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Sample records for hydrogen-deuterium exchange studies

  1. Synthesis, structural investigations, hydrogen-deuterium exchange studies, and molecular modeling of conformationally stablilized aromatic oligoamides.

    PubMed

    Yan, Yan; Qin, Bo; Ren, Changliang; Chen, Xiuying; Yip, Yeow Kwan; Ye, Ruijuan; Zhang, Dawei; Su, Haibin; Zeng, Huaqiang

    2010-04-28

    Biasing the conformational preferences of aromatic oligoamides by internally placing intramolecular hydrogen bonds has led to a series of stably folded molecular strands. This article presents the results from extensive solid-state, solution, and computational studies on these folding oligomers. Depending on its backbone length, an oligoamide adopts a crescent or helical conformation. Surprisingly, despite the highly repetitive nature of the backbone, the internally placed, otherwise very similar intramolecular hydrogen bonds showed significantly different stabilities as demonstrated by hydrogen-deuterium exchange data. It was also observed that the hydrogen-bonding strength can be tuned by adjusting the substituents attached to the exterior of the aromatic backbones. Examining the amide hydrogen-deuterium exchange rates of trimers revealed that a six-membered hydrogen bond nearing the ester end is the weakest among all the four intramolecular hydrogen bonds of a molecule. This observation was verified by ab initio quantum mechanical calculations at the level of B3LYP/6-31G*. Such a "weak point" creates the "battle of the bulge" where backbone twisting is centered, which is consistently observed in the solid-state structures of the four trimer molecules studied. In the solid state, the oligomers assemble into interesting one-dimensional structures. A pronounced columnar packing of short oligomers (i.e., dimers, trimers, and tetramer) and channel-like, potentially ion-conducting stacks of longer oligomers (i.e., tetramer, pentamer, and hexamer) were observed. PMID:20364840

  2. Dual Studies on a Hydrogen-Deuterium Exchange of Resorcinol and the Subsequent Kinetic Isotope Effect

    ERIC Educational Resources Information Center

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

    2014-01-01

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

  3. Dual Studies on a Hydrogen-Deuterium Exchange of Resorcinol and the Subsequent Kinetic Isotope Effect

    ERIC Educational Resources Information Center

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

    2014-01-01

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

  4. Dual Studies on a HydrogenDeuterium Exchange of Resorcinol and the Subsequent Kinetic Isotope Effect

    PubMed Central

    2015-01-01

    An efficient laboratory experiment has been developed for undergraduate students to conduct hydrogendeuterium (HD) exchange of resorcinol by electrophilic aromatic substitution using D2O and a catalytic amount of H2SO4. The resulting labeled product is characterized by 1H NMR. Students also visualize a significant kinetic isotope effect (kH/kD ? 3 to 4) by adding iodine tincture to solutions of unlabeled resorcinol and the HD exchange product. This method is highly adaptable to fit a target audience and has been successfully implemented in a pedagogical capacity with second-year introductory organic chemistry students as part of their laboratory curriculum. It was also adapted for students at the advanced high school level. PMID:25132687

  5. Study of the conformational change of adsorbed proteins on biomaterial surfaces using hydrogen-deuterium exchange with mass spectroscopy.

    PubMed

    Kim, Jinku

    2016-05-01

    There is no doubt that protein adsorption plays a crucial role in determining biocompatibility of biomaterials. Despite the information of the identity and composition of blood plasma/serum proteins adsorbed on surfaces of biomaterials to understand which proteins are involved in blood/biomaterial interactions, it still does not provide information about the conformations and orientations of adsorbed protein, which are very important in determining biological responses to biomaterials. Therefore, our laboratory has developed an experimental technology to probe protein conformations on materials that is applicable to mixtures of proteins. Herein, the new application of hydrogen/deuterium (H/D) exchange combined with mass spectrometry was applied to determine conformational changes of adsorbed proteins at biomaterial surfaces. The results suggest that there may be a significant conformational change in adsorbed proteins at 'low' bulk concentrations that leads to a large change in the kinetics of H/D exchange as compared to 'high' bulk concentrations. This technique may eventually be useful for the study of the kinetics of protein conformational changes. PMID:26896658

  6. Using Hydrogen/Deuterium Exchange Mass Spectrometry to Study Conformational Changes in Granulocyte Colony Stimulating Factor upon PEGylation

    NASA Astrophysics Data System (ADS)

    Wei, Hui; Ahn, Joomi; Yu, Ying Qing; Tymiak, Adrienne; Engen, John R.; Chen, Guodong

    2012-03-01

    PEGylation is the covalent attachment of polyethylene glycol to proteins, and it can be used to alter immunogenicity, circulating half life and other properties of therapeutic proteins. To determine the impact of PEGylation on protein conformation, we applied hydrogen/deuterium exchange mass spectrometry (HDX MS) to analyze granulocyte colony stimulating factor (G-CSF) upon PEGylation as a model system. The combined use of HDX automation technology and data analysis software allowed reproducible and robust measurements of the deuterium incorporation levels for peptic peptides of both PEGylated and non-PEGylated G-CSF. The results indicated that significant differences in deuterium incorporation were induced by PEGylation of G-CSF, although the overall changes observed were quite small. PEGylation did not result in gross conformational rearrangement of G-CSF. The data complexity often encountered in HDX MS measurements was greatly reduced through a data processing and presentation format designed to facilitate the comparison process. This study demonstrates the practical utility of HDX MS for comparability studies, process monitoring, and protein therapeutic characterization in the biopharmaceutical industry.

  7. Hydrogen-deuterium exchange in imidazole as a tool for studying histidine phosphorylation.

    PubMed

    Cebo, Małgorzata; Kielmas, Martyna; Adamczyk, Justyna; Cebrat, Marek; Szewczuk, Zbigniew; Stefanowicz, Piotr

    2014-12-01

    Isotope exchange at the histidine C2 atom of imidazole in D2O solution is well known to occur at a significantly slower rate than the exchange of amide protons. Analysis of the kinetics of this isotope-exchange reaction is proposed herein as a method of detecting histidine phosphorylation. This modification of His-containing peptides is challenging to pinpoint because of its instability under acidic conditions as well as during CID-MS analysis. In this work, we investigated the effect of phosphorylation of the histidine side chain in peptides on deuterium-hydrogen exchange (DHX) in the imidazole. The results demonstrate that phosphorylation dramatically slows the rate of the DHX reaction. This phenomenon can be applied to detect phosphorylation of peptides at the histidine residue (e.g., in enzymatic digests). We also found that the influence of the peptide sequence on the exchange kinetics is relatively small. A CID fragmentation experiment revealed that there was no detectable hydrogen scrambling in peptides deuterated at C2 of the imidazole ring. Therefore, MS/MS can be used to directly identify the locations of deuterium ions incorporated into peptides containing multiple histidine moieties. PMID:25354888

  8. Hydrogen-deuterium exchange in structural biology

    NASA Astrophysics Data System (ADS)

    Schoenborn, B. P.; Ramakrishnan, V.; Schneider, D.

    1986-03-01

    The large difference in neutron scattering length of hydrogen and deuterium atoms provides a unique tool to study biological macromolecules. These molecules exist in an aqueous environment and have an atomic composition of about 50% hydrogen atoms with the rest being mainly carbon, oxygen and nitrogen. By simply changing the ratio of hydrogen to deuterium the contrast of a sample constituent can be changed without altering the chemical composition. The scattering difference between the hydrogen isotopes has now been used to study structural details of proteins, viruses, nucleic acid protein complexes and membranes. The use of small-angle scattering analysis from proteins in solution is a particularly good example of the power of this new technique. From the first experiments with myoglobin, hemoglobin and TMV solutions in 1968 at the HFBR in Brookhaven it became, however, soon evident that the flux was low and the detection system of a conventional spectrometer was inadequate to measure precisely small differences in the scattering pattern. Since these solution scattering patterns are circularly symmetrical, a development of multidetector systems was the first step to alleviate the need for better data. From an early five detector system [1] the development of linear and two-dimensional position sensitive detectors continues to this day [2-6]. Today, position sensitive area-detectors with an efficiency of 80% and 1.3 mm resolution with an active area of 50 cm × 50 cms are available. These detectors have a counting rate capability of 2 × 10 5 neutrons/s. Other instrumentation developments to facilitate the study of biomolecules include (1) cold moderators, (2) thin film multilayer monochromators [7-9], (3) neutron guides made either of multilayer supermirrors or coated with 58Ni [10,11], (4) various crystal and mirror focusing devices [12,13]. Some of these features have been incorporated in a small-angle neutron spectrometer at the High Flux Beam Reactor at the Brookhaven National Laboratory. This spectrometer has a unique combination of features such as a high resolution area-detector, adjustable wavelength bandwidth and automated sample changer.

  9. Probing protein ensemble rigidity and hydrogen-deuterium exchange

    NASA Astrophysics Data System (ADS)

    Sljoka, Adnan; Wilson, Derek

    2013-10-01

    Protein rigidity and flexibility can be analyzed accurately and efficiently using the program floppy inclusion and rigid substructure topography (FIRST). Previous studies using FIRST were designed to analyze the rigidity and flexibility of proteins using a single static (snapshot) structure. It is however well known that proteins can undergo spontaneous sub-molecular unfolding and refolding, or conformational dynamics, even under conditions that strongly favor a well-defined native structure. These (local) unfolding events result in a large number of conformers that differ from each other very slightly. In this context, proteins are better represented as a thermodynamic ensemble of ‘native-like’ structures, and not just as a single static low-energy structure. Working with this notion, we introduce a novel FIRST-based approach for predicting rigidity/flexibility of the protein ensemble by (i) averaging the hydrogen bonding strengths from the entire ensemble and (ii) by refining the mathematical model of hydrogen bonds. Furthermore, we combine our FIRST-ensemble rigidity predictions with the ensemble solvent accessibility data of the backbone amides and propose a novel computational method which uses both rigidity and solvent accessibility for predicting hydrogen-deuterium exchange (HDX). To validate our predictions, we report a novel site specific HDX experiment which characterizes the native structural ensemble of Acylphosphatase from hyperthermophile Sulfolobus solfataricus (Sso AcP). The sub-structural conformational dynamics that is observed by HDX data, is closely matched with the FIRST-ensemble rigidity predictions, which could not be attained using the traditional single ‘snapshot’ rigidity analysis. Moreover, the computational predictions of regions that are protected from HDX and those that undergo exchange are in very good agreement with the experimental HDX profile of Sso AcP.

  10. Interdependence of coenzyme-induced conformational work and binding potential in yeast alcohol and porcine heart lactate dehydrogenases: a hydrogen-deuterium exchange study

    SciTech Connect

    De Weck, Z.; Pande, J.; Kaegi, J.H.R.

    1987-07-28

    Binding of NAD coenzymes to yeast alcohol dehydrogenase (YADH) and porcine heart lactate dehydrogenase (PHLDH) was studied by hydrogen-deuterium exchange with the infrared technique. Conformational changes in the enzymes specific to the coenzymes and their fragments were observed, and the pH dependence of the exchange reaction shows that it conforms to the EX-2 scheme. In both YADH and PHLDH the magnitude of the conformational change as measured by exchange retardation is considerably larger for the NAD/sup +/ than for NADH. Studies with coenzyme fragments like ADP-ribose, ADP, and AMP also highlight the lack of rigorous correlation between structural features such as charge and size and their influence on exchange behavior. Ternary complexes such as YADH-NAD/sup +/-pyrazole, PHLDH-NAD/sup +/-oxalate, and PHLDH-NADH-oxamate, which mimic the transition state, have a significantly more pronounced effect on exchange rates than the corresponding binary complexes. The outstanding feature of this study is the demonstration that in the binary enzyme-coenzyme complexes the more loosely bound NAD/sup +/ is more effective in retarding exchange than the more firmly bound NADH. These differences are attributed to the unequal structural constraints exerted by the two coenzymes upon the enzymes, which translate to unequal expenditure of transconformational work in the formation of the two complexes. The opposing variation in the free energy of binding and the transconformational work expended can be viewed as an unequal partitioning of the net free energy gain resulting from the protein-ligand interaction into a binding term and that required for conformational change.

  11. Recombinant Nepenthesin II for Hydrogen/Deuterium Exchange Mass Spectrometry.

    PubMed

    Yang, Menglin; Hoeppner, Morgan; Rey, Martial; Kadek, Alan; Man, Petr; Schriemer, David C

    2015-07-01

    The pitcher secretions of the Nepenthes genus of carnivorous plants contain a proteolytic activity that is very useful for hydrogen/deuterium exchange mass spectrometry (HX-MS). Our efforts to reconstitute pitcher fluid activity using recombinant nepenthesin I (one of two known aspartic proteases in the fluid) revealed a partial cleavage profile and reduced enzymatic stability in certain HX-MS applications. We produced and characterized recombinant nepenthesin II to determine if it complemented nepenthesin I in HX-MS applications. Nepenthesin II shares many properties with nepenthesin I, such as fast digestion at reduced temperature and pH, and broad cleavage specificity, but in addition, it cleaves C-terminal to tryptophan. Neither enzyme reproduces the C-terminal proline cleavage we observed in the natural extract. Nepenthesin II is considerably more resistant to chemical denaturants and reducing agents than nepenthesin I, and it possesses a stability profile that is similar to that of pepsin. Higher stability combined with the slightly broader cleavage specificity makes nepenthesin II a useful alternative to pepsin and a more complete replacement for pitcher fluid in HX-MS applications. PMID:25993527

  12. A Hydrogen-Deuterium Exchange Study on Nickel-based Binary-Ternary Amorphous and Crystalline Membranes

    NASA Astrophysics Data System (ADS)

    Adibhatla, Anasuya

    Hydrogen is a major role player in current global sustainable energy scenario. Research around the world is carried out to harness hydrogen from all possible sources. One of these sources is water gas shift reaction after the coal gasification process. Sustainable infrastructure can be viable in countries like USA and Australia, making this process viable. Various methods are used to harness this hydrogen from the water gas. One of these methods is the use of inorganic membranes based on Pd, Ag, Ni, Zr and other transition metals. Pd addition to the membranes makes the membranes more expensive for commercial use. Various bulk properties like hydrogen permeation and absorption are studied on Pd and Pd-based alloys. Alternate alloys based on Ni, V, Ta etc are being studied to substitute the use of Pd making this technology more cost efficient. A current balance in research in this area is fund to exist by coating the non-precious metal membranes with Pd to improve the surface interaction with hydrogen. The nature of membranes used for hydrogen separation is important aspect for the overall performance. Crystalline materials provide better bulk properties, however, are not durable under high temperature and hydrogen pressure. In this research, non-Pd coated Ni-based amorphous membranes were made by melt spin technique, which have been studied for their surface properties. Gas phase H2-D2 exchange reaction has been carried out on the membrane surface. This provides a measure of catalytic activity of the above mentioned membranes. More studies included the crystallographic phase change determination, bulk hydrogen solubility measurements, surface conduction measurements and surface morphological studies. During this research, it has been observed that crystalline materials provide more surface activity for hydrogen than their amorphous counterparts. Ni64Zr36 alloy has been shown to exhibit similar kinetic rates as metallic Ni. Also, microkinetic analysis was performed to determine the heat of hydrogen absorption and desorption on the alloy surface. Electrochemical Impedance Spectroscopy was conducted on the membranes to determine the surface resistance and it was found that Ni64Zr36 as-spun ribbon displayed highest resistance while Ni60Ta20Zr20 showed lowest resistance. Absorption studies on Ni60V 40 binary alloy and Ni60V20Zr20 ternary alloy indicated that the addition of Zr to these non-coated alloys increased the hydrogen solubility in the bulk. SEM and TEM analyses showed the presence of possible nano crystalline phases in Ni64Zr36 membrane. XRD and SEM studies conducted on post treated samples showed the possible phase segregation of Ni and ZrO2. Ni60Nb40 did not show any phase transformations after hydrogen heat treated unlike its ternary composition, Ni60Nb20Zr20. It is noteworthy to mention that bubbles were observed during SEM on Ni 64Zr36 post-treated sample on the surface due to possible hydrogen trapping and subsequent release of hydrogen gas.

  13. RNA-induced conformational changes in a viral coat protein studied by hydrogen/deuterium exchange mass spectrometry

    PubMed Central

    Morton, Victoria L.; Burkitt, William; O’Connor, Gavin; Stonehouse, Nicola J.; Stockley, Peter G.; Ashcroft, Alison E.

    2016-01-01

    A detailed knowledge of the capsid assembly pathways of viruses from their coat protein building blocks is required to devise novel therapeutic strategies to inhibit such assembly. In the quest for understanding how assembly of single-stranded RNA viruses is achieved at the molecular level, HDX-MS has been used to locate regions of a coat protein dimer that exhibit conformational/dynamical changes, and hence changes in their HDX kinetics, upon binding to a genomic RNA stem-loop known to trigger assembly initiation. The HDX-MS data highlight specific areas within the coat protein dimer that alter their exchange kinetics in the presence of the RNA. These include the known RNA-binding sites, β-strands E and G, which have a lower susceptibility to HDX when ligand-bound, as may have been expected. In contrast, several exposed regions are unaffected by ligand binding. Significantly in this example, the loop between β-strands F and G exhibits reduced HDX propensity when the RNA is bound, consistent with previous inferences from NMR and normal mode analysis that suggested a local conformational change at this loop induced by dynamic allostery. These results demonstrate the potential utility of HDX to probe conformational and dynamical changes within non-covalently bound protein-ligand complexes which are of widespread importance in many biomolecular systems. PMID:20877857

  14. Using hydrogen deuterium exchange mass spectrometry to engineer optimized constructs for crystallization of protein complexes: Case study of PI4KIIIβ with Rab11.

    PubMed

    Fowler, Melissa L; McPhail, Jacob A; Jenkins, Meredith L; Masson, Glenn R; Rutaganira, Florentine U; Shokat, Kevan M; Williams, Roger L; Burke, John E

    2016-04-01

    The ability of proteins to bind and interact with protein partners plays fundamental roles in many cellular contexts. X-ray crystallography has been a powerful approach to understand protein-protein interactions; however, a challenge in the crystallization of proteins and their complexes is the presence of intrinsically disordered regions. In this article, we describe an application of hydrogen deuterium exchange mass spectrometry (HDX-MS) to identify dynamic regions within type III phosphatidylinositol 4 kinase beta (PI4KIIIβ) in complex with the GTPase Rab11. This information was then used to design deletions that allowed for the production of diffraction quality crystals. Importantly, we also used HDX-MS to verify that the new construct was properly folded, consistent with it being catalytically and functionally active. Structures of PI4KIIIβ in an Apo state and bound to the potent inhibitor BQR695 in complex with both GTPγS and GDP loaded Rab11 were determined. This hybrid HDX-MS/crystallographic strategy revealed novel aspects of the PI4KIIIβ-Rab11 complex, as well as the molecular mechanism of potency of a PI4K specific inhibitor (BQR695). This approach is widely applicable to protein-protein complexes, and is an excellent strategy to optimize constructs for high-resolution structural approaches. PMID:26756197

  15. Conformational dynamics of human FXR-LBD ligand interactions studied by hydrogen/deuterium exchange mass spectrometry: Insights into the antagonism of the hypolipidemic agent Z-guggulsterone

    PubMed Central

    Yang, Liping; Broderick, David; Jiang, Yuan; Hsu, Victor; Maier, Claudia S.

    2014-01-01

    Farnesoid X Receptor (FXR) is a member of the nuclear receptor superfamily of transcription factors that plays a key role in the regulation of bile acids, lipid and glucose metabolisms. The regulative function of FXR is governed by conformational changes of the ligand binding domain (LBD) upon ligand binding. Although FXR is a highly researched potential therapeutic target, only a limited number of FXR-agonist complexes have been successfully crystallized and subsequently yielded high resolution structures. There is currently no structural information of any FXR-antagonist complexes publically available. We therefore explored the use of amide hydrogen/deuterium exchange (HDX) coupled with mass spectrometry for characterizing conformational changes in the FXR-LBD upon ligand binding. Ligand-specific deuterium incorporation profiles were obtained for three FXR ligand chemotypes: GW4064, a synthetic non-steroidal high affinity agonist; the bile acid chenodeoxycholic acid (CDCA), the endogenous low affinity agonist of FXR; and Z-guggulsterone (GG), an in vitro antagonist of the steroid chemotype. Comparison of the HDX profiles of their ligand-bound FXR-LBD complexes revealed a unique mode of interaction for GG. The conformational features of the FXR-LBD-antagonist interaction are discussed. PMID:24953769

  16. Using hydrogen deuterium exchange mass spectrometry to engineer optimized constructs for crystallization of protein complexes: Case study of PI4KIIIβ with Rab11

    PubMed Central

    Fowler, Melissa L.; McPhail, Jacob A.; Jenkins, Meredith L.; Masson, Glenn R.; Rutaganira, Florentine U.; Shokat, Kevan M.; Williams, Roger L.

    2016-01-01

    Abstract The ability of proteins to bind and interact with protein partners plays fundamental roles in many cellular contexts. X‐ray crystallography has been a powerful approach to understand protein‐protein interactions; however, a challenge in the crystallization of proteins and their complexes is the presence of intrinsically disordered regions. In this article, we describe an application of hydrogen deuterium exchange mass spectrometry (HDX‐MS) to identify dynamic regions within type III phosphatidylinositol 4 kinase beta (PI4KIIIβ) in complex with the GTPase Rab11. This information was then used to design deletions that allowed for the production of diffraction quality crystals. Importantly, we also used HDX‐MS to verify that the new construct was properly folded, consistent with it being catalytically and functionally active. Structures of PI4KIIIβ in an Apo state and bound to the potent inhibitor BQR695 in complex with both GTPγS and GDP loaded Rab11 were determined. This hybrid HDX‐MS/crystallographic strategy revealed novel aspects of the PI4KIIIβ‐Rab11 complex, as well as the molecular mechanism of potency of a PI4K specific inhibitor (BQR695). This approach is widely applicable to protein‐protein complexes, and is an excellent strategy to optimize constructs for high‐resolution structural approaches. PMID:26756197

  17. HDX Match Software for the Data Analysis of Top-Down ECD-FTMS Hydrogen/Deuterium Exchange Experiments

    NASA Astrophysics Data System (ADS)

    Petrotchenko, Evgeniy V.; Borchers, Christoph H.

    2015-11-01

    Hydrogen/deuterium exchange (HDX) combined with mass spectrometry is a powerful technique for studying protein structure. The recently developed top-down ECD-FTMS HDX approach (Pan J. et al., JACS, 2008) allows determination of the hydrogen/deuterium exchange of a protein's amide bonds, down to the single residue resolution. One of the existing limitations of this technology has been the laborious manual analysis of the MS/MS spectra. Here we present a software program for processing the data from these experiments. This program assigns the c- and z-fragment ion series of the protein, and calculates the number of the exchanged amide protons for each fragment by fitting the theoretically predicted isotopic envelopes of the deuterated fragments to the experimental data.

  18. 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.

  19. 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.

  20. HYDROGEN-DEUTERIUM EXCHANGE IN PHOTOLYZED METHANE-WATER ICES

    SciTech Connect

    Weber, Amanda S.; Hodyss, Robert; Johnson, Paul V.; Willacy, Karen; Kanik, Isik

    2009-09-20

    Previous work has concluded that H-D exchange occurs readily in polycyclic aromatic hydrocarbons frozen in deuterated water (D{sub 2}O) irradiated with ultraviolet light. Here, we examine H-D exchange in methane-water ices following exposure to ultraviolet radiation and analyze the products formed as a result. We find that H-D exchange also occurs in methane-water ices by means of ultraviolet photolysis. Exchange proceeds through a radical mechanism that implies that almost all organic species will undergo significant H-D exchange with the matrix in water ices exposed to ultraviolet radiation. Given sufficient energetic processing of the ice, the H/D ratio of an ice matrix may be transferred to the organic species in the ice.

  1. Solution and gas phase hydrogen/deuterium exchange of oligoamide complexes by nanoelectrospray mass spectrometry

    NASA Astrophysics Data System (ADS)

    Jiang, Honghai; Dolan, Anthony R.; Li, Minfeng; Moy, Marie A.; Gong, Bing; Wood, Troy D.

    2007-03-01

    Hydrogen bonding is crucial to biological systems and is intrinsic to non-covalent interactions. They are important in the formation of higher order structures of proteins as well as in the interactions of proteins with other biological molecules. Electrospray ionization (ESI) is an important tool in the study and characterization of molecular complexes and has proven to be extremely powerful and invaluable in the studying of biomolecular structures and non-covalent interactions. We have utilized solution and gas phase hydrogen/deuterium exchange (HDX) as a method to determine the specificity of supramolecular complex formation using monomers possessing sites containing hydrogen-bond donor and acceptor groups. By comparing the average number of exchanges for the monomer subunits to the average number of exchanges for the complex, we can distinguish if a specific complex is formed in solution, or whether it is the artifact of a gas phase process during ESI. In this paper we have investigated several non-covalent supramolecular complexes by nanoelectrospray (nanoESI) mass spectrometry (MS). By using the solution and gas phase HDX, we were able to identify several specific supramolecular complexes. Thus, solution and gas phase HDX combined with nanoESI-MS provides for a convenient method in ascertaining the origin and stability of non-covalent complexes.

  2. Structural analysis of the interleukin-8/glycosaminoglycan interactions by amide hydrogen/deuterium exchange mass spectrometry.

    PubMed

    Hofmann, Tommy; Samsonov, Sergey A; Pichert, Annelie; Lemmnitzer, Katharina; Schiller, Jürgen; Huster, Daniel; Pisabarro, M Teresa; von Bergen, Martin; Kalkhof, Stefan

    2015-11-01

    The recruitment of different chemokines and growth factors by glycosaminoglycans (GAGs) such as chondroitin sulfate or hyaluronan plays a critical role in wound healing processes. Thus, there is a special interest in the design of artificial extracellular matrices with improved properties concerning GAG interaction with common regulating proteins. In this study, amide hydrogen/deuterium (H/D) exchange mass spectrometry (HDX MS) combined with molecular modeling and docking experiments was used to obtain structural models of proinflammatory chemokine interleukin-8 (IL-8) in complex with hexameric chondroitin sulfate. Experiments on the intact protein showed a difference in deuterium labeling of IL-8 due to chondroitin sulfate binding. The extent of deuteration was reduced from 24% to 13% after 2 min exchange time, which corresponds to a reduced exchange of approximately 10 backbone amides. By local HDX MS experiments, H/D exchange information on the complete sequence of IL-8 could be obtained. A significantly reduced H/D exchange, especially of the C-terminal α-helical region comprising amino acids 70-77 and to the loop comprising amino acids 27-29 was observed in the presence of chondroitin sulfate. HDX MS data were used to model the IL-8/chondroitin sulfate complex. The binding interface of IL-8 and chondroitin sulfate determined this way correlated excellently with the corresponding NMR based atomistic model previously published. Our results demonstrate that HDX-MS in combination with molecular modeling is a valuable approach for the analysis of protein/GAG complexes at physiological pH, temperature, and salt concentration. The fact that HDX-MS requires only micrograms of protein and GAGs makes it a very promising technique to address protein-GAG interactions. PMID:25726910

  3. Conformational analysis of g protein-coupled receptor signaling by hydrogen/deuterium exchange mass spectrometry.

    PubMed

    Li, Sheng; Lee, Su Youn; Chung, Ka Young

    2015-01-01

    Conformational change and protein-protein interactions are two major mechanisms of membrane protein signal transduction, including G protein-coupled receptors (GPCRs). Upon agonist binding, GPCRs change conformation, resulting in interaction with downstream signaling molecules such as G proteins. To understand the precise signaling mechanism, studies have investigated the structural mechanism of GPCR signaling using X-ray crystallography, nuclear magnetic resonance (NMR), or electron paramagnetic resonance. In addition to these techniques, hydrogen/deuterium exchange mass spectrometry (HDX-MS) has recently been used in GPCR studies. HDX-MS measures the rate at which peptide amide hydrogens exchange with deuterium in the solvent. Exposed or flexible regions have higher exchange rates and excluded or ordered regions have lower exchange rates. Therefore, HDX-MS is a useful tool for studying protein-protein interfaces and conformational changes after protein activation or protein-protein interactions. Although HDX-MS does not give high-resolution structures, it analyzes protein conformations that are difficult to study with X-ray crystallography or NMR. Furthermore, conformational information from HDX-MS can help in the crystallization of X-ray crystallography by suggesting highly flexible regions. Interactions between GPCRs and downstream signaling molecules are not easily analyzed by X-ray crystallography or NMR because of the large size of the GPCR-signaling molecule complexes, hydrophobicity, and flexibility of GPCRs. HDX-MS could be useful for analyzing the conformational mechanism of GPCR signaling. In this chapter, we discuss details of HDX-MS for analyzing GPCRs using the β2AR-G protein complex as a model system. PMID:25950969

  4. Localizing Carbohydrate Binding Sites in Proteins Using Hydrogen/Deuterium Exchange Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Zhang, Jingjing; Kitova, Elena N.; Li, Jun; Eugenio, Luiz; Ng, Kenneth; Klassen, John S.

    2016-01-01

    The application of hydrogen/deuterium exchange mass spectrometry (HDX-MS) to localize ligand binding sites in carbohydrate-binding proteins is described. Proteins from three bacterial toxins, the B subunit homopentamers of Cholera toxin and Shiga toxin type 1 and a fragment of Clostridium difficile toxin A, and their interactions with native carbohydrate receptors, GM1 pentasaccharides (β-Gal-(1→3)-β-GalNAc-(1→4)[α-Neu5Ac-(2→3)]-β-Gal-(1→4)-Glc), Pk trisaccharide (α-Gal-(1→4)-β-Gal-(1→4)-Glc) and CD-grease (α-Gal-(1→3)-β-Gal-(1→4)-β-GlcNAcO(CH2)8CO2CH3), respectively, served as model systems for this study. Comparison of the differences in deuterium uptake for peptic peptides produced in the absence and presence of ligand revealed regions of the proteins that are protected against deuterium exchange upon ligand binding. Notably, protected regions generally coincide with the carbohydrate binding sites identified by X-ray crystallography. However, ligand binding can also result in increased deuterium exchange in other parts of the protein, presumably through allosteric effects. Overall, the results of this study suggest that HDX-MS can serve as a useful tool for localizing the ligand binding sites in carbohydrate-binding proteins. However, a detailed interpretation of the changes in deuterium exchange upon ligand binding can be challenging because of the presence of ligand-induced changes in protein structure and dynamics.

  5. Continuous and pulsed hydrogen-deuterium exchange and mass spectrometry characterize CsgE oligomerization.

    PubMed

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

    2015-10-27

    We report the use of hydrogen-deuterium amide exchange coupled to mass spectrometry (HDX-MS) to study the interfaces of and conformational changes accompanying CsgE oligomerization. This protein plays an important role in enteric bacteria biofilm formation. Biofilms provide protection for enteric bacteria from environmental extremes and raise concerns about controlling bacteria and infectious disease. Their proteinaceous components, called curli, are extracellular functional amyloids that initiate surface contact and biofilm formation. The highly regulated curli biogenesis involves a major subunit, CsgA, a minor subunit CsgB, and a series of other accessory proteins. CsgE, possibly functioning as oligomer, is a chaperonin-like protein that delivers CsgA to an outer-membrane bound oligomeric CsgG complex. No higher-order structure, or interfaces and dynamics of its oligomerization, however, are known. In this work, we determined regions involved in CsgE self-association by continuous HDX, and, on the basis of that, prepared a double mutant W48A/F79A, derived from interface alanine scan, and verified that it exists as monomer. Using pulsed HDX and MS, we suggest there is a structural rearrangement occurring during the oligomerization of CsgE. PMID:26418947

  6. 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

  7. Localized Hydration in Lyophilized Myoglobin by Hydrogen-Deuterium Exchange Mass Spectrometry. 1. Exchange Mapping

    PubMed Central

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

    2012-01-01

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

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

    PubMed Central

    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. PMID:26244343

  9. 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.

  10. Hydrogen/deuterium exchange on aromatic rings during atmospheric pressure chemical ionization mass spectrometry.

    PubMed

    Davies, Noel W; Smith, Jason A; Molesworth, Peter P; Ross, John J

    2010-04-15

    It has been demonstrated that substituted indoles fully labelled with deuterium on the aromatic ring can undergo substantial exchange back to partial and even fully protonated forms during atmospheric pressure chemical ionisation (APCI) liquid chromatography/mass spectrometry (LC/MS). The degree of this exchange was strongly dependent on the absolute quantity of analyte, the APCI desolvation temperature, the nature of the mobile phase, the mobile phase flow rate and the instrument used. Hydrogen/deuterium (H/D) exchange on several other aromatic ring systems during APCI LC/MS was either undetectable (nitrobenzene, aniline) or extremely small (acetanilide) compared to the effect observed for substituted indoles. This observation has major implications for quantitative assays using deuterium-labelled internal standards and for the detection of deuterium-labelled products from isotopically labelled feeding experiments where there is a risk of back exchange to the protonated form during the analysis. PMID:20213724

  11. Thermostability of endo-1,4-beta-xylanase II from Trichoderma reesei studied by electrospray ionization Fourier-transform ion cyclotron resonance MS, hydrogen/deuterium-exchange reactions and dynamic light scattering.

    PubMed Central

    Jänis, J; Rouvinen, J; Leisola, M; Turunen, O; Vainiotalo, P

    2001-01-01

    Endo-1,4-beta-xylanase II (XYNII) from Trichoderma reesei is a 21 kDa enzyme that catalyses the hydrolysis of xylan, the major plant hemicellulose. It has various applications in the paper, food and feed industries. Previous thermostability studies have revealed a significant decrease in enzymic activity of the protein at elevated temperatures in citrate buffer [Tenkanen, Puls and Poutanen (1992) Enzyme Microb. Technol. 14, 566-574]. Here, thermostability of XYNII was investigated using both conventional and nanoelectrospray ionization Fourier-transform ion cyclotron resonance MS and hydrogen/deuterium (H/D)-exchange reactions. In addition, dynamic light scattering (DLS) was used as a comparative method to observe possible changes in both tertiary and quaternary structures of the protein. We observed a significant irreversible conformational change and dimerization when the protein was exposed to heat. H/D exchange revealed two distinct monomeric protein populations in a narrow transition temperature region. The conformational change in both the water and buffered solutions occurred in the same temperature region where enzymic-activity loss had previously been observed. Approx. 10-30% of the protein was specifically dimerized when exposed to the heat treatment. However, adding methanol to the solution markedly lowered the transition temperature of conformational change as well as increased the dimerization up to 90%. DLS studies in water confirmed the change in conformation observed by electrospray ionization MS. We propose that the conformational change is responsible for the loss of enzymic activity at temperatures over 50 degrees C and that the functioning of the active site in the enzyme is unfeasible in a new, more labile solution conformation. PMID:11368772

  12. 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. PMID:23197791

  13. The hydrogen-deuterium exchange at α-carbon atom in N,N,N-trialkylglycine residue: ESI-MS studies.

    PubMed

    Rudowska, Magdalena; Wojewska, Dominika; Kluczyk, Alicja; Bąchor, Remigiusz; Stefanowicz, Piotr; Szewczuk, Zbigniew

    2012-06-01

    Derivatization of peptides as quaternary ammonium salts (QAS) is a known method for sensitive detection by electrospray ionization tandem mass spectrometry. Hydrogens at α-carbon atom in N,N,N-trialkylglycine residue can be easily exchanged by deuterons. The exchange reaction is base-catalyzed and is dramatically slow at lower pH. Introduced deuterons are stable in acidic aqueous solution and are not back-exchanged during LC-MS analysis. Increased ionization efficiency, provided by the fixed positive charge on QAS group, as well as the deuterium labeling, enables the analysis of trace amounts of peptides. PMID:22403022

  14. The Hydrogen-Deuterium Exchange at α-Carbon Atom in N,N,N-Trialkylglycine Residue: ESI-MS Studies

    NASA Astrophysics Data System (ADS)

    Rudowska, Magdalena; Wojewska, Dominika; Kluczyk, Alicja; Bąchor, Remigiusz; Stefanowicz, Piotr; Szewczuk, Zbigniew

    2012-06-01

    Derivatization of peptides as quaternary ammonium salts (QAS) is a known method for sensitive detection by electrospray ionization tandem mass spectrometry. Hydrogens at α-carbon atom in N, N, N-trialkylglycine residue can be easily exchanged by deuterons. The exchange reaction is base-catalyzed and is dramatically slow at lower pH. Introduced deuterons are stable in acidic aqueous solution and are not back-exchanged during LC-MS analysis. Increased ionization efficiency, provided by the fixed positive charge on QAS group, as well as the deuterium labeling, enables the analysis of trace amounts of peptides.

  15. Aspartic protease nepenthesin-1 as a tool for digestion in hydrogen/deuterium exchange mass spectrometry.

    PubMed

    Kadek, Alan; Mrazek, Hynek; Halada, Petr; Rey, Martial; Schriemer, David C; Man, Petr

    2014-05-01

    Hydrogen/deuterium exchange coupled to mass spectrometry (HXMS) utilizes enzymatic digestion of proteins to localize the information about altered exchange patterns in protein structure. The ability of the protease to produce small peptides and overlapping fragments and provide sufficient coverage of the protein sequence is essential for localizing regions of interest. Recently, it was shown that there is an interesting group of proteolytic enzymes from carnivorous pitcher plants of the genus Nepenthes. In this report, we describe successful immobilization and the use of one of these enzymes, nepenthesin-1, in HXMS workflow. In contrast to pepsin, it has different cleavage specificities, and despite its high inherent susceptibility to reducing and denaturing agents, it is very stable upon immobilization and withstands even high concentration of guanidine hydrochloride and reducing agents. We show that denaturing agents can alter digestion by reducing protease activity and/or substrate solubility, and additionally, they influence the trapping of proteolytic peptides onto the reversed phase resin. PMID:24661217

  16. Time-Resolved Pulsed Hydrogen/Deuterium Exchange Mass Spectrometry Probes Gaseous Proteins Structural Kinetics

    NASA Astrophysics Data System (ADS)

    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.

  17. Structural changes of ultrasonicated bovine serum albumin revealed by hydrogen-deuterium exchange and mass spectrometry.

    PubMed

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

    2014-11-01

    The structural changes of bovine serum albumin (BSA) under high-intensity ultrasonication were investigated by fluorescence spectroscopy and mass spectrometry. Evidence for the ultrasonication-induced conformational changes of BSA was provided by the intensity changes and maximum-wavelength shift in fluorescence spectrometry. Matrix-assisted laser desorption-ionization time-of-flight mass spectroscopy (MALDI-TOF MS) revealed the increased intensity of the peak at the charge state +5 and a newly emerged peak at charge state +6, indicating that the protein became unfolded after ultrasonication. Prevalent unfolding of BSA after ultrasonication was revealed by hydrogen-deuterium exchange coupled with mass spectrometry (HDX-MS). Increased intensity and duration of ultrasonication further promoted the unfolding of the protein. The unfolding induced by ultrasonication goes through an intermediate state similar to that induced by a low concentration of denaturant. PMID:25224638

  18. Improved Sequence Resolution by Global Analysis of Overlapped Peptides in Hydrogen/Deuterium Exchange Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Fajer, Piotr G.; Bou-Assaf, George M.; Marshall, Alan G.

    2012-07-01

    Management of the enormous amount of data produced during solution-phase hydrogen/deuterium exchange monitored by mass spectrometry has stimulated software analysis development. The proteolysis step of the experiment generates multiple peptide fragments, most of which overlap. Prior automated data reduction algorithms extract the deuteration level for individual peptides, but do not exploit the additional information arising from fragment overlap. Here, we describe an algorithm that determines discrete rate constant values to each of the amide hydrogens in overlapped fragments. By considering all of the overlapped peptide segments simultaneously, sequence resolution can be improved significantly, sometimes to the individual amino acid level. We have validated the method with simulated deuterium uptake data for seven overlapped fragments of a poly-Ala nonapeptide, and then applied it to extract rate constant values for the first 29 N-terminal amino acids of C22A FK506-binding protein.

  19. 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

  20. Hydrogen, Deuterium and Tritium in Palladium: An Elastic Constants Study

    SciTech Connect

    Bach, H.T.; Schwarz, R.B.; Tuggle, D.G.

    2005-07-15

    We have used resonant ultrasound spectroscopy to measure the three independent elastic constants of Pd-H, Pd-D, and Pd-T single crystal at 300K as a function of hydrogen, deuterium, and tritium concentration, respectively. The addition of interstitial H (D, or T) atoms, located at (0,1/2,0) in the fcc Pd lattice, affects all three elastic constants C', C{sub 44}, and B. In the mixed ({alpha}+{beta}) phase, and with increasing H isotope, the shear modulus C' shows an abnormal softening whereas C{sub 44} and B do not. This is explained in terms of Zener-type an elastic relaxations affecting the shape of the hydride phases in the coherent({alpha}+{beta}) two-phase mixture In the single {beta}-phase, C' shows a strong isotope dependence whereas C{sub 44} and B show none. This behavior is explained in terms of differences in the excitation of optical phonons. In Pd-T, {sup 3}He is produced by the radioactive decay of tritium. We have measured in situ the swelling and the change in the elastic constants in Pd-T as a function of aging time. Aging ({sup 3}He formation) affects all three elastic constants. These measurements are being used to understand the early stages of {sup 3}H-{sup 3}He cluster formation in aged Pd-T crystal.

  1. Hydrogen, deuterium and tritium in palladium: An eleastic constants study

    SciTech Connect

    Bach, H. T.; Schwarz, R. B.; Tuggle, D. G.

    2004-01-01

    We have used resonant ultrasound spectroscopy to measure the three independent elastic constants of Pd-H, Pd-D, and Pd-T single crystal at 300K as a junction of hydrogen, deuterium, and tritium concentration, respectively. The addition of interstitial H (D, or T) atoms, located at (0, 1/2, 0) in the fcc Pd lattice, affects all three elastic constants C, C{sub 44}, and B. In the mixed (a+{beta}) phase, and with increasing H isotope, the shear modulus C' shows an abnormal softening whereas C{sub 44} and B do not. This is explained in terms of Zener-type anelastic relaxations affecting the shape of the hydride phases in the coherent ({alpha}+{beta}) two-phase mixture In the single {beta}-phase, C' shows a strong isotope dependence whereas C{sub 44} and B show none. This behavior is explained in terms of differences in the excitation of optical phonons. In Pd-T, {sup 3}He is produced by the radioactive decay of tritium. We have measured in situ the swelling and the change in the elastic constants in Pd-T as a function of aging time. Aging ({sup 3}He formation) affects all three elastic constants. These measurements are being used to understand the early stages of {sup 3}H-{sup 3}He clusterformation in aged Pd-T crystal.

  2. Influence of domain interactions on conformational mobility of the progesterone receptor detected by hydrogen/deuterium exchange mass spectrometry

    PubMed Central

    Goswami, Devrishi; Callaway, Celetta; Pascal, Bruce D.; Kumar, Raj; Edwards, Dean P.; Griffin, Patrick R.

    2015-01-01

    Structural and functional details of the N-terminal activation function 1 (AF1) of most nuclear receptors are poorly understood due to the highly dynamic intrinsically disordered nature of this domain. A hydrogen/deuterium exchange (HDX) mass spectrometry based investigation of TATA box binding protein (TBP) interaction with various domains of progesterone receptor (PR) demonstrate that agonist bound PR interaction with TBP via AF1 impacts the mobility of the C-terminal AF2. Results from HDX and other biophysical studies involving agonist and antagonist bound full length PR and isolated PR domains reveals the molecular mechanism underlying synergistic transcriptional activation mediated by AF1 and AF2, dominance of PR-B isoform over PR-A, and the necessity of AF2 for full AF1-mediated transcriptional activity. These results provide a comprehensive picture elaborating the underlying mechanism of PR-TBP interactions as a model for studying NR-transcription factor functional interactions. PMID:24909783

  3. Differential Mobility Spectrometry-Hydrogen Deuterium Exchange (DMS-HDX) as a Probe of Protein Conformation in Solution.

    PubMed

    Zhu, Shaolong; Campbell, J Larry; Chernushevich, Igor; Le Blanc, J C Yves; Wilson, Derek J

    2016-06-01

    Differential mobility spectrometry (DMS) is an ion mobility technique that has been adopted chiefly as a pre-filter for small- to medium-sized analytes (<1 000 Da). With the exception of a handful of studies that employ an analogue of DMS-field asymmetric waveform ion mobility spectroscopy (FAIMS)-the application of DMS to intact biomacromolecules remains largely unexplored. In this work, we employ DMS combined with gas-phase hydrogen deuterium exchange (DMS-HDX) to probe the gas-phase conformations generated from proteins that were initially folded, partially-folded, and unfolded in solution. Our findings indicate that proteins with distinct structural features in solution exhibit unique deuterium uptake profiles as function of their optimal transmission through the DMS. Ultimately we propose that DMS-HDX can, if properly implemented, provide rapid measurements of liquid-phase protein structural stability that could be of use in biopharmaceuticals development. Graphical Abstract ᅟ. PMID:26965162

  4. Differential Mobility Spectrometry-Hydrogen Deuterium Exchange (DMS-HDX) as a Probe of Protein Conformation in Solution

    NASA Astrophysics Data System (ADS)

    Zhu, Shaolong; Campbell, J. Larry; Chernushevich, Igor; Le Blanc, J. C. Yves; Wilson, Derek J.

    2016-03-01

    Differential mobility spectrometry (DMS) is an ion mobility technique that has been adopted chiefly as a pre-filter for small- to medium-sized analytes (<1 000 Da). With the exception of a handful of studies that employ an analogue of DMS—field asymmetric waveform ion mobility spectroscopy (FAIMS)—the application of DMS to intact biomacromolecules remains largely unexplored. In this work, we employ DMS combined with gas-phase hydrogen deuterium exchange (DMS-HDX) to probe the gas-phase conformations generated from proteins that were initially folded, partially-folded, and unfolded in solution. Our findings indicate that proteins with distinct structural features in solution exhibit unique deuterium uptake profiles as function of their optimal transmission through the DMS. Ultimately we propose that DMS-HDX can, if properly implemented, provide rapid measurements of liquid-phase protein structural stability that could be of use in biopharmaceuticals development.

