,000 years at 500 °C and ∼30 min at 1400 °C. Diffusion distances for He in diamond are shorter than for H at all temperatures above ∼350 °C, but differences increase dramatically with temperature because of the higher activation energy for H diffusion. For example, a 50 μm diffusion distance for He would be attained in ∼40 Myr at 500 °C and 400 yr at 1400 �

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

Isotopic Exchange HPLC-HRMS/MS Applied to Cyclic Proanthocyanidins in Wine and Cranberries

NASA Astrophysics Data System (ADS)

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

2018-01-01

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

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.

Furfural to Furfuryl Alcohol: Computational Study of the Hydrogen Transfer on Lewis Acidic BEA Zeolites and Effects of Cation Exchange and Tetravalent Metal Substitution.

PubMed

Prasertsab, Anittha; Maihom, Thana; Probst, Michael; Wattanakit, Chularat; Limtrakul, Jumras

2018-06-04

The hydrogen transfer of furfural to furfuryl alcohol with i-propanol as the hydrogen source over cation-exchanged Lewis acidic BEA zeolite has been investigated by means of density functional calculations. The reaction proceeds in three steps. First the O-H bond of i-propanol is broken to form a propoxide intermediate. After that, the furylmethoxy intermediate is formed via hydrogen transfer process, and finally furylmethoxy abstracts the proton to form the furfuryl alcohol product. The second step is rate-determining by requiring the highest activation energy (23.8 kcal/mol) if the reaction takes place on Li-Sn-BEA zeolite. We find that the catalytic activity of various cation-exchanged Sn-BEA zeolites is in the order Li-Sn-BEA > Na-Sn-BEA > K-Sn-BEA. The lower activation energy for Li-Sn-BEA compared to Na-Sn-BEA and K-Sn-BEA can be explained by the larger charge transfer from the carbonyl bond to the catalyst, leading to its activation and to the attraction of the hydrogen being transferred. The larger charge transfer in turn is due to the smaller gap between the energies of furfural HOMO and the zeolite LUMO in Li-Sn-BEA, compared to both Na-Sn-BEA and K-Sn-BEA. In a similar way, we also compare the catalytic activity of tetravalent metal centers (Sn, Zr, and Hf) substituted into BEA and find in the order Zr ≥ Hf > Sn, based on activation energies. Finally we investigate statistically which property of the reactants is a suitable descriptor for an approximative prediction of the reaction rate in order to be able to quickly screen promising catalytic materials for this reaction.

Defect annealing and thermal desorption of deuterium in low dose HFIR neutron-irradiated tungsten

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

Masashi Shimada; M. Hara; T. Otsuka

2014-05-01

Accurately estimating tritium retention in plasma facing components (PFCs) and minimizing its uncertainty are key safety issues for licensing future fusion power reactors. D-T fusion reactions produce 14.1 MeV neutrons that activate PFCs and create radiation defects throughout the bulk of the material of these components. Recent studies show that tritium migrates and is trapped in bulk (>> 10 µm) tungsten beyond the detection range of nuclear reaction analysis technique [1-2], and thermal desorption spectroscopy (TDS) technique becomes the only established diagnostic that can reveal hydrogen isotope behavior in in bulk (>> 10 µm) tungsten. Radiation damage and its recoverymore » mechanisms in neutron-irradiated tungsten are still poorly understood, and neutron-irradiation data of tungsten is very limited. In this paper, systematic investigations with repeated plasma exposures and thermal desorption are performed to study defect annealing and thermal desorption of deuterium in low dose neutron-irradiated tungsten. Three tungsten samples (99.99 at. % purity from A.L.M.T. Co., Japan) irradiated at High Flux Isotope Reactor at Oak Ridge National Laboratory were exposed to high flux (ion flux of (0.5-1.0)x1022 m-2s-1 and ion fluence of 1x1026 m-2) deuterium plasma at three different temperatures (100, 200, and 500 °C) in Tritium Plasma Experiment at Idaho National Laboratory. Subsequently, thermal desorption spectroscopy (TDS) was performed with a ramp rate of 10 °C/min up to 900 °C, and the samples were annealed at 900 °C for 0.5 hour. These procedures were repeated three (for 100 and 200 °C samples) and four (for 500 °C sample) times to uncover damage recovery mechanisms and its effects on deuterium behavior. The results show that deuterium retention decreases approximately 90, 75, and 66 % for 100, 200, and 500 °C, respectively after each annealing. When subjected to the same TDS recipe, the desorption temperature shifts from 800 °C to 600 °C after 1st