  5. Characterizing rapid, activity-linked conformational transitions in proteins via sub-second hydrogen deuterium exchange mass spectrometry.

    PubMed

    Resetca, Diana; Wilson, Derek J

    2013-11-01

    This review outlines the application of time-resolved electrospray ionization mass spectrometry (TRESI-MS) and hydrogen-deuterium exchange (HDX) to study rapid, activity-linked conformational transitions in proteins. The method is implemented on a microfluidic chip which incorporates all sample-handling steps required for a 'bottom-up' HDX workflow: a capillary mixer for sub-second HDX labeling, a static mixer for HDX quenching, a microreactor for rapid protein digestion, and on-chip electrospray. By combining short HDX labeling pulses with rapid digestion, this approach provides a detailed characterization of the structural transitions that occur during protein folding, ligand binding, post-translational modification and catalytic turnover in enzymes. This broad spectrum of applications in areas largely inaccessible to conventional techniques means that microfluidics-enabled TRESI-MS/HDX is a unique and powerful approach for investigating the dynamic basis of protein function. PMID:23663649

  6. Peptide-Column Interactions and Their Influence on Back Exchange Rates in Hydrogen/Deuterium Exchange-MS

    NASA Astrophysics Data System (ADS)

    Sheff, Joey G.; Rey, Martial; Schriemer, David C.

    2013-07-01

    Hydrogen/deuterium exchange (HDX) methods generate useful information on protein structure and dynamics, ideally at the individual residue level. Most MS-based HDX methods involve a rapid proteolytic digestion followed by LC/MS analysis, with exchange kinetics monitored at the peptide level. Localizing specific sites of HDX is usually restricted to a resolution the size of the host peptide because gas-phase processes can scramble deuterium throughout the peptide. Subtractive methods may improve resolution, where deuterium levels of overlapping and nested peptides are used in a subtractive manner to localize exchange to smaller segments. In this study, we explore the underlying assumption of the subtractive method, namely, that the measured back exchange kinetics of a given residue is independent of its host peptide. Using a series of deuterated peptides, we show that secondary structure can be partially retained under quenched conditions, and that interactions between peptides and reversed-phase LC columns may both accelerate and decelerate residue HDX, depending upon peptide sequence and length. Secondary structure is induced through column interactions in peptides with a solution-phase propensity for structure, which has the effect of slowing HDX rates relative to predicted random coil values. Conversely, column interactions can orient random-coil peptide conformers to accelerate HDX, the degree to which correlates with peptide charge in solution, and which can be reversed by using stronger ion pairing reagents. The dependency of these effects on sequence and length suggest that subtractive methods for improving structural resolution in HDX-MS will not offer a straightforward solution for increasing exchange site resolution.

  7. Start2Fold: a database of hydrogen/deuterium exchange data on protein folding and stability

    PubMed Central

    Pancsa, Rita; Varadi, Mihaly; Tompa, Peter; Vranken, Wim F.

    2016-01-01

    Proteins fulfil a wide range of tasks in cells; understanding how they fold into complex three-dimensional (3D) structures and how these structures remain stable while retaining sufficient dynamics for functionality is essential for the interpretation of overall protein behaviour. Since the 1950's, solvent exchange-based methods have been the most powerful experimental means to obtain information on the folding and stability of proteins. Considerable expertise and care were required to obtain the resulting datasets, which, despite their importance and intrinsic value, have never been collected, curated and classified. Start2Fold is an openly accessible database (http://start2fold.eu) of carefully curated hydrogen/deuterium exchange (HDX) data extracted from the literature that is open for new submissions from the community. The database entries contain (i) information on the proteins investigated and the underlying experimental procedures and (ii) the classification of the residues based on their exchange protection levels, also allowing for the instant visualization of the relevant residue groups on the 3D structures of the corresponding proteins. By providing a clear hierarchical framework for the easy sharing, comparison and (re-)interpretation of HDX data, Start2Fold intends to promote a better understanding of how the protein sequence encodes folding and structure as well as the development of new computational methods predicting protein folding and stability. PMID:26582925

  8. Guanine nucleotide induced conformational change of Cdc42 revealed by hydrogen/deuterium exchange mass spectrometry.

    PubMed

    Yang, Sheng-Wei; Ting, Hsiu-Chi; Lo, Yi-Ting; Wu, Ting-Yuan; Huang, Hung-Wei; Yang, Chia-Jung; Chan, Jui-Fen Riva; Chuang, Min-Chieh; Hsu, Yuan-Hao Howard

    2016-01-01

    Cdc42 regulates pathways related to cell division. Dysregulation of Cdc42 can lead to cancer, cardiovascular diseases and neurodegenerative diseases. GTP induced activation mechanism plays an important role in the activity and biological functions of Cdc42. P-loop, Switch I and Switch II are critical regions modulating the enzymatic activity of Cdc42. We applied amide hydrogen/deuterium exchange coupled with liquid chromatography mass spectrometry (HDXMS) to investigate the dynamic changes of apo-Cdc42 after GDP, GTP and GMP-PCP binding. The natural substrate GTP induced significant decreases of deuteration in P-loop and Switch II, moderate changes of deuteration in Switch I and significant changes of deuteration in the ?7 helix, a region far away from the active site. GTP binding induced similar effects on H/D exchange to its non-hydrolysable analog, GMP-PCP. HDXMS results indicate that GTP binding blocked the solvent accessibility in the active site leading to the decrease of H/D exchange rate surrounding the active site, and further triggered a conformational change resulting in the drastic decrease of H/D exchange rate at the remote ?7 helix. Comparing the deuteration levels in three activation states of apo-Cdc42, Cdc42-GDP and Cdc42-GMP-PCP, the apo-Cdc42 has the most flexible structure, which can be stabilized by guanine nucleotide binding. The rates of H/D exchange of Cdc42-GDP are between the GMP-PCP-bound and the apo form, but more closely to the GMP-PCP-bound form. Our results show that the activation of Cdc42 is a process of conformational changes involved with P-loop, Switch II and ?7 helix for structural stabilization. PMID:26542736

  9. Optimization and Application of APCI Hydrogen-Deuterium Exchange Mass Spectrometry (HDX MS) for the Speciation of Nitrogen Compounds

    NASA Astrophysics Data System (ADS)

    Acter, Thamina; Cho, Yunju; Kim, Sungji; Ahmed, Arif; Kim, Byungjoo; Kim, Sunghwan

    2015-09-01

    A systematic study was performed to investigate the utility of atmospheric pressure chemical ionization hydrogen-deuterium exchange mass spectrometry (APCI HDX MS) to identify the structures of nitrogen-containing aromatic compounds. First, experiments were performed to determine the optimized experimental conditions, with dichloromethane and CH3OD found to be good cosolvents for APCI HDX. In addition, a positive correlation between the heated capillary temperature and the observed HDX signal was observed, and it was suggested that the HDX reaction occurred when molecules were contained in the solvent cluster. Second, 20 standard nitrogen-containing compounds were analyzed to investigate whether speciation could be determined based on the different types of ions produced from nitrogen-containing compounds with various functional groups. The number of exchanges occurring within the compounds correlated well with the number of active hydrogen atoms attached to nitrogen, and it was confirmed that APCI HDX MS could be used to determine speciation. The results obtained by APCI HDX MS were combined with the subsequent investigation of the double bond equivalence distribution and indicated that resins of shale oil extract contained mostly pyridine type nitrogen compounds. This study confirmed that APCI HDX MS can be added to previously reported chemical ionization, electrospray ionization, and atmospheric pressure photo ionization-based HDX methods, which can be used for structural elucidation by mass spectrometry.

  10. Optimization and Application of APCI Hydrogen-Deuterium Exchange Mass Spectrometry (HDX MS) for the Speciation of Nitrogen Compounds.

    PubMed

    Acter, Thamina; Cho, Yunju; Kim, Sungji; Ahmed, Arif; Kim, Byungjoo; Kim, Sunghwan

    2015-09-01

    A systematic study was performed to investigate the utility of atmospheric pressure chemical ionization hydrogen-deuterium exchange mass spectrometry (APCI HDX MS) to identify the structures of nitrogen-containing aromatic compounds. First, experiments were performed to determine the optimized experimental conditions, with dichloromethane and CH(3)OD found to be good cosolvents for APCI HDX. In addition, a positive correlation between the heated capillary temperature and the observed HDX signal was observed, and it was suggested that the HDX reaction occurred when molecules were contained in the solvent cluster. Second, 20 standard nitrogen-containing compounds were analyzed to investigate whether speciation could be determined based on the different types of ions produced from nitrogen-containing compounds with various functional groups. The number of exchanges occurring within the compounds correlated well with the number of active hydrogen atoms attached to nitrogen, and it was confirmed that APCI HDX MS could be used to determine speciation. The results obtained by APCI HDX MS were combined with the subsequent investigation of the double bond equivalence distribution and indicated that resins of shale oil extract contained mostly pyridine type nitrogen compounds. This study confirmed that APCI HDX MS can be added to previously reported chemical ionization, electrospray ionization, and atmospheric pressure photo ionization-based HDX methods, which can be used for structural elucidation by mass spectrometry. PMID:26115964

  11. 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 and mode of action of this unique class of phosphatases. PMID:19754155

  12. Gas-phase hydrogen/deuterium exchange in a travelling wave ion guide for the examination of protein conformations

    PubMed Central

    Rand, Kasper D.; Pringle, Steven D.; Murphy, James P.; Fadgen, Keith E.; Brown, Jeff; Engen, John R.

    2009-01-01

    Accumulating evidence suggests that solution-phase conformations of small globular proteins and large molecular protein assemblies can be preserved for milliseconds after electrospray ionization. Thus, the study of proteins in the gas-phase on this time-scale is highly desirable. Here we demonstrate that a travelling wave ion guide (TWIG) of a Synapt mass spectrometer offers a highly suitable environment for rapid and efficient gas-phase hydrogen/deuterium exchange (HDX). Gaseous ND3 was introduced into either the source TWIG or the TWIG located just after the ion mobility cell, such that ions underwent HDX as they passed through the ND3 on the way to the time-of-flight analyzer. The extent of deuterium labeling could be controlled by varying the quantity of ND3 or the speed of the travelling wave. The gas-phase HDX of model peptides corresponded to labeling of primarily fast exchanging sites due to the short labeling times (ranging from 0.1 to 10 ms). In addition to peptides, gas-phase HDX of ubiquitin, cytochrome c, lysozyme and apomyoglobin were examined. We conclude that HDX of protein ions in a TWIG is highly sensitive to protein conformation, enables the detection of conformers present on sub-milliseconds timescales and can readily be combined with ion mobility spectrometry. PMID:19921790

  13. Proton nuclear magnetic resonance spectroscopy of human transferrin N-terminal half-molecule: titration and hydrogen-deuterium exchange

    SciTech Connect

    Valcour, A.A.; Woodworth, R.C.

    1987-06-02

    The binding of Ga(III) to the proteolytically derived N-terminal half-molecule of human transferrin (HTF/2N) was studied by proton nuclear magnetic resonance spectroscopy. The pH-dependent titration curves of the histidinyl C(2) proton chemical shifts were altered upon formation of the GaIIIHTF/2N(C/sub 2/O/sub 4/) ternary complex. Two high-pK'a histidines failed to titrate when the metal and synergistic anion formed a complex with the protein. These results implicated two histidinyl residues as direct ligands to the metal. The rates of hydrogen-deuterium exchange for the C(2) protons of certain histidinyl residues were substantially decreased by metal ion binding. The two ligand histidines were protected from exchange, and a third, low-pK'a, histidinyl residue was protected. We propose that this third histidinyl residue is involved in anion binding and may serve as the base in the putative proton-relay scheme proposed for complex formation.

  14. Atmospheric Pressure Photo Ionization Hydrogen/Deuterium Exchange Mass Spectrometry—a Method to Differentiate Isomers by Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Ahmed, Arif; Kim, Sunghwan

    2013-12-01

    In this report, a method for in-source hydrogen/deuterium (H/D) exchange at atmospheric pressure is reported. The method was named atmospheric pressure photo ionization hydrogen/deuterium exchange mass spectrometry (APPI HDX MS). H/D exchange was performed by mixing samples dissolved in toluene with CH3OD solvent and analyzing the mixture using atmospheric pressure photo ionization mass spectrometry (APPI-MS). The APPI HDX spectra obtained with contact times between the analyte solution and methanol-OD (CH3OD) of < 0.5 s or 1 h showed the same pattern of H/D exchange. Therefore, it was concluded that APPI HDX occurred in the source but not in the solution. The proposed method does not require a specific type of mass spectrometer and can be performed at atmospheric pressure. H/D exchange can be performed in any laboratory with a mass spectrometer and a commercial APPI source. Using this method, multiple H/D exchanges of aromatic hydrogen and/or H/D exchange of active hydrogen were observed. These results demonstrated that H/D exchange can be used to distinguish between isomers containing primary, secondary, and tertiary amines, as well as pyridine and pyrrole functional groups.

  15. Measuring the hydrogen/deuterium exchange of proteins at high spatial resolution by mass spectrometry: overcoming gas-phase hydrogen/deuterium scrambling.

    PubMed

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

    2014-10-21

    Proteins are dynamic molecules that exhibit conformational flexibility to function properly. Well-known examples of this are allosteric regulation of protein activity and ligand-induced conformational changes in protein receptors. Detailed knowledge of the conformational properties of proteins is therefore pertinent to both basic and applied research, including drug development, since the majority of drugs target protein receptors and a growing number of drugs introduced to the market are therapeutic peptides or proteins. X-ray crystallography provides a static picture at atomic resolution of the lowest-energy structure of the native ensemble. There is a growing need for sensitive analytical tools to explore all of the significant molecular structures in the conformational landscape of proteins. Hydrogen/deuterium exchange monitored by mass spectrometry (HDX-MS) has recently emerged as a powerful method for characterizing protein conformational dynamics. The basis of this method is the fact that backbone amides in stable hydrogen-bonded structures (e.g., α-helices and β-sheets) are protected against exchange with the aqueous solvent. All protein structures are dynamic, however, and eventually all of the protecting hydrogen bonds will transiently break as the protein--according to thermodynamic principles--cycles through partially unfolded states that correspond to excited free energy levels. As a result, all of the backbone amides will eventually become temporarily solvent-exposed and exchange-competent over time. Consequently, a folded protein in D2O will gradually incorporate deuterium into its backbone amides, and the kinetics of the process can be readily monitored by mass spectrometry. The deuterium uptake kinetics for the intact protein (global exchange kinetics) represents the sum of the exchange kinetics for the individual backbone amides. Local exchange kinetics is typically achieved by using pepsin digestion under quench conditions (i.e., under cold acidic conditions where the amide hydrogen exchange rate is slowed by many orders of magnitude). The ability to localize the individual deuterated residues (the spatial resolution) is determined by the size (typically ∼7-15 residues) and the number of peptic peptides. These peptides provide a relatively coarse-grained picture of the protein dynamics. A fundamental understanding of the relationship between protein function/dysfunction and conformational dynamics requires in many cases higher resolution and ultimately single-residue resolution. In this Account, we summarize our efforts to achieve single-residue deuterium levels in proteins by electron-based or laser-induced gas-phase fragmentation methods. A crucial analytical requirement for this approach is that the pattern of deuterium labeling from solution is retained in the gas-phase fragment ions. It is therefore essential to control and minimize any occurrence of gas-phase randomization of the solution deuterium label (H/D scrambling) during the MS experiment. For this purpose, we have developed model peptide probes to accurately measure the onset and extent of H/D scrambling. Our analytical procedures to control the occurrence of H/D scrambling are detailed along with the physical parameters that induce it during MS analysis. In light of the growing use of gas-phase dissociation experiments to measure the HDX of proteins in order to obtain a detailed characterization and understanding of the dynamic conformations and interactions of proteins at the molecular level, we discuss the perspectives and challenges of future high-resolution HDX-MS methodology. PMID:25171396

  16. Influence of Murchison Minerals on Hydrogen-Deuterium Exchange of Amino Acids

    NASA Astrophysics Data System (ADS)

    Lerner, N. R.

    1993-07-01

    The amino acids found on the Murchison meteorite are deuterium enriched. For the glycine-alanine fraction, delta D = +2448 per mil, and for the alpha-amino isobutyric acid fraction, delta D = +149 per mil [1]. In order to retain such levels of deuterium enrichment, the amino acids found in Murchison must have not only retained the deuterium enrichment of their interstellar precursors (delta D > +1500 per mil [2]) during synthesis, as has been recently shown [3], but they must have also retained their deuterium label during the aqueous alteration phase [4]. By measuring the rates of deuterium exchange of amino acids with D(sub)2O, limits can be set on the length of time and the conditions under which the Murchison parent body experienced an aqueous environment. The rates of hydrogen-deuterium exchange of nondeuterated glycine, alanine, alpha-amino isobutyric acid, and amino diacetic acid have been measured in D(sub)2O as a function of temperature, pH, and the presence of Murchison minerals. In addition to the amino and carboxylic hydrogens, only the alpha- hydrogens of glycine, alanine, and amino diacetic acid are found to exchange. Even for solutions maintained for weeks at temperatures as high as 120 degrees C, no exchange was observed with the hydrogens of the methyl groups of alanine or alpha-amino isobutyric acid. The rate of exchange for alpha-hydrogens of amino acids is first-order with respect to the amino acid concentration. Increasing the pH of the solution markedly increases the rate of exchange. For example, at 115 degrees C and pH 4.0, 7.0, and 10 the rates are 14, 30, and 125 yr^-1 respectively for glycine and 2.0, 3.5, and 14 yr^-1 respectively for alanine. In a pH-6.0 D(sub)2O solution of amino acids containing Murchison dust the rates are 135 yr^-1 for glycine and 32 yr^-1 for alanine, rates close to those for the pH 10 solution. Activation energies for exchange were obtained from Arrhenius plots constructed from measurements made between 70 degrees C and 155 degrees C in solutions containing Murchison dust. For both glycine and alanine the activation energy is -25 kcal/mole. Using this value, we have calculated the half-lives for complete exchange of the alpha-hydrogens of glycine and alanine for the temperature range thought to have existed on the parent body during aqueous alteration [5]. The half-lives at 0 degrees C and 20 degrees C are 7500 yr and 300 yr respectively for glycine and 55,000 yr and 2100 yr respectively for alanine. Murchison amino acid fraction IV [1] was known to contain impurities and hence the measured delta D value represents a lower limit for alpha-amino isobutyric acid. Assuming that all the deuterium recovered from fraction IV came from alpha-amino isobutryric acid, and that one atom of nitrogen is recovered for each molecule of alpha-amino isobutyric acid, a maximum delta D value of +2600 per mil can be calculated for this amino acid. This is comparable to delta D for the glycine-alanine fraction, which is mainly glycine [6]. In an aqueous environment glycine loses deuterium relatively rapidly while alpha-amino isobutyric acid does not undergo exchange. Hence the similarity in the delta D values of both fractions indicates that the period of aqueous alteration is less than the half-life for hydrogen-deuterium exchange of glycine. References: [1] Pizzarello S. et al. (1991) GCA, 55, 905-910. [2] Zinner E. (1988) In Meteorites and the Early Solar System (J. R. Kerridge and M. S. Matthews, eds.), 956-983, Univ. of Arizona. [3] Lerner N. R. et al. (1993) GCA, in press. [4] Bunch T. E. and Chang S. (1980) GCA, 44, 1543-1577. [5] Clayton R. N. and Mayeda T. K. (1984) EPSL, 67, 151-161. [6] Shock E. L. and Shulte M. D. (1990) GCA, 54, 3159-3173.

  17. Fragmentation study on the phenolic alkaloid neferine and its analogues with anti-HIV activities by electrospray ionization tandem mass spectrometry with hydrogen/deuterium exchange and its application for rapid identification of in vitro microsomal metabolites of neferine.

    PubMed

    Zhou, Hui; Jiang, Huidi; Yao, Tongwei; Zeng, Su

    2007-01-01

    The application of mass spectrometry in drug discovery, especially in drug metabolites, is very important. This present paper is at first focused on the elucidation of fragmentation patterns of the phenolic bisbenzyltetrahydroisoquinoline alkaloid, neferine, together with its analogues isoliensinine and liensinine with anti-HIV activities using electrospray ionization tandem mass spectrometry (ESI-MS/MS) and hydrogen/deuterium (H/D) exchange. All title compounds displayed major diagnostic fragments that formed by the cleavage of the C1'--C9' bond resulting in positive group CD, and the loss of 4-ethyl-1-phenol or 4-ethyl-1-methoxybenzene following rearrangements. Their ESI-MS/MS spectra also showed the relatively stable fragment ions formed by the elimination of H2O, CH3NH2, CH3OH, and CH3-N==CH2. Secondly, the metabolites of neferine from dog hepatic microsomal incubations were analyzed and characterized by high-performance liquid chromatography (HPLC) and data-dependent ESI-MS/MS. Based on fragmentation patterns and compared with their retention times in LC, molecular weights and ultraviolet (UV) absorbances with standard compounds, six metabolites were identified as isoliensinine, liensinine and four novel bisbenzyltetrahydroisoquinoline alkaloids named as 6-O-desmethylneferine, 2'-N-desmethylneferine, 2'-N-6-O-didesmethylneferine, and 6,13-O-didesmethylneferine. All metabolites were desmethyl or didesmethyl products of neferine. The possible metabolic pathways for neferine have been proposed. The results suggest that N-demethylation and O-demethylation are two important metabolic pathways of neferine in dog hepatic microsomal incubations. This is critical for screening and development of phenolic bisbenzyltetrahydroisoquinoline alkaloids with anti-HIV activities such as neferine and its analogues isoliensinine and liensinine. PMID:17546644

  18. Characterization of Stress-Exposed Granulocyte Colony Stimulating Factor Using ELISA and Hydrogen/Deuterium Exchange Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Tsuchida, Daisuke; Yamazaki, Katsuyoshi; Akashi, Satoko

    2014-10-01

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

  19. 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.

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

    PubMed Central

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

    2013-01-01

    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. PMID:22298288

  1. 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

    2014-11-01

    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

  2. Screen-printed digital microfluidics combined with surface acoustic wave nebulization for hydrogen-deuterium exchange measurements.

    PubMed

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

    2016-03-25

    An inexpensive digital microfluidic (DMF) chip was fabricated by screen-printing electrodes on a sheet of polyimide. This device was manually integrated with surface acoustic wave nebulization (SAWN) MS to conduct hydrogen/deuterium exchange (HDX) of peptides. The HDX experiment was performed by DMF mixing of one aqueous droplet of angiotensin II with a second containing various concentrations of D2O. Subsequently, the degree of HDX was measured immediately by SAWN-MS. As expected for a small peptide, the isotopically resolved mass spectrum for angiotensin revealed that maximum deuterium exchange was achieved using 50% D2O. Additionally, using SAWN-MS alone, the global HDX kinetics of ubiquitin were found to be similar to published NMR data and back exchange rates for the uncooled apparatus using high inlet capillary temperatures was less than 6%. PMID:26826755

  3. 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.

  4. Effective application of bicelles for conformational analysis of G protein-coupled receptors by hydrogen/deuterium exchange mass spectrometry.

    PubMed

    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. PMID:25740347

  5. Differential isotopic enrichment to facilitate characterization of asymmetric multimeric proteins using hydrogen/deuterium exchange mass spectrometry

    PubMed Central

    Pascal, Bruce D.; Bauman, Joseph D.; Patel, Disha; Arnold, Eddy; Griffin, Patrick R.

    2015-01-01

    Hydrogen/deuterium exchange (HDX) coupled to mass spectrometry has emerged as a powerful tool for analyzing the conformational dynamics of protein-ligand and protein-protein interactions. Recent advances in instrumentation and methodology have expanded the utility of HDX for the analysis of large and complex proteins; however, asymmetric dimers with shared amino acid sequence present a unique challenge for HDX because assignment of peptides with identical sequence to their subunit of origin remains ambiguous. Here we report the use of differential isotopic labeling to facilitate HDX analysis of multimers using HIV-1 reverse transcriptase (RT) as a model. RT is an asymmetric heterodimer of 51 kDa (p51) and 66 kDa (p66) subunits. The first 440 residues of p51 and p66 are identical. In this study differentially labeled RT was reconstituted from isotopically enriched (15N-labeled) p51 and unlabeled p66. In order to enable detection of 15N-deuterated RT peptides, the software HDX Workbench was modified to follow a 100% 15N model. Our results demonstrated that 15N enrichment of p51 did not affect its conformational dynamics compared to unlabeled p51, but 15N-labeled p51 did show different conformational dynamics than p66 in the RT heterodimer. Differential HDX-MS of isotopically labeled RT in the presence of the nonnucleoside reverse transcriptase inhibitor (NNRTI) efavirenz (EFV) showed subunit-specific perturbation in the rate of HDX consistent with previously published results and the RT-EFV co-crystal structure. PMID:25763479

  6. Investigation of the gas-phase hydrogen/deuterium exchange behavior of aromatic dicarboxylic acids in a quadrupole ion trap

    NASA Astrophysics Data System (ADS)

    Chipuk, Joseph E.; Brodbelt, Jennifer S.

    2007-11-01

    Gas-phase hydrogen/deuterium (H/D) exchange reactions of four deprotonated aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid and 2,6-naphthalic acid) with D2O were performed in a quadrupole ion trap mass spectrometer. Experimental results showed significant differences in the rate and extent of exchange when the relative position of the carboxylic acid groups varied. Spontaneous and near complete exchange of one aromatic hydrogen atom occurred when the carboxylic acid groups were in the meta-position, whereas no additional exchange was observed for either the ortho- or para-isomers or for the structurally similar naphthalic acid. Computational investigations support the participation of several possible exchange mechanisms with the contribution of each relying heavily on the relative orientation of the acid moieties. A relay mechanism that bridges the deprotonation site and the labile hydrogen site appears to be responsible for the H/D exchange of not only the labile hydrogen atom of isophthalic acid, but also for the formation of a stable carbanion and corresponding subsequent exchange of one aromatic hydrogen atom. The impact of hydrogen bonding on the relay mechanism is demonstrated by the reaction of phthalic acid as the extent and rate of reaction are greatly retarded by the favorable interaction of the two carboxylic acid groups. Finally, a flip-flop mechanism is likely responsible for the exchange of both terephthalic acid and 2,6-naphthalic acid where the reactive sites are too remote for exchange via relay.

  7. ALKYL AND HYDRIDE BIS (TRIMETHYLSILYL)AMIDO DERIVATIVES OF THE ACTINIDE ELEMENTS: PREPARATION AND HYDROGEN-DEUTERIUM EXCHANGE

    SciTech Connect

    Simpson, Stephen J.; Turner, Howard W.; Andersen, Richard A.

    1980-09-01

    The monomeric, hydrocarbon-soluble monohydrides and monodeuterides of the actinide metals (thorium or uranium) of the type HM[N(SiMe{sub 3}){sub 2}]{sub 3} have been prepared. Their reaction chemistry, n-BuLi followed by MeBr yields MeM[N(SiMe{sub 3}){sub 2}]{sub 3} and borane in tetrahydrofuran yields BH{sub 4}M[N(SiMe{sub 3}){sub 2}]{sub 3}, suggests that the hydrogen atom is hydridic. Pyrolysis of the hydrides yields the novel, four-membered ring metallocycle, [(Me{sub 3}Si){sub 2}N]{sub 2} - MCH{sub 2}Si(Me){sub 2}NSiMe{sub 3} where M is Th or U. These metallocycles are the key intermediates in the hydrogen-deuterium exchange reaction that yields {[(CD{sub 3}){sub 3}Si]{sub 2}N}{sub 3}MD.

  8. Antibody structural integrity of site-specific antibody-drug conjugates investigated by hydrogen/deuterium exchange mass spectrometry.

    PubMed

    Pan, Lucy Yan; Salas-Solano, Oscar; Valliere-Douglass, John F

    2015-06-01

    We present the results of a hydrogen/deuterium exchange mass spectrometric (HDX-MS) investigation of an antibody-drug conjugate (ADC) comprised of drug-linkers conjugated to cysteine residues that have been engineered into heavy chain (HC) fragment crystallizable (Fc) domain at position 239. A side-by-side comparison of the HC Ser239 wild type (wt) monoclonal antibody (mAb) and the engineered Cys239 mAb indicates that site directed mutagenesis of Ser239 to cysteine has no impact on the HDX kinetics of the mAb. According to the crystal structure of a homologous immunoglobulin G1 (IgG1) antibody (PDB: 1HZH ), the backbone amide of Ser239 is hydrogen-bonded to Val264 backbone amide in the wt-mAb studied here. Replacing Ser239 with a Cys residue does not alter the exchange kinetics of the backbone amide of Val264 suggesting that either Ser or Cys at position 239 has similar amide-hydrogen bonding with Val264. However, a small segment in CH2 domain of the ADC ((264)VDVS) was found to have a slightly increased HDX rate compared to the wt- and C239-mAb constructs. The slightly increased HDX rate of the segment (264)VDVS in ADCs indicates that the further modification of Cys239 with drug-linkers only attenuates the local backbone amide hydrogen-bonding network between Cys239 and Val264. All other regions which are proximal to the site of drug conjugation are unaffected. The results demonstrate that the site-specific drug conjugation at the engineered Cys residue at the position 239 of HC does not impact the structural integrity of antibodies. The results also highlight the utility of applying HDX-MS to ADCs to gain a molecular level insight into the impact of site-specific conjugation technologies on the higher-order structure (HOS) of mAbs. The methodology can be applied generally to site-specific ADC modalities to understand the individual contributions of site-mutagenesis and drug-linker conjugation on the HOS of therapeutic candidate ADCs. PMID:25938577

  9. Application of atmospheric pressure photo ionization hydrogen/deuterium exchange high-resolution mass spectrometry for the molecular level speciation of nitrogen compounds in heavy crude oils.

    PubMed

    Cho, Yunju; Ahmed, Arif; Kim, Sunghwan

    2013-10-15

    We report here for the first time the application of atmospheric pressure photo ionization hydrogen/deuterium exchange (APPI HDX) coupled to high-resolution mass spectrometry for molecular level speciation of nitrogen containing compounds in crude oils. The speciation was done based on different combinations of ions produced from nitrogen containing compounds with various functional groups. To prove the concept, 20 nitrogen containing standard compounds were analyzed. As a result, it was shown that the nitrogen containing compound (M) with a primary amine functional group mainly produced a combination of [M - 2H + 2D](•+) and ([M - 2H + 2D] + D)(+) ions, one with a secondary amine including alkylated or phenylated pyrrole a combination of [M - H + D](•+) and ([M - H + D] + D)(+), one with a tertiary amine including N-alkylated or phenylated pyrrole a combination of [M](•+) and [M + D](+), and one with a pyridine functional group mostly [M + D](+) ions. The concept was successfully applied to do nitrogen speciation of resins fractions of two oil samples. Combined with the subsequent investigation of double bond equivalence distribution, it was shown that resins of Qinhuangdao crude oil sample contained mostly alkylated pyrrole and N-alkylated pyrrole type compounds but resins of shale oil extract contained mostly pyridine type nitrogen compounds. It was also shown that the speciation of individual elemental composition was also possible by use of this method. Overall, this study clearly shows that atmospheric pressure photo ionization hydrogen/deuterium exchange (APPI HDX) coupled to high-resolution mass spectrometry is a powerful analytical method to do nitrogen speciation of crude oil compounds at the molecular level. PMID:24033284

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

    NASA Astrophysics Data System (ADS)

    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 Å2 and 446 Å2; the [M + 3H]3+ ions also yield two different conformer types having collision cross sections of 340 Å2 and 367 Å2. 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).

  11. Combining Ion Mobility Spectrometry with Hydrogen-Deuterium Exchange and Top-Down MS for Peptide Ion Structure Analysis

    NASA Astrophysics Data System (ADS)

    Khakinejad, Mahdiar; Kondalaji, Samaneh Ghassabi; Maleki, Hossein; Arndt, James R.; Donohoe, Gregory C.; Valentine, Stephen J.

    2014-12-01

    The gas-phase conformations of electrosprayed ions of the model peptide KKDDDDIIKIIK have been examined by ion mobility spectrometry (IMS) and hydrogen deuterium exchange (HDX)-tandem mass spectrometry (MS/MS) techniques. [M+4H]4+ ions exhibit two conformers with collision cross sections of 418 Å2 and 471 Å2. [M+3H]3+ ions exhibit a predominant conformer with a collision cross section of 340 Å2 as well as an unresolved conformer (shoulder) with a collision cross section of ~367 Å2. Maximum HDX levels for the more compact [M+4H]4+ ions and the compact and partially-folded [M+3H]3+ ions are ~12.9, ~15.5, and ~14.9, respectively. Ion structures obtained from molecular dynamics simulations (MDS) suggest that this ordering of HDX level results from increased charge-site/exchange-site density for the more compact ions of lower charge. Additionally, a new model that includes two distance calculations (charge site to carbonyl group and carbonyl group to exchange site) for the computer-generated structures is shown to better correlate to the experimentally determined per-residue deuterium uptake. Future comparisons of IMS-HDX-MS data with structures obtained from MDS are discussed with respect to novel experiments that will reveal the HDX rates of individual residues.

  12. 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 0.24mL of CH3OD. The results showed that SFC separation and APPI/APCI HDX could be successfully performed using the suggested method. PMID:27020885

  13. Characterization of IgG1 Conformation and Conformational Dynamics by Hydrogen/Deuterium Exchange Mass Spectrometry

    SciTech Connect

    Houde, Damian; Arndt, Joseph; Domeier, Wayne; Berkowitz, Steven; Engen, John R.

    2009-04-22

    Protein function is dictated by protein conformation. For the protein biopharmaceutical industry, therefore, it is important to have analytical tools that can detect changes in protein conformation rapidly, accurately, and with high sensitivity. In this paper we show that hydrogen/deuterium exchange mass spectrometry (H/DX-MS) can play an important role in fulfilling this need within the industry. H/DX-MS was used to assess both global and local conformational behavior of a recombinant monoclonal IgG1 antibody, a major class of biopharmaceuticals. Analysis of exchange into the intact, glycosylated IgG1 (and the Fab and Fc regions thereof) showed that the molecule was folded, highly stable, and highly amenable to analysis by this method using less than a nanomole of material. With improved chromatographic methods, peptide identification algorithms and data-processing steps, the analysis of deuterium levels in peptic peptides produced after labeling was accomplished in 1--2 days. On the basis of peptic peptide data, exchange was localized to specific regions of the antibody. Changes to IgG1 conformation as a result of deglycosylation were determined by comparing exchange into the glycosylated and deglycosylated forms of the antibody. Two regions of the IgG1 (residues 236-253 and 292-308) were found to have altered exchange properties upon deglycosylation. These results are consistent with previous findings concerning the role of glycosylation in the interaction of IgG1 with Fc receptors. Moreover, the data clearly illustrate how H/DX-MS can provide important characterization information on the higher order structure of antibodies and conformational changes that these molecules may experience upon modification.

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

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

    Gas-phase hydrogen deuterium exchange (HDX), collision cross section (CCS) measurement, and molecular dynamics simulation (MDS) techniques were utilized to develop and compare three methods for estimating the relative surface area exposure of separate peptide chains within bovine insulin ions. Electrosprayed [M - 3H]3- and [M - 5H]5- insulin ions produced a single conformer type with respective collision cross sections of 528 ± 5 Å2 and 808 ± 2 Å2. [M - 4H]4- ions were comprised of more compact (Ω = 676 ± 3 Å2) and diffuse (i.e., more elongated, Ω = 779 ± 3 Å2) ion conformer types. Ions were subjected to HDX in the drift tube using D2O as the reagent gas. Collision-induced dissociation was used to fragment mobility-selected, isotopically labeled [M - 4H]4- and [M - 5H]5- ions into the protein subchains. Deuterium uptake levels of each chain can be explained by limited inter-chain isotopic scrambling upon collisional activation. Using nominal ion structures from MDS and a hydrogen accessibility model, the deuterium uptake for each chain was correlated to its exposed surface area. In separate experiments, the per-residue deuterium content for the protonated and deprotonated ions of the synthetic peptide KKDDDDDIIKIIK were compared. The differences in deuterium content indicated the regional HDX accessibility for cations versus anions. Using ions of similar conformational type, this comparison highlights the complementary nature of HDX data obtained from positive- and negative-ion analysis.

  15. 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.

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

    NASA Astrophysics Data System (ADS)

    Houde, Damian; Nazari, Zeinab E.; Bou-Assaf, George M.; Weiskopf, Andrew S.; Rand, Kasper D.

    2016-02-01

    When highly concentrated, an antibody solution can exhibit unusual behaviors, which can lead to unwanted properties, such as increased levels of protein aggregation and unusually high viscosity. Molecular modeling, along with many indirect biophysical measurements, has suggested that the cause for these phenomena can be due to short range electrostatic and/or hydrophobic protein-protein interactions. Hydrogen/deuterium exchange mass spectrometry (HDX-MS) is a useful tool for investigating protein conformation, dynamics, and interactions. However, "traditional" continuous dilution labeling HDX-MS experiments have limited utility for the direct analysis of solutions with high concentrations of protein. Here, we present a dialysis-based HDX-MS (di-HDX-MS) method as an alternative HDX-MS labeling format, which takes advantage of passive dialysis rather than the classic dilution workflow. We applied this approach to a highly concentrated antibody solution without dilution or significant sample manipulation, prior to analysis. Such a method could pave the way for a deeper understanding of the unusual behavior of proteins at high concentrations, which is highly relevant for development of biopharmaceuticals in industry.

  17. 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.

    2016-01-01

    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.

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

    NASA Astrophysics Data System (ADS)

    Houde, Damian; Nazari, Zeinab E.; Bou-Assaf, George M.; Weiskopf, Andrew S.; Rand, Kasper D.

    2016-04-01

    When highly concentrated, an antibody solution can exhibit unusual behaviors, which can lead to unwanted properties, such as increased levels of protein aggregation and unusually high viscosity. Molecular modeling, along with many indirect biophysical measurements, has suggested that the cause for these phenomena can be due to short range electrostatic and/or hydrophobic protein-protein interactions. Hydrogen/deuterium exchange mass spectrometry (HDX-MS) is a useful tool for investigating protein conformation, dynamics, and interactions. However, "traditional" continuous dilution labeling HDX-MS experiments have limited utility for the direct analysis of solutions with high concentrations of protein. Here, we present a dialysis-based HDX-MS (di-HDX-MS) method as an alternative HDX-MS labeling format, which takes advantage of passive dialysis rather than the classic dilution workflow. We applied this approach to a highly concentrated antibody solution without dilution or significant sample manipulation, prior to analysis. Such a method could pave the way for a deeper understanding of the unusual behavior of proteins at high concentrations, which is highly relevant for development of biopharmaceuticals in industry.

  19. 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.

  20. Automated Hydrogen/Deuterium Exchange Electron Transfer Dissociation High Resolution Mass Spectrometry Measured at Single-Amide Resolution

    NASA Astrophysics Data System (ADS)

    Landgraf, Rachelle R.; Chalmers, Michael J.; Griffin, Patrick R.

    2012-02-01

    Hydrogen deuterium exchange mass spectrometry (HDX-MS) is a well established method for the measurement of solution-phase deuterium incorporation into proteins, which can provide insight into protein conformational mobility. However, most HDX measurements are constrained to regions of the protein where pepsin proteolysis allows detection at peptide resolution. Recently, single-amide resolution deuterium incorporation has been achieved by limiting gas-phase scrambling in the mass spectrometer. This was accomplished by employing a combination of soft ionization and desolvation conditions coupled with the radical-driven fragmentation technique electron transfer dissociation (ETD). Here, a hybrid LTQ-Orbitrap XL is systematically evaluated for its utility in providing single-amide deuterium incorporation for differential HDX analysis of a nuclear receptor upon binding small molecule ligands. We are able to show that instrumental parameters can be optimized to minimize scrambling and can be incorporated into an established and fully automated HDX platform making differential single-amide HDX possible for bottom-up analysis of complex systems. We have applied this system to determine differential single amide resolution HDX data for the peroxizome proliferator activated receptor bound with two ligands of interest.

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

    PubMed Central

    Lindner, Robert; Heintz, Udo; Winkler, Andreas

    2015-01-01

    Rational design of optogenetic tools is inherently linked to the understanding of photoreceptor function. Structural analysis of elements involved in signal integration in individual sensor domains provides an initial idea of their mode of operation, but understanding how local structural rearrangements eventually affect signal transmission to output domains requires inclusion of the effector regions in the characterization. However, the dynamic nature of these assemblies renders their structural analysis challenging and therefore a combination of high- and low-resolution techniques is required to appreciate functional aspects of photoreceptors. This review focuses on the potential of hydrogen-deuterium exchange coupled to mass spectrometry (HDX-MS) for complementing the structural characterization of photoreceptors. In this respect, the ability of HDX-MS to provide information on conformational dynamics and the possibility to address multiple functionally relevant states in solution render this methodology ideally suitable. We highlight recent examples demonstrating the potential of HDX-MS and discuss how these results can help to improve existing optogenetic systems or guide the design of novel optogenetic tools. PMID:26157802

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

    PubMed

    Houde, Damian; Nazari, Zeinab E; Bou-Assaf, George M; Weiskopf, Andrew S; Rand, Kasper D

    2016-04-01

    When highly concentrated, an antibody solution can exhibit unusual behaviors, which can lead to unwanted properties, such as increased levels of protein aggregation and unusually high viscosity. Molecular modeling, along with many indirect biophysical measurements, has suggested that the cause for these phenomena can be due to short range electrostatic and/or hydrophobic protein-protein interactions. Hydrogen/deuterium exchange mass spectrometry (HDX-MS) is a useful tool for investigating protein conformation, dynamics, and interactions. However, "traditional" continuous dilution labeling HDX-MS experiments have limited utility for the direct analysis of solutions with high concentrations of protein. Here, we present a dialysis-based HDX-MS (di-HDX-MS) method as an alternative HDX-MS labeling format, which takes advantage of passive dialysis rather than the classic dilution workflow. We applied this approach to a highly concentrated antibody solution without dilution or significant sample manipulation, prior to analysis. Such a method could pave the way for a deeper understanding of the unusual behavior of proteins at high concentrations, which is highly relevant for development of biopharmaceuticals in industry. Graphical Abstract ᅟ. PMID:26860088

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

    PubMed

    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. Graphical Abstract ᅟ. PMID:26802030

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

    PubMed

    Iversen, Rasmus; Mysling, Simon; Hnida, Kathrin; Jrgensen, Thomas J D; Sollid, Ludvig M

    2014-12-01

    The multifunctional enzyme transglutaminase 2 (TG2) is the target of autoantibodies in the gluten-sensitive enteropathy celiac disease. In addition, the enzyme is responsible for deamidation of gluten peptides, which are subsequently targeted by T cells. To understand the regulation of TG2 activity and the enzyme's role as an autoantigen in celiac disease, we have addressed structural properties of TG2 in solution by using hydrogen/deuterium exchange monitored by mass spectrometry. We demonstrate that Ca(2+) binding, which is necessary for TG2 activity, induces structural changes in the catalytic core domain of the enzyme. Cysteine oxidation was found to abolish these changes, suggesting a mechanism whereby disulfide bond formation inactivates the enzyme. Further, by using TG2-specific human monoclonal antibodies generated from intestinal plasma cells of celiac disease patients, we observed that binding of TG2 by autoantibodies can induce structural changes that could be relevant for the pathogenesis. Detailed mapping of two of the main epitopes targeted by celiac disease autoantibodies revealed that they are located adjacent to each other in the N-terminal part of the TG2 molecule. PMID:25404341

  5. Amide-resolved hydrogen-deuterium exchange measurements from membrane-reconstituted polypeptides using exchange trapping and semiselective two-dimensional NMR.

    PubMed

    Dempsey, C E

    1994-11-01

    Amide-resolved, hydrogen-deuterium exchange from bee venom melittin reconstituted in fully hydrated vesicles suspended in D(2)O buffer was measured using a technique involving (1) trapping samples throughout an exchange time course by rapid freezing and lyophilization; and (2) dissolving the dried peptide/lipid mixtures in deuteromethanol to record high-resolution spectra using semiselective excitation pulses to select peptide amide signals in the presence of large excess lipid signals. Two-dimensional, amide-selective GaussNOESY and fingerprint-selective off-diagonal PingCOSY spectra are shown to be suitable for rapid acquisition of amide-selective spectra, obtained throughout a time course of amide exchange in the membrane-bound state. Membrane-reconstituted melittin is shown to contain two sequences of exchange-stable amides, corresponding to helical regions on either side of the single proline residue. PMID:22911389

  6. Thermodynamic and kinetic characterization of hydrogen-deuterium exchange in beta-phase palladium.

    PubMed

    Luo, Weifang; Cowgill, Donald F; Causey, Rion A

    2009-10-01

    A Sieverts' apparatus coupled with a residual gas analyzer (RGA) is an effective method to detect composition variations during isotopic exchange. This experimental setup provides a tool for the thermodynamic and kinetic characterization of H-D isotope exchange on Pd. The H or D concentrations in the gas and solid phases during the exchanges starting from (H(2) + Pd(x)D) and (D(2) + Pd(x)H) in beta-phase Pd were monitored over a temperature range from 173 to 298 K. The equilibrium properties, i.e., the H-D separation factors alpha and equilibrium constants K(HD), were obtained and found to be very close to those in the literature. The values of equilibrium constant reported here are the only experimental K(HD) data for H-D-Pd system. The H-D exchange rates on beta-Pd were measured for both exchange directions. A comprehensive kinetic model is proposed that correlates the exchange rate and the driving force composed of the reactant concentrations and the extent of deviation from equilibrium. The rate constants were obtained using this model for two exchange directions. The rates for the two exchange directions were found to be close to each other at 173 K, but they differ with temperature increase in such a way that the (D(2) + Pd(x)H) has a higher rate than (H(2) + Pd(x)D). The exchange activation energies obtained are 2.0 and 3.5 kJ/mol for the (H(2) + Pd(x)D) and (D(2) + Pd(x)H) directions, respectively. The difference in activation energies results from the difference in the energy states of (H(2) + Pd(x)D) and (D(2) + Pd(x)D). The calculated exchange profiles using this model agree with the experimental values reasonably well. PMID:19735117

  7. Analysis of distinct molecular assembly complexes of keratin K8 and K18 by hydrogen-deuterium exchange.

    PubMed

    Premchandar, Aiswarya; Kupniewska, Anna; Tarnowski, Krzysztof; Mücke, Norbert; Mauermann, Monika; Kaus-Drobek, Magdalena; Edelman, Aleksander; Herrmann, Harald; Dadlez, Michał

    2015-12-01

    Keratins are intermediate filament (IF) proteins that form complex filament systems in epithelial cells, thus serving as scaffolding elements and mechanical stress absorbers. The building blocks of keratin IFs are parallel coiled-coil dimers of two distinct sequence-related proteins distinguished as type I and type II keratins. To gain more insight into their structural dynamics, we resorted to hydrogen-deuterium exchange mass spectrometry of keratins K8 and K18, which are characteristic for simple epithelial cells. Using this powerful technique not employed with IFs before, we mapped patterns of protected versus unprotected regions in keratin complexes at various assembly levels. In particular, we localized protein segments exhibiting different hydrogen exchange patterns in tetramers versus filaments. We observed a general pattern of precisely positioned regions of stability intertwining with flexible regions, mostly represented by the non-α-helical segments. Notably, some regions within the coiled-coil domains are significantly more dynamic than others, while the IF-consensus motifs at the end domains of the central α-helical "rod" segment, which mediate the "head-to-tail" dimer-dimer interaction in the filament elongation process, become distinctly more protected upon formation of filaments. Moreover, to gain more insight into the dynamics of the individual keratins, we investigated the properties of homomeric preparations of K8 and K18. The physiological importance of keratins without a partner is encountered in both pathological and experimental situations when one of the two species is present in robust excess or completely absent, such as in gene-targeted mice. PMID:26434626

  8. Hydrogen/Deuterium Exchange and Electron-Transfer Dissociation Mass Spectrometry Determine the Interface and Dynamics of Apolipoprotein E Oligomerization

    PubMed Central

    Huang, Richard Y-C.; Garai, Kanchan; Frieden, Carl; Gross, Michael L.

    2011-01-01

    Apolipoprotein E, a 34 kDa protein, plays a key role in triglyceride and cholesterol metabolism. Of the three common isoforms (ApoE2, 3 and 4), only ApoE4 is a risk factor for Alzheimer’s Disease. All three isoforms of wild-type ApoE self-associate to form oligomers, a process that may have functional consequences. Although the C-terminal domain, residues 216–299, of ApoE is believed to mediate self-association, the specific residues involved in this process are not known. Here we report the use of hydrogen/deuterium exchange (H/DX) coupled with enzymatic digestion to identify those regions in the sequence of full-length apoE involved in oligomerization. For this determination, we compared the results of H/DX of the wild-type proteins and those of monomeric forms obtained by modifying four residues in the C-terminal domain. The three wild type and mutant isoforms show similar structures based on their similar H/DX kinetics and extents of exchange. Regions of the C-terminus (residues 230–270) of the ApoE isoforms show significant differences of deuterium uptake between oligomeric and monomeric forms, confirming that oligomerization occurs at these regions. To achieve single amino acid resolution, we examined the extents of H/DX by using electron transfer dissociation (ETD) fragmentation of peptides representing selected regions of both the monomeric and the oligomeric forms of ApoE4. From these experiments, we could identify the specific residues involved in ApoE oligomerization. In addition, our results verify that ApoE4 is composed of a compact structure at its N-terminal domain. Regions of C-terminal domain, however, appear to lack defined structure. PMID:21899263

  9. Synthesis, Spectroscopy, and Hydrogen/Deuterium Exchange in High-Spin Iron(II) Hydride Complexes

    PubMed Central

    2015-01-01

    Very few hydride complexes are known in which the metals have a high-spin electronic configuration. We describe the characterization of several high-spin iron(II) hydride/deuteride isotopologues and their exchange reactions with one another and with H2/D2. Though the hydride/deuteride signal is not observable in NMR spectra, the choice of isotope has an influence on the chemical shifts of distant protons in the dimers through the paramagnetic isotope effect on chemical shift. This provides the first way to monitor the exchange of H and D in the bridging positions of these hydride complexes. The rate of exchange depends on the size of the supporting ligand, and this is consistent with the idea that H2/D2 exchange into the hydrides occurs through the dimeric complexes rather than through a transient monomer. The understanding of H/D exchange mechanisms in these high-spin iron hydride complexes may be relevant to postulated nitrogenase mechanisms. PMID:24555749

  10. Construct Optimization for Protein NMR Structure Analysis Using Amide Hydrogen / Deuterium Exchange Mass Spectrometry

    PubMed Central

    Sharma, Seema; Zheng, Haiyan; Huang, Yuanpeng J.; Ertekin, Asli; Hamuro, Yoshitomo; Rossi, Paolo; Tejero, Roberto; Acton, Thomas B.; Xiao, Rong; Jiang, Mei; Zhao, Li; Ma, Li-Chung; Swapna, G. V. T.; Aramini, James M.; Montelione, Gaetano T.

    2009-01-01

    Disordered or unstructured regions of proteins, while often very important biologically, can pose significant challenges for resonance assignment and three-dimensional structure determination of the ordered regions of proteins by NMR methods. In this paper, we demonstrate the application of 1H/2H exchange mass spectrometry (DXMS) for the rapid identification of disordered segments of proteins and design of protein constructs that are more suitable for structural analysis by NMR. In this benchmark study, DXMS is applied to five NMR protein targets chosen from the Northeast Structural Genomics project. These data were then used to design optimized constructs for three partially disordered proteins. Truncated proteins obtained by deletion of disordered N- and C-terminal tails were evaluated using 1H-15N HSQC and 1H-15N heteronuclear NOE NMR experiments to assess their structural integrity. These constructs provide significantly improved NMR spectra, with minimal structural perturbations to the ordered regions of the protein structure. As a representative example, we compare the solution structures of the full length and DXMS-based truncated construct for a 77-residue partially disordered DUF896 family protein YnzC from Bacillus subtilis, where deletion of the disordered residues (ca. 40% of the protein) does not affect the native structure. In addition, we demonstrate that throughput of the DXMS process can be increased by analyzing mixtures of up to four proteins without reducing the sequence coverage for each protein. Our results demonstrate that DXMS can serve as a central component of a process for optimizing protein constructs for NMR structure determination. PMID:19306341

  11. Hydrogen-deuterium exchange of aromatic amines and amides using deuterated trifluoroacetic acid

    PubMed Central

    Giles, Richard; Lee, Amy; Jung, Erica; Kang, Aaron; Jung, Kyung Woon

    2014-01-01

    The H-D exchange of aromatic amines and amides, including pharmaceutically relevant compounds such as acetaminophen and diclofenac, was investigated using CF3COOD as both the sole reaction solvent and source of deuterium label. The described method is amenable to efficient deuterium incorporation for a wide variety of substrates possessing both electron-donating and electron-withdrawing substituents. Best results were seen with less basic anilines and highly activated acetanilides, reflecting the likelihood of different mechanistic pathways. PMID:25641994

  12. 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 techniques 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

  13. Comparative Analysis of Oxy-Hemoglobin and Aquomet-Hemoglobin by Hydrogen/Deuterium Exchange Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Sowole, Modupeola A.; Konermann, Lars

    2013-07-01

    The function of hemoglobin (Hb) as oxygen transporter is mediated by reversible O2 binding to Fe(2+) heme in each of the α and β subunits. X-ray crystallography revealed different subunit arrangements in oxy-Hb and deoxy-Hb. The deoxy state is stabilized by additional contacts, causing a rigidification that results in strong protection against hydrogen/deuterium exchange (HDX). Aquomet-Hb is a dysfunctional degradation product with four water-bound Fe(3+) centers. Heme release from aquomet-Hb is relatively facile, triggering oxidative damage of membrane lipids. Aquomet-Hb crystallizes in virtually the same conformation as oxy-Hb. Hence, it is commonly implied that the solution-phase properties of aquomet-Hb should resemble those of the oxy state. This work compares the structural dynamics of oxy-Hb and aquomet-Hb by HDX mass spectrometry (MS). It is found that the aquomet state exhibits a solution-phase structure that is significantly more dynamic, as manifested by elevated HDX levels. These enhanced dynamics affect the aquomet α and β subunits in a different fashion. The latter undergoes global destabilization, whereas the former shows elevated HDX levels only in the heme binding region. It is proposed that these enhanced dynamics play a role in facilitating heme release from aquomet-Hb. Our findings should be of particular interest to the MS community because oxy-Hb and aquomet-Hb serve as widely used test analytes for probing the relationship between biomolecular structure in solution and in the gas phase. We are not aware of any prior comparative HDX/MS experiments on oxy-Hb and aquomet-Hb.

  14. Hydrogen-deuterium exchange on plasma-exposed W and SS surface

    NASA Astrophysics Data System (ADS)

    Takagi, Ikuji; Nomura, Shinji; Minamimoto, Toshihiro; Akiyoshi, Masafumi; Kobayashi, Taishi; Sasaki, Takayuki

    2015-08-01

    The desorption cross section for hydrogen isotopes adsorbed on stainless steel (SS) and tungsten (W) has been evaluated experimentally to provide basic information on tritium exchange. One side of a sample sheet was alternately exposed to H and D plasma, and deuterium density on the surface was repeatedly observed using nuclear reaction analysis (NRA) under continuous plasma exposure. From the time dependent change in the deuterium density, the desorption cross sections for SS and W were estimated to be 6.9 ± 2.3 × 10-23 m2 and 4.6 ± 1.0 × 10-23 m2, respectively. No significant differences in the cross section between H and D plasma were observed. Recombinative desorption was found to dominate the desorption process owing to the low incident energy of hydrogen atoms.

  15. Structure-dependent degradation of polar compounds in weathered oils observed by atmospheric pressure photo-ionization hydrogen/deuterium exchange ultrahigh resolution mass spectrometry.

    PubMed

    Islam, Ananna; Kim, Donghwi; Yim, Un Hyuk; Shim, Won Joon; Kim, Sunghwan

    2015-10-15

    The resin fractions of fresh mixtures of three oils spilled during the M/V Hebei Spirit oil spill, as well as weathered oils collected at weathering stages II and IV from the oil spill site were analyzed and compared by atmospheric pressure photo-ionization hydrogen/deuterium exchange mass spectrometry (HDX MS). The significantly decreased abundance of N(+) and [N-H+D](+) ions suggested that secondary and tertiary amine-containing compounds were preferentially degraded during the early stage of weathering. [N+H](+) and [N+D](+) ions previously attributed to pyridine-type compounds degraded more slowly than secondary and tertiary amine-containing compounds. The preferential degradation of nitrogen-containing compounds was confirmed by photo-degradation experiments using 15 standard compounds. In addition, significant increases of [S1O1+H](+) and [S1O1+D](+) ions with higher DBE values were observed from fresh oil mixtures as compared to stages II and IV samples, and that could be linked with the decrease of higher DBE compounds of the S1 class. This study presented convincing arguments and evidence demonstrating that secondary and tertiary amines were more vulnerable to photo-degradation than compounds containing pyridine, and hence, preferential degradation depending on chemical structures must be considered in the production of hazardous or toxic components. PMID:25913675

  16. 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. Graphical Abstract Structural assignment of oxygen-containing compounds by (+/-) APCI/APPI HDX-MS and their speciation in degraded oil. PMID:26898203

  17. Structural basis of specific interactions of Lp-PLA2 with HDL revealed by hydrogen deuterium exchange mass spectrometry[S

    PubMed Central

    Cao, Jian; Hsu, Yuan-Hao; Li, Sheng; Woods, Virgil L.; Dennis, Edward A.

    2013-01-01

    Lipoprotein-associated phospholipase A2 (Lp-PLA2), specifically Group VIIA PLA2, is a member of the phospholipase A2 superfamily and is found mainly associated with LDL and HDL in human plasma. Lp-PLA2 is considered as a risk factor, a potential biomarker, a target for therapy in the treatment of cardiovascular disease, and evidence suggests that the level of Lp-PLA2 in plasma is associated with the risk of future cardiovascular and stroke events. The differential location of the enzyme in LDL/HDL lipoproteins has been suggested to affect Lp-PLA2 function and/or its physiological role and an abnormal distribution of the enzyme may correlate with diseases. Although a mutagenesis study suggested that a surface helix (residues 362–369) mediates the association between Lp-PLA2 and HDL, the molecular details and mechanism of association has remained unknown. We have now employed hydrogen deuterium exchange mass spectrometry to characterize the interaction between recombinant human Lp-PLA2 and human HDL. We have found that specific residues 113–120, 192–204, and 360–368 likely mediate HDL binding. In a previous study, we showed that residues 113–120 are important for Lp-PLA2-liposome interactions. We now find that residues 192–204 show a decreased deuteration level when Lp-PLA2 is exposed to apoA-I, but not apoA-II, the most abundant apoproteins in HDL, and additionally, residues 360–368 are only affected by HDL.The results suggest that apoA-I and phospholipid membranes play crucial roles in Lp-PLA2 localization to HDL. PMID:23089916

  18. Understanding the conformational impact of chemical modifications on monoclonal antibodies with diverse sequence variation using hydrogen/deuterium exchange mass spectrometry and structural modeling.

    PubMed

    Zhang, Aming; Hu, Ping; MacGregor, Paul; Xue, Yu; Fan, Haihong; Suchecki, Peter; Olszewski, Leonard; Liu, Aston

    2014-04-01

    Chemical modifications can potentially induce conformational changes near the modification site and thereby impact the safety and efficacy of protein therapeutics. Hydrogen/deuterium exchange mass spectrometry (HDX-MS) has emerged as a powerful analytical technique with high spatial resolution and sensitivity in detecting such local conformational changes. In this study, we utilized HDX-MS combined with structural modeling to examine the conformational impact on monoclonal antibodies (mAbs) caused by common chemical modifications including methionine (Met) oxidation, aspartic acid (Asp) isomerization, and asparagine (Asn) deamidation. Four mAbs with diverse sequences and glycosylation states were selected. The data suggested that the impact of Met oxidation was highly dependent on its location and glycosylation state. For mAbs with normal glycosylation in the Fc region, oxidation of the two conserved Met252 and Met428 (Kabat numbering) disrupted the interface interactions between the CH2 and CH3 domains, thus leading to a significant decrease in CH2 domain thermal stability as well as a slight increase in aggregation propensity. In contrast, Met oxidation in the variable region and CH3 domain had no detectable impact on mAb conformation. For aglycosylated mAb, Met oxidation could cause a more global conformational change to the whole CH2 domain, coincident with the larger decrease in thermal stability and significant increase in aggregation rate. Unlike Met oxidation, Asn deamidation and Asp isomerization mostly had very limited effects on mAb conformation, with the exception of succiminide intermediate formation which induced a measurable local conformational change to be more solvent protected. Structural modeling suggested that the succinimide intermediate was stabilized by adjacent aromatic amino acids through ring-ring stacking interactions. PMID:24597564

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

    SciTech Connect

    Yun, Youngjoo; Kim, Dong Kyun; Seo, Min-Duk; Kim, Kyeong-Man; Chung, Ka Young

    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 ubiquitously expressed and regulate a broad range of GPCRs, while arrestin1 and arrestin4 are expressed in the visual system. Although the functions of β-arrestin1 and β-arrestin2 widely overlap, β-arrestin2 has broader receptor selectivity, and a few studies have suggested that β-arrestin1 and β-arrestin2 have distinct cellular functions. Here, we compared the conformational dynamics of β-arrestin1 and β-arrestin2 by hydrogen/deuterium exchange mass spectrometry (HDX-MS). We also used the R169E mutant as a pre-activation model system. HDX-MS data revealed that β-strands II through IV were more dynamic in β-arrestin2 in the basal state, while the middle loop was more dynamic in β-arrestin1. With pre-activation, both β-arrestin1 and β-arrestin2 became more flexible, but broader regions of β-arrestin1 became flexible compared to β-arrestin2. The conformational differences between β-arrestin1 and β-arrestin2 in both the basal and pre-activated states might determine their different receptor selectivities and different cellular functions.

  20. Investigation of the structural stability of the human acidic fibroblast growth factor by hydrogen-deuterium exchange.

    PubMed

    Chi, Ya-Hui; Kumar, Thallampuranam Krishnaswamy S; Kathir, Karuppanan Muthusamy; Lin, Dong-Hai; Zhu, Guang; Chiu, Ing-Ming; Yu, Chin

    2002-12-24

    The conformational stability of the human acidic fibroblast growth factor (hFGF-1) is investigated using amide proton exchange and temperature-dependent chemical shifts, monitored by two-dimensional NMR spectroscopy. The change in free energy of unfolding (DeltaG(u)) of hFGF-1 is estimated to be 5.00 +/- 0.09 kcal.mol(-)(1). Amide proton-exchange rates of 74 residues (in hFGF-1) have been unambiguously measured, and the exchange process occurs predominately according to the conditions of the EX2 limit. The exchange rates of the fast-exchanging amide protons exposed to the solvent have been measured using the clean SEA-HSQC technique. The amide proton protection factor and temperature coefficient estimates show reasonably good correlation. Residues in beta-strands II and VI appear to constitute the stability core of the protein. Among the 12 beta-strands constituting the beta-barrel architecture of hFGF-1, beta-strand XI, located in the heparin binding domain, exhibits the lowest average protection factor value. Amide protons involved in the putative folding nucleation site in hFGF-1, identified by quench-flow NMR studies, do not represent the slow-exchanging core. Residues in portions of hFGF-1 experiencing high conformational flexibility mostly correspond to those involved in receptor recognition and binding. PMID:12484774

  1. Hydrogen-deuterium exchange between TpRu(PMe3)(L)X (L = PMe3 and X = OH, OPh, Me, Ph, or NHPh; L = NCMe and X = Ph) and deuterated arene solvents: evidence for metal-mediated processes.

    PubMed

    Feng, Yuee; Lail, Marty; Foley, Nicholas A; Gunnoe, T Brent; Barakat, Khaldoon A; Cundari, Thomas R; Petersen, Jeffrey L

    2006-06-21

    At elevated temperatures (90-130 degrees C), complexes of the type TpRu(PMe3)2X (X = OH, OPh, Me, Ph, or NHPh; Tp = hydridotris(pyrazolyl)borate) undergo regioselective hydrogen-deuterium (H/D) exchange with deuterated arenes. For X = OH or NHPh, H/D exchange occurs at hydroxide and anilido ligands, respectively. For X = OH, OPh, Me, Ph, or NHPh, isotopic exchange occurs at the Tp 4-positions with only minimal deuterium incorporation at the Tp 3- or 5-positions or PMe3 ligands. For TpRu(PMe3)(NCMe)Ph, the H/D exchange occurs at 60 degrees C at all three Tp positions and the phenyl ring. TpRu(PMe3)2Cl, TpRu(PMe3)2OTf (OTf = trifluoromethanesulfonate), and TpRu(PMe3)2SH do not initiate H/D exchange in C6D6 after extended periods of time at elevated temperatures. Mechanistic studies indicate that the likely pathway for the H/D exchange involves ligand dissociation (PMe3 or NCMe), Ru-mediated activation of an aromatic C-D bond, and deuteration of basic nondative ligand (hydroxide or anilido) or Tp positions via net D+ transfer. PMID:16771513

  2. The calcium-modulated structures of calmodulin and S100b proteins are useful to monitor hydrogen/deuterium exchange efficiency using matrix-assisted laser desorption ionization time-of-flight mass spectrometry.

    PubMed

    Pingerelli, Peter L; Ozols, Victor V; Saleem, Haroon; Anderson, Carly R; Burns, Richard S

    2009-01-01

    Hydrogen/deuterium exchange (HDX) using matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF) is a sensitive, salt-tolerant and high-throughput method useful to probe protein conformation and molecular interactions. However, a drawback of the MALDI HDX technique is that sample preparation methods can typically result in higher levels of artificial deuterium in-exchange and/or hydrogen back- exchange just prior to or during mass analysis; this may impair data reproducibility and impede structural and kinetic data interpretation. While methods to minimize effects of back-exchange during protein analyte deposition on MALDI plates have been reported, this study presents a readily available, highly sensitive protein control set to facilitate rapid MALDI HDX protocol workup. The Ca(2+)-induced solvent accessible surface area (ASA) changes of calmodulin (CaM) and S100 proteins were employed to monitor and optimize HDX protocol efficiency. Under non- stringent room temperature conditions, the Ca(2+)-induced deuterium exchange of CaM, DeltaD(ca2+ -apo), MH(+) shifts -17 to -24 Da, while S100 DeltaD(ca2+ -apo) MH(+) shifts +8 to +12 Da. By comparing the divergent CaM and S100 Ca(2+)-induced deuterium mass shift differences, HDX sample workup and MALDI plate spotting conditions can easily be monitored. PMID:19940340

  3. Correlating excipient effects on conformational and storage stability of an IgG1 monoclonal antibody with local dynamics as measured by hydrogen/deuterium-exchange mass spectrometry.

    PubMed

    Manikwar, Prakash; Majumdar, Ranajoy; Hickey, John M; Thakkar, Santosh V; Samra, Hardeep S; Sathish, Hasige A; Bishop, Steven M; Middaugh, C Russell; Weis, David D; Volkin, David B

    2013-07-01

    The effects of sucrose and arginine on the conformational and storage stability of an IgG1 monoclonal antibody (mAb) were monitored by differential scanning calorimetry (DSC) and size-exclusion chromatography (SEC), respectively. Excipient effects on protein physical stability were then compared with their effects on the local flexibility of the mAb in solution at pH 6, 25°C using hydrogen/deuterium-exchange mass spectrometry (H/D-MS). Compared with a 0.1 M NaCl control, sucrose (0.5 M) increased conformational stability (T(m) values), slowed the rate of monomer loss, reduced the formation of insoluble aggregates, and resulted in a global trend of small decreases in local flexibility across most regions of the mAb. In contrast, the addition of arginine (0.5 M) decreased the mAb's conformational stability, increased the rate of loss of monomer with elevated levels of soluble and insoluble aggregates, and led to significant increases in the local flexibility in specific regions of the mAb, most notably within the constant domain 2 of the heavy chain (C(H)2). These results provide new insights into the effect of sucrose and arginine on the local dynamics of IgG1 domains as well as preliminary correlations between local flexibility within specific segments of the C(H)2 domain (notably heavy chain 241-251) and the mAb's overall physical stability. PMID:23620222

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

    PubMed

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

    2016-03-01

    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

  5. 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

  6. NMR studies of metal-hydrogen systems lutetium trideuteride and zirconium beryllium (hydrogen/deuterium)

    NASA Astrophysics Data System (ADS)

    Kodibagkar, Vikram Divakar

    2002-11-01

    LuD3 is a complicated hcp rare-earth trihydride, with disorder evident in NMR and neutron diffraction. Deuterium NMR spectra were obtained and relaxation times T1 and T2 were measured at different values of temperature. Three-pulse spin alignment echo experiments were also conducted for detecting slower motions. Deuterium spectra below room-T show substantial disorder (with small distortions), in agreement with neutron diffraction. Above room-T, NMR spectral features sharpen, showing that the disorder/distortions are motionally averaged away. The overall NMR linewidth is independent of temperature and the high-T spectra fit reasonably to the sum of three quadrupolar doublets corresponding to three distinct deuterium sites. Long-range diffusion remains too slow (even at 364 K) to average the components into a single feature. 3-pulse spin-alignment echo data show diffusive motion down to 219 K. The motion of H/D atoms in ZrBe2(H/D)x (x ≈ 1.5) was also studied using deuterium and beryllium NMR. A temperature-induced structural transition was observed near 240 K in the deuteride and near 200 K in the hydride. In the deuteride, on decreasing the temperature below 240 K, T2 decreases rapidly and T1 increases rapidly, indicating that the D atom mobility is dramatically reduced. From the 9Be spectra of ZrBe2(H/D)x we see the presence of the transition in both the hydride and deuteride at 200 K and 235 K respectively. Above the transition temperature a single pair of quadrupolar satellites is seen. Each quadrupolar satellite splits into two resonances (with splittings nu Q1 and nuQ2) below the transition temperature in the hydride and deuteride. We propose that the transition involves ordering of the H/D vacancies (25% at x = 1.5). 9Be NMR also demonstrates a strong preferential alignment of the powder particles of ZrBe2Hx and ZrBe2Dx in the high magnetic fields used for NMR. This alignment, which indicates a high anisotropy in the magnetic susceptibility, is not seen in the bare compound ZrBe2.

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

    SciTech Connect

    Lewis, H.A.; Wang, C.; Zhao, X.; Hamuro, Y.; Conners, K.; Kearins, M.C.; Lu, F.; Sauder, J.M.; Molnar, K.S.; Coales, S.J.; Maloney, P.C.; Guggino, W.B.; Wetmore, D.R.; Weber, P.C.; Hunt, J.F.

    2012-04-30

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

  8. 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

    2014-08-01

    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. PMID:24988145

  9. Effect of Fc-Glycan Structure on the Conformational Stability of IgG Revealed by Hydrogen/Deuterium Exchange and Limited Proteolysis.

    PubMed

    Fang, Jing; Richardson, Jason; Du, Zhimei; Zhang, Zhongqi

    2016-02-16

    Human therapeutic immunoglobulin gamma (IgG) molecules contain an N-glycan on each of their Fc CH2 domains. These glycans include high-mannose, hybrid, and complex types. Recombinant IgG molecules containing high-mannose glycans have been shown to clear faster in human blood, and exhibit decreased thermal stability. The molecular mechanism behind these observations, however, is not well understood. In this work, we used hydrogen/deuterium exchange combined with mass spectrometry (HDX MS), as well as proteolytic degradation under a native-like condition, to assess the impact of different glycoforms on the molecular structure and stability of recombinant IgG1 and IgG2 molecules expressed from Chinese hamster ovary cells. Our HDX MS data indicate that the conformation of these IgG molecules was indeed influenced by the glycan structure. IgG molecules containing high-mannose and hybrid glycans showed more conformational flexibility in the CH2 domain. This conclusion was further supported by the analysis of glycopeptides released from these molecules by trypsin digestion under a native-like condition. The higher CH2 conformational flexibility of IgG molecules with high-mannose and hybrid glycans contributes to their decreased thermal stability. IgG molecules containing sialylated glycans in the CH2 domain exhibited similar enzymatic degradation behavior as high-mannose glycans, suggesting decreased CH2-domain stability compared to shorter complex glycans, likely resulting from steric effect that decreased the glycan-CH2 domain interaction. PMID:26812426

  10. A Binding Site on IL-17A for Inhibitory Macrocycles Revealed by Hydrogen/Deuterium Exchange Mass Spectrometry.

    PubMed

    Espada, Alfonso; Broughton, Howard; Jones, Spencer; Chalmers, Michael J; Dodge, Jeffrey A

    2016-03-10

    Computational assessment of the IL-17A structure identified two distinct binding pockets, the β-hairpin pocket and the α-helix pocket. The β-hairpin pocket was hypothesized to be the site of binding for peptide macrocycles. Support for this hypothesis was obtained using HDX-MS which revealed protection to exchange only within the β-hairpin pocket. This data represents the first direct structural evidence of a small molecule binding site on IL-17A that functions to disrupt the interaction with its receptor. PMID:26854023

  11. Conformational changes of the glucocorticoid receptor ligand binding domain induced by ligand and cofactor binding, and the location of cofactor binding sites determined by hydrogen/deuterium exchange mass spectrometry

    PubMed Central

    Frego, Lee; Davidson, Walter

    2006-01-01

    HXMS (hydrogen/deuterium exchange mass spectrometry) of the glucocorticoid receptor ligand-binding domain (GR LBD) complexed with the agonist dexamethasone and the antagonist RU-486 is described. Variations in the rates of exchange were observed in regions consistent with the published crystal structures of GR LBD complexed with RU-486 when compared with the GR dexamethasone complex. We also report the HXMS results for agonist-bound GR LBD with the coactivator transcriptional intermediary factor 2 (TIF2) and anatagonist-bound GR LBD with nuclear receptor corepressor (NCoR). Alterations in exchange rates observed for agonist-bound GR LBD with TIF2 present were consistent with the published crystal structural contacts for the complex. Alterations in exchange rates observed for antagonist-bound GR LBD with NCoR were a subset of those observed with TIF2 binding, suggesting a common or overlapping binding site for coactivator and corepressor. PMID:16600964

  12. Dimerization of the type IV pilin from Pseudomonas aeruginosa strain K122-4 results in increased helix stability as measured by time-resolved hydrogen-deuterium exchange

    PubMed Central

    Lento, Cristina; Wilson, Derek J.; Audette, Gerald F.

    2015-01-01

    Truncated pilin monomers from Pseudomonas aeruginosa strain K122-4 (ΔK122) have been shown to enter a monomer-dimer equilibrium in solution prior to oligomerization into protein nanotubes. Here, we examine the structural changes occurring between the monomeric and dimeric states of ΔK122 using time-resolved hydrogen-deuterium exchange mass spectrometry. Based on levels of deuterium uptake, the N-terminal α-helix and the loop connecting the second and third strands of the anti-parallel β-sheet contribute significantly to pilin dimerization. Conversely, the antiparallel β-sheet and αβ loop region exhibit increased flexibility, while the receptor binding domain retains a rigid conformation in the equilibrium state. PMID:26798830

  13. Neutron structure of subtilisin BPN prime : Effects of chemical environment on hydrogen-bonding geometrics and the pattern of hydrogen-deuterium exchange in secondary structure elements

    SciTech Connect

    Kossiakoff, A.A.; Ultsch, M. ); White, S. ); Eigenbrot, C. )

    1991-02-05

    The neutron structure of subtilisin BPN{prime} has been refined and analyzed at 2.0-{angstrom} resolution. The structure studied was a mutant variant of subtilisin, Met222 {yields} Gln, and was used because large, uninhibited crystals could be grown, which was not the case for the native molecule. Comparison of the structure with that of the native molecule indicated that the two structures are essentially the same. Using the capability of the neutron method to locate hydrogen and deuterium atoms, the protonation states of the six histidine residues were assigned. The active site histidine, His64, was found to be neutral at the pH of the analysis (pH 6.1). This group has an unexpectedly low pK{sub a} compared to assignments made by other techniques. The altered pK{sub a} of the group could result from electrostatic effects of other molecules in the crystal lattice. The dihedral conformations of a majority of the hydroxyl rotors were assigned. The hydrogen exchange pattern of subtilisin identified the {beta}-sheet and {alpha}-helix secondary structure elements to be the most resistant to exchange. Fifty-five percent of the peptide amide hydrogens were fully exchanged, 15% unexchanged, and 30% partially exchanged. The largest concentration of unexchanged sites was in the seven-stranded parallel {beta}-sheet, in which there were 11 fully protected groups. Little correlation was found between H-bound length and angle and a peptide group's susceptibility toward exchange. Of the five {alpha}-helices the most protected from exchange is the one defined by residues 224-236. The pattern of exchange identifies regions in this helix where the H-bonding regularity is disrupted.

  14. Isotopic effect study in the LHCD and LHH experiments in hydrogen/deuterium plasmas of the FT-2 tokamak

    SciTech Connect

    Lashkul, S. I.; Altukhov, A. B.; Gusakov, E. Z.; Dyachenko, V. V.; Esipov, L. A.; Irzak, M. A.; Kantor, M. Yu.; Kouprienko, D. V.; Saveliev, A. N.; Shatalin, S. V.; Stepanov, A. Yu.

    2014-02-12

    Results of comparative experimental studies of the efficiency of lower hybrid current drive (LHCD) and lower hybrid heating (LHH) in the FT-2 tokamak in hydrogen and deuterium plasmas are presented. In the new comparative experimental runs in deuterium/hydrogen plasmas suppression of the LHCD and beginning of the interaction of LH waves with ions is controlled by the plasma density rise. Role of parametric instabilities in CD switch-off is considered. In order to analyze the experimentally observed effect of LHCD the GRILL3D and FRTC codes has been used.

  15. 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

    2009-09-01

    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 undesired amide back exchange. PMID:19670873

  16. Characterization of water exchange and two-phase flow in porous gas diffusion materials by hydrogen-deuterium contrast neutron radiography

    NASA Astrophysics Data System (ADS)

    Manke, Ingo; Hartnig, Christoph; Kardjilov, Nikolay; Messerschmidt, Matthias; Hilger, André; Strobl, Markus; Lehnert, Werner; Banhart, John

    2008-06-01

    Liquid water exchange in two-phase flows within hydrophobic porous gas diffusion materials of polymer electrolyte membrane fuel cells was investigated spatially resolved with H-D contrast neutron radiography. A commonly used one-phase model is sufficient to describe water exchange characteristics at low water production rates. At higher rates, however, a significantly higher exchange velocity is found than predicted by a simple model. A new model for the water transport is derived based on an eruptive mechanism guided by Haines jumps, which is supported by recent experimental findings and leads to a very good agreement with the experiments.

  17. Fluoroketone Inhibition of Ca2+-Independent Phospholipase A2 through Binding Pocket Association Defined by Hydrogen/Deuterium Exchange and Molecular Dynamics

    PubMed Central

    2012-01-01

    The mechanism of inhibition of group VIA Ca2+-independent phospholipase A2 (iPLA2) by fluoroketone (FK) ligands is examined by a combination of deuterium exchange mass spectrometry (DXMS) and molecular dynamics (MD). Models for iPLA2 were built by homology with the known structure of patatin and equilibrated by extensive MD simulations. Empty pockets were identified during the simulations and studied for their ability to accommodate FK inhibitors. Ligand docking techniques showed that the potent inhibitor 1,1,1,3-tetrafluoro-7-phenylheptan-2-one (PHFK) forms favorable interactions inside an active-site pocket, where it blocks the entrance of phospholipid substrates. The polar fluoroketone headgroup is stabilized by hydrogen bonds with residues Gly486, Gly487, and Ser519. The nonpolar aliphatic chain and aromatic group are stabilized by hydrophobic contacts with Met544, Val548, Phe549, Leu560, and Ala640. The binding mode is supported by DXMS experiments showing an important decrease of deuteration in the contact regions in the presence of the inhibitor. The discovery of the precise binding mode of FK ligands to the iPLA2 should greatly improve our ability to design new inhibitors with higher potency and selectivity. PMID:23256506

  18. Hydrogen/Deuterium Exchange Reflects Binding of Human Centrin 2 to Ca2+ and Xeroderma Pigmentosum Group C Peptide: An Example of EX1 Kinetics

    PubMed Central

    Sperry, Justin B.; Ryan, Zachary C.; Kumar, Rajiv; Gross, Michael L.

    2012-01-01

    Xeroderma pigmentosum (XP) is a genetic disease affecting 1 in 10,000-100,000 and predisposes people to early-age skin cancer, a disease that is increasing. Those with XP have decreased ability to repair UV-induced DNA damage, leading to increased susceptibility of cancerous non-melanomas and melanomas. A vital, heterotrimeric protein complex is linked to the nucleotide excision repair pathway for the damaged DNA. The complex consists of XPC protein, human centrin 2, and RAD23B. One of the members, human centrin 2, is a ubiquitous, acidic, Ca2+-binding protein belonging to the calmodulin superfamily. The XPC protein contains a sequence motif specific for binding to human centrin 2. We report here the Ca2+-binding properties of human centrin 2 and its interaction with the XPC peptide motif. We utilized a region-specific H/D exchange protocol to localize the interaction of the XPC peptide with the C-terminal domain of centrin, the binding of which is different than that of calmodulin complexes. The binding dynamics of human centrin 2 to the XPC peptide in the absence and presence of Ca2+ are revealed by the observation of EX1 H/D exchange regime, indicating that a locally unfolded population exists in solution and undergoes fast H/D exchange. PMID:23439742

  19. A comparative neutronic feasibility study for a hydrogen, deuterium and helium cold neutron sources situated in the center of a nuclear reactor core

    NASA Astrophysics Data System (ADS)

    Chatila, Malek

    A tool was developed to calculate the average cold neutron flux that could be generated for a spherically shaped cold neutron source situated in the center of a nuclear reactor core. The tool also estimates the subsequent nuclear heating of the cold source. The results were compared for three different cold source mediums; hydrogen, deuterium and helium. The tool utilizes the consistent energy dependent P1 equations to generate the fast neutron energy spectrum, the Grueling-Goertzel equations to generate the slow spectrum and the Proton Gas Model to generate the cold energy spectrum. These spectrums are then used to collapse the group constants into three energy groups. The cold flux that can be generated in different mediums is then calculated by utilizing the three energy group constants in SN-6, 2 regions calculations.

  20. ETD in a Traveling Wave Ion Guide at Tuned Z-Spray Ion Source Conditions Allows for Site-Specific Hydrogen/Deuterium Exchange Measurements

    PubMed Central

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

    2012-01-01

    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. PMID:21952892

  1. "TOF2H": A precision toolbox for rapid, high density/high coverage hydrogen-deuterium exchange mass spectrometry via an LC-MALDI approach, covering the data pipeline from spectral acquisition to HDX rate analysis

    PubMed Central

    Nikamanon, Pornpat; Pun, Elroy; Chou, Wayne; Koter, Marek D; Gershon, Paul D

    2008-01-01

    Background Protein-amide proton hydrogen-deuterium exchange (HDX) is used to investigate protein conformation, conformational changes and surface binding sites for other molecules. To our knowledge, software tools to automate data processing and analysis from sample fractionating (LC-MALDI) mass-spectrometry-based HDX workflows are not publicly available. Results An integrated data pipeline (Solvent Explorer/TOF2H) has been developed for the processing of LC-MALDI-derived HDX data. Based on an experiment-wide template, and taking an ab initio approach to chromatographic and spectral peak finding, initial data processing is based on accurate mass-matching to fully deisotoped peaklists accommodating, in MS/MS-confirmed peptide library searches, ambiguous mass-hits to non-target proteins. Isotope-shift re-interrogation of library search results allows quick assessment of the extent of deuteration from peaklist data alone. During raw spectrum editing, each spectral segment is validated in real time, consistent with the manageable spectral numbers resulting from LC-MALDI experiments. A semi-automated spectral-segment editor includes a semi-automated or automated assessment of the quality of all spectral segments as they are pooled across an XIC peak for summing, centroid mass determination, building of rates plots on-the-fly, and automated back exchange correction. The resulting deuterium uptake rates plots from various experiments can be averaged, subtracted, re-scaled, error-barred, and/or scatter-plotted from individual spectral segment centroids, compared to solvent exposure and hydrogen bonding predictions and receive a color suggestion for 3D visualization. This software lends itself to a "divorced" HDX approach in which MS/MS-confirmed peptide libraries are built via nano or standard ESI without source modification, and HDX is performed via LC-MALDI using a standard MALDI-TOF. The complete TOF2H package includes additional (eg LC analysis) modules. Conclusion "TOF2H" provides a comprehensive HDX data analysis package that has accelerated the processing of LC-MALDI-based HDX data in the authors' lab from weeks to hours. It runs in a standard MS Windows (XP or Vista) environment, and can be downloaded or obtained from the authors at no cost. PMID:18803853

  2. Diffusion of hydrogen, deuterium, and tritium in niobium

    SciTech Connect

    Matusiewicz, Gerald Robert

    1981-01-01

    The diffusion of hydrogen in niobium was investigated over the temperature range 148 to 500 degrees Kelvin, using measurements of the elastic after effect caused by long range diffusion (the Gorsky Effect). Relaxation curves for pure annealed niobium were generally not of the single exponential form expected from the Gorsky Effect theory, but were described well by a sum of two exponential curves with different amplitudes and relaxation times. The effects of oxygen and nitrogen interstitials on the diffusion were studied and were not in agreement with conventional trapping models. Deuterium and tritium diffusion in niobium were also studied, and a non-classical isotope effect was observed. Hydrogen diffusion coefficients in several Nb-Ta alloys were measured, and the diffusivity in all these alloys exhibited a non-Arrhenius temperature dependence. Experimental results were compared to several models for diffusion and trapping. A model is presented which can account for the form of the relaxation curves observed in pure, annealed niobium.

  3. Computation of hyperfine energies of hydrogen, deuterium and tritium quantum dots

    NASA Astrophysics Data System (ADS)

    Çakır, Bekir; Özmen, Ayhan; Yakar, Yusuf

    2016-01-01

    The hyperfine energies and hyperfine constants of the ground and excited states of hydrogen, deuterium and tritium quantum dots(QDs) are calculated. Quantum genetic algorithm (QGA) and Hartree-Fock-Roothaan (HFR) methods are employed to calculate the unperturbed wave functions and energy eigenvalues. The results show that in the medium and strong confinement regions the hyperfine energy and hyperfine constant are strongly affected by dot radius, impurity charge, electron spin orientation, impurity spin and impurity magnetic moment. Besides, in all dot radii, the hyperfine splitting and hyperfine constant of the confined hydrogen and tritium atoms are approximately equivalent to each other and they are greater than the confined deuterium atom.

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

    SciTech Connect

    David Gaskell

    2001-05-01

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

  5. The ground state properties of spin-aligned atomic hydrogen, deuterium, and tritium

    NASA Technical Reports Server (NTRS)

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

    1975-01-01

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

  6. The effect of the cw hydrogen/deuterium fluoride chemical laser with different diluents

    SciTech Connect

    Jiang, Z.; Hua, W.; Chen, J.; Zhao, Y.

    1996-12-31

    The He is usually used as diluent in combustion cw hydrogen/deuterium fluoride (HF/DF) chemical lasers. Sometimes the N{sub 2} is also used as diluent in cw HF/DF chemical laser because N{sub 2} is cheaper than the He. It was thought that the efficiency of cw HF/DF laser with N{sub 2} diluent was lower than that of HF/DF laser with He diluent since the molecular weight of N{sub 2} is heavier than that of He. In this paper, the performance of cw DF chemical lasers with He and N{sub 2} diluent was investigated. The small signal gain, power spectral distributions, cavity pressure, power and the efficiency of DF lasers with these two diluents have been calculated using a finite-difference technique for the numerical integration of the steady and unsteady Navier-Stokes equation with reactive flow (compressibility scaling method -- CSM), which was developed in the chemical gas dynamic laboratory of the state institute of applied chemistry in Russia. The numerical results show that the efficiency of DF lasers with Na{sub 2} diluent is not lower than that of the lasers with He diluent.

  7. ARTICLES: Numerical investigation of a purely chemical generator of atomic gaseous hydrogen (deuterium) and of a cw H(D)-O3-CO2 laser utilizing this generator

    NASA Astrophysics Data System (ADS)

    Bashkin, A. S.; Gamzatov, N. M.; Oraevskiĭ, A. N.

    1987-02-01

    A numerical investigation is reported of a generator of atomic gaseous hydrogen (or deuterium) and of a cw low-toxicity H(D)-O3-CO2 laser utilizing this generator. A high nonequilibrium concentration of H (D) atoms is achieved in a supersonic oxygen-hydrogen (or oxygen-deuterium) flame in this generator. Hydrogen (deuterium) combustion regimes convenient for experimental realization and characterized by a molar concentration of atomic hydrogen (deuterium) in the flame by up to ~15%, are identified. Numerical optimization of all the components of a cw laser system in respect of the principal parameters is used to show that a cw D-O3-CO2 laser utilizing this chemical generator of deuterium atoms can have high output characteristics: a specific output power of ~140 W·sec·g-1, a chemical efficiency of ~10%, and an inversion zone of over 30 cm length in the downstream direction.

  8. Liquid droplet heat exchanger studies

    NASA Technical Reports Server (NTRS)

    Bruckner, A. P.; Hedges, D. E.; Yungster, S.

    1987-01-01

    Recent analytical and experimental investigations of the liquid droplet heat exchanger (LDHX) concept for space power applications are described. The performance of the LDHX is compared to that of a conventional heat exchanger for heat rejection applications in a Brayton cycle, using the mass-specific heat exchanger effectiveness as a figure of merit. It is shown that the LDHX has an order of magnitude advantage over the conventional heat exchanger. Furthermore, significant improvement in cycle efficiency and power to mass ratio is possible. Two-phase flow experiments in a laboratory scale LDHX, using air and water as the two media, show very good agreement with the quasi-one-dimensional model used in the parametric studies.

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

    PubMed

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

    2006-09-21

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

  10. Applications of mass spectrometry to the study of protein aggregation.

    PubMed

    Bronsoms, Sílvia; Trejo, Sebastián A

    2015-01-01

    Mass spectrometry is an analytical technique that measures the mass-to-charge ratio of charged particles. Nowadays mass spectrometry-based approaches play a pivotal role in both detection and characterization of proteins. Here we describe two applications to study insoluble proteins: (a) hydrogen/deuterium exchange combined with mass spectrometry to analyze structural properties of amyloid fibrils and (b) the screening for inhibitors of the aggregation process by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. PMID:25447874

  11. A substrate-induced change in the stereospecificity of the serine-hydroxymethyltransferase-catalysed exchange of the alpha-protons of amino acids--evidence for a second catalytic site.