The stereospecificity and catalytic efficiency of the tryptophan synthase-catalysed exchange of the α-protons of amino acids

PubMed Central

2004-01-01

13C-NMR has been used to follow the tryptophan synthase (EC 4.2.1.20) catalysed hydrogen–deuterium exchange of the pro-2R and pro-2S protons of [2-13C]glycine at pH 7.8. 1H-NMR has also been used to follow the tryptophan-synthase-catalysed hydrogen–deuterium exchange of the α-protons of a range of L- and D-amino acids at pH 7.8. The pKa values of the α-protons of these amino acids have been estimated and we have determined whether or not their exchange rates can be predicted from their pKa values. With the exception of tryptophan and norleucine, the stereospecificities of the first-order α-proton exchange rates are independent of the size and electronegativity of the amino acid R-group. Similar results are obtained with the second-order α-proton exchange rates, except that both L-tryptophan and L-serine have much higher stereospecificities than all the other amino acids studied. PMID:15107013

Methods for measuring exchangeable protons in glycosaminoglycans.

PubMed

Beecher, Consuelo N; Larive, Cynthia K

2015-01-01

Recent NMR studies of the exchangeable protons of GAGs in aqueous solution, including those of the amide, sulfamate, and hydroxyl moieties, have demonstrated potential for the detection of intramolecular hydrogen bonds, providing insights into secondary structure preferences. GAG amide protons are observable by NMR over wide pH and temperature ranges; however, specific solution conditions are required to reduce the exchange rate of the sulfamate and hydroxyl protons and allow their detection by NMR. Building on the vast body of knowledge on detection of hydrogen bonds in peptides and proteins, a variety of methods can be used to identify hydrogen bonds in GAGs including temperature coefficient measurements, evaluation of chemical shift differences between oligo- and monosaccharides, and relative exchange rates measured through line shape analysis and EXSY spectra. Emerging strategies to allow direct detection of hydrogen bonds through heteronuclear couplings offer promise for the future. Molecular dynamic simulations are important in this effort both to predict and confirm hydrogen bond donors and acceptors.

Mechanism of Pd(NHC)-catalyzed transfer hydrogenation of alkynes.

PubMed

Hauwert, Peter; Boerleider, Romilda; Warsink, Stefan; Weigand, Jan J; Elsevier, Cornelis J

2010-12-01

The transfer semihydrogenation of alkynes to (Z)-alkenes shows excellent chemo- and stereoselectivity when using a zerovalent palladium(NHC)(maleic anhydride)-complex as precatalyst and triethylammonium formate as hydrogen donor. Studies on the kinetics under reaction conditions showed a broken positive order in substrate and first order in catalyst and hydrogen donor. Deuterium-labeling studies on the hydrogen donor showed that both hydrogens of formic acid display a primary kinetic isotope effect, indicating that proton and hydride transfers are separate rate-determining steps. By monitoring the reaction with NMR, we observed the presence of a coordinated formate anion and found that part of the maleic anhydride remains coordinated during the reaction. From these observations, we propose a mechanism in which hydrogen transfer from coordinated formate anion to zerovalent palladium(NHC)(MA)(alkyne)-complex is followed by migratory insertion of hydride, after which the product alkene is liberated by proton transfer from the triethylammonium cation. The explanation for the high selectivity observed lies in the competition between strongly coordinating solvent and alkyne for a Pd(alkene)-intermediate.

A high deuterium abundance at redshift z = 0.7.