    PubMed

    Fitzpatrick, T B; Malthouse, J P

    1998-02-15

    NMR has been used to study the catalysis of the hydrogen-deuterium exchange of the alpha-protons of amino acids by serine hydroxymethyltransferase (EC 2.1.2.1) from Escherichia coli. 13C-NMR was used to follow the exchange of the alpha-protons of [2-13C]glycine. The enzyme-catalysed first-order exchange rate of the pro-2S proton of glycine was approximately 7000 times more efficient than that of the pro-2R proton of glycine at both pH 7.0 and 7.8. 1H-NMR was used to follow the hydrogen-deuterium exchange rates of the alpha-protons of L- and D-2-amino derivatives of butyric, pentanoic and hexanoic acids at pH 7.8. Increasing the size of the R-group leads to a progressive change in the stereospecificity of the exchange reaction from the pro-2S proton of glycine to the 2R proton of L-amino acids. The stereospecificity for the alpha-protons of L-amino acids increased as the size of the R-group increased. With glycine, removal of tetrahydrofolate led to a large decrease in the stereospecificity of the exchange reaction but did not affect the exchange rates of the alpha-protons of any of the larger amino acids studied. We show that the Schiff base formed between L-2-aminohexanoic acid (L-norleucine) and pyridoxal 5'-phosphate binds at a different site from the Schiff base between glycine and pyridoxal 5'-phosphate. The molecular basis of these results is discussed. PMID:9523719

  12. Detection of weak hydrogen bonding to fluoro and nitro groups in solution using H/D exchange.

    PubMed

    Shugrue, C R; DeFrancisco, J R; Metrano, A J; Brink, B D; Nomoto, R S; Linton, B R

    2016-02-21

    Hydrogen/deuterium (H/D) exchange can be a sensitive technique for measuring the strength of hydrogen bonding to neutral organic nitro and fluoro groups. The slower rates of reaction in comparison to suitable controls suggest that hydrogen bonding is present, albeit rather weak. PMID:26782121

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

    NASA Astrophysics Data System (ADS)

    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.

  14. 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. PMID:26810432

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

    NASA Astrophysics Data System (ADS)

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

    2016-01-01

    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.

  16. Quantitative Assessment of Protein Structural Models by Comparison of H/D Exchange MS Data with Exchange Behavior Accurately Predicted by DXCOREX

    NASA Astrophysics Data System (ADS)

    Liu, Tong; Pantazatos, Dennis; Li, Sheng; Hamuro, Yoshitomo; Hilser, Vincent J.; Woods, Virgil L.

    2012-01-01

    Peptide amide hydrogen/deuterium exchange mass spectrometry (DXMS) data are often used to qualitatively support models for protein structure. We have developed and validated a method (DXCOREX) by which exchange data can be used to quantitatively assess the accuracy of three-dimensional (3-D) models of protein structure. The method utilizes the COREX algorithm to predict a protein's amide hydrogen exchange rates by reference to a hypothesized structure, and these values are used to generate a virtual data set (deuteron incorporation per peptide) that can be quantitatively compared with the deuteration level of the peptide probes measured by hydrogen exchange experimentation. The accuracy of DXCOREX was established in studies performed with 13 proteins for which both high-resolution structures and experimental data were available. The DXCOREX-calculated and experimental data for each protein was highly correlated. We then employed correlation analysis of DXCOREX-calculated versus DXMS experimental data to assess the accuracy of a recently proposed structural model for the catalytic domain of a Ca2+-independent phospholipase A2. The model's calculated exchange behavior was highly correlated with the experimental exchange results available for the protein, supporting the accuracy of the proposed model. This method of analysis will substantially increase the precision with which experimental hydrogen exchange data can help decipher challenging questions regarding protein structure and dynamics.

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

    NASA Astrophysics Data System (ADS)

    Meezan, N. B.; Berzak Hopkins, L. F.; Le Pape, S.; Divol, L.; MacKinnon, A. J.; Döppner, T.; Ho, D. D.; Jones, O. S.; Khan, S. F.; Ma, T.; Milovich, J. L.; Pak, A. E.; Ross, J. S.; Thomas, C. A.; Benedetti, L. R.; Bradley, D. K.; Celliers, P. M.; Clark, D. S.; Field, J. E.; Haan, S. W.; Izumi, N.; Kyrala, G. A.; Moody, J. D.; Patel, P. K.; Ralph, J. E.; Rygg, J. R.; Sepke, S. M.; Spears, B. K.; Tommasini, R.; Town, R. P. J.; Biener, J.; Bionta, R. M.; Bond, E. J.; Caggiano, J. A.; Eckart, M. J.; Gatu Johnson, M.; Grim, G. P.; Hamza, A. V.; Hartouni, E. P.; Hatarik, R.; Hoover, D. E.; Kilkenny, J. D.; Kozioziemski, B. J.; Kroll, J. J.; McNaney, J. M.; Nikroo, A.; Sayre, D. B.; Stadermann, M.; Wild, C.; Yoxall, B. E.; Landen, O. L.; Hsing, W. W.; Edwards, M. J.

    2015-06-01

    High Density Carbon (or diamond) is a promising ablator material for use in near-vacuum hohlraums, as its high density allows for ignition designs with laser pulse durations of <10 ns. A series of Inertial Confinement Fusion (ICF) experiments in 2013 on the National Ignition Facility [Moses et al., Phys. Plasmas 16, 041006 (2009)] culminated in a deuterium-tritium (DT) layered implosion driven by a 6.8 ns, 2-shock laser pulse. This paper describes these experiments and comparisons with ICF design code simulations. Backlit radiography of a tritium-hydrogen-deuterium (THD) layered capsule demonstrated an ablator implosion velocity of 385 km/s with a slightly oblate hot spot shape. Other diagnostics suggested an asymmetric compressed fuel layer. A streak camera-based hot spot self-emission diagnostic (SPIDER) showed a double-peaked history of the capsule self-emission. Simulations suggest that this is a signature of low quality hot spot formation. Changes to the laser pulse and pointing for a subsequent DT implosion resulted in a higher temperature, prolate hot spot and a thermonuclear yield of 1.8 × 1015 neutrons, 40% of the 1D simulated yield.

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

    SciTech Connect

    Meezan, N. B. Hopkins, L. F. Berzak; Pape, S. Le; Divol, L.; MacKinnon, A. J.; Döppner, T.; Ho, D. D.; Jones, O. S.; Khan, S. F.; Ma, T.; Milovich, J. L.; Pak, A. E.; Ross, J. S.; Thomas, C. A.; Benedetti, L. R.; Bradley, D. K.; Celliers, P. M.; Clark, D. S.; Field, J. E.; Haan, S. W.; and others

    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. 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.

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

    SciTech Connect

    Gertsman, Ilya; Komives, Elizabeth A.; Johnson, John E.

    2010-03-22

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

  20. Exchange Studies as Actor-Networks: Following Korean Exchange Students in Swedish Higher Education

    ERIC Educational Resources Information Center

    Ahn, Song-ee

    2011-01-01

    This article explores how Korean exchange students organized their studies during exchange programs in Swedish higher education. For most students, the programs became a disordered period in relation to their education. The value of exchange studies seems mainly to be extra-curricular. Drawing upon actor network theory, the article argues that the…

  1. Erosion and redeposition behavior of selected NET-candidate materials under high-flux hydrogen, deuterium plasma bombardment in pisces

    NASA Astrophysics Data System (ADS)

    Franconi, E.; Hirooka, Y.; Conn, R. W.; Leung, W. K.; Labombard, B.; Nygren, R. E.

    1989-04-01

    Plasma erosion and redeposition behavior of selected candidate materials for plasma-facing components in the NET-machine have been investigated using the PISCES-A facility. Materials studied include SiC-impregnated graphite, 2D graphite weaves with and without CVD-SiC coatings, and isotropic graphite. These specimens were exposed to continuous hydrogen or deuterium plasmas under the following conditions: electron temperature range from 5 to 35 eV; plasma density range from 5 10 11 to 1 10 12 cm -3; flux range from 5 10 17 to 2 10 18 ions cm -2 s -1; fluence of the order from 10 21 to 10 22 ions/cm 2; bombarding energies of 50 and 100 eV; target temperature range from 300 to 1000C. The erosion yield of SiC-impregnated graphite due to deuterium plasma bombardment is found to be a factor of 2 to 3 less than that of isotropic graphite materials. A further factor of 2-3 reduction in the erosion yield is observed in when redeposition associated with reionization of sputtered particle becomes significant. From post-bombardment surface analysis with AES, the surface composition in terms of the Si/C of SiC-impregnated graphite ratio is found to increase from 0.15 to 0.7 after hydrogen plasma bombardment to a fluence around 4 10 21 ions/cm 2 at 350 C. However, the final surface composition appears to remain unchanged up to 4 10 22 ions/cm 2, the highest fluence in the present study. Significant surface morphological modifications of SiC-impregnated graphite are observed after the high-fluence plasma exposure. Several structural problems such as coating-substrate adhesion have been pointed out for SiC-coated 2D graphite weave.

  2. Use of H/D isotope effects to gather information about hydrogen bonding and hydrogen exchange rates

    NASA Astrophysics Data System (ADS)

    Takeda, Mitsuhiro; Miyanoiri, Yohei; Terauchi, Tsutomu; Yang, Chun-Jiun; Kainosho, Masatsune

    2014-04-01

    Polar side-chains in proteins play important roles in forming and maintaining three-dimensional structures, and thus participate in various biological functions. Until recently, most protein NMR studies have focused on the non-exchangeable protons of amino acid residues. The exchangeable protons attached to polar groups, such as hydroxyl (OH), sulfhydryl (SH), and amino (NH2) groups, have mostly been ignored, because in many cases these hydrogen atoms exchange too quickly with water protons, making NMR observations impractical. However, in certain environments, such as deep within the hydrophobic interior of a protein, or in a strong hydrogen bond to other polar groups or interacting ligands, the protons attached to polar groups may exhibit slow hydrogen exchange rates and thus become NMR accessible. To explore the structural and biological implications of the interactions involving polar side-chains, we have developed versatile NMR methods to detect such cases by observing the line shapes of 13C NMR signals near the polar groups, which are affected by deuterium-proton isotope shifts in a mixture of H2O and D2O. These methods allow the detection of polar side-chains with slow hydrogen-deuterium exchange rates, and therefore provide opportunities to retrieve information about the polar side-chains, which might otherwise be overlooked by conventional NMR experiments. Future prospects of applications using deuterium-proton isotope shifts to retrieve missing structural and dynamic information of proteins are discussed.

  3. On the role of atomic metastability in the production of Balmer line radiation from ‘cold’ atomic hydrogen, deuterium and hydrogenic ion impurities in fusion edge plasmas

    NASA Astrophysics Data System (ADS)

    Hey, J. D.

    2012-03-01

    Published arguments, which assign an important role to atomic metastability in the production of ‘narrow’ Zeeman component radiation from the boundary region of fusion plasmas, are examined critically in relation to l-redistribution by proton and electron collisions, and mixing of unperturbed atomic states by the ion microfield and microfield gradient. It is concluded that these important processes indeed severely constrain the contribution from ‘metastable’ states to the generation of the hydrogen Balmer spectra, for electron concentrations above 1012 cm-3, as pointed out before by the present author (Hey et al 1999 J. Phys. B: At. Mol. Opt. Phys. 32 3555). The analysis of collision-induced l-redistribution represents an extension of that used previously (Hey et al 1996 Contrib. Plasma Phys. 36 583), applicable up to higher electron densities. For comparison purposes, we also consider the question of metastability of ionized helium in a low-temperature plasma, and that of some common hydrogenic impurities (C5+ and Ne9+) in a hydrogen (deuterium) fusion plasma. While for low nuclear charge Z the metastability of 2s1/2 levels is quenched by the plasma environment, it is much reduced in high-Z ions owing to the rapid increase with Z of the two-photon electric dipole (2E1) and magnetic dipole (M1) spontaneous transition rates to the ground state, whereas the role of the plasma in these cases is less important. The main new principle elaborated in this work is the sensitivity of atomic line strengths, and hence collision strengths, to perturbation by the plasma environment for transitions between fine-structure sublevels of the same principal quantum number. As the plasma microfield strength grows, ‘allowed’ transitions diminish in strength, while ‘forbidden’ transitions grow. However, owing to violation of the parity selection rule, there is an overall loss of collision strength available to transitions, resulting from the appearance of significant ‘self-strength’ contributions, in accord with the sum rules for the line strengths, which remain valid over the range of fields considered. Thus, the relative effectiveness per perturber of both electron and ion collisions, for inducing population transfer between fine-structure sublevels, diminishes as the sublevels evolve from a fine-structure dominated to a Stark-effect-dominated regime. In the concluding discussion, we mention that this finding may have a bearing on discrepancies claimed between Stark broadening theory developed by Griem (1967 Astrophys. J. 148 547) and by Watson (2006 J. Phys.B: At. Mol. Opt. Phys. 39 1889), and the measurements of Bell and co-workers (2000 Publ. Astron. Soc. Pac. 112 1236; 2011 Astrophys. Space Sci. 335 451) for high-n radio recombination lines from galactic H II regions. In the absence of detailed modelling to test this suggestion, however, it would be premature to attempt to draw any firm conclusions along these lines. This manuscript is dedicated to the memory of my esteemed colleague Dr. rer. nat. Manfred Korten (1940-2010).

  4. 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.

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

    PubMed

    Gabričević, Mario; Lente, Gábor; Fábián, István

    2015-12-24

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

  6. Kinetics of deuterium exchange on resorcinol in D{sub 2}O at high pressure and high temperature

    SciTech Connect

    Bai, S.; Palmer, B.J.; Yonker, C.R.

    2000-01-13

    The kinetics of deuteration of resorcinol in pure D{sub 2}O were studied for the first time using a flow-through capillary tubular reactor with on-line, proton, and deuterium NMR detection at high temperatures and high pressure. The global rate constants for hydrogen/deuterium (H/D) exchange were determined from temperatures of 200--450 C (723 K) at a pressure of {approximately}400 bar (the critical temperature and pressure of water are 374.2 C and 218.3 bar, respectively). The H/D exchange rate in resorcinol (1,3-dihydroxybenzene) under these extreme conditions was determined using proton NMR as a function of the resorcinol residence time in a capillary tubular reactor, which also served as a high-pressure NMR cell. The {sup 1}H and {sup 2}H NMR results indicate that H/D exchange in resorcinol for the ring protons was observed at temperatures as low as 200 C. The kinetics of H/D exchange in resorcinol and the activation energy was extracted from the experimental {sup 1}H NMR data.

  7. Design study of plastic film heat exchanger

    NASA Astrophysics Data System (ADS)

    Guyer, E. C.; Brownell, D. L.

    1986-02-01

    This report presents the results of an effort to develop and design a unique thermoplastic film heat exchanger for use in an industrial heat pump evaporator system and other energy recovery applications. The concept for the exchanger is that of individual heat exchange elements formed by two adjoining and freely hanging plastic films. Liquid flows downward in a regulated fashion between the films due to the balance of hydrostatic and frictional forces. The fluid stream on the outside of film may be a free-falling liquid film, a condensing gas, or a noncondensing gas. The flow and structural principles are similar to those embodied in an earlier heat exchange system developed for use in waste water treatment systems (Sanderson). The design allows for high heat transfer rates while working within the thermal and structural limitations of thermoplastic materials. The potential of this new heat exchanger design lies in the relatively low cost of plastic film and the high inherent corrosion and fouling resistance. This report addresses the selection of materials, the potential heat transf er performance, the mechanical design and operation of a unit applied in a low pressure steam recovery system, and the expected selling price in comparison to conventional metallic shell and tube heat exchangers.

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

  9. EXCHANGE

    SciTech Connect

    Boltz, J.C.

    1992-09-01

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

  10. High temperature heat exchanger studies for applications to gas turbines

    NASA Astrophysics Data System (ADS)

    Min, June Kee; Jeong, Ji Hwan; Ha, Man Yeong; Kim, Kui Soon

    2009-12-01

    Growing demand for environmentally friendly aero gas-turbine engines with lower emissions and improved specific fuel consumption can be met by incorporating heat exchangers into gas turbines. Relevant researches in such areas as the design of a heat exchanger matrix, materials selection, manufacturing technology, and optimization by a variety of researchers have been reviewed in this paper. Based on results reported in previous studies, potential heat exchanger designs for an aero gas turbine recuperator, intercooler, and cooling-air cooler are suggested.

  11. Protein-like proton exchange in a synthetic host cavity.

    PubMed

    Hart-Cooper, William M; Sgarlata, Carmelo; Perrin, Charles L; Toste, F Dean; Bergman, Robert G; Raymond, Kenneth N

    2015-12-15

    The mechanism of proton exchange in a metal-ligand enzyme active site mimic (compound 1) is described through amide hydrogen-deuterium exchange kinetics. The type and ratio of cationic guest to host in solution affect the rate of isotope exchange, suggesting that the rate of exchange is driven by a host whose cavity is occupied by water. Rate constants for acid-, base-, and water-mediated proton exchange vary by orders of magnitude depending on the guest, and differ by up to 200 million-fold relative to an alanine polypeptide. These results suggest that the unusual microenvironment of the cavity of 1 can dramatically alter the reactivity of associated water by magnitudes comparable to that of enzymes. PMID:26621709

  12. Microscopic insight into role of protein flexibility during ion exchange chromatography by nuclear magnetic resonance and quartz crystal microbalance approaches.

    PubMed

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

    2016-03-18

    Driven by the prevalent use of ion exchange chromatography (IEC) for polishing therapeutic proteins, many rules have been formulated to summarize the different dependencies between chromatographic data and various operational parameters of interest based on statically determined interactions. However, the effects of the unfolding of protein structures and conformational stability are not as well understood. This study focuses on how the flexibility of proteins perturbs retention behavior at the molecular scale using microscopic characterization approaches, including hydrogen-deuterium (H/D) exchange detected by NMR and a quartz crystal microbalance (QCM). The results showed that a series of chromatographic retention parameters depended significantly on the adiabatic compressibility and structural flexibility of the protein. That is, softer proteins with higher flexibility tended to have longer retention times and stronger affinities on SP Sepharose adsorbents. Tracing the underlying molecular mechanism using NMR and QCM indicated that an easily unfolded flexible protein with a more compact adsorption layer might contribute to the longer retention time on adsorbents. The use of NMR and QCM provided a previously unreported approach for elucidating the effect of protein structural flexibility on binding in IEC systems. PMID:26896917

  13. Direct experimental study of the exchange spring formation process

    NASA Astrophysics Data System (ADS)

    Gornakov, V. S.; Nikitenko, V. I.; Shapiro, A. J.; Shull, R. D.; Jiang, J. Samuel; Bader, S. D.

    2002-04-01

    The remagnetization of a soft ferromagnetic film exchange coupled with a high-coercivity ferromagnetic film is studied by a magneto-optic imaging technique. If the magnetic field is antiparallel to the macroscopic unidirectional in-plane anisotropy, the soft layer reverses via the formation of exchange springs consisting of subdomains with opposite spin twistings. However, if the field is instead rotated in-plane, remagnetization initially proceeds via formation of a single uniform exchange spring. Then, at a critical angle, the spring incoherently untwists, leading again to subdomains with opposite chirality. These phenomena are attributed to the influence of inhomogeneity in the unidirectional magnetic anisotropy.

  14. Proton translocation in cytochrome c oxidase: insights from proton exchange kinetics and vibrational spectroscopy.

    PubMed

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

    2015-01-01

    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. This article is part of a Special Issue entitled: Vibrational spectroscopies and bioenergetic systems. PMID:25268561

  15. 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

  16. Ligand exchange in quaternary alloyed nanocrystals--a spectroscopic study.

    PubMed

    Gabka, Grzegorz; Bujak, Piotr; Giedyk, Kamila; Kotwica, Kamil; Ostrowski, Andrzej; Malinowska, Karolina; Lisowski, Wojciech; Sobczak, Janusz W; Pron, Adam

    2014-11-14

    Exchange of initial, predominantly stearate ligands for pyridine in the first step and butylamine (BA) or 11-mercaptoundecanoic acid (MUA) in the second one was studied for alloyed quaternary Cu-In-Zn-S nanocrystals. The NMR results enabled us to demonstrate, for the first time, direct binding of the pyridine labile ligand to the nanocrystal surface as evidenced by paramagnetic shifts of the three signals attributed to its protons to 7.58, 7.95 and 8.75 ppm. XPS investigations indicated, in turn, a significant change in the composition of the nanocrystal surface upon the exchange of initial ligands for pyridine, which being enriched in indium in the 'as prepared' form became enriched in zinc after pyridine binding. This finding indicated that the first step of ligand exchange had to involve the removal of the surface layer enriched in indium with simultaneous exposure of a new, zinc-enriched layer. In the second ligand exchange step (replacement of pyridine with BA or MUA) the changes in the nanocrystal surface compositions were much less significant. The presence of zinc in the nanocrystal surface layer turned out necessary for effective binding of pyridine as shown by a comparative study of ligand exchange in Cu-In-Zn-S, Ag-In-Zn-S and CuInS2, carried out by complementary XPS and NMR investigations. PMID:25252174

  17. 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.

  18. A piloted simulation study of data link ATC message exchange

    NASA Technical Reports Server (NTRS)

    Waller, Marvin C.; Lohr, Gary W.

    1989-01-01

    Data link Air Traffic Control (ATC) and Air Traffic Service (ATS) message and data exchange offers the potential benefits of increased flight safety and efficiency by reducing communication errors and allowing more information to be transferred between aircraft and ground facilities. Digital communication also presents an opportunity to relieve the overloading of ATC radio frequencies which hampers message exchange during peak traffic hours in many busy terminal areas. A piloted simulation study to develop pilot factor guidelines and assess potential flight crew benefits and liabilities from using data link ATC message exchange was completed. The data link ATC message exchange concept, implemented on an existing navigation computer Control Display Unit (CDU) required maintaining a voice radio telephone link with an appropriate ATC facility. Flight crew comments, scanning behavior, and measurements of time spent in ATC communication activities for data link ATC message exchange were compared to similar measures for simulated conventional voice radio operations. The results show crew preference for the quieter flight deck environment and a perception of lower communication workload.

  19. Use of SAR in Regional Methane Exchange Studies

    NASA Technical Reports Server (NTRS)

    Morrissey, L. A.; Livingston, G. P.; Durden, S. L.

    1994-01-01

    Significant sources of uncertainty in global trace gas budgets are due to lack of knowledge concerning the areal and temporal extent of source and sink areas. Synthetic aperture radar (SAR) is particularly suited to studies of northern ecosystems because of its all-weather operating capability which enables the acquisition of seasonal data. As key controls on methane exchange, the ability to differentiate major vegetation communities, inundation, and leaf area index (LAI) with satellite and airborne SAR data would increase the accuracy and precision of regional and seasonal estimates of methane exchange. The utility of SAR data for monitoring key controls on methane emissions from Arctic and boreal ecosystems is examined.

  20. TRACER STUDY OF VERTICAL EXCHANGE BY CUMULUS CLOUDS

    EPA Science Inventory

    The exchange of material by convective cloud processes between the mixed layer and the overlying free troposphere is examined. The paper describes results of a field experiment that was conducted in Lexington, Kentucky during the period from July 20 to August 24, 1983 to study th...

  1. Functional studies of split "Arabidopsis" Ca(2+)/H(+) exchangers

    Technology Transfer Automated Retrieval System (TEKTRAN)

    In plants, high capacity tonoplast cation/H (+) antiport is mediated in part by a family of cation exchanger (CAX) transporters. Functional association between CAX1 and CAX3 has previously been shown. In this study, we further examine the interactions between CAX protein domains using nonfunctional ...

  2. Structure-resonance theory and the kinetics of the electrophilic deuterium-hydrogen exchange in benzenoid hydrocarbons

    SciTech Connect

    Shawali, A.S.; Parkanyi, C.; Herndon, W.C.

    1982-01-01

    Structure-resonance theory has recently been shown to correlate and to predict various physical and chemical properties of ..pi..-electron hydrocarbons. The major advantage of this theory is its simplicity. Its application requires only an enumeration of Kekule' structures, since it has been shown that an algorithm, logarithm of the Kekule' corrected structure count, gives an excellent approximation of the gound-state eigenvalues of the structure-function Hamiltonian matrix. The purpose of this contribution is to show that the structure-resonance theory can be used to correlate the rates of both the deuterium-hydrogen and hydrogen-deuterium exchange reactions of benzenoid hydrocarbons. Logarithms of the rates of deuterodeprotonation of nine alternant hydrocarbons and protodedeuteration of five hydrocarbons containing 17 and 12 different reaction sites, respectively, are correlated with the logarithms of the structure counts of the intermediate, ln SC/sub I/, and the reactant, ln SC/sub R/, and with their ratio, ln (SC/sub I//SC/sub R/). The quality of the correlations is very good. The results indicate that the differences in reactivities of benzenoid hydrocarbons in aromatic substitution reactions are due to differences in their resonance energies and that hyperconjugation does not play a significant role in the stabilization of the intermediates in the reaction studied.

  3. Conformational characterization of the charge variants of a human IgG1 monoclonal antibody using H/D exchange mass spectrometry

    PubMed Central

    Tang, Liangjie; Sundaram, Shanmuuga; Zhang, Jingming; Carlson, Ping; Matathia, Alice; Parekh, Babita; Zhou, Qinwei; Hsieh, Ming-Ching

    2013-01-01

    MAb1, a human IgG1 monoclonal antibody produced in a NS0 cell line, exhibits charge heterogeneity because of the presence of variants formed by processes such as N-terminal glutamate cyclization, C-terminal lysine truncation, deamidation, aspartate isomerization and sialylation in the carbohydrate moiety. Four major charge variants of MAb1 were isolated and the conformations of these charge variants were studied using hydrogen/deuterium exchange mass spectrometry, including the H/D exchange time course (HX-MS) and the stability of unpurified proteins from rates of H/D exchange (SUPREX) techniques. HX-MS was used to evaluate the conformation and solution dynamics of MAb1 charge variants by measuring their deuterium buildup over time at the peptide level. The SUPREX technique evaluated the unfolding profile and relative stability of the charge variants by measuring the exchange properties of globally protected amide protons in the presence of a chemical denaturant. The H/D exchange profiles from both techniques were compared among the four charge variants of MAb1. The two techniques together offered extensive understanding about the local and subglobal/global unfolding of the charge variants of MAb1. Our results demonstrated that all four charge variants of MAb1 were not significantly different in conformation, solution dynamics and chemical denaturant-induced unfolding profile and stability, which aids in understanding the biofunctions of the molecules. The analytical strategy used for conformational characterization may also be applicable to comparability studies done for antibody therapeutics. PMID:23222183

  4. Conformational characterization of the charge variants of a human IgG1 monoclonal antibody using H/D exchange mass spectrometry.

    PubMed

    Tang, Liangjie; Sundaram, Shanmuuga; Zhang, Jingming; Carlson, Ping; Matathia, Alice; Parekh, Babita; Zhou, Qinwei; Hsieh, Ming-Ching

    2013-01-01

    MAb1, a human IgG1 monoclonal antibody produced in a NS0 cell line, exhibits charge heterogeneity because of the presence of variants formed by processes such as N-terminal glutamate cyclization, C-terminal lysine truncation, deamidation, aspartate isomerization and sialylation in the carbohydrate moiety. Four major charge variants of MAb1 were isolated and the conformations of these charge variants were studied using hydrogen/deuterium exchange mass spectrometry, including the H/D exchange time course (HX-MS) and the stability of unpurified proteins from rates of H/D exchange (SUPREX) techniques. HX-MS was used to evaluate the conformation and solution dynamics of MAb1 charge variants by measuring their deuterium buildup over time at the peptide level. The SUPREX technique evaluated the unfolding profile and relative stability of the charge variants by measuring the exchange properties of globally protected amide protons in the presence of a chemical denaturant. The H/D exchange profiles from both techniques were compared among the four charge variants of MAb1. The two techniques together offered extensive understanding about the local and subglobal/global unfolding of the charge variants of MAb1. Our results demonstrated that all four charge variants of MAb1 were not significantly different in conformation, solution dynamics and chemical denaturant-induced unfolding profile and stability, which aids in understanding the biofunctions of the molecules. The analytical strategy used for conformational characterization may also be applicable to comparability studies done for antibody therapeutics. PMID:23222183

  5. Separation of organic ion exchange resins from sludge -- engineering study

    SciTech Connect

    Duncan, J.B.

    1998-08-25

    This engineering study evaluates the use of physical separation technologies to separate organic ion exchange resin from KE Basin sludge prior to nitric acid dissolution. This separation is necessitate to prevent nitration of the organics in the acid dissolver. The technologies under consideration are: screening, sedimentation, elutriation. The recommended approach is to first screen the Sludge and resin 300 microns then subject the 300 microns plus material to elutriation.

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

    NASA Astrophysics Data System (ADS)

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

    2015-11-01

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

  7. Studying Gas-Phase Interconversion of Tautomers Using Differential Mobility Spectrometry

    NASA Astrophysics Data System (ADS)

    Campbell, J. Larry; Yang, Amy Meng-Ci; Melo, Luke R.; Hopkins, W. Scott

    2016-04-01

    In this study, we report on the use of differential mobility spectrometry (DMS) as a tool for studying tautomeric species, allowing a more in-depth interrogation of these elusive isomers using ion/molecule reactions and tandem mass spectrometry. As an example, we revisit a case study in which gas-phase hydrogen-deuterium exchange (HDX)—a probe of ion structure in mass spectrometry—actually altered analyte ion structure by tautomerization. For the N- and O-protonated tautomers of 4-aminobenzoic acid, when separated using DMS and subjected to subsequent HDX with trace levels of D2O, the anticipated difference between the exchange rates of the two tautomers is observed. However, when using higher levels of D2O or a more basic reagent, equivalent and almost complete exchange of all labile protons is observed. This second observation is a result of the interconversion of the N-protonated tautomer to the O-protonated form during HDX. We can monitor this transformation experimentally, with support from detailed molecular dynamics and electronic structure calculations. In fact, calculations suggest the onset of bulk solution phase properties for 4-aminobenzoic acid upon solvation with eight CH3OH molecules. These findings also underscore the need for choosing HDX reagents and conditions judiciously when separating interconvertible isomers using DMS.

  8. Synthetic ion-exchange resins: Soil and environmental studies

    SciTech Connect

    Skogley, E.O.; Dobermann, A.

    1996-01-01

    The use of synthetic ion-exchangers (commonly referred to as resins) to study natural media has steadily increased. These materials allow new and different ways to solve problems that cannot be resolved through usual approaches. A lack of knowledge or limited experience, however, has led to apparent confusion concerning appropriate use of resins for soil and environmental studies. The objective of this paper was to provide basic information on ion-exchange resins, their physical and chemical properties, and to review how resins have been used to expand our understanding of soils and other environmental media. A review of the literature is presented as an aid to better understanding, and to provide additional sources for details concerning resin applications. A classification scheme for resin systems is presented, with the intent that it will assist in the development of more uniformity and comparability in the use of resins for soil and environmental studies. Applications of various systems and their limitations are discussed, including a system developed to provide universal adsorption of ions and bioavailability indexes from tests run either in the laboratory or in situ. 142 refs., 2 figs., 3 tabs.

  9. Observational Studies of Parameters Influencing Air-Sea Gas Exchange

    NASA Astrophysics Data System (ADS)

    Schimpf, U.; Frew, N. M.; Kalkenings, R.; Garbe, C.; Jaehne, B.

    2003-04-01

    A physically-based modeling of the air-sea gas transfer that can be used to predict the gas transfer rates with sufficient accuracy as a function of micrometeorological parameters is still lacking. State of the art are still simple transfer rate versus wind speed relationships. Measurements from the Coastal Ocean Experiment on the North Atlantic revealed positive correlations between the transfer coefficient and mean square slope of short wind waves. A strong negative correlation between mean square slope and the fluorescence of surface-enriched colored dissolved organic matter was observed. Using heat as a proxy tracer for gases the exchange process at the air/water interface and the micro turbulence at the water surface are investigated. The analysis of infrared image sequences allows the estimation of the net heat flux at the ocean surface, the temperature gradient across the air-sea interface and thus the heat transfer velocity. Using Schmidt number scaling fast and reliable estimates of the gas transfer velocity are obtained. Laboratory studies were carried out in the Heidelberg wind-wave facility. Direct measurements of the Schmidt number exponent were done in conjunction with classical mass balance methods to estimate gas transfer velocities. The laboratory results allowed validating the basic assumptions of the controlled flux technique by applying different tracers for the gas exchange over a large regime of Schmidt numbers. Thus, modeling the Schmidt number exponent can fill the gap between laboratory and field measurements. Both the results from the laboratory and the field measurements give an detailed insight into the mechanisms controlling the transport processes across the aqueous boundary layer and relate the forcing functions of air sea gas exchange to parameters measured by remote sensing.

  10. A Role for Altimeter Radars in Gas Exchange Studies

    NASA Astrophysics Data System (ADS)

    Frew, N. M.; Glover, D. M.; McCue, S. J.

    2006-07-01

    Accurate estimates of air-sea transfer rates of radiatively active gases are needed for studies of regional and global gas cycling and for climate change studies. However, estimates using traditional wind speed - gas transfer velocity parameterizations vary by a factor of 2- 3, contributing significantly to error budgets in global modeling of gas exchange and the carbon cycle. A decade of research has shown the utility of sea surface roughness, represented by the mean square surface slope (mss) due to gravity-capillary scale waves, as a proxy for gas exchange. Normalized backscatter of altimeter radars can be used in scattering models to estimate mss by combining coordinated ship-based measurements of mss with satellite overflights. These coordinated field experiments over the last decade have begun to provide the data necessary to calibrate mss estimates from altimeter radars. Now we have developed this technique into an alternative approach for assessing global gas transfer velocity fields remotely. This paper will trace the evolution of this concept from key laboratory and in situ observations to remote sensing observations and construction of a decade-long time series from the TOPEX and Jason-1 data streams.

  11. An Effective Deuterium Exchange Method for Neutron Crystal Structure Analysis with Unfolding-Refolding Processes.

    PubMed

    Kita, Akiko; Morimoto, Yukio

    2016-02-01

    A method of hydrogen/deuterium (H/D) exchange with an unfolding-refolding process has been applied to hen egg-white lysozyme (HWL), and accurate evaluation of its deuteration was carried out by time-of-flight mass spectroscopy. Neutron crystallography requires a suitable crystal with enough deuterium exchanged in the protein to decrease incoherent scattering from hydrogens. It is very expensive to prepare a fully deuterated protein, and therefore a simple H/D exchange technique is desirable for this purpose. Acid or base addition to protein solutions with heating effectively increased the number of deuterium up to more than 20 % of that of all hydrogen atoms, and refolded structures were determined by X-ray structure analysis at 1.8 Å resolution. Refolded HWL had increased deuterium content in its protein core and its native structure, determined at atomic resolution, was fully preserved. PMID:26718545

  12. 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.

  13. Monte Carlo study of double exchange interaction in manganese oxide

    SciTech Connect

    Naa, Christian Fredy; Suprijadi, Viridi, Sparisoma Djamal, Mitra; Fasquelle, Didier

    2015-09-30

    In this paper we study the magnetoresistance properties attributed by double exchange (DE) interaction in manganese oxide by Monte Carlo simulation. We construct a model based on mixed-valence Mn{sup 3+} and Mn{sup 4+} on the general system of Re{sub 2/3}Ae{sub 1/3}MnO{sub 3} in two dimensional system. The conduction mechanism is based on probability of e{sub g} electrons hopping from Mn{sup 3+} to Mn{sup 4+}. The resistivity dependence on temperature and the external magnetic field are presented and the validity with related experimental results are discussed. We use the resistivity power law to fit our data on metallic region and basic activated behavior on insulator region. On metallic region, we found our result agree well with the quantum theory of DE interaction. From general arguments, we found our simulation agree qualitatively with experimental results.

  14. Tracer studies for determining dispersion coefficients in isotope exchange columns

    SciTech Connect

    Junker, D.M.

    1990-07-16

    Tracer studies were run in ion exchange columns to determine dispersion coefficients. These coefficients are applicable to N{sup 15}{minus}N{sup 14} isotope separation by displacement band chromatography. In conjunction with a model that describes the mass conservation of such a system, the feasibility of this separation method can be estimated. The traces were run at superficial velocities between 0.0487 and 0.2436 cm/s in three columns with diameters of 0.66, 1.0, and 2.54 cm. Dispersion coefficients were obtained in the range of 0.00319 to 0.0302 cm{sup 2}/s. These coefficients were extracted by the method of moments from traces of a nonabsorbing but porous matrix. Dispersion increased as flow rate and column diameter increased, although dependence on column diameter was not strong. 15 refs., 11 figs., 3 tabs.

  15. Monte Carlo study of double exchange interaction in manganese oxide

    NASA Astrophysics Data System (ADS)

    Naa, Christian Fredy; Suprijadi, Viridi, Sparisoma; Fasquelle, Didier; Djamal, Mitra

    2015-09-01

    In this paper we study the magnetoresistance properties attributed by double exchange (DE) interaction in manganese oxide by Monte Carlo simulation. We construct a model based on mixed-valence Mn3+ and Mn4+ on the general system of Re2/3Ae1/3MnO3 in two dimensional system. The conduction mechanism is based on probability of eg electrons hopping from Mn3+ to Mn4+. The resistivity dependence on temperature and the external magnetic field are presented and the validity with related experimental results are discussed. We use the resistivity power law to fit our data on metallic region and basic activated behavior on insulator region. On metallic region, we found our result agree well with the quantum theory of DE interaction. From general arguments, we found our simulation agree qualitatively with experimental results.

  16. Simulation of Dyadic Exchange: Proposal of a Method to Study Power in Family Relationships.

    ERIC Educational Resources Information Center

    Osmond, Marie W.; Martin, Patricia Y.

    "Reciprocity," a social simulation game based on exchange theory, was developed by the author to study the dynamics of power relationships in the context of marriage and the family. The simulation can be manipulated to test specific aspects of three major exchange formulations: Blau's social exchange formulation; Emerson's power-dependence…

  17. Spectroscopic studies of bacteriorhodopsin fragments dissolved in organic solution.

    PubMed Central

    Torres, J; Padrós, E

    1995-01-01

    Fourier transform infrared and UV fourth-derivative spectroscopies were used to study the secondary structure of bacteriorhodopsin and its chymotryptic and one of the sodium borohydride fragments dissolved in chloroform-methanol (1:1, v/v), 0.1 M LiClO4. The C1 fragment (helices C, D, E, F, and G) showed an alpha-helical content of about 53%, whereas C2 (helices A and B) had about 60%, and B2 (helices F and G) about 65% alpha-helix. The infrared main band indicated differences in alpha-helical properties between these fragments. These techniques were also used to obtain information on the interactions among helices. According to the results obtained from the hydrogen/deuterium exchange kinetics, about 40% of the amide protons of C2 are particularly protected against exchange, whereas for the C1 fragment this process is unexpectedly fast. UV fourth-derivative spectra of these samples were used to obtain information about the environment of Trp side chains. The results showed that the Trp residues of C2 are more shielded from the solvent than those of C1 or B2. The results of this work indicate that the specific interactions existing between the transmembrane segments induce different types of helical conformations in native bacteriorhodopsin. PMID:7612847

  18. Technology Solutions Case Study: Foundation Heat Exchanger, Oak Ridge, Tennessee

    SciTech Connect

    2014-03-01

    The foundation heat exchanger, developed by Oak Ridge National Laboratory, is a new concept for a cost-effective horizontal ground heat exchanger that can be connected to water-to-water or water-to-air heat pump systems for space conditioning as well as domestic water heating.

  19. Observational Studies of Parameters Influencing Air-sea Gas Exchange

    NASA Astrophysics Data System (ADS)

    Schimpf, U.; Frew, N. M.; Bock, E. J.; Hara, T.; Garbe, C. S.; Jaehne, B.

    A physically-based modeling of the air-sea gas transfer that can be used to predict the gas transfer rates with sufficient accuracy as a function of micrometeorological parameters is still lacking. State of the art are still simple gas transfer rate/wind speed relationships. Previous measurements from Coastal Ocean Experiment in the Atlantic revealed positive correlations between mean square slope, near surface turbulent dis- sipation, and wind stress. It also demonstrated a strong negative correlation between mean square slope and the fluorescence of surface-enriched colored dissolved organic matter. Using heat as a proxy tracer for gases the exchange process at the air/water interface and the micro turbulence at the water surface can be investigated. The anal- ysis of infrared image sequences allow the determination of the net heat flux at the ocean surface, the temperature gradient across the air/sea interface and thus the heat transfer velocity and gas transfer velocity respectively. Laboratory studies were carried out in the new Heidelberg wind-wave facility AELOTRON. Direct measurements of the Schmidt number exponent were done in conjunction with classical mass balance methods to estimate the transfer velocity. The laboratory results allowed to validate the basic assumptions of the so called controlled flux technique by applying differ- ent tracers for the gas exchange in a large Schmidt number regime. Thus a modeling of the Schmidt number exponent is able to fill the gap between laboratory and field measurements field. Both, the results from the laboratory and the field measurements should be able to give a further understanding of the mechanisms controlling the trans- port processes across the aqueous boundary layer and to relate the forcing functions to parameters measured by remote sensing.

  20. Monte Carlo study on exchange bias and coercivity properties in coupled ferromagnetic/antiferromagnetic films

    NASA Astrophysics Data System (ADS)

    Jiang, Liqin; Shen, Shuangjuan; Zhang, Jian-Min; Feng, Qian; Huang, Zhigao

    2015-12-01

    Based on Monte Carlo simulation, a model consisting of an antiferromagnetic (AFM) film coupled to a ferromagnetic (FM) film is developed to study the exchange bias and coercivity phenomenon. It is suggested that exchange bias is a consequence of exchange coupling in the AFM/FM interface, and the AFM anisotropy needs to have a threshold value for the occurrence of exchange bias. Simultaneously, exchange bias and coercivity as functions of the value of anisotropy, exchange coupling and film thickness are studied. By inducing a thickness dependence of the anisotropy in FM film, the coercivity can be reduced or enhanced by choosing suitable magnetic parameters, which can better account for the discrepancies found in previous studies. The results also provide evidence for the absence of a direct correlation between coercivity and exchange bias, which is in agreement with other studies.

  1. Study on heat transfer of heat exchangers in the Stirling engine - Performance of heat exchangers in the test Stirling engine

    NASA Astrophysics Data System (ADS)

    Kanzaka, Mitsuo; Iwabuchi, Makio

    1992-11-01

    The heat transfer performance of the actual heat exchangers obtained from the experimental results of the test Stirling engine is presented. The heater for the test engine has 120 heat transfer tubes that consist of a bare-tube part and a fin-tube part. These tubes are located around the combustion chamber and heated by the combustion gas. The cooler is the shell-and-tube-type heat exchanger and is chilled by water. It is shown that the experimental results of heat transfer performance of the heater and cooler of the test Stirling engine are in good agreement with the results calculated by the correlation proposed in our previous heat transfer study under the periodically reversing flow condition. Our correlation is thus confirmed to be applicable to the evaluation of the heat transfer coefficient and the thermal design of the heat exchangers in the Stirling engine.

  2. Study of transient behavior of finned coil heat exchangers

    NASA Astrophysics Data System (ADS)

    Rooke, S. P.; Elissa, M. G.

    1993-11-01

    The status of research on the transient behavior of finned coil cross-flow heat exchangers using single phase fluids is reviewed. Applications with available analytical or numerical solutions are discussed. Investigation of water-to-air type cross-flow finned tube heat exchangers is examined through the use of simplified governing equations and an up-wind finite difference scheme. The degenerate case of zero air-side capacitance rate is compared with available exact solution. Generalization of the numerical model is discussed for application to multi-row multi-circuit heat exchangers.

  3. Study of transient behavior of finned coil heat exchangers

    NASA Technical Reports Server (NTRS)

    Rooke, S. P.; Elissa, M. G.

    1993-01-01

    The status of research on the transient behavior of finned coil cross-flow heat exchangers using single phase fluids is reviewed. Applications with available analytical or numerical solutions are discussed. Investigation of water-to-air type cross-flow finned tube heat exchangers is examined through the use of simplified governing equations and an up-wind finite difference scheme. The degenerate case of zero air-side capacitance rate is compared with available exact solution. Generalization of the numerical model is discussed for application to multi-row multi-circuit heat exchangers.

  4. Using satellite data for soil cation exchange capacity studies

    NASA Astrophysics Data System (ADS)

    Ghaemi, M.; Astaraei, A. R.; Sanaeinejad, S. H.; Zare, H.

    2013-12-01

    This study was planned to examine the use of LandSat ETM+ images to develop a model for monitoring spatial variability of soil cation exchange capacity in a semi-arid area of Neyshaboor. 300 field data were collected from specific GPS registered points, 277 of which were error free, to be analysed in the soil laboratory.The statistical analysis showed that therewas a small R-Squared value, 0.17, when we used the whole data set. Visual interpretation of the graphs showed a trend among some of the data in the data set. Forty points were filtered based on the trends, and the statistical analysis was repeated for those data. It was discovered that the 40 series were more or less in the same environmental conditions; most of them were located in disturbed soils or abandoned lands with sparse vegetation cover. The soil was classified into high and medium salinity, with variable carbon (1.0 to 1.6%), heavy textured and with high silt and clay. Finally it was concluded that two different models could be fitted in the data based on their spatial dependency. The current models are able to explain spatial variability in almost 45 to 65% of the cases.

  5. HDXFinder: Automated Analysis and Data Reporting of Deuterium/Hydrogen Exchange Mass Spectrometry

    NASA Astrophysics Data System (ADS)

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

    2012-02-01

    Hydrogen/deuterium exchange in combination with mass spectrometry (H/D MS) is a sensitive technique for detection of changes in protein conformation and dynamics. However, wide application of H/D MS has been hindered, in part, by the lack of computational tools necessary for efficient analysis of the large data sets associated with this technique. We report a novel web-based application for automatic analysis of H/D MS experimental data. This application relies on the high resolution of mass spectrometers to extract all isotopic envelopes before correlating these envelopes with individual peptides. Although a fully automatic analysis is possible, a variety of graphical tools are included to aid in the verification of correlations and rankings of the isotopic peptide envelopes. As a demonstration, the rate constants for H/D exchange of peptides from rabbit muscle pyruvate kinase are mapped onto the structure of this protein.

  6. XAFS Studies of Silver Environments in Ion-Exchanged Glasses

    SciTech Connect

    Yang, X. C.; Dubiel, M.