PubMed

Webb, J K; Carswell, R F; Lanzetta, K M; Ferlet, R; Lemoine, M; Vidal-Madjar, A; Bowen, D V

1997-07-17

Of the light elements, the primordial abundance of deuterium relative to hydrogen, (D/H)p, provides the most sensitive diagnostic for the cosmological mass density parameter, omegaB. Recent high-redshift D/H measurements are highly discrepant, although this may reflect observational uncertainties. The larger primordial D/H values imply a low omegaB (requiring the Universe to be dominated by non-baryonic matter), and cause problems for galactic chemical evolution models, which have difficulty in reproducing the steep decline in D/H to the present-day values. Conversely, the lower D/H values measured at high redshift imply an omegaB greater than that derived from 7Li and 4He abundance measurements, and may require a deuterium-abundance evolution that is too low to easily explain. Here we report the first measurement of D/H at intermediate redshift (z = 0.7010), in a gas cloud selected to minimize observational uncertainties. Our analysis yields a value of D/H ((2.0 +/- 0.5) x 10[-4]) which is at the upper end of the range of values measured at high redshifts. This finding, together with other independent observations, suggests that there may be inhomogeneity in (D/H)p of at least a factor of ten.

Implanted Deuterium Retention and Release in Carbon-Coated Beryllium

NASA Astrophysics Data System (ADS)

Anderl, R. A.; Longhurst, G. R.; Pawelko, R. J.; Oates, M. A.

1997-06-01

Deuterium implantation experiments have been conducted on samples of clean and carbon-coated beryllium. These studies entailed preparation and characterization of beryllium samples coated with carbon thicknesses of 100, 500, and 1000 Å. Heat treatment of a beryllium sample coated with carbon to a thickness of approximately 100 Å revealed that exposure to a temperature of 400°C under high vacuum conditions was sufficient to cause substantial diffusion of beryllium through the carbon layer, resulting in more beryllium than carbon at the surface. Comparable concentrations of carbon and beryllium were observed in the bulk of the coating layer. Higher than expected oxygen levels were observed throughout the coating layer as well. Samples were exposed to deuterium implantation followed by thermal desorption without exposure to air. Differences were observed in deuterium retention and postimplantation release behavior in the carbon-coated samples as compared with bare samples. For comparable implantation conditions (sample temperature of 400°C and an incident deuterium flux of approximately 6 × 1019 D/m2-s), the quantity of deuterium retained in the bare sample was less than that retained in the carbon-coated samples. Further, the release of the deuterium took place at lower temperatures for the bare beryllium surfaces than for carbon-coated beryllium samples.

Kinetics of exchange between zero-, one-, and two-hydrogen-bonded states of methyl and ethyl acetate in methanol.

PubMed

Chuntonov, Lev; Pazos, Ileana M; Ma, Jianqiang; Gai, Feng

2015-03-26

It has recently been shown that the ester carbonyl stretching vibration can be used as a sensitive probe of local electrostatic field in molecular systems. To further characterize this vibrational probe and extend its potential applications, we studied the kinetics of chemical exchange between differently hydrogen-bonded (H-bonded) ester carbonyl groups of methyl acetate (MA) and ethyl acetate (EA) in methanol. We found that, while both MA and EA can form zero, one, or two H-bonds with the solvent, the population of the 2hb state in MA is significantly smaller than that in EA. Using a combination of linear and nonlinear infrared measurements and numerical simulations, we further determined the rate constants for the exchange between these differently H-bonded states. We found that for MA the chemical exchange reaction between the two dominant states (i.e., 0hb and 1hb states) has a relaxation rate constant of 0.14 ps(-1), whereas for EA the three-state chemical exchange reaction occurs in a predominantly sequential manner with the following relaxation rate constants: 0.11 ps(-1) for exchange between 0hb and 1hb states and 0.12 ps(-1) for exchange between 1hb and 2hb states.