    2007-02-02

    The X-ray absorption fine structure (XAFS) technique was used to analyze the structural geometry of Ag atoms introduced into soda-lime silicate glass and soda aluminosilicate glass by ion-exchange methods. The results show that Ag+ ions in aluminosilicate glass are coordinated by about two oxygens and the nearest-neighbor Ag-O distance increases when the Ag+-for-Na+ ion-exchange ratio is larger than 0.47. When the exchange ratio is low, the introduced Ag+ ions are stabilized at the non-bridge oxygen (NBO) site with a Ag-O distance of 2.20 A, and the Na+ ions in the AlO4 site are exchanged by Ag+ ions after full replacement of the NBO sites with a Ag-O distance of 2.28 A. The disorder of Ag-O coordination increases with increasing ion-exchange ratio in aluminosilicate glass where Ag+ ions are coordinated by NBO and bridge oxygen (BO)

  7. Analytical Study on Thermal and Mechanical Design of Printed Circuit Heat Exchanger

    SciTech Connect

    Su-Jong Yoon; Piyush Sabharwall; Eung-Soo Kim

    2013-09-01

    The analytical methodologies for the thermal design, mechanical design and cost estimation of printed circuit heat exchanger are presented in this study. In this study, three flow arrangements of parallel flow, countercurrent flow and crossflow are taken into account. For each flow arrangement, the analytical solution of temperature profile of heat exchanger is introduced. The size and cost of printed circuit heat exchangers for advanced small modular reactors, which employ various coolants such as sodium, molten salts, helium, and water, are also presented.

  8. Conformational lability in the class II MHC 310 helix and adjacent extended strand dictate HLA-DM susceptibility and peptide exchange

    PubMed Central

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

    2011-01-01

    HLA-DM is required for efficient peptide exchange on class II MHC molecules, but its mechanism of action is controversial. We trapped an intermediate state of class II MHC HLA-DR1 by substitution of ?F54, resulting in a protein with increased HLA-DM binding affinity, weakened MHC-peptide hydrogen bonding as measured by hydrogen-deuterium exchange mass spectrometry, and increased susceptibility to DM-mediated peptide exchange. Structural analysis revealed a set of concerted conformational alterations at the N-terminal end of the peptide-binding site. These results suggest that interaction with HLA-DM is driven by a conformational change of the MHC II protein in the region of the ?-subunit 310 helix and adjacent extended strand region, and provide a model for the mechanism of DM-mediated peptide exchange. PMID:22084083

  9. Experimental Studies on Coherent Synchrotron Radiation at an Emittance Exchange Beamline

    SciTech Connect

    Thangaraj, J.C.T.; Thurman-Keup, R.; Ruan, J.; Johnson, A.S.; Lumpkin, A.H.; Santucci, J.; /Fermilab

    2012-04-01

    One of the goals of the Fermilab A0 photoinjector is to experimentally investigate the transverse to longitudinal emittance exchange (EEX) principle. Coherent synchrotron radiation in the emittance exchange line could limit the performance of the emittance exchanger at short bunch lengths. In this paper, we present experimental and simulation studies of the coherent synchrotron radiation (CSR) in the emittance exchange line at the A0 photoinjector. We report on time-resolved CSR studies using a skew-quadrupole technique. We also demonstrate the advantages of running the EEX with an energy chirped beam.

  10. Magnetic exchange coupling through superconductors: A trilayer study

    NASA Astrophysics Data System (ADS)

    Sá de Melo, C. A.

    2000-11-01

    The possibility of magnetic exchange coupling between two ferromagnets (F) separated by a superconductor (S) spacer is analyzed using the functional integral method. For this coupling to occur three prima facie conditions need to be satisfied. First, an indirect exchange coupling between the ferromagnets must exist when the superconductor is in its normal state. Second, superconductivity must not be destroyed due to the proximity to ferromagnetic boundaries. Third, roughness of the F/S interfaces must be small. Under these conditions, when the superconductor is cooled to below its critical temperature, the magnetic coupling changes. The appearance of the superconducting gap introduces a new length scale (the coherence length of the superconductor) and modifies the temperature dependence of the indirect exchange coupling existent in the normal state. The magnetic coupling is oscillatory both above and below the the critical temperature of the superconductor, as well as strongly temperature-dependent. However, at low temperatures the indirect exchange coupling decay length is controlled by the coherence length of the superconductor, while at temperatures close to and above the critical temperature of the superconductor the magnetic coupling decay length is controlled by the thermal length.

  11. Analytical Study on Multi-stream Heat Exchanger Include Longitudinal Heat Conduction and Parasitic Heat Loads

    NASA Astrophysics Data System (ADS)

    Zhu, Weiping; Xie, Xiujuan; Yang, Huihui; Li, Laifeng; Gong, Linghui

    High performance heat exchangers are critical component in many cryogenic systems and its performance is typically very sensitive to longitudinal heat conduction, parasitic heat loads and property variations. This paper gives an analytical study on 1-D model for multi-stream parallel-plate fin heat exchanger by using the method of decoupling transformations. The results obtained in the present paper are valuable for the reference on optimization for heat exchanger design.

  12. 77 FR 48491 - Regulatory New Drug Review: Solutions for Study Data Exchange Standards; Notice of Meeting...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-08-14

    ...The Food and Drug Administration (FDA) is announcing a meeting entitled ``Regulatory New Drug Review: Solutions for Study Data Exchange Standards'' the purpose of which is to solicit input from industry, technology vendors, and other members of the public regarding the advantages and disadvantages of current and emerging open, consensus-based standards for the exchange of regulated study data.......

  13. Analytical lessons learned from selected therapeutic protein drug comparability studies.

    PubMed

    Federici, Marcia; Lubiniecki, Anthony; Manikwar, Prakash; Volkin, David B

    2013-05-01

    The successful implementation of process and product changes for a therapeutic protein drug, both during clinical development and after commercialization, requires a detailed evaluation of their impact on the protein's structure and biological functionality. This analysis is called a comparability exercise and includes a data driven assessment of biochemical equivalence and biological characterization using a cadre of analytical methodologies. This review focuses on describing analytical results and lessons learned from selected published therapeutic protein comparability case studies both for bulk drug substance and final drug product. An overview of the currently available analytical methodologies typically used is presented as well as a discussion of new emerging analytical techniques. The potential utility of several novel analytical approaches to comparability studies is discussed including distribution and stability of protein drugs in vivo, and enhanced evaluation of higher-order protein structure in actual formulations using hydrogen/deuterium exchange mass spectrometry, two-dimensional nuclear magnetic resonance fingerprinting or empirical phase diagrams. In addition, new methods for detecting and characterizing protein aggregates and particles are presented as these degradants are of current industry-wide concern. The critical role that analytical methodologies play in elucidating the structure-function relationships for therapeutic protein products during the overall assessment of comparability is discussed. PMID:23146362

  14. Experimental study of coherent synchrotron radiation in the emittance exchange line at the A0-photoinjector

    SciTech Connect

    Thangaraj, Jayakar C.T.; Thurman-Keup, R.; Johnson, A.; Lumpkin, A.H.; Edwards, H.; Ruan, J.; Santucci, J.; Sun, Y.E.-; Church, M.; Piot, P.; /Fermilab /Northern Illinois U.

    2010-08-01

    Next generation accelerators will require a high current, low emittance beam with a low energy spread. Such accelerators will employ advanced beam conditioning systems such as emittance exchanger to manipulate high brightness beams. One of the goals of the Fermilab A0 photoinjector is to investigate the transverse to longitudinal emittance exchange principle. Coherent synchrotron radiation could limit high current operation of the emittance exchanger. In this paper, we report on the preliminary experimental and simulation study of the coherent synchroton radiation (CSR) in the emittance exchange line at A0 photoinjector.

  15. Experimental Study of Coherent Synchrotron Radiation in the Emittance Exchange Line at the A0-Photoinjector

    NASA Astrophysics Data System (ADS)

    Thangaraj, Jayakar C. T.; Thurman-Keup, R.; Johnson, A.; Lumpkin, A. H.; Edwards, H.; Ruan, J.; Santucci, J.; Sun, Y. E.; Church, M.; Piot, P.

    2010-11-01

    Next generation accelerators will require a high current, low emittance beam with a low energy spread. Such accelerators will employ advanced beam conditioning systems such as emittance exchangers to manipulate high brightness beams. One of the goals of the Fermilab A0 photoinjector is to investigate the transverse to longitudinal emittance exchange principle. Coherent synchrotron radiation could limit high current operation of the emittance exchanger. In this paper, we report on the preliminary experimental and simulation study of the coherent synchroton radiation (CSR) in the emittance exchange line at the A0 photoinjector.

  16. Feasibility Study of Secondary Heat Exchanger Concepts for the Advanced High Temperature Reactor

    SciTech Connect

    Piyush Sabharwall

    2011-09-01

    The work reported herein represents a significant step in the preliminary design of heat exchanger options (material options, thermal design, selection and evaluation methodology with existing challenges). The primary purpose of this study is to aid in the development and selection of the required heat exchanger for power production using either a subcritical or supercritical Rankine cycle.

  17. Molecular biological studies of the cardiac sodium-calcium exchanger.

    PubMed

    Kraev, A; Chumakov, I; Carafoli, E

    1996-04-15

    The intron-exon organization of the entire human Na-Ca-exchanger gene NCX1 and of the central part of the related gene NCX2 has been determined. The NCX1 gene is at least 75 kb long and consists of at least 12 exons, the two largest (the 2nd and the 12th) coding for the N-terminal half of the exchanger sequence and for the last three C-terminal transmembrane domains. They also code for the 3.3-kb 3'-untranslated region and account for more than 90% of the length of the mature mRNA. The remainder of the NCX1 (NCX2) gene, coding for a putative cytoplasmic regulatory domain, is split into 9 (7) small exons. In spite of the limited (65%) average homology of the two cDNAs, analogous exons are readily identified within this portion of the two genes based on their high (80-95%) pairwise homology and similar patterns of differential splicing in brain. Human YAC clones have been identified in the CEPH library, which contain the entire NCX1/2 and NCKX1 (retinal rod exchanger) genes, and are used for chromosomal localization of the three genes. A distant homolog of the mammalian NCX genes has been identified in the C. elegans EST database and has been completely sequenced. It encodes a 20% shorter protein, which has an average 55% homology to human NCX1, and lacks most of the region that is known to be encoded by multiple differentially spliced exons in vertebrates. Comparison of available data on the gene structure of the NCX homologs in various species suggests that this protein has emerged in the primitive nervous system and has been subsequently adapted to other cellular environments by the use of novel domains, encoded in additional exons. PMID:8659815

  18. Isotope dilution study of exchangeable oxygen in premium coal samples

    SciTech Connect

    Finseth, D.

    1987-01-01

    A difficulty with improving the ability to quantitate water in coal is that truly independent methods do not always exist. The true value of any analytical parameter is always easier to determine if totally independent methods exist to determine that parameter. This paper describes the possibility of using a simple isotope dilution technique to determine the water content of coal and presents a comparison of these isotope dilution measurements with classical results for the set of Argonne coals from the premium coal sample program. Isotope dilution is a widely used analytical method and has been applied to the analysis of water in matrices as diverse as chicken fat, living humans, and coal. Virtually all of these applications involved the use of deuterium as the diluted isotope. This poses some problems if the sample contains a significant amount of exchangeable organic hydrogen and one is interested in discriminating exchangeable organic hydrogen from water. This is a potential problem in the coal system. To avoid this potential problem /sup 18/O was used as the diluted isotope in this work.

  19. ATP-induced dimerization of the F0F1 ε subunit from Bacillus PS3: a hydrogen exchange-mass spectrometry study.

    PubMed

    Rodriguez, Antony D; Dunn, Stanley D; Konermann, Lars

    2014-06-24

    F0F1 ATP synthase harnesses a transmembrane electrochemical gradient for the production of ATP. When operated in reverse, this multiprotein complex catalyzes ATP hydrolysis. In bacteria, the ε subunit is involved in regulating this ATPase activity. Also, ε is essential for coupling ATP hydrolysis (or synthesis) to proton translocation. The ε subunit consists of a β sandwich and two C-terminal helices, α1 and α2. The protein can switch from a compact fold to an alternate conformation where α1 and α2 are separated, resulting in an extended structure. ε from the thermophile Bacillus PS3 (Tε) binds ATP with high affinity such that this protein may function as an intracellular ATP level sensor. ATP binding to isolated Tε triggers a major conformational transition. Earlier data were interpreted in terms of an ATP + Tεextended → ATP·Tεcompact transition that may mimic aspects of the regulatory switching within F0F1 (Yagi et al. (2007) Proc. Natl. Acad. Sci. U.S.A., 104, 11233–11238). In this work, we employ complementary biophysical techniques for examining the ATP-induced conformational switching of isolated Tε. CD spectroscopy confirmed the occurrence of a large-scale conformational transition upon ATP binding, consistent with the formation of stable helical structure. Hydrogen/deuterium exchange (HDX) mass spectrometry revealed that this transition is accompanied by a pronounced stabilization in the vicinity of the ATP-binding pocket. Surprisingly, dramatic stabilization is also seen in the β8−β9 region, which is remote from the site of ATP interaction. Analytical ultracentrifugation uncovered a previously unrecognized feature of Tε: a high propensity to undergo dimerization in the presence of ATP. Comparison with existing crystallography data strongly suggests that the unexpected β8−β9 HDX protection is due to newly formed protein–protein contacts. Hence, ATP binding to isolated Tε proceeds according to 2ATP + 2Tεextended → (ATP·Tεcompact)2. Implications of this dimerization propensity for the possible role of Tε as an antibiotic target are discussed. PMID:24870150

  20. Continuation of Studies on Development of ODS Heat Exchanger Tubing

    SciTech Connect

    Lawrence Brown; David Workman; Bimal Kad; Gaylord Smith; Archie Robertson; Ian Wright

    2008-04-15

    The Department of Energy (DOE), National Energy Technology Center (NETL), has initiated a strategic plan for the development of advanced technologies needed to design and build fossil fuel plants with very high efficiency and environmental performance. These plants, referred to as 'Vision 21' and FutureGen programs by DOE, will produce electricity, chemicals, fuels, or a combination of these products, and possibly secondary products such as steam/heat for industrial use. MA956 is a prime candidate material being considered for a high temperature heat exchanger in the 'Vision 21' and FutureGen programs. This material is an oxide dispersion strengthened (ODS) alloy; however, there are some gaps in the data required to commit to the use of these alloys in a full-size plant. To fill the technology gaps for commercial production and use of the material for 'Advanced Power Generation Systems' this project has performed development activity to significant increase in circumferential strength of MA956 as compared to currently available material, investigated bonding technologies for bonding tube-to-tube joints through joining development, and performed tensile, creep and fire-side corrosion tests to validate the use and fabrication processes of MA956 to heat exchanger tubing applications. Development activities within this projected has demonstrated increased circumferential strength of MA956 tubes through flow form processing. Of the six fabrication technologies for bonding tube-to-tube joints, inertia friction welding (IFW) and flash butt welding (FBW) were identified as processes for joining MA956 tubes. Tensile, creep, and fire-side corrosion test data were generated for both base metal and weld joints. The data can be used for design of future systems employing MA956. Based upon the positive development activities, two test probes were designed and fabricated for field exposure testing at 1204 C ({approx}2200 F) flue gas. The probes contained tube portions with FBW and IFW welded MA956. Field testing of the probes and remaining heat exchanger design activity will be performed by Oak Ridge National Laboratory under DOE Contract DE-AC05-00OR22725.

  1. HDX workbench: software for the analysis of H/D exchange MS data.

    PubMed

    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 . PMID:22692830

  2. Two-photon exchange effect studied with neural networks

    SciTech Connect

    Graczyk, Krzysztof M.

    2011-09-15

    An approach to the extraction of the two-photon exchange (TPE) correction from elastic ep scattering data is presented. The cross-section, polarization transfer (PT), and charge asymmetry data are considered. It is assumed that the TPE correction to the PT data is negligible. The form factors and TPE correcting term are given by one multidimensional function approximated by the feedforward neural network (NN). To find a model-independent approximation, the Bayesian framework for the NNs is adapted. A large number of different parametrizations is considered. The most optimal model is indicated by the Bayesian algorithm. The obtained fit of the TPE correction behaves linearly in {epsilon} but it has a nontrivial Q{sup 2} dependence. A strong dependence of the TPE fit on the choice of parametrization is observed.

  3. Study of thermal energy storage using fluidized bed heat exchangers

    NASA Technical Reports Server (NTRS)

    Weast, T. E.; Shannon, L. J.; Ananth, K. P.

    1980-01-01

    The technical and economic feasibility of fluid bed heat exchangers (FBHX) for thermal energy storage (TES) in waste heat recovery applications is assessed by analysis of two selected conceptual systems, the rotary cement kiln and the electric arc furnace. It is shown that the inclusion of TES in the energy recovery system requires that the difference in off-peak and on-peak energy rates be large enough so that the value of the recovered energy exceeds the value of the stored energy by a wide enough margin to offset parasitic power and thermal losses. Escalation of on-peak energy rates due to fuel shortages could make the FBHX/TES applications economically attractive in the future.

  4. Separation and identification of degradation products in eprinomectin formulation using LC, LTQ FT-MS, H/D exchange, and NMR.

    PubMed

    Awasthi, Atul; Razzak, Majid; Al-Kassas, Raida; Greenwood, David R; Harvey, Joanne; Garg, Sanjay

    2012-04-01

    The aim of this study was to evaluate the suitability of the compendial active pharmaceutical ingredient (API) method for the analysis of finished products and characterization of degradation products in eprinomectin (EPM) samples. Heat stressed sample tests revealed a limitation of the API method in distinguishing an impurity merging with the principal analyte peak. A new selective, specific and sensitive method was therefore developed for the determination of EPM in formulations that separates its degradation products currently undetectable with the official method. The determination was carried out by reversed-phase HPLC using an isocratic solvent elution. The method was validated and found to be precise, accurate and specific; the detector response was linear over 50-150 μg/ml (EPM) and 0.1-3 μg/ml (degradation product) range of concentrations. Two major degradation products detected with the new method were isolated from sample matrices and characterized using LC-PDA, high resolution FT-ICR MS, NMR and hydrogen/deuterium exchange (HX-MS) studies. FTMS analysis showed accurate mass of molecular ion peaks for EPM and its two degradation products at m/z 914.52505 (mass error ≤ 1 ppm) with almost identical fragmentation patterns. Given the isomeric nature of the compounds, all three were further evaluated by ¹H, ¹³C, 1D NOESY and 2D (COSY) NMR experiments. The interpretation of experimental data positively identified Unknown 1 as the 2-epimer of EPM and Unknown 2 as the structural isomer Δ2,3-EPM containing a conjugated enoate. The new HPLC method and identification exercise is useful for analysis of EPM and its degradation products. PMID:22341479

  5. Partially Unfolded Forms of the Prion Protein Populated under Misfolding-promoting Conditions: CHARACTERIZATION BY HYDROGEN EXCHANGE MASS SPECTROMETRY AND NMR.

    PubMed

    Moulick, Roumita; Das, Ranabir; Udgaonkar, Jayant B

    2015-10-16

    The susceptibility of the cellular prion protein (PrP(C)) to convert to an alternative misfolded conformation (PrP(Sc)), which is the key event in the pathogenesis of prion diseases, is indicative of a conformationally flexible native (N) state. In the present study, hydrogen-deuterium exchange (HDX) in conjunction with mass spectrometry and nuclear magnetic resonance spectroscopy were used for the structural and energetic characterization of the N state of the full-length mouse prion protein, moPrP(23-231), under conditions that favor misfolding. The kinetics of HDX of 34 backbone amide hydrogens in the N state were determined at pH 4. In contrast to the results of previous HDX studies on the human and Syrian hamster prion proteins at a higher pH, various segments of moPrP were found to undergo different extents of subglobal unfolding events at pH 4, a pH at which the protein is known to be primed to misfold to a β-rich conformation. No residual structure around the disulfide bond was observed for the unfolded state at pH 4. The N state of the prion protein was observed to be at equilibrium with at least two partially unfolded forms (PUFs). These PUFs, which are accessed by stochastic fluctuations of the N state, have altered surface area exposure relative to the N state. One of these PUFs resembles a conformation previously implicated to be an initial intermediate in the conversion of monomeric protein into misfolded oligomer at pH 4. PMID:26306043

  6. Interlaboratory collaborative study on sister chromatid exchange induction in vivo

    SciTech Connect

    Tice, R.R.

    1985-01-01

    Nine laboratories participated in a comparative analysis of the ability of BP/PYR and 2AAF/4AAF to induce sister chromatid exchanges (SCEs) in vivo, using mice, rats and Chinese hamsters. Bone marrow, intestinal epithelium and peripheral blood lymphocytes were used as target tissues, following either gavage or intraperitoneal (ip) administration of the test chemical. Based on a statistical analysis of the SCE data by ANOVA and using an ..cap alpha.. of 0.05, BP induced a highly significant increase in SCEs in every tissue sampled in each species and among all strains of mice by both routes. Treatment with PYR induced a marginally positive SCE response in 5 of 15 experiments (considering male and female responses separately). By both routes, treatment with 2AAF induced a highly significant increase in SCE frequency in bone marrow cells of all mouse strains, in bone marrow and intestinal epithelial cells of Chinese hamsters. Treatment with 4AAF indiced a marginally positive SCE response in 6 of 15 experiments (considering male and female responses separately). The 2 carcinogens, BP and 2AAF, were clearly active regardless of species, strain, sex, tissue and route of administration and more potent than either of the two purportedly non-carcinogenic structural analogues, PYR and 4AAF, respectively. 40 refs., 10 figs., 19 tabs.

  7. Nuclear magnetic resonance study of proton exchanged LiNbO3

    NASA Astrophysics Data System (ADS)

    de Souza, Ricardo E.; Engelsberg, M.; Pacobahyba, L. H.; Do Nascimento, George C.

    1995-01-01

    Nuclear magnetic resonance (NMR) of 1H was employed to study the population of different sites in proton exchanged LiNbO3 using a variety of exchange conditions and proton donors. At least two different proton sites of vastly different mobilities were always found to be present. The ratio of their populations was measured in annealed and as-prepared samples and found to be strongly dependent upon the exchange conditions. A correlation between our NMR data and recent results obtained using other techniques is discussed in connection with various mechanisms that have been proposed for the changes in the refractive indexes.

  8. Numerical Study on Crossflow Printed Circuit Heat Exchanger for Advanced Small Modular Reactors

    SciTech Connect

    Yoon, Su-Jong; Sabharwall, Piyush; Kim, Eung-Soo

    2014-03-01

    Various fluids such as water, gases (helium), molten salts (FLiNaK, FLiBe) and liquid metal (sodium) are used as a coolant of advanced small modular reactors (SMRs). The printed circuit heat exchanger (PCHE) has been adopted as the intermediate and/or secondary heat exchanger of SMR systems because this heat exchanger is compact and effective. The size and cost of PCHE can be changed by the coolant type of each SMR. In this study, the crossflow PCHE analysis code for advanced small modular reactor has been developed for the thermal design and cost estimation of the heat exchanger. The analytical solution of single pass, both unmixed fluids crossflow heat exchanger model was employed to calculate a two dimensional temperature profile of a crossflow PCHE. The analytical solution of crossflow heat exchanger was simply implemented by using built in function of the MATLAB program. The effect of fluid property uncertainty on the calculation results was evaluated. In addition, the effect of heat transfer correlations on the calculated temperature profile was analyzed by taking into account possible combinations of primary and secondary coolants in the SMR systems. Size and cost of heat exchanger were evaluated for the given temperature requirement of each SMR.

  9. Contemporary approaches to studying and mapping of active water exchange zone of ground water

    NASA Astrophysics Data System (ADS)

    Moraru, C. Ye

    2016-03-01

    The article deals with a zone of ground water active exchange. New principles of the zone study and mapping under the platform hydrogeological condition are discussed. The assessment and distribution techniques are suggested for the active water exchange zone under the condition of hydrogeological parameterization uncertainty. The efficiency and significance of the suggested techniques are proved using the example of ground water in the southwest of Black Sea artesian basin.

  10. New data on Cu-exchanged phillipsite: a multi-methodological study

    NASA Astrophysics Data System (ADS)

    Gatta, G. Diego; Cappelletti, Piergiulio; de'Gennaro, Bruno; Rotiroti, Nicola; Langella, Alessio

    2015-10-01

    The cation exchange capacity of a natural phillipsite-rich sample from the Neapolitan Yellow Tuff, Southern Italy (treated in order to obtain a 95 wt% zeolite-rich sample composed mainly of phillipsite and minor chabazite) for Cu was evaluated using the batch exchange method. The sample had previously been exchanged into its monocationic form (Na), and then used for the equilibrium studies of the exchange reaction 2Na+ ⇆ Cu2+. Reversibility ion exchange tests were performed. The isotherm displays an evident hysteresis loop. Interestingly, the final Cu-exchanged polycrystalline material was green-bluish. Natural, Na- and Cu-exchanged forms were analyzed by X-ray powder diffraction, and the Cu-phillipsite was also investigated by transmission electron microscopy (TEM). Structure refinement of Cu-phillipsite was performed by the Rietveld method using synchrotron data, and it indicates a small, but significant, fraction of Cu sharing with Na two-three independent extra-framework sites. The TEM experiment shows sub-spherical nano-clusters of crystalline species (with average size of 5 nm) lying on the surfaces of zeolite crystals or dispersed in the amorphous fraction, with electron diffraction patterns corresponding to those of CuO (tenorite-like structure) and Cu(OH)2 (spertiniite-like structure). X-ray and TEM investigations show that Cu is mainly concentrated in different species (crystalline or amorphous) within the sample, not only in phillipsite. The experimental findings based on X-ray and TEM investigations, along with the hysteresis loop of the ion exchange tests, are discussed and some general considerations about the mechanisms of exchange reactions involving divalent cations with high hydration energy are provided.

  11. In situ NRA study of hydrogen isotope exchange in self-ion damaged tungsten exposed to neutral atoms

    NASA Astrophysics Data System (ADS)

    Markelj, S.; Založnik, A.; Schwarz-Selinger, T.; Ogorodnikova, O. V.; Vavpetič, P.; Pelicon, P.; Čadež, I.

    2016-02-01

    Isotope exchange was studied in-situ by Nuclear Reaction Analysis in the bulk of self-ion damaged tungsten at 600 K. Both variations of isotope exchange of H by D and of D by H were measured. The deuterium isothermal desorption was also studied and evaluated in order to be able to resolve the self-desorption from the isotope exchange at 600 K. The isotope exchange was also studied on the surface by Elastic Recoil Detection Analysis at 480 K and 380 K. The exchange mechanism was effective both on the surface and in the bulk of damaged tungsten. A simple model was introduced to describe the exchange efficiency on the surface and in the bulk obtaining the exchange cross sections on the surface and in bulk. In both cases an isotope effect was observed, where the exchange of H atoms by D atoms was more efficient than for the reverse sequence.

  12. Coming to Canada to Study: Factors that Influence Student's Decisions to Participate in International Exchange

    ERIC Educational Resources Information Center

    Massey, Jennifer; Burrow, Jeff

    2012-01-01

    Increasing numbers of students are participating in study abroad programs. Outcomes associated with these programs have been studied extensively, but relatively little is known about what motivates and influences students to participate. This study investigated factors that motivate and influence students to study on exchange and explored how…

  13. Brillouin light scattering study of spin waves in NiFe/Co exchange spring bilayer films

    SciTech Connect

    Haldar, Arabinda; Banerjee, Chandrima; Laha, Pinaki; Barman, Anjan

    2014-04-07

    Spin waves are investigated in Permalloy(Ni{sub 80}Fe{sub 20})/Cobalt(Co) exchange spring bilayer thin films using Brillouin light scattering (BLS) experiment. The magnetic hysteresis loops measured by magneto-optical Kerr effect show a monotonic decrease in coercivity of the bilayer films with increasing Py thickness. BLS study shows two distinct modes, which are modelled as Damon-Eshbach and perpendicular standing wave modes. Linewidths of the frequency peaks are found to increase significantly with decreasing Py layer thickness. Interfacial roughness causes to fluctuate exchange coupling at the nanoscale regimes and the effect is stronger for thinner Py films. A quantitative analysis of the magnon linewidths shows the presence of strong local exchange coupling field which is much larger compared to macroscopic exchange field.

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

    PubMed

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

    2013-10-25

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

  15. Preliminary time-of-flight neutron diffraction studies of Escherichia coli ABC transport receptor phosphate-binding protein at the Protein Crystallography Station.

    PubMed

    Sippel, K H; Bacik, J; Quiocho, F A; Fisher, S Z

    2014-06-01

    Inorganic phosphate is an essential molecule for all known life. Organisms have developed many mechanisms to ensure an adequate supply, even in low-phosphate conditions. In prokaryotes phosphate transport is instigated by the phosphate-binding protein (PBP), the initial receptor for the ATP-binding cassette (ABC) phosphate transporter. In the crystal structure of the PBP-phosphate complex, the phosphate is completely desolvated and sequestered in a deep cleft and is bound by 13 hydrogen bonds: 12 to protein NH and OH donor groups and one to a carboxylate acceptor group. The carboxylate plays a key recognition role by accepting a phosphate hydrogen. PBP phosphate affinity is relatively consistent across a broad pH range, indicating the capacity to bind monobasic (H2PO4-) and dibasic (HPO4(2-)) phosphate; however, the mechanism by which it might accommodate the second hydrogen of monobasic phosphate is unclear. To answer this question, neutron diffraction studies were initiated. Large single crystals with a volume of 8 mm3 were grown and subjected to hydrogen/deuterium exchange. A 2.5 Å resolution data set was collected on the Protein Crystallography Station at the Los Alamos Neutron Science Center. Initial refinement of the neutron data shows significant nuclear density, and refinement is ongoing. This is the first report of a neutron study from this superfamily. PMID:24915101

  16. Preliminary time-of-flight neutron diffraction studies of Escherichia coli ABC transport receptor phosphate-binding protein at the Protein Crystallography Station

    PubMed Central

    Sippel, K. H.; Bacik, J.; Quiocho, F. A.; Fisher, S. Z.

    2014-01-01

    Inorganic phosphate is an essential molecule for all known life. Organisms have developed many mechanisms to ensure an adequate supply, even in low-phosphate conditions. In prokaryotes phosphate transport is instigated by the phosphate-binding protein (PBP), the initial receptor for the ATP-binding cassette (ABC) phosphate transporter. In the crystal structure of the PBP–phosphate complex, the phosphate is completely desolvated and sequestered in a deep cleft and is bound by 13 hydrogen bonds: 12 to protein NH and OH donor groups and one to a carboxylate acceptor group. The carboxylate plays a key recognition role by accepting a phosphate hydrogen. PBP phosphate affinity is relatively consistent across a broad pH range, indicating the capacity to bind monobasic (H2PO4 −) and dibasic (HPO4 2−) phosphate; however, the mechanism by which it might accommodate the second hydrogen of monobasic phosphate is unclear. To answer this question, neutron diffraction studies were initiated. Large single crystals with a volume of 8 mm3 were grown and subjected to hydrogen/deuterium exchange. A 2.5 Å resolution data set was collected on the Protein Crystallography Station at the Los Alamos Neutron Science Center. Initial refinement of the neutron data shows significant nuclear density, and refinement is ongoing. This is the first report of a neutron study from this superfamily. PMID:24915101

  17. A Prospective Study on Exchange Transfusion in Neonatal Unconjugated Hyperbilirubinemia - in a Tertiary Care Hospital, Nepal.

    PubMed

    Malla, T; Singh, S; Poudyal, P; Sathian, B; Bk, G; Malla, K K

    2015-01-01

    Background An exchange transfusion involves replacing patient's blood with donor blood in order to remove abnormal blood components and circulating toxins while maintaining adequate circulating blood volume. Objective To observe the incidence, causes of jaundice requiring Exchange and any adverse event of exchange transfusion in newborns with unconjugated hyperbilirubinemia. Method Prospective study undertaken at Neonatal Intensive Care Unit (NICU) of Manipal Teaching Hospital, Pokhara, Nepal from March 2014 to April 2015. For both mothers and neonates blood group and Rh typing and for all newborns pre and post exchange complete blood count with peripheral smear, serum bilirubin, hemoglobin, calcium, potassium, random blood sugar, C-reactive protein and blood culture and where ever required Direct Coombs test, reticulocyte count, G6PD activity and thyroid function test were done. The incidence, indications, positive outcome, complications and mortality were noted. Result Out of 481 cases of unconjugated hyperbilirubinemia 29(6%) required exchange transfusion. 55.2% Pathological Jaundice [13.8% ABO incompatibility, sepsis and hypothyroidism was commonest causes] and 44.8% exaggerated physiological jaundice [27.6% with no underlying pathology, 10.3% preterms 3.4% cephalhematoma] required exchange transfusion. Post transfusion, bilirubin level decreased significantly (p< 0.001). The commonest adverse events noted were anemia (89.7% / p< 0.018), hyperglycemia(51.7% / p< 0.001), hypocalcaemia (48.3% /p< 0.001)), sepsis(10.3%), hypernatremia (13.8%), hyperkalaemia, bradycardia, apnea and feed intolerance (6.9%). None of them had kernicterus and there was no mortalities. Conclusion Exchange transfusion is an effective procedure to decrease bilirubin levels but is associated with many complications. Hypothyroidism was one of the commonest cause of jaundice requiring Exchange transfusion. PMID:26643826

  18. A system for studying the gas exchange of whole plants at subambient total gas pressures.

    PubMed

    Stahl, R S; Etter, B D

    1996-01-01

    A whole-plant gas exchange system that has been designed and constructed to study the feasibility of growing plants at subambient total gas pressures is described. This system will allow for the study of whole-plant gas exchange over the entire life cycle of a plant. The system also will allow for the regulation of atmospheric composition by providing control over the amount of nitrogen, oxygen, and carbon dioxide in a chamber atmosphere. The chamber's environmental performance is discussed in relation to selected design requirements. This system is a major technological advance over other systems used to study low-pressure effects on plant growth. PMID:11539156

  19. Experimental study of a novel manifold structure of micro-channel heat exchanger

    NASA Astrophysics Data System (ADS)

    Xu, Bo; Xu, Kunhao; Wei, Wei; Han, Qing; Chen, Jiangping

    2013-07-01

    Refrigerant flow distribution with phase change heat transfer was experimentally studied for a micro-channel heat exchanger having horizontal headers. In order to solve the problem of maldistribution, a novel manifold structure with orifice and bypass tube was proposed and experimentally studied compared to the conventional structure. Tests were conducted with downward flow for mass flux from 70 to 110 kg m-2s-1 (air side flow velocity from 1 to 2ms-1). The surface temperature distribution of the heat exchanger recorded by thermal imager and the square deviation of it were used to judge the uniformity of flow distribution. It is shown that as mass flux increased, better flow distribution is obtained (small square deviation of temperature distribution means better flow distribution: conventional structure from 32 to 27, novel structure from 19 to 14), and flow distribution of the novel structure was much better than that of the conventional one. The heat transfer performances of the two heat exchangers were also studied. The cooling capacity of the novel heat exchanger was 14.8% higher than that of the conventional because of the better flow distribution. And the refrigerant pressure drop was 120% higher because of bigger mass flow and the resistance of the orifice. It's worth noting that the air pressure drop of novel heat exchanger was also higher (about 28.3%)than that of the conventional one, even when they have same fin and flat tube structure. From the pictures of the heat exchanger surfaces, it was found that some surface area of the conventional heat exchanger was not wet because of the low mass flow and high superheat, which leaded to a poor performance and relatively small air pressure drop.

  20. Web-Based Exchange of Views Enhances "Global Studies"

    ERIC Educational Resources Information Center

    Ahamer, Gilbert; Kumpfmuller, Karl A.; Hohenwarter, Michaela

    2011-01-01

    Purpose: The aim of this article is to present the development-oriented Master's curriculum "Global Studies" (GS) at the University of Graz, Austria, as an example of interdisciplinary academic training with the purpose of fostering inter-"cultural" understanding. It aims to show that scientific disciplines can be understood as "cultures of…

  1. Computational Studies of Water Exchange around Aqueous Li+ with Polarizable Potential Models

    SciTech Connect

    Dang, Liem X.; Annapureddy, Harsha V.

    2013-08-28

    To enhance our understanding of the mechanism of water-exchange around the aqueous Li+, we carried out a systematic study on this system using molecular dynamics simulations with many-body potential models. The mechanistic properties associated with the water-exchange process, such as potentials of mean force, time dependent transmission coefficients, and the corresponding rate constants, were examined using transition rate theory, the reactive flux method, and Grote-Hynes treatments of the dynamic response of the solvent. We compared the computed rate theory results with the results from previous corresponding studies in which classical non-polarizable force fields were used. Our computed barrier heights for water exchange are significantly larger than those obtained using classical non-polarizable force fields. We also studied the effect of pressure on water-exchange rates and the corresponding activation volume. Our computed rate results for water exchange increase with pressure; therefore, a small negative activation volume is observed. This work was funded by the Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences (BES), of the U.S. Department of Energy (DOE). Battelle operates Pacific Northwest National Laboratory for DOE. The calculations were carried out using computer resources provided by BES.

  2. SuperLig Ion Exchange Resin Swelling and Buoyancy Study

    SciTech Connect

    Hassan, N.M.

    2000-07-27

    The objective of this study was to achieve a fundamental understanding of SuperLig resin swelling and shrinking characteristics, which lead to channeling and early breakthrough during loading cycles. The density of salt solution that causes resin floating was also determined to establish a limit for operation. Specific tests performed include (a) pH dependence, (b) ionic strength dependence and (c) buoyancy effect vs. simulant composition.

  3. Heat Exchanger Design Options and Tritium Transport Study for the VHTR System

    SciTech Connect

    Chang H. Oh; Eung S. Kim

    2008-09-01

    This report presents the results of a study conducted to consider heat exchanger options and tritium transport in a very high temperature reactor (VHTR) system for the Next Generation Nuclear Plant Project. The heat exchanger options include types, arrangements, channel patterns in printed circuit heat exchangers (PCHE), coolant flow direction, and pipe configuration in shell-and-tube designs. Study considerations include: three types of heat exchanger designs (PCHE, shell-and-tube, and helical coil); single- and two-stage unit arrangements; counter-current and cross flow configurations; and straight pipes and U-tube designs in shell-and-tube type heat exchangers. Thermal designs and simple stress analyses were performed to estimate the heat exchanger options, and the Finite Element Method was applied for more detailed calculations, especially for PCHE designs. Results of the options study show that the PCHE design has the smallest volume and heat transfer area, resulting in the least tritium permeation and greatest cost savings. It is theoretically the most reliable mechanically, leading to a longer lifetime. The two-stage heat exchanger arrangement appears to be safer and more cost effective. The recommended separation temperature between first and second stages in a serial configuration is 800oC, at which the high temperature unit is about one-half the size of the total heat exchanger core volume. Based on simplified stress analyses, the high temperature unit will need to be replaced two or three times during the plant’s lifetime. Stress analysis results recommend the off-set channel pattern configuration for the PCHE because stress reduction was estimated at up to 50% in this configuration, resulting in a longer lifetime. The tritium transport study resulted in the development of a tritium behavior analysis code using the MATLAB Simulink code. In parallel, the THYTAN code, previously performed by Ohashi and Sherman (2007) on the Peach Bottom data, was revived and verified. The 600 MWt VHTR core input file developed in preparation for the transient tritium analysis of VHTR systems was replaced with the original steady-state inputs for future calculations. A Finite Element Method analysis was performed using COMSOL Multiphysics software to accurately predict tritium permeation through the PCHE type heat exchanger walls. This effort was able to estimate the effective thickness for tritium permeations and develop a correlation for general channel configurations, which found the effective thickness to be much shorter than the average channel distance because of dead spots on the channel side.

  4. Theoretical study of electron exchange in Mg2+-B collisions

    NASA Astrophysics Data System (ADS)

    Amami, M.; Zaidi, A.; Moussa, A.; Lahmar, S.; Bacchus-Montabonel, M.-C.

    2015-03-01

    The electron capture of Mg2+ ions in collisions with boron atoms has been investigated using ab initio quantum chemical approaches. The potential energies of the electronic states implicated in the process together with the non adiabatic coupling matrix elements have been calculated by multi-reference configuration interaction methods. Total and partial cross sections for the charge transfer reaction are determined in the (1-600) keV impact energy range by means of semi-classical approaches. A detailed analysis of the electron capture mechanism taking into account radial and rotational interactions has been performed and compared to previous studies on collision systems involving the Mg2+ projectile ion.

  5. Quantitative Synthesis and Component Analysis of Single-Participant Studies on the Picture Exchange Communication System

    ERIC Educational Resources Information Center

    Tincani, Matt; Devis, Kathryn

    2011-01-01

    The "Picture Exchange Communication System" (PECS) has emerged as the augmentative communication intervention of choice for individuals with autism spectrum disorder (ASD), with a supporting body of single-participant studies. This report describes a meta-analysis of 16 single-participant studies on PECS with percentage of nonoverlapping data…

  6. Studies of Tropical/Mid-Latitude Exchange Using UARS Observations

    NASA Technical Reports Server (NTRS)

    Avallone, Linnea

    2001-01-01

    At the time this proposal was submitted, recent publications had suggested an important role for transport of midlatitude air into the tropical lower stratosphere. Most of these studies had employed data that gave only a time-averaged picture, making it difficult to determine the nature of the transport processes responsible for the observed behavior. We proposed to analyze observations of long-lived trace gases, such as nitric acid, methane, nitrous oxide, and chlorofluorocarbons, made from the Upper Atmosphere Research Satellite, to investigate the seasonal behavior of mixing between the midlatitudes and tropics. We planned to construct probability distributions of the concentrations of these species over small altitude ranges and to compare them to expectations based on modeled mean concentrations and knowledge of instrument precision. Differences from expectation were to be analyzed with respect to meteorological parameters to determine whether wave activity may have induced apparent mixing.

  7. A review of studies on ion thruster beam and charge-exchange plasmas

    NASA Technical Reports Server (NTRS)

    Carruth, M. R., Jr.

    1982-01-01

    Various experimental and analytical studies of the primary beam and charge-exchange plasmas of ion thrusters are reviewed. The history of plasma beam research is recounted, emphasizing experiments on beam neutralization, expansion of the beam, and determination of beam parameters such as electron temperature, plasma density, and plasma potential. The development of modern electron bombardment ion thrusters is treated, detailing experimental results. Studies on charge-exchange plasma are discussed, showing results such as the relationship between neutralizer emission current and plasma beam potential, ion energies as a function of neutralizer bias, charge-exchange ion current collected by an axially moving Faraday cup-RPA for 8-cm and 30-cm ion thrusters, beam density and potential data from a 15-cm ion thruster, and charge-exchange ion flow around a 30-cm thruster. A 20-cm thruster electrical configuration is depicted and facility effects are discussed. Finally, plasma modeling is covered in detail for plasma beam and charge-exchange plasma.

  8. Semi-Empirical Study of the Indirect Exchange Interaction in the Rem - Al System

    NASA Astrophysics Data System (ADS)

    Shakarov, Kh. O.

    2016-05-01

    The Ruderman-Kittel-Kasuya-Yosida exchange interaction (RKKY) is semi-empirically studied for the first time in compounds of binary REM - Al systems (REM - rare-earth metals: Gd, Dy, Ho, Er) using experimental values of paramagnetic Curie point (θp) of these compounds. Prediction of the RKKY theory was confirmed, i.e. there is a direct proportional dependence of θp value on de Gennes factor for equiatomic compounds of heavy REM with aluminum, just as in the case of pure REM. Values of the indirect exchange interaction parameter were semi-empirically estimated for the studied compounds. In general, it was established that RKKY-type exchange interaction is typical for REM compounds with aluminum, just as for pure REM.

  9. Benefits and problems of electronic information exchange as perceived by health care professionals: an interview study

    PubMed Central

    2011-01-01

    Background Various countries are currently implementing a national electronic patient record (n-EPR). Despite the assumed positive effects of n-EPRs, their overall adoption remains low and meets resistance from health care providers. This study aims to increase our understanding of health care providers' attitude towards the n-EPR, by investigating their perceptions of the benefits and problems of electronic information exchange in health care and the n-EPR in particular. Methods The study was conducted in three Dutch health care settings: acute care, diabetes care, and ambulatory mental health care. Two health care organisations were included per setting. Between January and June 2010, interviews were conducted with 17 stakeholders working in these organisations. Relevant themes were deduced by means of thematic qualitative analysis. Results Health care providers perceived electronic information exchange to promote the efficiency and quality of care. The problems they perceived in electronic information exchange mainly concerned the confidentiality and safety of information exchange and the reliability and quality of patient data. Many problems perceived by health care providers did not specifically apply to the n-EPR, but to electronic information exchange in general. Conclusions The implementation of the Dutch n-EPR has mainly followed a top-down approach, thereby neglecting the fact that the perceptions and preferences of its users (health care providers) need to be addressed in order to achieve successful implementation. The results of this study provide valuable suggestions about how to promote health care providers' willingness to adopt electronic information exchange, which can be useful for other countries currently implementing an n-EPR. Apart from providing information about the benefits and usefulness of electronic information exchange, efforts should be focused on minimising the problems as perceived by health care providers. The safety and confidentiality of electronic information exchange can be improved by developing tools to evaluate the legitimacy of access to electronic records, by increasing health care providers' awareness of the need to be careful when using patient data, and by measures to limit access to sensitive patient data. Improving health care providers' recording behaviour is important to improve the reliability and quality of electronically exchanged patient data. PMID:21982395

  10. Transformations of metal species in ageing humic hydrocolloids studied by competitive ligand and metal exchange.

    PubMed

    Burba, Peter; Van den Bergh, Johan

    2004-03-01

    Transformations of metal species (particularly Al, Ca, Fe, Mg, Mn, Zn) in ageing humic hydrocolloids were studied, applying a competitive ligand and metal exchange approach. For this purpose, metal-containing hydrocolloids, freshly collected from humic-rich German bog lake waters (Hohlohsee (HO), Black Forest; Venner Moor (VM), Muensterland; Arnsberger Wald (AW), Northrhine-Westfalia) and conventionally pre-filtered through 0.45 microm membranes, were subjected on-site to an exchange with EDTA and Cu(II) ions, respectively, as a function of time. EDTA complexes gradually formed, metal fractions exchanged by Cu(II) (as well as free Cu(II) concentrations) were operationally discriminated by means of a small time-controlled tangential-flow ultrafiltration unit (nominal cutoff: 1 kDa). Metal and DOM (dissolved organic matter) fractions obtained this way were determined off-site using instrumental methods (AAS, ICP-OES, carbon analyzer). After weeks of storage, the collected hydrocolloids were studied again by this approach. The EDTA availability of colloid-bound metals (particularly Al and Fe) exhibited different ageing trends, dependent on the sample (VM: decrease of Fe availability (98-76%), HO: increase of Fe availability (76-82%)). In contrast, the Cu(II) exchange equilibria of colloid-bound metals revealed merely low availability of Al (16-38%) and Fe (5-11%) towards Cu(II) ions, also dependent on ageing effects. In particular, the conditional copper exchange constants Kex obtained from the exchange between Cu(II) ions and available metal species (such as Ca, Mg, Mn, Zn) exhibited a strong decrease (by a factor of 2-100) during sample storage, indicating considerable non-equilibria complexation of these metal ions in the original bogwaters studied on-site. PMID:15214428

  11. Triple oxygen isotope exchange between chondrule melt and water vapor: An experimental study

    NASA Astrophysics Data System (ADS)

    Di Rocco, Tommaso; Pack, Andreas

    2015-09-01

    We have conducted time and ƒO2-dependent oxygen isotope exchange experiments between chondrule analogue melts and H2O in the phase. The aim of our study is to address the question whether the oxygen isotope composition of chondrules is the result of exchange with the ambient nebular gas or has been inherited from the precursor material. The silicate melt-H2O vapor exchange experiments were carried out in a vertical gas-mixing furnace using the metal loop technique at 1500 °C. The duration ranged from 5 to 1440 min and ƒO2 was set between IW - 3.8 and IW - 1.3 using the H2O/H2 buffer. Our experiments show that 50% exchange between H2O gas and silicate melt occurs in ∼4 h at ƒO2 = IW - 3.8 and in ∼1 h at ƒO2 = IW - 1.3. At solar nebula conditions, significant exchange occurs only if chondrule-melting times were several hours.

  12. A comparison study of compact plate fin-and-tube heat exchangers

    SciTech Connect

    Chi, K.Y.; Chang, Y.P.; Wang, C.C.; Chang, Y.J.

    1998-12-31

    Experimental investigation of the heat transfer and friction characteristics of plate fin-and-tube heat exchangers having 7 mm (0.276 in.) tube was carried out. In the present study, eight samples of commercially available plate fin-and-tube heat exchangers were tested. The rest results indicated that the effect of fin pitch is negligible for four-row coils, and there is a detectable decrease of heat transfer performance with increase of fin pitch for two-row coil. In addition, the heat transfer enhancement ratios decrease with decrease of fin pitch.

  13. Semi-aerobic stabilized landfill leachate treatment by ion exchange resin: isotherm and kinetic study

    NASA Astrophysics Data System (ADS)

    Zamri, Mohd Faiz Muaz Ahmad; Kamaruddin, Mohamad Anuar; Yusoff, Mohd Suffian; Aziz, Hamidi Abdul; Foo, Keng Yuen

    2015-03-01

    This study was carried out to investigate the treatability of ion exchange resin (Indion MB 6 SR) for the removal of chromium (VI), aluminium (III), zinc (II), copper (II), iron (II), and phosphate (PO4)3-, chemical oxygen demand (COD), ammonia nitrogen (NH3-N) and colour from semi-aerobic stabilized leachate by batch test. A range of ion exchange resin dosage was tested towards the removal efficiency of leachate parameters. It was observed that equilibrium data were best represented by the Langmuir model for metal ions and Freundlich was ideally fit for COD, NH3-N and colour. Intra particle diffusion model, pseudo first-order and pseudo second-order isotherm models were found ideally fit with correlation of the experimental data. The findings revealed that the models could describe the ion exchange kinetic behaviour efficiently, which further suggests comprehensive outlook for the future research in this field.

  14. Study regarding the influence of the crimping angle on the performances of the heat exchangers

    NASA Astrophysics Data System (ADS)

    Irimie, O.; Bode, F.; Opruta, D.

    2013-04-01

    The aim of this study is to determine the geometry of a plate for heat exchanger with high heat flow and low values for pressure losses. For this, in Solid Work software, were designed three plate geometries with different crimping angles for the flow channels. Was analyzed the influence of the crimping angle β on the fluid distribution and heat transfer. Also, were compared the data resulted from Computational Fluid Dynamics numeric simulation with the experimental ones for the plate heat exchangers with gaskets. The analysis of the vortices and temperature field distribution was achieved with the aid of simulation software Fluent. In order to validate the numerical simulation's results experimental research were carried out on a heat exchangers stand

  15. Isotope exchange study of the dissociation of metal humic substance complexes

    NASA Astrophysics Data System (ADS)

    Mizera, J.; Jansov, A.; Hvodov, I.; Bene, P.; Novk, F.

    2003-01-01

    Isotope exchange was employed to study dissociation of metal cations from their complexes with humic substances (HS). Dissociation of cation from HS controls the rate of isotope exchange between two identical metal-HS solutions (but for the presence of a radiotracer) divided by a dialysis membrane. The rate of isotope exchange of Eu/152Eu and Co/60Co in the systems with various HS was monitored as a function of pH, ionic strength, and the degree of HS loading with metal. The apparent rate of Eu-HS dissociation was found to be enhanced by decreasing pH, increasing ionic strength, and increasing metal loading. Co-HS dissociation was too fast to be followed by the method. For interpretation of the experimental kinetic data, the multiple first order law has been applied. Based on the results, a concept of HS as a mixture of two types of binding sites is discussed.

  16. Development of a Direct Contact Heat Exchanger, Phase 1 Study Report

    NASA Technical Reports Server (NTRS)

    Manvi, R.

    1978-01-01

    Electric power generation from geothermal brine requires, first, bringing the hot brine to the surface and then converting the heat to electric power. Binary conversion schemes were proposed, with the heat transfer between the brine and the working organic fluid taking place in a conventional tube and shell heat exchanger. If the brine is heavily laden with dissolved solids, however, solids buildup on the heat exchanger surfaces leads to a considerable degree of fouling and an accompanying drop in performance is experienced. A possible solution to this problem is the use of a direct contact exchanger with the secondary fluid power cycle. The proposed concept involves the formation of fluid sheets and bells as heat angles. Results of a study concerning the fluid mechanics of such surfaces are given.

  17. A molecular dynamics study of bond exchange reactions in covalent adaptable networks.

    PubMed

    Yang, Hua; Yu, Kai; Mu, Xiaoming; Shi, Xinghua; Wei, Yujie; Guo, Yafang; Qi, H Jerry

    2015-08-21

    Covalent adaptable networks are polymers that can alter the arrangement of network connections by bond exchange reactions where an active unit attaches to an existing bond then kicks off its pre-existing peer to form a new bond. When the polymer is stretched, bond exchange reactions lead to stress relaxation and plastic deformation, or the so-called reforming. In addition, two pieces of polymers can be rejoined together without introducing additional monomers or chemicals on the interface, enabling welding and reprocessing. Although covalent adaptable networks have been researched extensively in the past, knowledge about the macromolecular level network alternations is limited. In this study, molecular dynamics simulations are used to investigate the macromolecular details of bond exchange reactions in a recently reported epoxy system. An algorithm for bond exchange reactions is first developed and applied to study a crosslinking network formed by epoxy resin DGEBA with the crosslinking agent tricarballylic acid. The trace of the active units is tracked to show the migration of these units within the network. Network properties, such as the distance between two neighboring crosslink sites, the chain angle, and the initial modulus, are examined after each iteration of the bond exchange reactions to provide detailed information about how material behaviors and macromolecular structure evolve. Stress relaxation simulations are also conducted. It is found that even though bond exchange reactions change the macroscopic shape of the network, microscopic network characteristic features, such as the distance between two neighboring crosslink sites and the chain angle, relax back to the unstretched isotropic state. Comparison with a recent scaling theory also shows good agreement. PMID:26166382

  18. Multicultural Contacts in Education: A Case Study of an Exchange Project between Different Ethnic Groups

    ERIC Educational Resources Information Center

    Schuitema, Jaap; Veugelers, Wiel

    2011-01-01

    One important aim of citizenship education is learning to deal with cultural diversity. To this end, schools organise exchange projects to bring students into contact with different social and cultural groups. The aim of this study is to investigate the effects of intergroup contact in educational settings and to understand what the most…

  19. Research on Study Abroad, Mobility, and Student Exchange in Comparative Education Scholarship

    ERIC Educational Resources Information Center

    Streitwieser, Bernhard T.; Le, Emily; Rust, Val

    2012-01-01

    For many years there has been research on study abroad, student mobility and international student exchange; however in the last two decades the volume and scope of this work has increased significantly. There are now specific academic journals, a host of new books each year, expansive reports by international research organizations, and an…

  20. DETERMINING CARBON ISOTOPE SIGNATURES FROM MICROMETEOROLOGICAL MEASUREMENTS: IMPLICATIONS FOR STUDYING BIOSPHERE-ATMOSPHERE EXCHANGE PROCESSES

    Technology Transfer Automated Retrieval System (TEKTRAN)

    In recent years considerable effort has been focused on combining micrometeorological and stable isotope techniques to elucidate and study biosphere-atmosphere exchange processes. At the ecosystem scale, these methods are increasingly being used to address a number of challenging problems, including...

  1. Interpersonal Exchanges in Discussion Forums: A Study of Learning Communities in Distance Learning Settings

    ERIC Educational Resources Information Center

    Scherer Bassani, Patricia B.

    2011-01-01

    Cooperative relationships are the foundation of a model of online learning based on communities. The development of a community depends on the interaction between community members. This study is based on the belief that the dynamics of exchange of thought, from a Piagetian perspective, are one possibility for understanding the process of…

  2. Research on Study Abroad, Mobility, and Student Exchange in Comparative Education Scholarship

    ERIC Educational Resources Information Center

    Streitwieser, Bernhard T.; Le, Emily; Rust, Val

    2012-01-01

    For many years there has been research on study abroad, student mobility and international student exchange; however in the last two decades the volume and scope of this work has increased significantly. There are now specific academic journals, a host of new books each year, expansive reports by international research organizations, and an

  3. 77 FR 57055 - Regulatory New Drug Review: Solutions for Study Data Exchange Standards; Notice of Meeting...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-09-17

    ..., 2012 (77 FR 48491). The document announced a meeting entitled ``Regulatory New Drug Review: Solutions for Study Data Exchange Standards.'' The document was published with an incorrect email address. This...Standards@fda.hhs.gov . SUPPLEMENTARY INFORMATION: In FR Doc. 2012-19748, appearing on page 48491 in...

  4. Using the level set method to study the effects of heterogeneity and anisotropy on hyporheic exchange

    NASA Astrophysics Data System (ADS)

    Chen, Cheng; Zeng, Lingzao

    2015-05-01

    The level set method was used to simulate the interface movement when a conservative solute migrated from stream water to subsurface water, and study the effects of streambed heterogeneity and anisotropy on solute penetration. The level set method is a numerical technique for tracking moving interfaces based on the idea that the interface is a level set curve of a higher-dimensional function. Numerical simulations were compared to experiments conducted in a recirculating flume. Streambed heterogeneity led to water exchange between multiple bed forms, while in homogeneous streambeds the water exchange was restricted within a single bed form. A thin layer of homogeneous sediments at the top of the heterogeneous streambeds significantly increased the interfacial water influx, resulting in faster solute penetration and stream concentration decrease. Streambed heterogeneity generated horizontal preferential flow paths in the upper part of the bed while decreasing pore water velocities deeper in the bed, which hindered vertical penetration and consequently led to slower stream concentration decrease. Decreasing vertical permeability or increasing horizontal permeability led to slower vertical penetration and stream concentration decrease. Decreasing vertical permeability had a much more significant impact on solute penetration than increasing horizontal permeability, because mass transfer in hyporheic exchange is greatly dominated by vertical advection which depends primarily on the vertical permeability. This study was the first to apply the level set method in the study of hyporheic exchange. The theoretical and numerical methods have important applications in subsurface flow and transport processes.

  5. Lead exchange in teeth and bone--a pilot study using stable lead isotopes.

    PubMed Central

    Gulson, B L; Gillings, B R

    1997-01-01

    Stable lead isotopes and lead concentrations were measured in the enamel and dentine of permanent (n = 37) and deciduous teeth (n = 14) from 47 European immigrants to Australia to determine whether lead exchange occurs in teeth and how it relates to lead exchange in bone. Enamel exhibits no exchange of its European-origin lead with lead from the Australian environment. In contrast, dentine lead exchanges with Australian lead to the extent of approximately 1% per year. In one subject, trabecular bone from the tooth socket exchanged almost all its European lead with Australian lead over a a 15-year period (turnover of approximately 6% per year), similar to the approximately 8% per year proposed for lead turnover in trabecular bone. The repository characteristics of intact circumpulpal dentine were investigated by analyses of four sets of contiguous slices from six teeth: 1) a set consisting of slices with intact circumpulpal dentine and cementum; 2) a set in which these areas were removed; 3) another set consisting of slices with intact circumpulpal dentine and cementum; and 4) a set without cementum. These analyses show relatively small differences in isotopic composition between contiguous slices except that circumpulpal dentine appears to be the dominant control on lead concentration. There is a significant correlation (R2 = 0.19, p = 0.01, n = 34) of dentine lead concentration and rate of exchange with residence time from the country of origin and Australian lead, but there is no such correlation with enamel lead concentration. Analyses of permanent and deciduous teeth of subjects from other countries who have resided in Australia for varying lengths of time should resolve some of the questions arising from this pilot study. Images Figure 1. PMID:9347897

  6. 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. PMID:26456784

  7. Experimental study of mixed convection heat transfer in vertical helically coiled tube heat exchangers

    SciTech Connect

    Ghorbani, N.; Taherian, H.; Gorji, M.; Mirgolbabaei, H.

    2010-10-15

    In this study the mixed convection heat transfer in a coil-in-shell heat exchanger for various Reynolds numbers, various tube-to-coil diameter ratios and different dimensionless coil pitch was experimentally investigated. The experiments were conducted for both laminar and turbulent flow inside coil. Effects of coil pitch and tube diameters on shell-side heat transfer coefficient of the heat exchanger were studied. Different characteristic lengths were used in various Nusselt number calculations to determine which length best fits the data and several equations were proposed. The particular difference in this study in comparison with the other similar studies was the boundary conditions for the helical coils. The results indicate that the equivalent diameter of shell is the best characteristic length. (author)

  8. Parametric Sensivity Study of Operating and Design Variables in Wellbore Heat Exchangers

    SciTech Connect

    G. Michael Shook; Gopi Nalla; Gregory L. Mines; K. Kit Bloomfield

    2004-05-01

    This report documents the results of an extensive sensitivity study conducted by the Idaho National Engineering and Environmental Laboratory. This study investigated the effects of various operating and design parameters on wellbore heat exchanger performance to determine conditions for optimal thermal energy extraction and evaluate the potential for using a wellbore heat exchanger model for power generation. Variables studied included operational parameters such as circulation rates, wellbore geometries and working fluid properties, and regional properties including basal heat flux and formation rock type. Energy extraction is strongly affected by fluid residence time, heat transfer contact area, and formation thermal properties. Water appears to be the most appropriate working fluid. Aside from minimal tubing insulation, tubing properties are second order effects. On the basis of the sensitivity study, a best case model was simulated and the results compared against existing low-temperature power generation plants. Even assuming ideal work conversion to electric power, a wellbore heat exchange model cannot generate 200 kW (682.4e+3 BTU/h) at the onset of pseudosteady state. Using realistic conversion efficiency, the method is unlikely to generate 50 kW (170.6e+3 BTU/h).

  9. Parametric Sensitivity Study of Operating and Design Variables in Wellbore Heat Exchangers

    SciTech Connect

    Nalla, G.; Shook, G.M.; Mines, G.L.; Bloomfield, K.K.

    2004-05-01

    This report documents the results of an extensive sensitivity study conducted by the Idaho National Engineering and Environmental Laboratory. This study investigated the effects of various operating and design parameters on wellbore heat exchanger performance to determine conditions for optimal thermal energy extraction and evaluate the potential for using a wellbore heat exchanger model for power generation. Variables studied included operational parameters such as circulation rates, wellbore geometries and working fluid properties, and regional properties including basal heat flux and formation rock type. Energy extraction is strongly affected by fluid residence time, heat transfer contact area, and formation thermal properties. Water appears to be the most appropriate working fluid. Aside from minimal tubing insulation, tubing properties are second order effects. On the basis of the sensitivity study, a best case model was simulated and the results compared against existing low-temperature power generation plants. Even assuming ideal work conversion to electric power, a wellbore heat exchange model cannot generate 200 kW (682.4e+3 BTU/h) at the onset of pseudosteady state. Using realistic conversion efficiency, the method is unlikely to generate 50 kW (170.6e+3 BTU/h).

  10. NMR and molecular modeling study of ligand exchange induced structural changes in diruthenium complexes

    NASA Astrophysics Data System (ADS)

    Santos, Joana Mara; Formiga, André Luiz B.; Daniel Figueroa-Villar, J.

    2002-05-01

    In this work we have studied, by molecular modeling using PM3tm quantum chemical calculations, the structural changes observed by NMR during the ligand exchange in solvolysis of the [Ru 2(μ-O)(μ-O 2CCH 3) 2(4-pic) 6] 2+ complex, where 4-pic means 4-picoline. To validate the calculation procedures, we have first carried out a molecular modeling study of four (μ-oxo)bis(μ-acetato)diruthenium(III) with monodentate ligands, whose X-ray crystallographic structures are reported in the literature. The comparison between calculated and X-ray bond lengths and angles for these compounds shows very good agreement between the data (a variation of less than 3%) and also gives a good overview of the structural changes induced by the ligand exchange reactions. However, inability to predict trans influences is a limitation of these semi-empirical calculations.

  11. Numerical study of a round tube heat exchanger with louvered fins and delta winglets

    NASA Astrophysics Data System (ADS)

    Huisseune, H.; T'Joen, C.; De Jaeger, P.; Ameel, B.; De Paepe, M.

    2012-11-01

    Louvered fin and round tube heat exchangers are widely used in air conditioning devices and heat pumps. In this study the effect of punching delta winglet vortex generators in the louvered fin surface is studied numerically. The delta winglets are located in a common-flow-down orientation behind each tube of the staggered tube layout. It is shown that the generated vortices significantly reduce the size of the tube wakes. Three important heat transfer enhancement mechanisms can be distinguished: a better flow mixing, boundary layer thinning and a delay in flow separation from the tube surface. The compound heat exchanger has a better thermal hydraulic performance then when only louvers or only delta winglets are used. Comparison to other enhanced fin designs clearly shows its potential, especially for low Reynolds number applications.

  12. Repeated Diagnostic Imaging Studies in Ontario and the Impact of Health Information Exchange Systems.

    PubMed

    Welk, Blayne; Liu, Kuan; Al-Jaishi, Ahmed; McArthur, Eric; Jain, Arsh K; Ordon, Michael

    2016-01-01

    Health information exchange systems can link the results of diagnostic imaging tests across hospitals and geographic areas. One of the potential benefits of these systems is a reduction in imaging studies ordered by physicians who do not know about or have access to the previous imaging results. We used administrative data from Ontario, Canada (from the year 2013), to measure how frequently the same cross-sectional imaging study is repeated in a patient. Overall, 12.8% of the specified imaging tests were repeated within 90 days. An area of Southwestern Ontario with a health information exchange system for diagnostic imaging tests had a 13% lower rate of repeat cross-sectional imaging compared with the rest of the province (11.2 vs 12.8%, p < 0.01). The use of linked radiology systems may be able to reduce the number of repeated imaging tests and improve patient safety and hospital efficiency. PMID:27133604

  13. Kinetic Method for Hydrogen-Deuterium-Tritium Mixture Distillation Simulation

    SciTech Connect

    Sazonov, A.B.; Kagramanov, Z.G.; Magomedbekov, E.P.

    2005-07-15

    Simulation of hydrogen distillation plants requires mathematical procedures suitable for multicomponent systems. In most of the present-day simulation methods a distillation column is assumed to be composed of theoretical stages, or plates. However, in the case of a multicomponent mixture theoretical plate does not exist.An alternative kinetic method of simulation is depicted in the work. According to this method a system of mass-transfer differential equations is solved numerically. Mass-transfer coefficients are estimated with using experimental results and empirical equations.Developed method allows calculating the steady state of a distillation column as well as its any non-steady state when initial conditions are given. The results for steady states are compared with ones obtained via Thiele-Geddes theoretical stage technique and the necessity of using kinetic method is demonstrated. Examples of a column startup period and periodic distillation simulations are shown as well.

  14. Design study of a transverse-to-longitudinal emittance exchange proof-of-principle experiment

    SciTech Connect

    Sun, Y.-E.; Kim, K.-J.; Power, J. G.; Piot, P.; Rihaoui, M. M.; Northern Illinois Univ.; FNL

    2008-01-01

    Transverse-to-longitudinal emittance exchange can be achieved through certain arrangements of dipole magnets and a dipole mode rf cavity. Theory on such schemes has been developed in the past several years. In this paper we report our numerical simulations to optimize a low energy (E sime 15 MeV) proof-of-principle experiment planned at the Argonne Wakefield Accelerator (AWA). Parametric studies of the dipole magnets and cavity strengths, as well as initial beam parameters, are presented.

  15. Comparative study of key exchange and authentication methods in application, transport and network level security mechanisms

    NASA Astrophysics Data System (ADS)

    Fathirad, Iraj; Devlin, John; Jiang, Frank

    2012-09-01

    The key-exchange and authentication are two crucial elements of any network security mechanism. IPsec, SSL/TLS, PGP and S/MIME are well-known security approaches in providing security service to network, transport and application layers; these protocols use different methods (based on their requirements) to establish keying materials and authenticates key-negotiation and participated parties. This paper studies and compares the authenticated key negotiation methods in mentioned protocols.

  16. An experimental study of the influence of the temperature difference field uniformity on cross-flow heat exchanger performance

    SciTech Connect

    Lu, B.; Lloyd, J.R.; Guo, Z.Y.; Zhou, S.Q.

    1996-12-31

    An experimental study of heat exchanger performance has been conducted utilizing a basic cross-flow heat exchanger configuration. Six different cross-flow, finned-tube heat exchanger flow configurations were tested in a specially designed wind tunnel system to investigate the importance of the Temperature Difference Uniformity on the effectiveness of heat exchanger performance. The Temperature Difference Field (TDF) and the Temperature Difference Uniformity Factor, {Phi}, were employed as design factors to characterize and evaluate heat exchanger thermal performance. A base heat exchanger configuration was established, and then five modifications on the base configuration were made in a systematic study to enhance the performance. The fluids were air on the outside, and hot water inside the tubes. The basic configurations included either 28 or 56 tubes in the bank. The results of the experiments have clearly demonstrated the importance of flow distribution and how it can be used to control the Temperature Difference Field; which, as a design parameter, is an important component of heat exchanger performance optimization. Heat exchanger effectiveness for the best flow distribution was found to increase by 4.3% over that of the conventional flow distribution with no associated increase in pressure drop. This promotes a new path for them to increase heat exchanger heat transfer effectiveness. Comments on further possible performance enhancement strategies are presented.

  17. Folding Study of Venus Reveals a Strong Ion Dependence of Its Yellow Fluorescence under Mildly Acidic Conditions*

    PubMed Central

    Hsu, Shang-Te Danny; Blaser, Georg; Behrens, Caroline; Cabrita, Lisa D.; Dobson, Christopher M.; Jackson, Sophie E.

    2010-01-01

    Venus is a yellow fluorescent protein that has been developed for its fast chromophore maturation rate and bright yellow fluorescence that is relatively insensitive to changes in pH and ion concentrations. Here, we present a detailed study of the stability and folding of Venus in the pH range from 6.0 to 8.0 using chemical denaturants and a variety of spectroscopic probes. By following hydrogen-deuterium exchange of 15N-labeled Venus using NMR spectroscopy over 13 months, residue-specific free energies of unfolding of some highly protected amide groups have been determined. Exchange rates of less than one per year are observed for some amide groups. A super-stable core is identified for Venus and compared with that previously reported for green fluorescent protein. These results are discussed in terms of the stability and folding of fluorescent proteins. Under mildly acidic conditions, we show that Venus undergoes a drastic decrease in yellow fluorescence at relatively low concentrations of guanidinium chloride. A detailed study of this effect establishes that it is due to pH-dependent, nonspecific interactions of ions with the protein. In contrast to previous studies on enhanced green fluorescence protein variant S65T/T203Y, which showed a specific halide ion-binding site, NMR chemical shift mapping shows no evidence for specific ion binding. Instead, chemical shift perturbations are observed for many residues primarily located in both lids of the β-barrel structure, which suggests that small scale structural rearrangements occur on increasing ionic strength under mildly acidic conditions and that these are propagated to the chromophore resulting in fluorescence quenching. PMID:19901033

  18. A Study of Jordanian University Students' Perceptions of Using Email Exchanges with Native English Keypals for Improving Their Writing Competency

    ERIC Educational Resources Information Center

    Mahfouz, Safi Mahmoud

    2010-01-01

    English foreign language learners generally tend to consider email exchanges with native speakers (NSs) as an effective tool for improving their foreign language proficiency. This study investigated Jordanian university students' perceptions of using email exchanges with native English keypals (NEKs) for improving their writing competency. A…

  19. Study of the large reduced density gradient limit for the exchange energy

    NASA Astrophysics Data System (ADS)

    Gazquez, Jose; Carmona-Espindola, Javier; Vela, Alberto; Trickey, Sam

    The generalized gradient approximation (GGA) for the Kohn-Sham exchange-correlation functional has become widely used in electronic structure calculations of small, medium and large systems, because it provides rather reasonable results with moderate computational effort. Usually the GGA for exchange (X) is expressed in terms of an analytical expression of the X enhancement function, Fx(s), where s is the reduced density gradient. When a non-empirical approach based on constraint satisfaction is followed, the analytical expression of Fx(s) is the result of interpolating between the small- and large-s limits. However, neither of those limits is uniquely defined. In both cases there are several possibilities. The present work is a study of the influence of the several large-s limit possibilities upon the calculation of properties that depend on energy differences, versus those that depend on response functions, and excitation energies.

  20. Charge-exchange erosion studies of accelerator grids in ion thrusters

    NASA Technical Reports Server (NTRS)

    Peng, Xiaohang; Ruyten, Wilhelmus M.; Keefer, Dennis

    1993-01-01

    A particle simulation model is developed to study the charge-exchange grid erosion in ion thrusters for both ground-based and space-based operations. Because the neutral gas downstream from the accelerator grid is different for space and ground operation conditions, the charge-exchange erosion processes are also different. Based on an assumption of now electric potential hill downstream from the ion thruster, the calculations show that the accelerator grid erosion rate for space-based operating conditions should be significantly less than experimentally observed erosion rates from the ground-based tests conducted at NASA Lewis Research Center (LeRC) and NASA Jet Propulsion Laboratory (JPL). To resolve this erosion issue completely, we believe that it is necessary to accurately measure the entire electric potential field downstream from the thruster.

  1. Engineering study for the treatment of spent ion exchange resin resulting from nuclear process applications

    SciTech Connect

    Place, B.G.

    1990-09-01

    This document is an engineering study of spent ion exchange resin treatment processes with the purpose of identifying one or more suitable treatment technologies. Classifications of waste considered include all classes of low-level waste (LLW), mixed LLW, transuranic (TRU) waste, and mixed TRU waste. A total of 29 process alternatives have been evaluated. Evaluation parameters have included economic parameters (both total life-cycle costs and capital costs), demonstrated operability, environmental permitting, operational availability, waste volume reduction, programmatic consistency, and multiple utilization. The results of this study suggest that there are a number of alternative process configurations that are suitable for the treatment of spent ion exchange resin. The determinative evaluation parameters were economic variables (total life-cycle cost or capital cost) and waste volume reduction. Immobilization processes are generally poor in volume reduction. Thermal volume reduction processes tend to have high capital costs. There are immobilization processes and thermal volume reduction processes that can treat all classifications of spent ion exchange resin likely to be encountered. 40 refs., 19 figs., 17 tabs.

  2. The effect of histidine-228 on the catalytic efficiency and stereospecificity of the serine hydroxymethyltransferase catalysed exchange of the alpha-protons of amino acids.

    PubMed

    Fitzpatrick, T B; Malthouse, J P

    1998-07-28

    13C-NMR has been used to determine how replacing the histidine-228 residue of serine hydroxymethyltransferase (EC 2.1.2.1) by an asparagine residue effects the catalysis of the hydrogen-deuterium exchange of the alpha-protons of [2-13C]glycine at pH 7.8. The H228N mutation did not lead to a large change in the stereospecificity of the first order exchange rates of the alpha-protons of glycine both in the presence and in the absence of tetrahydrofolate. However, the mutation did lead to large decreases in the stereospecificity of the second order exchange rate in both the presence and the absence of tetrahydrofolate. In the absence of tetrahydrofolate this decrease in stereospecificity was largely due to the decrease in the second order exchange rate of the pro-2S proton, while in the presence of tetrahydrofolate the large increase in the second order exchange rate of the pro-2R proton of glycine made a major contribution. We conclude that the H228N mutation has significant effects on the catalytic efficiency and stereospecificity of the second order exchange reactions, but only a small effect on the corresponding first order exchange reactions. PMID:9675289

  3. Study of junction flows in louvered fin round tube heat exchangers using the dye injection technique

    SciTech Connect

    Huisseune, H.; Willockx, A.; De Paepe, M.; T'Joen, C.; De Jaeger, P.

    2010-11-15

    Detailed studies of junction flows in heat exchangers with an interrupted fin design are rare. However, understanding these flow structures is important for design and optimization purposes, because the thermal hydraulic performance of heat exchangers is strongly related to the flow behaviour. In this study flow visualization experiments were performed in six scaled-up models of a louvered fin round tube heat exchanger. The models have three tube rows in a staggered layout and differ only in their fin spacing and louver angle. A water tunnel was designed and built and the flow visualizations were carried out using dye injection. At low Reynolds numbers the streakline follows the tube contours, while at higher Reynolds numbers a horseshoe vortex is developed ahead of the tubes. The two resulting streamwise vortex legs are destroyed by the downstream louvers (i.e. downstream the turnaround louver), especially at higher Reynolds numbers, smaller fin pitches and larger louver angles. Increasing the fin spacing results in a larger and stronger horseshoe vortex. This illustrates that a reduction of the fin spacing results in a dissipation of vortical motion by mechanical blockage and skin friction. Furthermore it was observed that the vortex strength and number of vortices in the second tube row is larger than in the first tube row. This is due to the thicker boundary layer in the second tube row, and the flow deflection, which is typical for louvered fin heat exchangers. Visualizations at the tube-louver junction showed that in the transition part between the angled louver and the flat landing a vortex is present underneath the louver surface which propagates towards the angled louver. (author)

  4. Experimental study of the airside performance of tube row spacing in finned tube heat exchangers

    NASA Astrophysics Data System (ADS)

    Halici, Fethi; Taymaz, Imdat

    2006-07-01

    Almost all of the studies in dehumidifying coils are experimental studies. In this study, effect of tube regulation space on heat and mass transfer and friction factor for heat exchangers made from aluminum fins and cooper tubes are identified experimentally. External surface heat transfer coefficient, Colburn factor and friction factor was calculated by the help of the computer program by using experimental values done. After the diagrams investigated, with the decreasing of tube row spacing the external surface heat transfer in the dry surface and friction factor increased. If wet and dry surfaces are compared, Colburn and friction factor in wet surfaces is larger than Colburn and friction factor in dry surfaces.

  5. Laboratory Studies of X-ray Spectra Formed by Charge Exchange

    NASA Astrophysics Data System (ADS)

    Beiersdorfer, Peter; Ali, R.; Brown, G. V.; Koutroumpa, D.; Kelley, R. L.; Kilbourne, C.; Leutenegger, M. A.; Porter, F.

    2013-04-01

    Charge exchange between ions and neutral atoms or molecules has been accepted at an important soft producing process in our solar system. By extension, charge exchange may contribute to the X-ray emission of circumstellar material. It may also produce X-ray emission at the boundaries of supernova ejecta and star burst galaxies, or whenever hot plasma collides with neutral matter. X-ray spectra of K-shell and L-shell ions formed by charge exchange have now been studied in a variety of laboratory settings. These experiments have shown several characteristic features of line formation by charge exchange when compared to the X-ray emission produced by electron-impact excitation, e.g., enhancement emission of forbidden lines and of lines from levels with high principal quantum number. They have also shown a dependence on the interaction gas and on the energy of the ion-neutral collision. Moreover, the transfer of multiple electrons is typically preferred, provided the donor molecules or atoms have multiple valence-shell electrons. The laboratory measurements are in qualitative agreement with theory. However, the details of the observed X-ray spectra, especially those recorded with high spectral resolution, can differ substantially from predictions, especially for spectra produced at collision velocities equal to or lower than those found in thermal plasmas or produced with neutral gases other than atomic hydrogen. Puzzling discrepancies can be noted, such as enhanced emission from an upper level with the 'wrong' principal quantum number. Even more puzzling is a recent experiment in which two, co-mixed bare ion species of similar atomic number produce very different Lyman series emission upon charge exchange with a given neutral gas, defying both theoretical predictions and empirical scaling. Laboratory measurements have also shown that some of the characteristic features of charge exchange can be reproduced by radiative electron capture, i.e., by capture of a continuum electron. This process dominates in cold, photo-ionized plasmas, or when hot and cold plasmas mix. Work was performed under the auspices of the DOE by LLNL under contract DE-AC52-07NA27344 and supported in part by an award from NASA's APRA program.

  6. Health Information Exchange Implementation: Lessons Learned and Critical Success Factors From a Case Study

    PubMed Central

    2014-01-01

    Background Much attention has been given to the proposition that the exchange of health information as an act, and health information exchange (HIE), as an entity, are critical components of a framework for health care change, yet little has been studied to understand the value proposition of implementing HIE with a statewide HIE. Such an organization facilitates the exchange of health information across disparate systems, thus following patients as they move across different care settings and encounters, whether or not they share an organizational affiliation. A sociotechnical systems approach and an interorganizational systems framework were used to examine implementation of a health system electronic medical record (EMR) system onto a statewide HIE, under a cooperative agreement with the Office of the National Coordinator for Health Information Technology, and its collaborating organizations. Objective The objective of the study was to focus on the implementation of a health system onto a statewide HIE; provide insight into the technical, organizational, and governance aspects of a large private health system and the Virginia statewide HIE (organizations with the shared goal of exchanging health information); and to understand the organizational motivations and value propositions apparent during HIE implementation. Methods We used a formative evaluation methodology to investigate the first implementation of a health system onto the statewide HIE. Qualitative methods (direct observation, 36 hours), informal information gathering, semistructured interviews (N=12), and document analysis were used to gather data between August 12, 2012 and June 24, 2013. Derived from sociotechnical concepts, a Blended Value Collaboration Enactment Framework guided the data gathering and analysis to understand organizational stakeholders’ perspectives across technical, organizational, and governance dimensions. Results Several challenges, successes, and lessons learned during the implementation of a health system to the statewide HIE were found. The most significant perceived success was accomplishing the implementation, although many interviewees also underscored the value of a project champion with decision-making power. In terms of lessons learned, social reasons were found to be very significant motivators for early implementation, frequently outweighing economic motivations. It was clear that understanding the guides early in the project would have mitigated some of the challenges that emerged, and early communication with the electronic health record vendor so that they have a solid understanding of the undertaking was critical. An HIE implementations evaluation framework was found to be useful for assessing challenges, motivations, value propositions for participating, and success factors to consider for future implementations. Conclusions This case study illuminates five critical success factors for implementation of a health system onto a statewide HIE. This study also reveals that organizations have varied motivations and value proposition perceptions for engaging in the exchange of health information, few of which, at the early stages, are economically driven. PMID:25599991

  7. Exchange-bias in amorphous ferromagnetic and polycrystalline antiferromagnetic bilayers: Structural study and micromagnetic modeling

    NASA Astrophysics Data System (ADS)

    Kohn, A.; Dean, J.; Kovacs, A.; Zeltser, A.; Carey, M. J.; Geiger, D.; Hrkac, G.; Schrefl, T.; Allwood, D.

    2011-04-01

    We study the role of the structure of antiferromagnetic polycrystalline metallic films in determining the magnetic properties of an exchange-coupled amorphous ferromagnetic layer. The bilayers are sputter-deposited, highly textured {111} Ir22Mn78 and Co65.5Fe14.5B20 thin films. We focus on structural characterization of Ir22Mn78 as a function of layer thickness in the range having the strongest influence over the exchange-bias field and training effect. We have used transmission electron microscopy to characterize defects in the form of interface steps and roughness, interdiffusion, twin- and grain-boundaries. Such defects can result in uncompensated magnetic spins in the antiferromagnet, which then contribute to exchange-bias. These experimental results form the basis of a general model, which uses finite element micromagnetic simulations. The model incorporates the experimental structural parameters of the bilayer by implementing a surface integral technique that allows numerical calculations to solve the transition from an amorphous to a granular structure. As a result, a detailed calculation of the underlying magnetic structure within the antiferromagnetic material is achieved. These calculations are in good agreement with micromagnetic imaging using Lorentz transmission electron microscopy and the macro-magnetic properties of these bilayers.

  8. A Comparative Data-Based Modeling Study on Respiratory CO2 Gas Exchange during Mechanical Ventilation

    PubMed Central

    Kim, Chang-Sei; Ansermino, J. Mark; Hahn, Jin-Oh

    2016-01-01

    The goal of this study is to derive a minimally complex but credible model of respiratory CO2 gas exchange that may be used in systematic design and pilot testing of closed-loop end-tidal CO2 controllers in mechanical ventilation. We first derived a candidate model that captures the essential mechanisms involved in the respiratory CO2 gas exchange process. Then, we simplified the candidate model to derive two lower-order candidate models. We compared these candidate models for predictive capability and reliability using experimental data collected from 25 pediatric subjects undergoing dynamically varying mechanical ventilation during surgical procedures. A two-compartment model equipped with transport delay to account for CO2 delivery between the lungs and the tissues showed modest but statistically significant improvement in predictive capability over the same model without transport delay. Aggregating the lungs and the tissues into a single compartment further degraded the predictive fidelity of the model. In addition, the model equipped with transport delay demonstrated superior reliability to the one without transport delay. Further, the respiratory parameters derived from the model equipped with transport delay, but not the one without transport delay, were physiologically plausible. The results suggest that gas transport between the lungs and the tissues must be taken into account to accurately reproduce the respiratory CO2 gas exchange process under conditions of wide-ranging and dynamically varying mechanical ventilation conditions. PMID:26870728

  9. Studies on PVA based nanocomposite Proton Exchange Membrane for Direct methanol fuel cell (DMFC) applications

    NASA Astrophysics Data System (ADS)

    Bahavan Palani, P.; Kannan, R.; Rajashabala, S.; Rajendran, S.; Velraj, G.

    2015-02-01

    Different concentrations of Poly (vinyl alcohol)/Montmorillonite (PVA/MMT) based proton exchange membranes (PEMs) have been prepared by solution casting method. The structural and electrical properties of these composite membranes have been characterized by using X-ray diffraction (XRD), Fourier transform infrared spectroscopic (FTIR) and AC impedance spectroscopic methods. The conductivity of the PEMs has been estimated for the different concentration of MMT. Water/Methanol uptake measurement were also analyzed for the prepared PEMs and presented. The proton conductivity studies were carried out at room temperature with 100% of humidity.

  10. Homopolymer Adsorption on Hexagonal Surfaces: A Replica-Exchange Monte Carlo Study

    NASA Astrophysics Data System (ADS)

    Liewehr, B.; Bachmann, M.

    2016-01-01

    The adsorption behavior and thermodynamic properties of a coarse-grained flexible homopolymer, grafted on a hexagonal patterned surface, are investigated by means of parallel-tempering replica-exchange Monte Carlo simulations. In this study, the strength of the polymer-surface interaction, which is based on a standard Lennard-Jones potential, is changed systematically, mimicking different honeycomb-structured substrate materials. Utilizing specific order parameters, measured over a range of various temperatures and surface adsorption strengths, different structural phases are discriminated into classes of expanded, globular, droplet, and compact conformations. Finally, we construct the hyperphase diagram for a polymer with 55 monomers and discuss representative polymer structures.

  11. Fundamental basis and implementation of shell and tube heat exchanger project design: condenser and evaporator study

    NASA Astrophysics Data System (ADS)

    Dalkilic, A. S.; Acikgoz, O.; Tapan, S.; Wongwises, S.

    2016-03-01

    A shell and tube heat exchanger is used as a condenser and an evaporator in this theoretical study. Parametric performance analyses for various actual refrigerants were performed using well-known correlations in open sources. Condensation and evaporation were occurred in the shell side while the water was flowing in the tube side of heat exchanger. Heat transfer rate from tube side was kept constant for condenser and evaporator design. Condensing temperatures were varied from 35 to 60 °C whereas evaporating temperatures were ranging from -15 to 10 °C for the refrigerants of R12, R22, R134a, R32, R507A, R404A, R502, R407C, R152A, R410A and R1234ZE. Variation of convective heat transfer coefficients of refrigerants, total heat transfer coefficients with Reynolds numbers and saturation temperatures were given as validation process considering not only fouling resistance and omission of it but also staggered (triangular) and line (square) arrangements. The minimum tube lengths and necessary pumping powers were calculated and given as case studies for the investigated refrigerants considering validation criteria. It was understood that refrigerant type, fouling resistance and arrangement type are one of the crucial issues regarding the determination of heat exchanger's size and energy consumption. Consequently, R32 and R152a were found to require the shortest tube length and lowest pumping power in the condenser, whereas R507 and R407C have the same advantages in the evaporator. Their heat transfer coefficients were also determined larger than others as expectedly.

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

    NASA Astrophysics Data System (ADS)

    Savkov, Boris; Maksakov, Vladimir; Kuratieva, Natalia

    2015-10-01

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

  13. Tantalum acetabular augments in one-stage exchange of infected total hip arthroplasty: a case-control study.

    PubMed

    Klatte, Till Orla; Kendoff, Daniel; Sabihi, Reza; Kamath, Atul F; Rueger, Johannes M; Gehrke, Thorsten

    2014-07-01

    During the one-stage exchange procedure for periprosthetic joint infection (PJI) after total hip arthroplasty (THA), acetabular defects challenge reconstructive options. Porous tantalum augments are an established tool for addressing acetabular destruction in aseptic cases, but their utility in septic exchange is unknown. This retrospective case-control study presents the initial results of tantalum augmentation during one-stage exchange for PJI. Primary endpoints were rates of re-infection and short-term complications associated with this technique. Study patients had no higher risk of re-infection with equivalent durability at early follow-up with a re-infection rate in both groups of 4%. In conclusion, tantalum augments are a viable option for addressing acetabular defects in one-stage exchange for septic THA. Further study is necessary to assess long-term durability when compared to traditional techniques for acetabular reconstruction. PMID:24559522

  14. New Missions and the Future of Solar Wind Charge Exchange Studies

    NASA Astrophysics Data System (ADS)

    Kuntz, K. D.

    2016-04-01

    Several newly approved missions in astrophysics and heliophysics will study solar wind charge-exchange (SWCX) directly as either primary or secondary science goals. Of these, SMILE and CuPID will study the magnetosheath by means of the SWCX emission and will provide a direct measure of the magnetospheric emission from in both the 1/4 keV and 3/4 keV bands. HaloSAT observations will be designed to minimize the magnetospheric component for its observations of the Galactic Halo, but will make at least some dedicated observations of heliospheric SWCX. I will outline the simulation needs and observational strategies required to study SWCX for astrophysical purposes.

  15. A study of PV/T collector with honeycomb heat exchanger

    NASA Astrophysics Data System (ADS)

    Hussain, F.; Othman, M. Y. H.; Yatim, B.; Ruslan, H.; Sopian, K.; Ibarahim, Z.

    2013-11-01

    This paper present a study of a single pass photovoltaic/thermal (PV/T) solar collector combined with honeycomb heat exchanger. A PV/T system is a combination of photovoltaic panel and solar thermal components in one integrated system. In order to enhance the performance of the system, a honeycomb heat exchanger is installed horizontally into the channel located under the PV module. Air is used as the heat remover medium. The system is tested with and without the honeycomb at irradiance of 828 W/m2 and mass flow rate spanning from 0.02 kg/s to 0.13 kg/s. It is observed that the aluminum honeycomb is capable of enhancing the thermal efficiency of the system efficiently. At mass flow rate of 0.11 kg/s, the thermal efficiency of the system without honeycomb is 27% and with honeycomb is 87 %. Throughout the range of the mass flow rate, the electrical efficiency of the PV module improved by 0.1 %. The improved design is suitable to be further investigated as solar drying system and space heating.

  16. Exchange interaction in hexagonal MnRhP from first-principles studies

    SciTech Connect

    Liu, X. B. Zhang, Qiming; Ping Liu, J.; Yue, M.; Altounian, Z.

    2014-05-07

    Electronic structure and magnetic properties for MnRhP have been studied from a first-principles density functional calculation. The calculated lattice constants, a = 6.228 Å and c = 3.571 Å, are in good agreement with the experimental values of a = 6.223 Å and c = 3.585 Å. The calculated moment of Mn is 3.1 μ{sub B}/atom, resulting in a total moment of 3.0 μ{sub B}/atom due to small moments induced at Rh and P sites. The magnetic moment of Mn decreases with unit cell size. The exchange interactions are dominated by positive Mn-Mn exchange coupling (J{sub Mn−Mn}), implying a stable ferromagnetic ordering in Mn sublattice. In particular, J{sub Mn−Mn} shows a maximum value (1.5 mRy) at the the optimized unit cell size. The structural distortion or unit cell size change will affect J{sub Mn−Mn}, which is intimately related to the magneto-elastic and magneto-caloric effect.