Study of Hydrogen Production Method using Latent Heat of Liquefied Natural Gas

NASA Astrophysics Data System (ADS)

Ogawa, Masaru; Seki, Tatsuyoshi; Honda, Hiroshi; Nakamura, Motomu; Takatani, Yoshiaki

In recent years, Fuel Cell Electrical Vehicle is expected to improve urban environment. Particularly a hydrogen fuel type FCEV expected for urban use, because its excellent characters such as short startup time, high responsibility and zero emission. On the other hand, as far as hydrogen production is concerned, large amount of CO2 is exhausted into the atmosphere by the process of LNG reforming. In our research, we studied the utilization of LNG latent heat for hydrogen gas production process as well as liquefied hydrogen process. Furthermore, CO2---Capturing as liquid state or solid state from hydrogen gas production process by LNG is also studied. Results of research shows that LNG latent heat is very effect to cool hydrogen gas for conventional hydrogen liquefied process. However, the LNG latent heat is not available for LNG reforming process. If we want to use LNG latent heat for this process, we have to develop new hydrogen gas produce process. In this new method, both hydrogen and CO2 is cooled by LNG directly, and CO2 is removed from the reforming gas. In order to make this method practical, we should develop a new type heat-exchanger to prevent solid CO2 from interfering the performance of it.

Capture of heavy hydrogen isotopes in a metal-organic framework with active Cu(I) sites

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

Weinrauch, Ingrid; Savchenko, Ievgeniia L.; Denysenko, D.

The production of pure deuterium and the removal of tritium from nuclear waste are the key challenges in separation of light isotopes. Presently, the technological methods are extremely energy- and cost-intensive. Here we report the capture of heavy hydrogen isotopes from hydrogen gas by selective adsorption at Cu(I) sites in a metal-organic framework. At the strongly binding Cu(I) sites (32 kJ mol -1) nuclear quantum effects result in higher adsorption enthalpies of heavier isotopes. The capture mechanism takes place most efficiently at temperatures above 80 K, when an isotope exchange allows the preferential adsorption of heavy isotopologues from the gasmore » phase. Large difference in adsorption enthalpy of 2.5 kJ mol -1 between D 2 and H 2 results in D 2-over-H 2 selectivity of 11 at 100 K, to the best of our knowledge the largest value known to date. Combination of thermal desorption spectroscopy, Raman measurements, inelastic neutron scattering and first principles calculations for H 2/D 2 mixtures allows the prediction of selectivities for tritium-containing isotopologues.« less

Capture of heavy hydrogen isotopes in a metal-organic framework with active Cu(I) sites

DOE PAGES

Weinrauch, Ingrid; Savchenko, Ievgeniia L.; Denysenko, D.; ...

2017-03-06

The production of pure deuterium and the removal of tritium from nuclear waste are the key challenges in separation of light isotopes. Presently, the technological methods are extremely energy- and cost-intensive. Here we report the capture of heavy hydrogen isotopes from hydrogen gas by selective adsorption at Cu(I) sites in a metal-organic framework. At the strongly binding Cu(I) sites (32 kJ mol -1) nuclear quantum effects result in higher adsorption enthalpies of heavier isotopes. The capture mechanism takes place most efficiently at temperatures above 80 K, when an isotope exchange allows the preferential adsorption of heavy isotopologues from the gasmore » phase. Large difference in adsorption enthalpy of 2.5 kJ mol -1 between D 2 and H 2 results in D 2-over-H 2 selectivity of 11 at 100 K, to the best of our knowledge the largest value known to date. Combination of thermal desorption spectroscopy, Raman measurements, inelastic neutron scattering and first principles calculations for H 2/D 2 mixtures allows the prediction of selectivities for tritium-containing isotopologues.« less

Container for hydrogen isotopes

DOEpatents

Solomon, David E.

1977-01-01

A container for the storage, shipping and dispensing of hydrogen isotopes such as hydrogen, deuterium, tritium, or mixtures of the same which has compactness, which is safe against fracture or accident, and which is reusable. The container consists of an outer housing with suitable inlet and outlet openings and electrical feed elements, the housing containing an activated sorber material in the form, for example, of titanium sponge or an activated zirconium aluminate cartridge. The gas to be stored is introduced into the chamber under conditions of heat and vacuum and will be retained in the sorber material. Subsequently, it may be released by heating the unit to drive off the stored gas at desired rates.

SN-EXCHANGED HYDROTALCITES AS CATALYSTS FOR CLEAN AND SELECTIVE BAEYER-VILLIGER OXIDATION OF KETONES USING HYDROGEN PEROXIDE