  17. ApoE: In Vitro Studies of a Small Molecule Effector.

    PubMed

    Mondal, Tridib; Wang, Hanliu; DeKoster, Gregory T; Baban, Berevan; Gross, Michael L; Frieden, Carl

    2016-05-10

    Apolipoprotein E4 (apoE4), one of three isoforms of apoE, is the major risk factor for developing late onset Alzheimer's disease. The only differences among these isoforms (apoE2, apoE3, and apoE4) are single amino acid changes. Yet these proteins are functionally very different. One approach to ameliorating the effect of apoE4 with respect to Alzheimer's disease would be to find small molecular weight compounds that affect the behavior of apoE4. Few studies of this approach have been carried out in part because there was no complete structure of any full-length apoE isoform until 2011. Here, we focus on one small molecular weight compound, EZ-482, and explore the effects of its binding to apoE. Using hydrogen-deuterium exchange, we determined that EZ-482 binds to the C-terminal domains of both apoE3 and apoE4. The binding to apoE4, however, is accompanied by a unique N-terminal allosteric effect. Using fluorescence methods, we determined an apparent dissociation constant of approximately 8 μM. Although EZ-482 binds to the C-terminal domain, it blocks heparin binding to the N-terminal domain. The residues of apoE that bind heparin are the same as those involved in apoE binding to LDL and LRP-1 receptors. The methods and the data presented here may serve as a template for future studies using small molecular weight compounds to modulate the behavior of apoE. PMID:27065061

  18. Resonance Raman Study of an Anion Channelrhodopsin: Effects of Mutations near the Retinylidene Schiff Base.

    PubMed

    Yi, Adrian; Mamaeva, Natalia; Li, Hai; Spudich, John L; Rothschild, Kenneth J

    2016-04-26

    Optogenetics relies on the expression of specific microbial rhodopsins in the neuronal plasma membrane. Most notably, this includes channelrhodopsins, which when heterologously expressed in neurons function as light-gated cation channels. Recently, a new class of microbial rhodopsins, termed anion channel rhodopsins (ACRs), has been discovered. These proteins function as efficient light-activated channels strictly selective for anions. They exclude the flow of protons and other cations and cause hyperpolarization of the membrane potential in neurons by allowing the inward flow of chloride ions. In this study, confocal near-infrared resonance Raman spectroscopy (RRS) along with hydrogen/deuterium exchange, retinal analogue substitution, and site-directed mutagenesis were used to study the retinal structure as well as its interactions with the protein in the unphotolyzed state of an ACR from Guillardia theta (GtACR1). These measurements reveal that (i) the retinal chromophore exists as an all-trans configuration with a protonated Schiff base (PSB) very similar to that of bacteriorhodopsin (BR), (ii) the chromophore RRS spectrum is insensitive to changes in pH from 3 to 11, whereas above this pH the Schiff base (SB) is deprotonated, (iii) when Ser97, the homologue to Asp85 in BR, is replaced with a Glu, it remains in a neutral form (i.e., as a carboxylic acid) but is deprotonated at higher pH to form a blue-shifted species, (iv) Asp234, the homologue of the protonated retinylidene SB counterion Asp212 in BR, does not serve as the primary counteranion for the protonated SB, and (v) substitution of Glu68 with an Gln increases the pH at which SB deprotonation is observed. These results suggest that Glu68 and Asp234 located near the SB exist in a neutral state in unphotolyzed GtACR1 and indicate that other unidentified negative charges stabilize the protonated state of the GtACR1 SB. PMID:27039989

  19. Conformational changes of ubiquitin during electrospray ionization as determined by in-ESI source H/D exchange combined with high-resolution MS and ECD fragmentation.

    PubMed

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

    2014-10-01

    In the paper, we have demonstrated the possibility of performing hydrogen/deuterium (H/D) exchange of proteins in the region of gas-phase ion formation in an electrospray ion source by saturating the electrospray ionization source with vapors of a deuterating agent (D(2)O or MeOD). In this region, charged droplets are shrinking and the protein ions transfer into the gas phase. As a model protein, we have used ubiquitin whose ion mobility spectrometry and gas-phase H/D exchange in the vacuum part of a mass spectrometer demonstrated the presence of gas-phase conformers with different cross sections and H/D exchange rates. In our experiments, we observed monomodal deuterium distributions for all solvents, charge states, desolvating capillary temperature and types of deuterating agent. Also, we found that the number of H/D exchanges increases with an increasing desolvating capillary temperature and decreasing charge state. We observed that solution composition (49?:?50?:?1 H(2)O?:?MeOH?:?formic acid or 99?:?1 H(2)O?:?formic acid) influences the charge-state distribution but did not change the degree of H/D exchange for the same charge state. Electron-capture dissociation fragmentation shows that higher charge states contain a segment that is protected from access by the deuterating agent. PMID:25303388

  20. Study of X(3872) from effective field theory with pion-exchange interaction.

    PubMed

    Wang, P; Wang, X G

    2013-07-26

    We study DD[over ¯]* (D*D[over ¯]) scattering in the framework of unitarized heavy meson chiral perturbation theory with pion exchange and a contact interaction. 3S1-3D1 mixing effects are taken into account. A loosely bound state X(3872), with the pole position being Mpole}=(3871.70-i0.39)  MeV, is found. The result is not sensitive to the strength of the contact interaction. Our calculation provides a theoretical confirmation of the existence of the 1++ state X(3872). The light quark mass dependence of the pole position indicates it has a predominately DD[over ¯]* (D*D[over ¯]) molecular nature. When the π mass is larger than 142 MeV, the pole disappears, which makes impossible the lattice simulation of this state at large quark mass. PMID:23931357

  1. Study of the operation temperature in the spin-exchange relaxation free magnetometer

    NASA Astrophysics Data System (ADS)

    Fang, Jiancheng; Li, Rujie; Duan, Lihong; Chen, Yao; Quan, Wei

    2015-07-01

    We study the influence of the cell temperature on the sensitivity of the spin-exchange relaxation free (SERF) magnetometer and analyze the possibility of operating at a low temperature. Utilizing a 25 × 25 × 25 mm3 Cs vapor cell with a heating temperature of 85 ∘C, which is almost half of the value of potassium, we obtain a linewidth of 1.37 Hz and achieve a magnetic field sensitivity of 55 fT/Hz1/2 in a single channel. Theoretical analysis shows that fundamental sensitivity limits of this device with an active volume of 1 cm3 could approach 1 fT/Hz1/2. Taking advantage of the higher saturated vapor pressure, SERF magnetometer based on Cs opens up the possibility for low cost and portable sensors and is particularly appropriate for lower temperature applications.

  2. Changes of Respiratory Exchange Ratio in Children and Adolescents: A Longitudinal Study.

    PubMed

    Jelec, Zeljko; Matković, Branka R; Lebo, Ana; Jelec, Drazen; Matković, Andro

    2015-09-01

    We conducted a longitudinal study to examine changes in the respiratory exchange ratio (RER) during progressively increasing body exertion in children and adolescents of female sex. In this analysis we only included 23 examinees for which we had all yearly measurements from examinee's age 9 years until 18 years of age. The data were analyzed according to the chronological and biological age. According to both criteria, the highest RER values were recorded at moments of maximum exertion and they did not increase with age. We found the highest RER values were in the year of the menarche. We interpret these results as related to the effect of estrogen. The beginning of sexual development involves a gradual increase in estrogen plasma concentrations. At one point serum levels of estrogen reach a level high, enough to allow for maximum RER values, i.e. causing the optimum anaerobic capacity of the examinee. This threshold estrogen value varies between individuals. PMID:26898052

  3. A study on the transport process in gas diffusion layer of proton exchange membrane fuel cells

    NASA Astrophysics Data System (ADS)

    Tan, Zetao; Jia, Li; Zhang, Zhuqian

    2011-10-01

    Gas diffusion layer (GDL) plays a great important role in proton exchange membrane fuel cell (PEMFC). Water transport mechanism in GDL is still not clear. In the present study, an ex-situ transparent setup is built to visualize the transport phenomena and to measure the threshold pressure of water in GDL at different temperatures. It is found that the relationship between the breakthrough pressure and the temperature is nearly linear (i.e. the pressure decreases linearly with the increase of temperature). To avoid the problems faced by the continuum models, the pore network model is developed to simulate the liquid water transport through the carbon paper. A uniform pressure boundary condition is used in simulation and the results are similar to the ones obtained in the experiment. The reason is that the contact angle and surface tension coefficient of water in GDLs change accordingly with the change of temperature.

  4. Study on passive momentum exchange landing gear using two-dimensional analysis

    NASA Astrophysics Data System (ADS)

    Watanabe, Tsubasa; Hara, Susumu; Otsuki, Masatsugu

    2014-12-01

    This paper discusses a landing response control system based on the momentum exchange principle for planetary exploration spacecraft. In the past, landing gear systems with cantilever designs that incorporate honeycomb materials to dissipate shock energy through plastic deformation have been used, but once tested before launch, the system cannot be used in a real mission. The sky crane system used for the Mars Science Laboratory by NASA can achieve a safe and precise landing, but it is highly complex. This paper introduces a momentum exchange impact damper (MEID) that absorbs the controlled object's momentum with extra masses called damper masses. The MEID is reusable, which makes it easy to ensure the landing gear's reliability. In this system, only passive elements such as springs are needed. A single-axis (SA) model has already been used to verify the effectiveness of MEIDs through simulations and experiments measuring the rebound height of the spacecraft. However, the SA model cannot address the rotational motion and tipping of the spacecraft. This paper presents a two-landing-gear-system (TLGS) model in which multiple MEIDs are equipped for two-dimensional analysis. Unlike in the authors' previous studies, in this study each MEID is launched when the corresponding landing gear lands and the MEIDs do not contain active actuators. This mechanism can be used to realize advanced control specifications, and it is simply compared with previous mechanisms including actuators, in which all of the MEIDs are launched simultaneously. If each MEID works when the corresponding gear lands, the rebound height of each gear can be minimized, and tipping can be prevented, as demonstrated by the results of our simulations.

  5. Experimental study of high temperature oxygen isotope exchange during chondrule formation

    NASA Astrophysics Data System (ADS)

    Yu, Yang; Hewins, Roger H.; Clayton, Robert N.; Mayeda, Toshiko K.

    1995-05-01

    Laboratory experiments have been conducted to determine rates and other details of the oxygen isotopic exchange process between meteoritic material and water vapor. The meteoritic samples were totally or partially melted, or completely unmelted. The furnace atmosphere consisted of water vapor and hydrogen, and was diluted with helium for some of the experiments. Both isothermal and flash heating experiments were performed. Extensive oxygen isotope exchange has been observed between chondrule analogue melt and surrounding dilute water vapor, such that 50% equilibration occurs in charges near their liquidus in five minutes or less. The principal rate-limiting mechanism of the exchange is diffusion within the melt. The initial exchange rate also depends on the partial pressure of water, which points to the effect of the surface exchange process. The kinetics of the surface reaction have not been determined due to the restrictions of our experimental configuration. The extent of exchange observed in short time isothermal runs and in flash heating runs suggests that much of the isotopic variability of natural chondrules can be produced during chondrule-forming events by the gas/melt isotopic exchange processes. However, due to the very low gas densities in the nebula, multiple melting events might be needed to produce the chondrules with highly exchanged isotopic compositions. For a partially melted sample, as is often the case in natural chondrules, the rate of isotopic change of the bulk sample is determined by the exchange rates of both the melt and unmelted relict minerals. If the melt and relict minerals have a large difference in isotopic compositions, the exchange trajectory becomes markedly nonlinear. These observations are consistent with the observed dependence of extent of exchange in natural chondrules on the degree of melting, and imply that for each of the linear trends on the three-isotope diagram observed for natural chondrules, only two initial isotopic reservoirs might have existed.

  6. Element exchange between minerals at hydrothermal conditions: A case study with spinel

    NASA Astrophysics Data System (ADS)

    Jonas, L.; Muller, T.; Dohmen, R.

    2013-12-01

    It is generally believed that the presence of a fluid phase enhances the reactivity of minerals and promotes exchange reactions between minerals that are physically separated from each other. Two end-member mechanisms can be considered for the bulk equilibration of the mineral with the fluid: volume diffusion and dissolution-precipitation. A key parameter, which may control the overall kinetic behavior, is the solubility of the relevant elements within the fluid (e.g., [1]). We investigated the reaction mechanism of a model system to identify the role of the various parameters, in particular those controlling the solubility. Two polished spinel crystals (hercynite with xFe=0.6 and synthetic Mg-spinel) react in the presence of H2O at 750 °C and 0.2 GPa in a welded-shut Au-capsule for 1-24 hrs. The crystals are physically separated by a tube of noble metal dividing the capsule into two connected chambers. The surface of the reacted crystals is analyzed using optical methods and SEM and the near surface chemistry is studied via RBS. From the latter we are able to extract Fe-concentration depth profiles. First results show an increasing surface concentration of Fe in Mg-spinel with time. The depth profiles for experiments up to 8 hours reveal a decrease of Fe-concentration within the first 100 nm from the surface towards the center of the Mg-spinel. The Fe depth profiles can be simulated with a simplified diffusion model, assuming a fixed surface concentration and their shapes indicate that the inter-diffusion coefficient in spinel is concentration dependent. Our derived Fe-Mg diffusion coefficient [D(Fe-Mg) ≈ 1x10-19 m2/s for pure MgAl2O4) and its compositional dependence is consistent with an independent experimental study using thin film diffusion couples that were annealed at dry conditions at 1 atm [2]. The observed kinetic behavior of the experimental system was simulated using the model of [1]. The model geometry is identical to the present experimental setup and for the mineral fluid interaction a pure exchange of elements is considered without any mass transfer. From the simulations we obtain constraints for the effective transport rate of Fe through the fluid, which is basically controlled by the diffusion coefficient in the fluid and the solubility of Fe. Our calculations suggest that the concentration of dissolved Fe is up to two orders of magnitude higher than predicted by theoretical solubility calculations. The reaction mechanism map reveals that the reaction is controlled by diffusion in both the solid and the fluid. These results highlight the importance of the concentration of dissolved species for the exchange process. The solubility of the mineral phases is an important factor controlling the development of compositional profiles and may even control the reaction mechanism. This study demonstrates that the following common wisdoms are wrong in the general case: (I) The presence of fluid enhances the rate of the overall exchange reaction. (II) The presence of H2O enhances diffusion in the solid phase. [1] Dohmen & Chakraborty (2003), AmMin, 88, pp. 1251-1270; [2] Vogt (2009), Msc-Thesis, Ruhr-Universität Bochum, p.78

  7. Resonance Raman Studies of Bovine and OCTOPUS Visual Pigments

    NASA Astrophysics Data System (ADS)

    Huang, Liewen

    1995-01-01

    We have regenerated bovine and octopus visual pigments with retinals containing isotopic labels at three positions, i.e., 8-^{13}C -11,12-D_2, 10-^{13 }C-11,12-D_2, 11- ^{13}C-11,12-D_2 , 14-^{13}C-11,12 -D_2, for the studies of bound chromophore ethylenic and Schiff base vibrational modes by resonance Raman spectroscopy. Also regenerated were octopus visual pigments with singly or doubly ^{13 }C labeled retinals, i.e., 9-^ {13}C, 10,11-^{13 }C_2, 12,13- ^{13}C_2, 13-^{13}C, 14,15- ^{13}C_2, 14,15-^{13}C_2 -ND, for the studies of vibrational modes in the fingerprint region. We have analyzed the resonance Raman spectra based upon the observation of the response of individual bands in the spectrum of rhodopsin, isorhodopsin, or bathorhodopsin to a particular label. The observed peaks in the fingerprint and ethylenic regions have been tentatively assigned to specific C-C and C=C stretches. We have also studied a model retinal protonated Schiff base analog and its isotopically labeled derivatives as well as calculations using ab initio methods. Based on the vibrational analysis, new criteria to determine the Schiff base C=N configuration from Raman spectroscopy have been developed, and the C=N configuration in octopus rhodopsin, isorhodopsin and bathorhodopsin has been determined. We have continued the resonance Raman study of the Schiff base hydrogen/deuterium exchange for rhodopsin and bacteriorhodopsin by employing the continuous-flow experiment. The exchange of a deuteron on the Schiff base with a proton is very fast, with half-times of 6.9 +/- 0.9 and 1.3 +/- 0.3 ms for rhodopsin and bacteriorhodopsin, respectively, faster than the proton-deuteron exchange rate of a protonated Schiff base in aqueous solution (16 +/- 2 ms). This anomalous result can be understand if a structural water molecule (or molecules) is present next to the protonated Schiff base in the two pigments.

  8. Muon spin relaxation study of exchange coupling in dilute AgMn alloys

    SciTech Connect

    Heffner, R.H.; Cooke, D.W.; Hutson, R.L.; Schillaci, M.E.; Dodds, S.A.; Gist, G.A.; MacLaughlin, D.E.

    1985-01-01

    We have observed for the first time conduction-electron mediated muon-impurity coupling, and deduced the strength of the conduction electron-Mn exchange coupling. Our results are marginally consistent with a wave-vector dependent exchange model. 16 refs.

  9. 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…

  10. Educators Exchange Program Report, 1998-99. Program Report and Evaluation Study.

    ERIC Educational Resources Information Center

    Fawson, Kenneth D.; Abina, Armando; Alvarez, Rafael; Armstrong, William B.; Buyukkaya, Sonia; Kardos, Althea; Schubert, Cynthia

    In 1998, the San Diego Community College District (SDCCD) completed a successful third cycle of Educators Exchange Program (EEP) activities. The goal of EEP is to promote binational cooperation, cultural understanding and economic development through faculty exchange and technical assistance programs. During the last six years of program…

  11. 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

  12. Water Sorption and Vapor-Phase Deuterium Exchange Studies on Methemoglobin CC, SC, SS, AS, and AA

    PubMed Central

    Killion, Philip J.; Cameron, Bruce F.

    1972-01-01

    Five hemoglobins whose genetic relationship to one another involves one set of alleles, hemoglobins CC, SC, SS, AS, and AA, were studied in the Met form. Two different investigations were conducted at 28°C on these methemoglobins within a McBain gravimetric sorption system: sorption of H2O vapor and vapor-phase deuterium-hydrogen exchange. For each of the five samples there was close agreement between the per cent hydration of polar sites as determined from sorption studies and the maximum per cent of labile hydrogens that were exchanged during the vapor-phase deuterium exchange study. Both studies measured a slight increase in the number of polar sites accessible to H2O or D2O vapor for those samples in which the substituent in the sixth position from the N-terminus of the two β-chains had a positively charged side chain and a slight decrease for those in which the substituent had a negatively charged side chain. The in-exchange of deuterium for hydrogen occurred at a faster observed rate than the out-exchange of hydrogen for deuterium. PMID:5030563

  13. A computational study of an HCCI engine with direct injection during gas exchange

    SciTech Connect

    Su, Haiyun; Vikhansky, Alexander; Mosbach, Sebastian; Kraft, Markus; Bhave, Amit; Kim, Kyoung-Oh; Kobayashi, Tatsuo; Mauss, Fabian

    2006-10-15

    We present a new probability density function (PDF)-based computational model to simulate a homogeneous charge compression ignition (HCCI) engine with direct injection (DI) during gas exchange. This stochastic reactor model (SRM) accounts for the engine breathing process in addition to the closed-volume HCCI engine operation. A weighted-particle Monte Carlo method is used to solve the resulting PDF transport equation. While simulating the gas exchange, it is necessary to add a large number of stochastic particles to the ensemble due to the intake air and EGR streams as well as fuel injection, resulting in increased computational expense. Therefore, in this work we apply a down-sampling technique to reduce the number of stochastic particles, while conserving the statistical properties of the ensemble. In this method some of the most important statistical moments (e.g., concentration of the main chemical species and enthalpy) are conserved exactly, while other moments are conserved in a statistical sense. Detailed analysis demonstrates that the statistical error associated with the down-sampling algorithm is more sensitive to the number of particles than to the number of conserved species for the given operating conditions. For a full-cycle simulation this down-sampling procedure was observed to reduce the computational time by a factor of 8 as compared to the simulation without this strategy, while still maintaining the error within an acceptable limit. Following the detailed numerical investigation, the model, intended for volatile fuels only, is applied to simulate a two-stroke, naturally aspirated HCCI engine fueled with isooctane. The in-cylinder pressure and CO emissions predicted by the model agree reasonably well with the measured profiles. In addition, the new model is applied to estimate the influence of engine operating parameters such as the relative air-fuel ratio and early direct injection timing on HCCI combustion and emissions. The qualitative trends observed in the parametric variation study match well with experimental data in literature. (author)

  14. Recent Advances in Computational Studies of Charge Exchange X-ray Emission

    NASA Astrophysics Data System (ADS)

    Cumbee, Renata

    2016-06-01

    Interest in astrophysical sources of charge exchange (CX) has grown since X-ray emission from comet Hyakutake was first observed, the origin of which is primarily due to CX processes between neutral species in the comet’s atmosphere and highly charged ions from the solar wind. More recent observations have shown that CX may have a significant contribution to the X-ray emission spectra of a wide variety of environments within our solar system including solar wind charge exchange (SWCX) with neutral gases in the heliosphere and in planetary atmospheres, as well as beyond the solar system in galaxy clusters, supernova remnants, and star forming galaxies.While the basic process of CX has been studied for many decades, the reliability of the existing data is not uniform, and the coverage of the astrophysically important projectile and target combinations and collisional velocities is insufficient. The need for reliable and robust CX X-ray emission models will only be amplified with the with the high resolution X-ray spectra expected from the soft X-ray imaging calorimeter spectrometer (SXS) onboard the Hitomi X-ray observatory. In this talk, I will discuss recent advances in theoretical CX cross sections and X-ray modeling with a focus on CX diagnostics. The need for experimental X-ray spectra and cross sections for benchmarking current theory will also be highlighted. This work was performed in collaboration with David Lyons, Patrick Mullen, David Schultz, Phillip Stancil, and Robin Shelton. Work at UGA was partially supported by NASA grant NNX09AC46G.

  15. Theoretical and Experimental Studies of Energy Exchange from Jackrabbit Ears and Cylindrically Shaped Appendages

    PubMed Central

    Wathen, Patricia; Mitchell, John W.; Porter, Warren P.

    1971-01-01

    Convection properties of jackrabbit ears were examined in a wind tunnel and in the field in an attempt to study the possible thermal role of the large ears. This work was part of a study on energy exchange of appendages. Cylindrical copper models of various shapes, aluminum castings of domestic and jackrabbit ears, and an amputated jackrabbit ear were studied in a wind tunnel (a) to define the range for convective heat loss for appendages of various shapes, and (b) to study the effect on convection of model shape and orientation to the wind. Shape, i.e. length and closure, proved important. Orientation to the wind produced no consistent or significant variation in the convection coefficient. The convection coefficients from the ear castings fell within the range generated from the cylindrical models. The convection coefficients for the amputated rabbit ear fell partially within the range. Net thermal radiation loss at midday from the jackrabbit ears was found to be small. Convection from the ears, however, could account for the loss of over 100% of the animal's metabolic heat at an air temperature of 30°C. If air temperature exceeds body temperature, the animal must either store heat or resort to the evaporation of water. ImagesFIGURE 1FIGURE 2 PMID:5134209

  16. Aquatic flower-inspired cell culture platform with simplified medium exchange process for facilitating cell-surface interaction studies.

    PubMed

    Hong, Hyeonjun; Park, Sung Jea; Han, Seon Jin; Lim, Jiwon; Kim, Dong Sung

    2016-02-01

    Establishing fundamentals for regulating cell behavior with engineered physical environments, such as topography and stiffness, requires a large number of cell culture experiments. However, cell culture experiments in cell-surface interaction studies are generally labor-intensive and time-consuming due to many experimental tasks, such as multiple fabrication processes in sample preparation and repetitive medium exchange in cell culture. In this work, a novel aquatic flower-inspired cell culture platform (AFIP) is presented. AFIP aims to facilitate the experiments on the cell-surface interaction studies, especially the medium exchange process. AFIP was devised to capture and dispense cell culture medium based on interactions between an elastic polymer substrate and a liquid medium. Thus, the medium exchange can be performed easily and without the need of other instruments, such as a vacuum suction and pipette. An appropriate design window of AFIP, based on scaling analysis, was identified to provide a criterion for achieving stability in medium exchange as well as various surface characteristics of the petal substrates. The developed AFIP, with physically engineered petal substrates, was also verified to exchange medium reliably and repeatedly. A closed structure capturing the medium was sustained stably during cell culture experiments. NIH3T3 proliferation results also demonstrated that AFIP can be applied to the cell-surface interaction studies as an alternative to the conventional method. PMID:26683462

  17. Exchange bias study of epitaxial LSMO/Cr2O3 thin film heterostructures integrated on Si(100)

    NASA Astrophysics Data System (ADS)

    Punugupati, Sandhyarani; Hunte, Frank; Narayan, Jagdish

    2015-03-01

    FM/AFM exchange bias continues to be an interesting phenomenon from both a fundamental physics and an applications point of view. Recent studies of multiferroic materials have also seen a revival of interest in the magnetoelectric (ME) and antiferromagnetic (AFM) material Cr2O3. The study of exchange bias in heterostructures consisting of ferromagnet (FM) and ME thin films provides an additional mechanism of switching the magnetization of the FM by the application of an electric field. La0.7Sr0.3MnO3 (LSMO) is a FM material with TC above room temperature and shows colossal magnetoresistance. We have studied exchange bias in epitaxial thin film heterostructures of LSMO/Cr2O3 grown on C-YSZ/Si(100) by the PLD technique. We present a detailed structural characterization of the films by XRD (2O and ?) and TEM which confirm that the films were grown epitaxially. The heterostructures exhibited exchange bias as measured by SQUID magnetometry. The effects of LSMO deposition conditions, crystal orientation, temperature, and cooling field on the exchange bias will be discussed. Part of this research is supported by the National Science Foundation and the Army Research Office.

  18. Conformation study of ɛ-cyclodextrin: Replica exchange molecular dynamics simulations.

    PubMed

    Khuntawee, Wasinee; Rungrotmongkol, Thanyada; Wolschann, Peter; Pongsawasdi, Piamsook; Kungwan, Nawee; Okumura, Hisashi; Hannongbua, Supot

    2016-05-01

    There is growing interest in large-ring cyclodextrins (LR-CDs) which are known to be good host molecules for larger ligands. The isolation of a defined size LR-CD is an essential prerequisite for studying their structural properties. Unfortunately the purification procedure of these substances turned out to be very laborious. Finally the problem could be circumvented by a theoretical consideration: the highly advantageous replica exchange molecular dynamics (REMD) simulation (particularly suitable for studies of conformational changes) offers an ideal approach for studying the conformational change of ɛ-cyclodextrin (CD10), a smaller representative of LR-CDs. Three carbohydrate force fields and three solvent models were tested. The conformational behavior of CD10 was analyzed in terms of the flip (turn) of the glucose subunits within the macrocyclic ring. In addition a ranking of conformations with various numbers of turns was preformed. Our findings might be also helpful in the temperature controlled synthesis of LR-CDs as well as other experimental conditions, in particular for the host-guest reaction. PMID:26877001

  19. A numerical study of flow and thermal fields in finned tube heat exchangers (Effect of the tube diameter)

    SciTech Connect

    Torikoshi, Kunikazu; Xi, G.

    1995-12-31

    Enhancement of air-side heat transfer in heat exchangers used in air-conditioning machines can be considered as a way to solve the problem caused by use of alternative refrigerants. Related with this, the present study aims to investigate the flow and thermal fields in finned tube heat exchangers. In previous papers (Torikoshi et al., 1994 and Xi et al., 1994, 1995), numerical schemes that used a compound grid system for finned tube heat exchangers were described. The schemes were validated with experimental data. In the present paper, a three-dimensional unsteady numerical computation for a model of a two-row finned tube heat exchanger located in a uniform flow field has been performed to see the effect of tube diameter on the flow and thermal fields. Several features were found in the study. One interesting finding was that increasing the tube diameter almost does not improve heat transfer performance but increases the resistance of the fluid flow inside the heat exchanger.

  20. Tuning magnetic properties of antiferromagnetic chains by exchange interactions: ab initio studies.

    PubMed

    Tao, Kun; Guo, Qing; Jena, Puru; Xue, Desheng; Stepanyuk, Valeri S

    2015-10-21

    The possibility of using exchange interactions to manipulate the spin state of an antiferromagnetic nanostructure is explored using ab initio calculations. By considering M (M = Mn, Fe, Co) mono-atomic chains supported on Cu2N islands on a Cu(001) surface as a model system, it is demonstrated that two indistinguishable Nel states of an antiferromagnetic chain can be tailored into a preferred state by the exchange interaction with a magnetic STM tip. The magnitude and direction of the anisotropy for antiferromagnetic chains can also be tuned by exchange coupling upon varying the tip-chain separation. PMID:26387802

  1. Improving DNA data exchange: validation studies on a single 6 dye STR kit with 24 loci.

    PubMed

    Martín, Pablo; de Simón, Lourdes Fernández; Luque, Gracia; Farfán, María José; Alonso, Antonio

    2014-11-01

    The idea of developing a new multiplex STR amplification system was conceived in 2011 as an effective way to implement the new European standard set (ESS) of 12 STR markers adopted by The Council of the European Union in 2009 while maintaining an effective compatibility and information exchange with the historical DNA profiles contained in the Spanish national DNA database (around 200,000 DNA profiles) mainly based on the 13 CODIS core STR loci plus D19S433 and D2S1338 markers. With this goal in mind we proposed to test and validate a single STR amplification system for simultaneous analysis of 21 STR markers covering both CODIS and ESS core STR loci plus three additional markers (D19S433, D2S1338, and SE33) also contained in commonly used STR kits and national DNA databases. In 2012, we started the first beta-testing with a 6-dye STR kit prototype containing 24 loci (now known as the GlobalFiler™ PCR Amplification Kit) developed by Life Technologies in response to the CODIS Core Loci Working Group's recommendation to expand the CODIS Core Loci. This prototype included our proposal of 21 autosomal STR markers and two Y-chromosome markers (DYS391 and Y-indel) and maximizes concordance with established databases and previously analyzed samples by maintaining primer sequences of previous Identifiler(®)/NGM SElect™ kits for the 21 STR markers except for TPOX. This paper describes the validation studies conducted with the first commercial available 6-dye STR kit for casework using a 3500 genetic analyzer for fragment detection that included the analysis of the following parameters and aspects: analytical threshold, sensitivity & stochastic threshold, heterozygous balance, stutter threshold, precision and accuracy, repeatability and reproducibility, genotype concordance, DNA mixtures, species specificity, and stability studies with case type samples. The studies demonstrated that the GlobalFiler™ system provided equivalent overall performance to previous forensic STR PCR kits, but with enhanced discrimination power for a better match efficiency that would reduce the chance of adventitious matches during DNA data exchange among national DNA databases. PMID:25082138

  2. Heat Exchanger/Humidifier Trade Study and Conceptual Design for the Constellation Space Suit Portable Life Support System Ventilation Subsystem

    NASA Technical Reports Server (NTRS)

    Paul, Heather L.; Conger, Bruce; Sompyrac, Robert; Chamberlain, Mateo

    2008-01-01

    As development of the Constellation Space Suit Element progresses, designing the most effective and efficient life support systems is critical. The baseline schematic analysis for the Portable Life Support System (PLSS) indicates that the ventilation loop will need some method of heat exchange and humidification prior to entering the helmet. A trade study was initiated to identify the challenges associated with conditioning the spacesuit breathing gas stream for temperature and water vapor control, to survey technological literature and resources on heat exchanger and humidifiers to provide solutions to the problems of conditioning the spacesuit breathing gas stream, and to propose potential candidate technologies to perform the heat exchanger and humidifier functions. This paper summarizes the results of this trade study and also describes the conceptual designs that NASA developed to address these issues.

  3. Heat Exchanger/Humidifier Trade Study and Conceptual Design for the Constellation Space Suit Portable Life Support System Ventilation Subsystem

    NASA Technical Reports Server (NTRS)

    Paul, Heather L.; Sompayrac, Robert; Conger, Bruce; Chamberlain, Mateo

    2009-01-01

    As development of the Constellation Space Suit Element progresses, designing the most effective and efficient life support systems is critical. The baseline schematic analysis for the Portable Life Support System (PLSS) indicates that the ventilation loop will need some method of heat exchange and humidification prior to entering the helmet. A trade study was initiated to identify the challenges associated with conditioning the spacesuit breathing gas stream for temperature and water vapor control, to survey technological literature and resources on heat exchanger and humidifiers to provide solutions to the problems of conditioning the spacesuit breathing gas stream, and to propose potential candidate technologies to perform the heat exchanger and humidifier functions. This paper summarizes the results of this trade study and also describes the conceptual designs that NASA developed to address these issues.

  4. The effect of different amino acid side chains on the stereospecificity and catalytic efficiency of the tryptophan synthase-catalysed exchange of the alpha-protons of amino acids.

    PubMed

    Milne, J J; Malthouse, J P

    1996-03-15

    1H-NMR has been used to follow the tryptophan synthase (EC 4.2.1.20) c catalysed hydrogen-deuterium exchange of the alpha-protons of L- and D-alanine and -tryptophan. The first-order and second-order rate constants for exchange have been determined at pH 7.8 in the presence and absence of the allosteric effector, DL-alpha-glycerol 3-phosphate. In the presence of DL-alpha-glycerol 3-phosphate the stereospecificity of the tryptophan synthase-catalyzed first-order exchange rates was in the order tryptophan > alanine > glycine. This increase in stereospecificity was largely due to the decrease in the magnitude of the first-order exchange rate of the slowly exchanged alpha-proton. A similar increase in the stereospecificity of the second-order exchange rates for alanine was also largely due to the decrease in the magnitude of the first-order exchange rate of the slowly exchanged alpha-proton of D-alanine. Adding DL-alpha-glycerol 3-phosphate produced an increase in the stereospecificity of the second-order exchange rate observed with alanine but no significant change in the stereospecificity of the first-order exchange rate with tryptophan. The alpha-subunits are shown to increase the exchange rates of the alpha-protons of L-alanine and L-tryptophan. We conclude that the contribution of the R-group of an amino acid to the stereospecificity of the exchange reactions of its alpha-proton can be similar to or larger than that of its alpha-carboxylate group. Possible mechanisms that could explain the stereospecificity of these exchange reactions are discussed. PMID:8615770

  5. High-resolution Studies of Charge Exchange in Supernova Remnants with Magellan, XMM-Newton, and Micro-X

    NASA Astrophysics Data System (ADS)

    Heine, Sarah N.; Figueroa-Feliciano, Enectali; Castro, Daniel

    2015-01-01

    Charge exchange, the semi-resonant transfer of an electron from a neutral atom to an excited state in an energetic ion, can occur in plasmas where energetic ions are incident on a cold, at least partially neutral gas. Supernova remnants, especially in the immediate shock region, provide conditions conducive to charge exchange. The emission from post charge-exchange ions as the captured electron cascades down to the ground state, can shed light on the physical conditions of the shock and the immediate post-shock material, providing an important tool to understanding supernova explosions and their aftermath.I present a study of charge exchange in the galactic supernova remnant G296.1-0.5 in two bands: the optical and the X-ray. The optical study, performed using both imaging and spectroscopy from the IMACS instrument on the Magellan Baade Telescope at Las Companas Observatory, seeks to identify `Balmer-dominated shocks' in the remnant, which occur when charge exchange occurs between hot, post-shock protons and colder neutral hydrogen in the environment. The X-ray study probes line ratios in dispersed spectral data obtained with XMM-Newton RGS from an X-ray lobe in the NW of the remnant to hunt for signatures of charge exchange. The dispersed data are degraded by the extended nature of the source, blending many of the lines.We are working towards the future of spectroscopic studies in the X-ray for such extended sources with Micro-X: a sounding rocket-borne, high energy resolution X-ray telescope, utilizing an array of microcalorimeters to achieve high energy resolution for extended sources. I describe the design and commissioning of the payload and the steps toward launch, which is anticipated in the summer of 2015.

  6. Low Mass MS/MS Fragments of Protonated Amino Acids Used for Distinction of Their 13C- Isotopomers in Metabolic Studies

    NASA Astrophysics Data System (ADS)

    Ma, Xin; Dagan, Shai; Somogyi, Árpád; Wysocki, Vicki H.; Scaraffia, Patricia Y.

    2013-04-01

    Glu, Gln, Pro, and Ala are the main amino acids involved in ammonia detoxification in mosquitoes. In order to develop a tandem mass spectrometry method (MS2) to monitor each carbon of the above isotopically-labeled 13C-amino acids for metabolic studies, the compositions and origins of atoms in fragments of the protonated amino acid should be first elucidated. Thus, various electrospray (ESI)-based MS2 tools were employed to study the fragmentation of these unlabeled and isotopically-labeled amino acids and better understand their dissociation pathways. A broad range of fragments, including previously-undescribed low m/z fragments was revealed. The formulae of the fragments (from m/z 130 down to m/z 27) were confirmed by their accurate masses. The structures and conformations of the larger fragments of Glu were also explored by ion mobility mass spectrometry (IM-MS) and gas-phase hydrogen/deuterium exchange (HDX) experiments. It was found that some low m/z fragments ( m/z 27-30) are common to Glu, Gln, Pro, and Ala. The origins of carbons in these small fragments are discussed and additional collision induced dissociation (CID) MS2 fragmentation pathways are proposed for them. It was also found that small fragments (≤ m/z 84) of protonated, methylated Glu, and methylated Gln are the same as those of the underivatized Glu and Gln. Taken together, the new approach of utilizing low m/z fragments can be applied to distinguish, identify, and quantify 13C-amino acids labeled at various positions, either in the backbone or side chain.

  7. Low Mass MS/MS Fragments of Protonated Amino Acids used for Distinction of their 13C- Isotopomers in Metabolic Studies

    PubMed Central

    Ma, Xin; Dagan, Shai; Somogyi, Árpád; Wysocki, Vicki H.; Scaraffia, Patricia Y.

    2013-01-01

    Glu, Gln, Pro and Ala are the main amino acids involved in ammonia detoxification in mosquitoes. In order to develop a tandem mass spectrometry method (MS2) to monitor each carbon of the above isotopically-labeled 13C-amino acids for metabolic studies, the compositions and origins of atoms in fragments of the protonated amino acid should be first elucidated. Thus, various electrospray (ESI)-based MS2 tools were employed to study the fragmentation of these unlabeled and isotopically-labeled amino acids and better understand their dissociation pathways. A broad range of fragments, including previously-undescribed low m/z fragments was revealed. The formulae of the fragments (from m/z 130 down to m/z 27) were confirmed by their accurate masses. The structures and conformations of the larger fragments of Glu were also explored by ion mobility mass spectrometry (IM-MS) and gas-phase hydrogen/deuterium exchange (HDX) experiments. It was found that some low m/z fragments (m/z 27-30) are common to Glu, Gln, Pro and Ala. The origins of carbons in these small fragments are discussed and additional collision induced dissociation (CID) MS2 fragmentation pathways are proposed for them. It was also found that small fragments (≤ m/z 84) of protonated, methylated Glu and methylated Gln are the same as those of the underivatized Glu and Gln. Taken together, the new approach of utilizing low m/z fragments can be applied to distinguish, identify and quantify 13C-amino acids labeled at various positions, either in the backbone or side chain. PMID:23444051

  8. Custom-tailored adsorbers: A molecular dynamics study on optimal design of ion exchange chromatography material.

    PubMed

    Lang, Katharina M H; Kittelmann, Jörg; Pilgram, Florian; Osberghaus, Anna; Hubbuch, Jürgen

    2015-09-25

    The performance of functionalized materials, e.g., ion exchange resins, depends on multiple resin characteristics, such as type of ligand, ligand density, the pore accessibility for a molecule, and backbone characteristics. Therefore, the screening and identification process for optimal resin characteristics for separation is very time and material consuming. Previous studies on the influence of resin characteristics have focused on an experimental approach and to a lesser extent on the mechanistic understanding of the adsorption mechanism. In this in silico study, a previously developed molecular dynamics (MD) tool is used, which simulates any given biomolecule on resins with varying ligand densities. We describe a set of simulations and experiments with four proteins and six resins varying in ligand density, and show that simulations and experiments correlate well in a wide range of ligand density. With this new approach simulations can be used as pre-experimental screening for optimal adsorber characteristics, reducing the actual number of screening experiments, which results in a faster and more knowledge-based development of custom-tailored adsorbers. PMID:26319376

  9. Ultrafast Study of Dynamic interfacial Exchange Coupling in Ferromagnet/Oxide/Semiconductor Heterostructures

    NASA Astrophysics Data System (ADS)

    Ou, Yu-Sheng; Chiu, Yi-Hsin; Harmon, Nicholas; Odenthal, Patrick; Sheffield, Matthew; Chilcote, Michael; Kawakami, Roland; Flatté, Michael; Johnston-Halperin, Ezekiel

    Time-resolved Kerr/Faraday rotation (TRKR/TRFR) is employed to study GaAs spin dynamics in the regime of strong and dynamic exchange coupling to an adjacent MgO/Fe layer. This study reveals a dramatic, resonant suppression in the inhomogeneous spin lifetime (T2*) in the GaAs layer. Further investigation of the magnetization dynamics of the neighboring Fe layer, also using TRKR/TRFR, reveals not only the expected Kittel-dispersion but also additional lower frequency modes with very short lifetime (65 ps) that are not easily observed with conventional ferromagnetic resonance (FMR) techniques. These results suggest the intriguing possibility of resonant dynamic spin transfer between the GaAs and Fe spin systems. We discuss the potential for this work to establish GaAs spin dynamics as an efficient detector of spin dissipation and transport in the regime of dynamically-driven spin injection in ferromagnet/semiconductor heterostructures. Center for Emergent Materials; U.S. Department of Energy.

  10. Knowledge flow and exchange in interdisciplinary primary health care teams (PHCTs): an exploratory study

    PubMed Central

    Sibbald, Shannon L.; Wathen, C. Nadine; Kothari, Anita; Day, Adam M. B.

    2013-01-01

    Objective: Improving the process of evidence-based practice in primary health care requires an understanding of information exchange among colleagues. This study explored how clinically oriented research knowledge flows through multidisciplinary primary health care teams (PHCTs) and influences clinical decisions. Methods: This was an exploratory mixed-methods study with members of six PHCTs in Ontario, Canada. Quantitative data were collected using a questionnaire and analyzed with social network analysis (SNA) using UCINet. Qualitative data were collected using semi-structured interviews and analyzed with content analysis procedures using NVivo8. Results: It was found that obtaining research knowledge was perceived to be a shared responsibility among team members, whereas its application in patient care was seen as the responsibility of the team leader, usually the senior physician. PHCT members acknowledged the need for resources for information access, synthesis, interpretation, or management. Conclusion: Information sharing in interdisciplinary teams is a complex and multifaceted process. Specific interventions need to be improved such as formalizing modes of communication, better organizing knowledge-sharing activities, and improving the active use of allied health professionals. Despite movement toward team-based models, senior physicians are often gatekeepers of uptake of new evidence and changes in practice. PMID:23646028

  11. Disturbance-free rapid solution exchange for magnetic tweezers single-molecule studies

    PubMed Central

    Le, Shimin; Yao, Mingxi; Chen, Jin; Efremov, Artem K.; Azimi, Sara; Yan, Jie

    2015-01-01

    Single-molecule manipulation technologies have been extensively applied to studies of the structures and interactions of DNA and proteins. An important aspect of such studies is to obtain the dynamics of interactions; however the initial binding is often difficult to obtain due to large mechanical perturbation during solution introduction. Here, we report a simple disturbance-free rapid solution exchange method for magnetic tweezers single-molecule manipulation experiments, which is achieved by tethering the molecules inside microwells (typical dimensions–diameter (D): 40–50 μm, height (H): 100 μm; H:D∼2:1). Our simulations and experiments show that the flow speed can be reduced by several orders of magnitude near the bottom of the microwells from that in the flow chamber, effectively eliminating the flow disturbance to molecules tethered in the microwells. We demonstrate a wide scope of applications of this method by measuring the force dependent DNA structural transitions in response to solution condition change, and polymerization dynamics of RecA on ssDNA/SSB-coated ssDNA/dsDNA of various tether lengths under constant forces, as well as the dynamics of vinculin binding to α-catenin at a constant force (< 5 pN) applied to the α-catenin protein. PMID:26007651

  12. Speciation study of aluminium in beverages by Competitive Ligand Exchange-Adsorptive Stripping Voltammetry.

    PubMed

    Magnier, A; Fekete, V; Van Loco, J; Bolle, F; Elskens, M

    2014-05-01

    Competitive Ligand Exchange-Adsorptive Stripping Voltammetry (CLE-AdSV) was used for determining the speciation of aluminium in commonly consumed beverages (water, tea, infusion, coffee, orange juice, tomato juice, beer and red wine). Aluminium determination involves the adsorption of Al-complexes with the ligand cupferron onto a hanging mercury drop electrode. All samples were studied at pH 6.5 with an accumulation step at -0.60 V (all potential values in the paper are given versus the Ag/AgCl, [KCl]=3 M reference electrode) during 60 s, and a final cupferron concentration of 4 × 10(-4)M. These conditions were used to establish (i) the concentration of electro-labile aluminium, (ii) the range of ligand concentrations and (iii) the conditional stability constants of beverage samples using titration procedures. The results based on Ruzic plots were compared to computer simulation with Visual MINTEQ. This comparison suggests that labile monomeric Al-forms and soluble organic complexes of low molecular weight can be quantified by the CLE-AdSV procedure. Overall the relative uncertainties on the determination of the electro-active Al fraction and the complexing parameters, i.e., concentration and conditional stability constant of natural ligands in the samples, are less than 15%. Thanks to these results, information on Al bioavailability in beverages was collected and discussed. This study also illustrates the value of computer simulations when complex, time-consuming voltammetric techniques are applied. PMID:24720958

  13. Application of AVHRR vegetation index to study atmosphere-biosphere exchange of CO2

    NASA Technical Reports Server (NTRS)

    Fung, I. Y.; Tucker, C. J.; Prentice, K. C.

    1985-01-01

    The Advanced Very High Resolution Radiometer (AVHRR) satellite-borne sensor is presently used, together with field data, to determine the geographic distributions of the seasonal exchange of CO2 between the earth's atmosphere and the terrestrial biota. The exchange functions thus obtained are validated in virtue of the ability to reproduce the observed annual cycle of atmospheric CO2 in a three-dimensional tracer transport model. The AVHRR is carried by the TIROS-N series of polar-orbiting satellites.

  14. Impact: a case study examining the closure of a large urban fixed site needle exchange in Canada

    PubMed Central

    2010-01-01

    Introduction In 2008, one of the oldest fixed site needle exchanges in a large urban city in Canada was closed due to community pressure. This service had been in existence for over 20 years. Case Description This case study focuses on the consequences of the switch to mobile needle exchange services immediately after the closure and examines the impact of the closure on changes in risk behavior related to drug use, needle distribution and access to services The context surrounding the closure was also examined. Discussion and Evaluation After the closure of the fixed site exchange, access to needle exchange services decreased as evidenced by the sharp decline in numbers of clients reached, and the numbers of needles distributed and collected monthly. Reports related to needle reuse and selling of syringes suggest changes in risk behaviors. Thousands of needles remain unaccounted for in the community. To date, a new fixed site has not been found. Conclusion Closing the fixed site needle exchange had an adverse effect on already vulnerable clients and reduced access to comprehensive harm reduction services. While official public policy supports a fixed site, politicization of the issue has meant a significant setback for harm reduction with reduced potential to meet public health targets related to reducing the spread of blood borne diseases. This situation is unacceptable from a public health perspective. PMID:20500870

  15. Material Studies Related to the Use of NaK Heat Exchangers Coupled to Stirling Heater Heads

    NASA Technical Reports Server (NTRS)

    Locci, Ivan E.; Bowman, Cheryl L.; Geng, Steven M.; Robbie, Malcolm G.

    2011-01-01

    NASA has been supporting design studies and technology development that could provide power to an outpost on the Moon, Mars, or an asteroid. Technology development efforts have included fabrication and evaluation of components used in a Stirling engine power conversion system. Destructive material evaluation was performed on a NaK shell heat exchanger that was developed by the NASA Glenn Research Center (GRC) and integrated with a commercial 1 kWe Stirling convertor from Sunpower Incorporated. The NaK Stirling test demonstrated Stirling convertor electrical power generation using a pumped liquid metal heat source under thermal conditions that represent the heat exchanger liquid metal loop in a Fission Power Systems (FPS) reactor. The convertors were operated for a total test time of 66 hr at a maximum temperature of 823 K. After the test was completed and NaK removed, the heat exchanger assembly was sectioned to evaluate any material interactions with the flowing liquid metal. Several dissimilar-metal braze joint options, crucial for the heat exchanger transfer path, were also investigated. A comprehensive investigation was completed and lessons learned for future heat exchanger development efforts are discussed.

  16. Development of Carbon Sequestration Options by Studying Carbon Dioxide-Methane Exchange in Hydrates

    NASA Astrophysics Data System (ADS)

    Horvat, Kristine Nicole

    Gas hydrates form naturally at high pressures (>4 MPa) and low temperatures (<4 °C) when a set number of water molecules form a cage in which small gas molecules can be entrapped as guests. It is estimated that about 700,000 trillion cubic feet (tcf) of methane (CH4) exist naturally as hydrates in marine and permafrost environments, which is more than any other natural sources combined as CH4 hydrates contain about 14 wt% CH4. However, a vast amount of gas hydrates exist in marine environments, which makes gas extraction an environmental challenge, both for potential gas losses during extraction and the potential impact of CH4 extraction on seafloor stability. From the climate change point of view, a 100 ppm increase in atmospheric carbon dioxide (CO2) levels over the past century is of urgent concern. A potential solution to both of these issues is to simultaneously exchange CH4 with CO 2 in natural hydrate reserves by forming more stable CO2 hydrates. This approach would minimize disturbances to the host sediment matrix of the seafloor while sequestering CO2. Understanding hydrate growth over time is imperative to prepare for large scale CH4 extraction coupled with CO2 sequestration. In this study, we performed macroscale experiments in a 200 mL high-pressure Jerguson cell that mimicked the pressure-temperature conditions of the seafloor. A total of 13 runs were performed under varying conditions. These included the formation of CH4 hydrates, followed by a CO2 gas injection and CO2 hydrate formation followed by a CH4 gas injection. Results demonstrated that once gas hydrates formed, they show "memory effect" in subsequent charges, irrespective of the two gases injected. This was borne out by the induction time data for hydrate formation that reduced from 96 hours for CH4 and 24 hours for CO2 to instant hydrate formation in both cases upon injection of a secondary gas. During the study of CH4-CO2 exchange where CH4 hydrates were first formed and CO2 gas was injected into the system, gas chromatographic (GC) analysis of the cell indicated a pure CH4 gas phase, i.e., all injected CO2 gas entered the hydrate phase and remained trapped in hydrate cages for several hours, though over time some CO2 did enter the gas phase. Alternatively, during the CH 4-CO2 exchange study where CO2 hydrates were first formed, the injected CH4 initially entered the hydrate phase, but quickly gaseous CO2 exchanged with CH4 in hydrates to form more stable CO2 hydrates. These results are consistent with the better thermodynamic stability of CO2 hydrates, and this appears to be a promising method to sequester CO2 in natural CH4 hydrate matrices. The macroscale study described above was complemented by a microscale study to visualize hydrate growth. This first-of-its-kind in-situ study utilized the x-ray computed microtomography (CMT) technique to visualize microscale CO2, CH4, and mixed CH 4-CO2 hydrate growth phenomenon in salt solutions in the presence or absence of porous media. The data showed that under the experimental conditions used, pure CH4 formed CH4 hydrates as mostly spheres, while pure CO2 hydrates were more dendritic branches. Additionally, varying ratios of mixed CH4-CO2 hydrates were also formed that had needle-like growth. In porous media, CO2 hydrates grew, consistent with known growth models in which the solution was the sediment wetting phase. When glass beads and Ottawa sand were used as a host, the system exhibited pore-filling hydrate growth, while the presence of liquid CO2 and possible CO2 hydrates in Ottawa sand initially were pore-filling that over time transformed into a grain-displacing morphology. The data appears promising to develop a method that would supplant our energy supply by extracting CH4 from naturally occurring hydrates while CO2 is sequestered in the same formations.

  17. Bioisosteric Exchange of Csp3 -Chloro and Methyl Substituents: Synthesis and Initial Biological Studies of Atpenin A5 Analogues.

    PubMed

    Krautwald, Simon; Nilewski, Christian; Mori, Mihoko; Shiomi, Kazuro; Ōmura, Satoshi; Carreira, Erick M

    2016-03-14

    Asymmetric synthesis and initial biological studies of two analogues of a naturally occurring chlorinated antifungal agent, atpenin A5, are described. These analogues were selected on the basis of Cl→CH3 or H3 C→Cl exchanges in the side-chain of atpenin A5. The interchange of chloro and methyl substituents led to complex II inhibitors with equal IC50 values. This suggests that Cl↔Me bioisosteric exchange can be realized in aliphatic settings. PMID:26891236

  18. Experimental studies on pressure drop characteristics of cryogenic cross-counter flow coiled finned tube heat exchangers

    NASA Astrophysics Data System (ADS)

    Gupta, Prabhat Kumar; Kush, P. K.; Tiwari, Ashesh

    2010-04-01

    Cross-counter flow coiled finned tube heat exchangers used in medium capacity helium liquefiers/refrigerators were developed in our lab. These heat exchangers were developed using integrated low finned tubes. Experimental studies have been performed to know the pressure drop characteristics of tube side and shell side flow of these heat exchangers. All experiments were performed at room temperature in the Reynolds number range of 3000-30,000 for tube side and 25-155 for shell side. The results of present experiments indicate that available correlations for tube side can not be used for prediction of tube side pressure drop data due to complex surface formation at inner side of tube during formation of fins over the outer surface. Results also indicate that surface roughness effect becomes more pronounced as the value of di/ D m increases. New correlations based on present experimental data are proposed for predicting the friction factors for tube side and shell side.

  19. Theoretical study of a screened Hartree–Fock exchange potential using position-dependent atomic dielectric constants

    SciTech Connect

    Shimazaki, Tomomi; Nakajima, Takahito

    2015-02-21

    Dielectric-dependent screened Hartree–Fock (HF) exchange potential and Slater-formula have been reported, where the ratio of the HF exchange term mixed into potentials is inversely proportional to the dielectric constant of the target semiconductor. This study introduces a position-dependent dielectric constant method in which the dielectric constant is partitioned between the atoms in a semiconductor. These partitioned values differ depending on the electrostatic environment surrounding the atoms and lead to position-dependent atomic dielectric constants. These atomic dielectric constants provide atomic orbital-based matrix elements for the screened exchange potentials. Energy band structures of several semiconductors and insulators are also presented to validate this approach.

  20. Experimental study of heat and mass transfer in a buoyant countercurrent exchange flow

    NASA Astrophysics Data System (ADS)

    Conover, Timothy Allan

    Buoyant Countercurrent Exchange Flow occurs in a vertical vent through which two miscible fluids communicate, the higher-density fluid, residing above the lower-density fluid, separated by the vented partition. The buoyancy- driven zero net volumetric flow through the vent transports any passive scalars, such as heat and toxic fumes, between the two compartments as the fluids seek thermodynamic and gravitational equilibrium. The plume rising from the vent into the top compartment resembles a pool fire plume. In some circumstances both countercurrent flows and pool fires can ``puff'' periodically, with distinct frequencies. One experimental test section containing fresh water in the top compartment and brine (NaCl solution) in the bottom compartment provided a convenient, idealized flow for study. This brine flow decayed in time as the concentrations approached equilibrium. A second test section contained fresh water that was cooled by heat exchangers above and heated by electrical elements below and operated steadily, allowing more time for data acquisition. Brine transport was reduced to a buoyancy- scaled flow coefficient, Q*, and heat transfer was reduced to an analogous coefficient, H*. Results for vent diameter D = 5.08 cm were consistent between test sections and with the literature. Some results for D = 2.54 cm were inconsistent, suggesting viscosity and/or molecular diffusion of heat become important at smaller scales. Laser Doppler Velocimetry was used to measure velocity fields in both test sections, and in thermal flow a small thermocouple measured temperature simultaneously with velocity. Measurement fields were restricted to the plume base region, above the vent proper. In baseline periodic flow, instantaneous velocity and temperature were ensemble averaged, producing a movie of the average variation of each measure during a puffing flow cycle. The temperature movie revealed the previously unknown cold core of the puff during its early development. The renewal-length model for puffing frequency of pool fire plumes was extended to puffing countercurrent flows by estimating inflow dilution. Puffing frequencies at several conditions were reduced to Strouhal number based on dilute plume density. Results for D = 5.08 cm compared favorably to published measurements of puffing pool fires, suggesting that the two different flows obey the same periodic dynamic process.

  1. A Numerical Study of Circulation and Water Exchange in the Arabian Gulf

    NASA Astrophysics Data System (ADS)

    Azhar, Muchamad Al; Temimi, Marouane; Zhao, Jun; Ghedira, Hosni

    2015-04-01

    Ocean circulation and water mass variability in semi-enclosed and marginal sea of the Arabian Gulf are numerically simulated using a three-dimensional model of Regional Ocean Modeling System (ROMS). The model is forced by relatively high-frequency of atmospheric forcing and tides. The numerical simulations are compared with a set data of moored and spatially distributed measurements of temperature, salinity, current velocity, and sea-surface height. The model results generally agree well with temporal variation of the observed current velocity during spring and neap tide, as well as seasonal variation of temperature and salinity in surface and sub-surface depths. Seasonal variability of water mass and circulation in the Arabian Gulf affected by the propagation of Indian Ocean Surface Water to the Arabian Gulf, air-sea heat fluxes, and mesoscale eddy activities are discussed. Sensitivity study using different source of atmospheric data for forcing of the model, as well as climatology data and global ocean model for specifying values in open boundaries of the model are conducted towards implementation of the model operationally. Further development of the model by coupling it with atmospheric model most likely will increase the skill of the model and provide better understanding on how the complex air-sea interaction affecting circulation and water mass exchange in this region.

  2. Anion-exchange chromatographic study of the chlorine isotope effect accompanying hydration.

    PubMed

    Musashi, Masaaki; Oi, Takao; Eggenkamp, Hans G M; Yato, Yumio; Matsuo, Motoyuki

    2007-01-26

    The single-stage separation factor for chlorine isotopes ((35)Cl and (37)Cl) was determined to be 1.00034 by anion exchange chromatography on a 4.5-m column operated in reverse breakthrough manner at 25 degrees C. This value is in good agreement with those obtained in our previous works. It was confirmed that the lighter isotope ((35)Cl) was preferentially fractionated into the resin phase, whereas the heavier isotope ((37)Cl) partitioned into the aqueous phase. This observation, however, contradicts the experimental results for Cl isotope fractionation during NaCl precipitation and the recent theoretical results on Cl isotope fractionation: the (37)Cl isotope selectively enriched into the solid phase and not into the aqueous phase. This discrepancy is discussed based on the theory of isotope distribution between two phases. It is suggested that the chromatographic results reflect an isotope effect accompanying hydration rather than an isotope effect due to a phase change, whereas the reverse is the case for the results in the NaCl precipitation study. PMID:17141790

  3. Carbonylation of formaldehyde over ion exchange resin catalysts. 1. Batch reactor studies

    SciTech Connect

    Sang Young Lee; Jae Chang Kim; Jae Sung Lee; Young Gul Kim )

    1993-02-01

    Methyl glycolate was synthesized as a precursor to ethylene glycol from the catalytic carbonylation of formaldehyde followed by esterification with methanol. Various cation exchange polystyrene-sulfonic acid resins showed excellent activity and methyl glycolate selectivity. The perfluorinated sulfonic acid resin Nafion-H showed higher activity per proton site, yet was less effective per weight of the catalyst. The effects of process variables such as pressure, temperature, catalyst loading, and solvent were studied. High CO pressures were required to promote formaldehyde carbonylation relative to side reactions between formaldehyde. The presence of water reduced the reaction rate, yet improved the selectivity to methyl glycolate. 1,4-Dioxane was found to be the best solvent in the presence of water. At 135 C, 3,500 psig, and reactant mole ratio of HCHO:H[sub 2]O:H[sup +] = 10:10:1, complete conversion of formaldehyde was achieved in 2-4 h with selectivities of methyl glycolate better than 80%. Catalysts did not show any significant deterioration in performance in repeated use up to 10 batches.

  4. Variable-ratio matching with fine balance in a study of the Peer Health Exchange.

    PubMed

    Pimentel, Samuel D; Yoon, Frank; Keele, Luke

    2015-12-30

    In some observational studies of treatment effects, matched samples are created so treated and control groups are similar in terms of observable covariates. Traditionally, such matched samples consist of matched pairs. However, alternative forms of matching may have desirable features. One strategy that may improve efficiency is to match a variable number of control units to each treated unit. Another strategy to improve balance is to adopt a fine balance constraint. Under a fine balance constraint, a nominal covariate is exactly balanced, but it does not require individually matched treated and control subjects for this variable. Here, we propose a method to allow for fine balance constraints when each treated unit is matched to a variable number of control units, which is not currently possible using existing matching network flow algorithms. Our approach uses the entire number to first determine the optimal number of controls for each treated unit. For each stratum of matched treated units, we can then apply a fine balance constraint. We then demonstrate that a matched sample for the evaluation of the Peer Health Exchange, an intervention in schools designed to decrease risky health behaviors among youths, using a variable number of controls and fine balance constraint is superior to simply using a variable-ratio match. Copyright © 2015 John Wiley & Sons, Ltd. PMID:26182888

  5. Inhibiting the Na+/H+ exchanger reduces reperfusion injury: a small animal MRI study

    PubMed Central

    Ferrazzano, Peter; Shi, Yejie; Manhas, Namratta; Wang, Yanping; Hutchinson, Beth; Chen, Xinzhi; Chanana, Vishal; Gerdts, Josiah; Meyerand, Mary Elizabeth; Sun, Dandan

    2010-01-01

    We used magnetic resonance imaging (MRI) to assess the efficacy of Na+/H+ exchanger isoform 1 (NHE-1) inhibition following cerebral ischemia. Transient focal cerebral ischemia was induced in wild-type controls (NHE-1+/+), NHE-1 genetic knockdown mice (NHE-1+/?), and NHE-1+/+ mice treated with the selective NHE-1 inhibitor HOE642. Diffusion weighted imaging (DWI) revealed a brain lesion as early as 1 hour following reperfusion and illustrated significant protection in NHE-1+/? mice (16.2 +/? 7.9 mm3 in NHE-1+/? mice vs. 47.5 +/? 16.6 mm3 in NHE-1+/+ mice). Knockdown of NHE-1 showed significantly smaller infarct at 72 hours on T2 imaging (21.2 +/? 12.6 mm3 in NHE-1+/? mice vs. 64.6 +/? 2.5 mm3 in NHE-1+/+ mice). Administration of HOE642 prior to reperfusion or during early reperfusion reduced ischemic damage. Thus, high resolution T2 images can be used for consistent and precise calculation of lesion volumes, while changes of DWI are a sensitive early marker of ischemic injury. The results of this study demonstrate the therapeutic potential for inhibition of NHE-1 in treating cerebral ischemia. PMID:21196287

  6. Preliminary study of iron removal from hydrochloric pickling liquor by ion exchange

    SciTech Connect

    Maranon, E.; Suarez, F.; Alonso, F.; Fernandez, Y.; Sastre, H.

    1999-07-01

    Hydrochloric acid from exhausted pickling baths is a residue that has to be managed adequately because of its high pollutant potential. In this work, an ion exchange treatment for removing iron from the spent acid was studied in an attempt to make the re-utilization of said acid viable for industry while reducing the amount of waste generated. Several cationic, anionic, and chelating resins were tested. Cationic and chelating resins are able to remove Fe(II) that is present as a cation in the acid, whereas anionic resins are able to remove Fe(III) that forms anionic complexes with the chloride anion. The capacity of the cationic and chelating resins, although not high, does improve as the iron concentration in the hydrochloric acid increases and when the acid concentration decreases, because there is less competition between the ferrous cation and the protons. The anionic resins showed higher capacity for removing iron, especially the Lewatit MP-500, and this capacity also increased with iron concentration.

  7. Solar Wind Charge Exchange Studies of Highly Charged Ions on Atomic Hydrogen

    SciTech Connect

    Draganic, Ilija N; Seely, D. G.; McCammon, D; Havener, Charles C

    2011-01-01

    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.

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

    SciTech Connect

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

    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.

  9. ANION EXCHANGE METHOD FOR THE DETERMINATION OF PLUTONIUM IN WATER: SINGLE-LABORATORY EVALUATION AND INTERLABORATORY COLLABORATIVE STUDY

    EPA Science Inventory

    This report gives the results of a single-laboratory evaluation and an interlaboratory collaborative study of a method for determining plutonium in water. The method was written for the analysis of 1-liter samples and involved coprecipitation, acid dissolution, anion exchange, el...

  10. Study of the Relationship between Leader-Member Exchange (LMX) and Individual Objective Performance within a University Learning Community

    ERIC Educational Resources Information Center

    Aikens, Shontarius D.

    2012-01-01

    The study examined the relationship between leader-member exchange (LMX) and individual objective performance. While the LMX literature suggests a positive correlation between LMX and performance, a closer look at the research examined showed that the performance measurements were based on subjective measurements rather than objective…

  11. A Longitudinal Study of the Moderating Role of Extraversion: Leader-Member Exchange, Performance, and Turnover during New Executive Development

    ERIC Educational Resources Information Center

    Bauer, Talya N.; Erdogan, Berrin; Liden, Robert C.; Wayne, Sandy J.

    2006-01-01

    Identifying factors that help or hinder new executives in "getting up to speed" quickly and remaining with an organization is vital to maximizing the effectiveness of executive development. The current study extends past research by examining extraversion as a moderator of relationships between leader-member exchange (LMX) and performance,…

  12. Picture Exchange Communication System with Individuals with Developmental Disabilities: A Meta-Analysis of Single Subject Studies

    ERIC Educational Resources Information Center

    Hart, Stephanie L.; Banda, Devender R.

    2010-01-01

    Picture Exchange Communication System (PECS) is a picture-based communication strategy used to teach communication skills to persons with developmental disabilities including autism. This article systematically reviews 13 published single-subject studies to examine the effectiveness of PECS, the effects of PECS on speech and problem behaviors,…

  13. F- and H-Area Seepage Basins Water Treatment System Process Optimization and Alternative Chemistry Ion Exchange/Sorbent Material Screening Clearwell Overflow Study

    SciTech Connect

    Serkiz, S.M.

    2000-08-30

    This study investigated alternative ion exchange/sorbent materials and polishing chemistries designed to remove specific radionuclides not removed during the neutralization/precipitation/clarification process.

  14. Dynamics of heat, water, and soluble gas exchange in the human airways: 1. A model study.

    PubMed

    Tsu, M E; Babb, A L; Ralph, D D; Hlastala, M P

    1988-01-01

    In order to provide a means for analysis of heat, water, and soluble gas exchange with the airways during tidal ventilation, a one dimensional theoretical model describing heat and water exchange in the respiratory airways has been extended to include soluble gas exchange with the airway mucosa and water exchange with the mucous layer lining the airways. Not only do heat, water, and gas exchange occur simultaneously, but they also interact. Heating and cooling of the airway surface and mucous lining affects both evaporative water and soluble gas exchange. Water evaporation provides a major source of heat exchange. The model-predicted mean airway temperature profiles agree well with literature data for both oral and nasal breathing validating that part of the model. With model parameters giving the best fit to experimental data, the model shows: (a) substantial heat recovery in the upper airways, (b) minimal respiratory heat and water loss, and (c) low average mucous temperatures and maximal increases in mucous thickness. For resting breathing of room air, heat and water conservation appear to be more important than conditioning efficiency. End-tidal expired partial pressures of very soluble gases eliminated by the lungs are predicted to be lower than the alveolar partial pressures due to the absorption of the expired gases by the airway mucosa. The model may be usable for design of experiments to examine mechanisms associated with the local hydration and dehydration dynamics of the mucosal surface, control of bronchial perfusion, triggering of asthma, mucociliary clearance and deposition of inhaled pollutant gases. PMID:3228218

  15. A droplet microchip with substance exchange capability for the developmental study of C. elegans.

    PubMed

    Wen, Hui; Yu, Yue; Zhu, Guoli; Jiang, Lei; Qin, Jianhua

    2015-04-21

    The nematode Caenorhabditis elegans (C. elegans) has been widely used as a multicellular organism in developmental research due to its simplicity, short lifecycle, and its relevance to human genetics and biology. Droplet microfluidics is an attractive platform for the study of C. elegans in integrated mode with flexibility at the single animal resolution. However, it is still challenging to conduct the developmental study of worms within droplets initiating at the L1 larval stage, due to the small size, active movement, and the difficulty in achieving effective substance exchange within the droplets. Here, we present a multifunctional droplet microchip to address these issues and demonstrate the usefulness of this device for investigating post-embryonic development in individual C. elegans initiating at the larval L1 stage. The key components of this device consist of multiple functional units that enable parallel worm loading, droplet formation/trapping, and worm encapsulation in parallel. In particular, it exhibits superior functions in encapsulating and trapping individual larval L1 worms into droplets in a controlled way. Continuous food addition and expulsion of waste by mixing the static worm-in-droplet with moving medium plugs allows for the long-term culture of worms under a variety of conditions. We used this device to investigate the development processes of C. elegans in transgenic strains with deletion and overexpression of the hypoxia-inducible factor (HIF-1), a highly conserved transcript factor in regulating an organism's response to hypoxia. This microdevice may be a useful tool for the high throughput analysis of individual worms starting at the larval stage, and facilitates the study of developmental worms in response to multiple drugs or environmental toxins. PMID:25715864

  16. Radiology Reporting System Data Exchange With the Electronic Health Record System: A Case Study in Iran

    PubMed Central

    Ahmadi, Maryam; Ghazisaeidi, Marjan; Bashiri, Azadeh

    2015-01-01

    Introduction: In order to better designing of electronic health record system in Iran, integration of health information systems based on a common language must be done to interpret and exchange this information with this system is required. Background: This study provides a conceptual model of radiology reporting system using unified modeling language. The proposed model can solve the problem of integration this information system with the electronic health record system. By using this model and design its service based, easily connect to electronic health record in Iran and facilitate transfer radiology report data. Methods: This is a cross-sectional study that was conducted in 2013. The study population was 22 experts that working at the Imaging Center in Imam Khomeini Hospital in Tehran and the sample was accorded with the community. Research tool was a questionnaire that prepared by the researcher to determine the information requirements. Content validity and test-retest method was used to measure validity and reliability of questioner respectively. Data analyzed with average index, using SPSS. Also Visual Paradigm software was used to design a conceptual model. Result: Based on the requirements assessment of experts and related texts, administrative, demographic and clinical data and radiological examination results and if the anesthesia procedure performed, anesthesia data suggested as minimum data set for radiology report and based it class diagram designed. Also by identifying radiology reporting system process, use case was drawn. Conclusion: According to the application of radiology reports in electronic health record system for diagnosing and managing of clinical problem of the patient, with providing the conceptual Model for radiology reporting system; in order to systematically design it, the problem of data sharing between these systems and electronic health records system would eliminate. PMID:26156904

  17. A comparison study of ionic polymer-metal composites (IPMCs) fabricated with Nafion and other ion exchange membranes

    NASA Astrophysics Data System (ADS)

    Park, Jiyeon; Palmre, Viljar; Kim, Kwang; Shin, Dongsuk; Kim, Daniel H.; Yim, Woosoon; Bae, Chulsung

    2013-04-01

    Ionic polymer-metal composites (IPMCs) have been and still are one of the best candidates with great potential to be used as actuators and sensors particularly in bioengineering where the environmental conditions are in an aqueous medium. Each component of an IPMC is important. However, the ion exchange membrane should be more emphasized because it is where ions migrate when electrical stimulation is applied and eventually it produces deformation of the IPMC. So far, the most commonly used ion exchange membrane is Nafion and many studies have been conducted with it for IPMC applications. There are a number of other commercially available ion exchange membranes now, but only a few studies have been done on those membranes to be used in IPMC applications. In this study, four commercially available membranes, (1) Nafion N115 (DuPont), (2) CMI7000S (Membranes International Inc.), (3) F-14100 (fumatech), (4) GEFC-700 (Golden Energy Fuel Cell) were selected and fabricated in IPMCs and their potentials as actuators were examined by conducting various characterizations such as water uptake, ion exchange capacity, SEM, DSC, blocking force and bending displacement.

  18. The study of RMB exchange rate complex networks based on fluctuation mode

    NASA Astrophysics Data System (ADS)

    Yao, Can-Zhong; Lin, Ji-Nan; Zheng, Xu-Zhou; Liu, Xiao-Feng

    2015-10-01

    In the paper, we research on the characteristics of RMB exchange rate time series fluctuation with methods of symbolization and coarse gaining. First, based on fluctuation features of RMB exchange rate, we define the first type of fluctuation mode as one specific foreign currency against RMB in four days' fluctuating situations, and the second type as four different foreign currencies against RMB in one day's fluctuating situation. With the transforming method, we construct the unique-currency and multi-currency complex networks. Further, through analyzing the topological features including out-degree, betweenness centrality and clustering coefficient of fluctuation-mode complex networks, we find that the out-degree distribution of both types of fluctuation mode basically follows power-law distributions with exponents between 1 and 2. The further analysis reveals that the out-degree and the clustering coefficient generally obey the approximated negative correlation. With this result, we confirm previous observations showing that the RMB exchange rate exhibits a characteristic of long-range memory. Finally, we analyze the most probable transmission route of fluctuation modes, and provide probability prediction matrix. The transmission route for RMB exchange rate fluctuation modes exhibits the characteristics of partially closed loop, repeat and reversibility, which lays a solid foundation for predicting RMB exchange rate fluctuation patterns with large volume of data.

  19. Heat exchanger optimization

    NASA Astrophysics Data System (ADS)

    Lee, Ik-Sang

    A computer code was developed which would analyze a shell-and-tube heat exchanger, and it was used in conjunction with a computer code for numerical optimization program. The problem is to find the smallest shell-and-tube heat exchanger with the minimum number of exchangers in series and parallel which will satisfy the heat duty and pressure drop requirements within the constraints imposed. The MINOS (Modular In-core Nonlinear Optimization System) programming code was used in the optimization of a shell-and-tube heat exchanger. MINOS purpose is to optimize a user written objective function. For heat exchanger design, it is necessary to develop two FORTRAN subroutines in order to analyze a heat exchanger. To get the generalized optimal heat exchanger design, the calculation method and data in Process Heat Transfer by Kern, was used. All the data, including material specifications were given as typical. Three types of case studies were studied and are discussed.

  20. Plasma-exchange treatment for severe carbamazepine intoxication: a case study.

    PubMed

    Kozanoglu, Ilknur; Kahveci, Suat; Asma, Suheyl; Yeral, Mahmut; Noyan, Aytul; Boga, Can; Ozdogu, Hakan

    2014-06-01

    Acute poisoning is an important cause of morbidity and mortality during childhood. This manuscript reports the positive outcome of a pediatric case with a history of accidental carbamazepine intake treated using plasma exchange. A 3-year-old male presented with severe carbamazepine intoxication. He was comatose and had generalized tonic clonic seizure, ventricular tachycardia, and hypotension. Although he did not respond to classical therapies, we performed two sessions of plasma exchange. The patient recovered rapidly and was discharged from the hospital six days from the time of carbamazepine ingestion with no complication or neurologic impairment. Plasma exchange can be performed safely in very small children, and it might be the first line treatment, particularly for intoxication with drugs that have high plasma-protein-binding properties. PMID:24136443

  1. A proton-magnetic-resonance study of hydrogen-exchange reactions of yeast tryptophan synthase.

    PubMed

    Bailey, C J; Malthouse, J P

    1991-02-01

    1H n.m.r. was used to observe tryptophan formation from indole and L-serine, proton exchange at C-2 of L-tryptophan, and proton exchange at C-2 of L-serine, catalysed by yeast tryptophan synthase in the presence of 2H2O. Tryptophan synthesis took place with compulsory replacement of C-2 hydrogen by solvent hydrogen. The exponential decay rate (kobs) of the serine exchange reaction was insensitive to serine concentration in the range 2-20mM and was used to calculate kcat./Km values. However, kobs. was very sensitive to pH* values in the range 6.5-8.5 and the data require that the free enzyme is active in the base form resulting from two inseparable ionizations of pKa 7.3, and inactive after a third ionization controlled by a pKa of 7.5. Initial rates measured by u.v. absorbance and colorimetric procedures were used to calculate kinetic parameters of the tryptophan synthesis reaction. From pH 6.5 to 7, kcat./Km values for L-serine in the tryptophan synthesis and hydrogen exchange reactions were indistinguishable and increased rapidly under the control of two acid-base groups of pKa 6.7 and 7.2. Above pH 7, this equivalence breaks down because the exchange reaction alone is responsive to the third pKa value of the free enzyme. The pH dependence of the catalytic constant for tryptophan synthesis was qualitatively similar to that of the kobs. for serine exchange. A mechanism to explain the results is contrasted with recent proposals for the Escherichia coli system. PMID:1899998

  2. Two-dimensional Pulsed EPR Studies of Vanadium-Exchanged ZSM-5

    SciTech Connect

    Woodworth, James F.; Bowman, Michael K.; Larsen, Sarah C.

    2004-10-14

    The pulsed electron paramagnetic resonance (EPR) technique of hyperfine sublevel correlation spectroscopy (HYSCORE) was used to obtain structural information about vanadium(VO2+) exchanged ZSM-5. HYSCORE spectra were obtained for vanadium exchanged ZSM-5 before and after dehydration and after adsorption of ammonia. For the hydrated samples, proton hyperfine coupling constants were measured and assigned to equatorial water ligands with orientations perpendicular and parallel to the equatorial plane. Nitrogen hyperfine coupling constants for adsorbed ammonia were also determined from the HYSCORE spectra. The results were compared with previous density functional theory (DFT) calculations of hyperfine coupling constants for vanadyl model complexes.

  3. Retrospective Study of Rapid-Exchange Monorail Versus Over-the-Wire Technique for Femoropopliteal Angioplasty

    SciTech Connect

    Jahnke, Thomas Schaefer, Jost Philipp; Bolte, Hendrik; Schaefer, Fritz; Michalek, Jens; Charalambous, Nicholas; Sapoval, Marc; Mueller-Huelsbeck, Stefan

    2008-09-15

    PurposeThe purpose of this study was to compare procedural outcome of rapid-exchange (RX) monorail versus conventional over-the-wire (OTW) technique for femoropopliteal angioplasty.Materials and MethodsDemographic data, procedure details, angioplasty success, and complications of 328 consecutive percutaneous transluminal angioplasties (PTAs) were collected from a prospective database and retrospectively analyzed. Procedure details included duration of fluoroscopy, area-dose product, amount of contrast agent, sheath sizes, access route, length of stenosis, presence of total occlusion, technical and anatomical success (residual stenosis <30% in the absence of complications), need for bail-out stenting, and periprocedural complications. The RX technique alone was used in 102 of 328 cases (31%); the OTW technique, in 226 of 328 of cases (68%).ResultsTechnical success was 98% for the RX versus 95.4% for the OTW technique (p = 0.2). A significantly greater number of stents had to be implanted due to angioplasty failure when the OTW technique was used (RX, 5.9%; OTW, 13.7%; p = 0.04). There were no significant differences in fluorocopy time, dose-area product, or amount of contrast medium used. The RX system facilitated the use of smaller sheath sizes (5 Fr = 38% and 6 Fr = 59% for RX versus 5 Fr = 16.8% and {>=}6 Fr = 82.5% for OTW) but showed only a tendency toward lower overall complication rates (16.6% [17/102] in the RX group versus 19.9% [45/226] in the OTW group; p = 0.09). There was no effect on length of hospitalization. RX monorail systems were not associated with higher procedural costs when compared to conventional OTW technique.ConclusionWe conclude that RX monorail systems seem to enhance the technical success of femoropopliteal angioplasty. Although smaller sheath sizes can be used due to the lower profile of the RX systems, there is only a tendency toward lower complication rates.

  4. Atmosphere-ocean ozone exchange: A global modeling study of biogeochemical, atmospheric, and waterside turbulence dependencies

    NASA Astrophysics Data System (ADS)

    Ganzeveld, L.; Helmig, D.; Fairall, C. W.; Hare, J.; Pozzer, A.

    2009-12-01

    The significance of the removal of tropospheric ozone by the oceans, covering ˜2/3 of the Earth's surface, has only been addressed in a few studies involving water tank, aircraft, and tower flux measurements. On the basis of results from these few observations of the ozone dry deposition velocity (VdO3), atmospheric chemistry models generally apply an empirical, constant ocean uptake rate of 0.05 cm s-1. This value is substantially smaller than the atmospheric turbulent transport velocity for ozone. On the other hand, the uptake is higher than expected from the solubility of ozone in clean water alone, suggesting that there is an enhancement in oceanic ozone uptake, e.g., through a chemical destruction mechanism. We present an evaluation of a global-scale analysis with a new mechanistic representation of atmosphere-ocean ozone exchange. The applied atmosphere chemistry-climate model includes not only atmospheric but also waterside turbulence and the role of waterside chemical loss processes as a function of oceanic biogeochemistry. The simulations suggest a larger role of biogeochemistry in tropical and subtropical ozone oceanic uptake with a relative small temporal variability, whereas in midlatitude and high-latitude regions, highly variable ozone uptake rates are expected because of the stronger influence of waterside turbulence. Despite a relatively large range in the explicitly calculated ocean uptake rate, there is a surprisingly small sensitivity of simulated Marine Boundary Layer ozone concentrations compared to the sensitivity for the commonly applied constant ocean uptake approach. This small sensitivity points at compensating effects through inclusion of the process-based ocean uptake mechanisms to consider variability in oceanic O3 deposition consistent with that in atmospheric and oceanic physical, chemical, and biological processes.

  5. In situ efficiency of ion exchange resins in studies of nitrogen transformation

    SciTech Connect

    Kjoenaas, O.J.

    1999-03-01

    Mixed-bed ion-exchange resin bags have previously been used in studies of soil N transformation rates with NH{sub 4}-N and NO{sub 3}-N being adsorbed from the solution percolating through the incubated soil core. An evaluation of the in situ adsorption efficiency of mixed-bed resin bags was performed by comparing dissolved inorganic nitrogen accumulated in resins with DIN fluxes in throughfall (TF) and with DIN concentrations in soil water. A significant correlation was found between DIN fluxes in TF and accumulated DIN in resins placed at the soil surface. The ratio of accumulated DIN in resins to DIN flux in TF was significantly affected by season. A low but significant correlation was found between NO{sub 3}-N concentrations in soil water and NO{sub 3}-N contents in resins deployed in the bottom of soil cylinders, however, when only the winter periods were taken into account, the correlation improved. As little water and few nutrients are removed from the soil water by the vegetation during the dormant season, the conditions inside and outside the core were more comparable. For NH{sub 4}-N there was no correlation between accumulated amounts in the resins and concentrations in soil water sampled at depths of 13 cm and 20 cm, respectively, probably due to the strong depth gradient in the NH{sub 4}-N concentrations of the soil. Although the resin bags were unable to adsorb all the incoming DIN, they gave valuable information on small-scale input of N and on small-scale differences in NO{sub 3}-N leaching.

  6. High desolvation temperature facilitates the ESI-source H/D exchange at non-labile sites of hydroxybenzoic acids and aromatic amino acids.

    PubMed

    Zherebker, Alexander; Kostyukevich, Yury; Kononikhin, Alexey; Roznyatovsky, Vitaliy A; Popov, Igor; Grishin, Yuri K; Perminova, Irina V; Nikolaev, Eugene

    2016-04-11

    Hydrogen/deuterium exchange coupled with high-resolution mass spectrometry has become a powerful analytical approach for structural investigations of complex organic matrices. Here we report the feasibility of the site-specific H/D exchange of non-labile hydrogens directly in the electrospray ionization (ESI) source, which was facilitated by an increase in the desolvation temperature from 200 °C up to 400 °C. We have found that the exchanges at non-labile sites were observed only for the model compounds capable of keto-enol tautomeric transformations (e.g., 2,3-, 2,4-dihydroxybenzoic acids, gallic acid, DOPA), and only when water was used as a solvent. We hypothesized that the detected additional exchanges were induced by the presence of hydroxyls in the sprayed water droplets generated in the negative ESI mode. It was indicative of the exchange reactions taking place in the sprayed droplets rather than in the gas phase. To support this hypothesis, the H/D exchange experiments were run in deuterated water under base-catalyzed conditions for three model compounds, which showed the most intensive exchanges in the MS experiments: DOPA, 2,4-DHB, and 5-acetylsalicylic acid. (2)H NMR spectroscopy has confirmed keto-enolic transformations of the model compounds leading to the specific labeling of the corresponding non-labile sites. We believe that the proposed technique will be useful for structural investigations of natural complex mixtures (e.g. proteins, humic substances) using site-specific H/D exchange. PMID:27002310

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

    PubMed

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

    2014-12-01

    Gas-phase hydrogen/deuterium exchange (HDX) is a fast and sensitive, yet unharnessed analytical approach for providing information on the structural properties of biomolecules, in a complementary manner to mass analysis. Here, we describe a simple setup for ND3-mediated millisecond gas-phase HDX inside a mass spectrometer immediately after ESI (gas-phase HDX-MS) and show utility for studying the primary and higher-order structure of peptides and proteins. HDX was achieved by passing N2-gas through a container filled with aqueous deuterated ammonia reagent (ND3/D2O) and admitting the saturated gas immediately upstream or downstream of the primary skimmer cone. The approach was implemented on three commercially available mass spectrometers and required no or minor fully reversible reconfiguration of gas-inlets of the ion source. Results from gas-phase HDX-MS of peptides using the aqueous ND3/D2O as HDX reagent indicate that labeling is facilitated exclusively through gaseous ND3, yielding similar results to the infusion of purified ND3-gas, while circumventing the complications associated with the use of hazardous purified gases. Comparison of the solution-phase- and gas-phase deuterium uptake of Leu-Enkephalin and Glu-Fibrinopeptide B, confirmed that this gas-phase HDX-MS approach allows for labeling of sites (heteroatom-bound non-amide hydrogens located on side-chains, N-terminus and C-terminus) not accessed by classical solution-phase HDX-MS. The simple setup is compatible with liquid chromatography and a chip-based automated nanoESI interface, allowing for online gas-phase HDX-MS analysis of peptides and proteins separated on a liquid chromatographic time scale at increased throughput. Furthermore, online gas-phase HDX-MS could be performed in tandem with ion mobility separation or electron transfer dissociation, thus enabling multiple orthogonal analyses of the structural properties of peptides and proteins in a single automated LC-MS workflow. PMID:25375223

  8. Allelic Exchange.

    PubMed

    Lehman, McKenzie K; Bose, Jeffrey L; Bayles, Kenneth W

    2016-01-01

    Methods used to understand the function of a gene/protein are one of the hallmarks of modern molecular genetics. The ability to genetically manipulate bacteria has become a fundamental tool in studying these organisms and while basic cloning has become a routine task in molecular biology laboratories, generating directed mutations can be a daunting task. This chapter describes the method of allelic exchange in Staphylococcus aureus using temperature-sensitive plasmids that have successfully produced a variety of chromosomal mutations, including in-frame deletions, insertion of antibiotic-resistance cassettes, and even single-nucleotide point mutations. PMID:25646609

  9. EPR Studies of Spin-Spin Exchange Processes: A Physical Chemistry Experiment.

    ERIC Educational Resources Information Center

    Eastman, Michael P.

    1982-01-01

    Theoretical background, experimental procedures, and analysis of experimental results are provided for an undergraduate physical chemistry experiment on electron paramagnetic resonance (EPR) linewidths. Source of line broadening observed in a spin-spin exchange process between radicals formed in aqueous solutions of potassium peroxylamine

  10. EPR Studies of Spin-Spin Exchange Processes: A Physical Chemistry Experiment.

    ERIC Educational Resources Information Center

    Eastman, Michael P.

    1982-01-01

    Theoretical background, experimental procedures, and analysis of experimental results are provided for an undergraduate physical chemistry experiment on electron paramagnetic resonance (EPR) linewidths. Source of line broadening observed in a spin-spin exchange process between radicals formed in aqueous solutions of potassium peroxylamine…

  11. Study Abroad Programs: Elements of Effective International Student and Faculty Exchange Programs. CRB 09-006

    ERIC Educational Resources Information Center

    Martin, Pam

    2009-01-01

    As part of Assembly Concurrent Resolution 146 (Solorio), the California Research Bureau was asked to report on the programmatic and funding elements of an effective international student and faculty exchange program, including good practices nationally, with an emphasis on public higher education institutions in California and Mexico. The CRB…

  12. Studying the Early Stages of Protein Aggregation Using Replica Exchange Molecular Dynamics Simulations.

    PubMed

    Shea, Joan-Emma; Levine, Zachary A

    2016-01-01

    The simulation of protein aggregation poses several computational challenges due to the disparate time and lengths scales that are involved. This chapter focuses on the use of atomistically detailed simulations to probe the initial steps of aggregation, with an emphasis on the Tau peptide as a model system, run under a replica exchange molecular dynamics protocol. PMID:26453216

  13. Synchronous Online Exchanges: A Study of Modification Devices on Non-Native Discourse.

    ERIC Educational Resources Information Center

    Lee, Lina

    2002-01-01

    Reports the types of modification devices nonnative speakers of an intermediate level of proficiency employed during synchronous online exchanges. Results show that request for help, clarification check, and self correction were the most used strategies for negotiation among students. Data suggest these modification devices facilitate…

  14. Promoting Intercultural Exchanges with Blogs and Podcasting: A Study of Spanish-American Telecollaboration

    ERIC Educational Resources Information Center

    Lee, Lina

    2009-01-01

    Blogs and podcasts open new ways for global communication and development of intercultural awareness. This article reports a Spanish-American telecollaborative project through which students created blogs and podcasts for intercultural exchanges in light of the sociocultural perspectives. The article outlines the methodology for the project…

  15. Study and development of a cryogenic heat exchanger for life support systems

    NASA Technical Reports Server (NTRS)

    Soliman, M. M.

    1973-01-01

    A prototype cryogenic heat exchanger for removal of waste heat from a spacecraft environmental control life support system was developed. The heat exchanger uses the heat sink capabilities of the cryogenic propellants and, hence, can operate over all mission phases from prelaunch to orbit, to post landing, with quiescent periods during orbit. A survey of candidate warm fluids resulted in the selection of E-2, a fluorocarbon compound, because of its low freezing point and high boiling point. The final design and testing of the heat exchanger was carried out, however, using Freon-21, which is similar to E-2 except for its low boiling point. This change was motivated by the desire for cost effectiveness of the experimental program. The transient performance of the heat exchanger was demonstrated by an analog simulation of the heat sink system. Under the realistic transient heat load conditions (20 sec ramp from minimum to maximum Freon-21 inlet temperature), the control system was able to maintain the warm fluid outlet temperature within + or - 3 F. For a 20-sec ramp from 0 F to -400 F in the hydrogen inlet temperature, at maximum heat load, the warm fluid outlet temperature was maintained within + or - 7 F.

  16. RESIDENTIAL AIR EXCHANGE RATES FOR USE IN INDOOR AIR AND EXPOSURE MODELING STUDIES

    EPA Science Inventory

    Data on air exchange rates are important inputs to indoor air quality models. ndoor air models, in turn, are incorporated into the structure of total human exposure models. ragmentary data on residential ventilation rates are available in various governmental reports, journal art...

  17. "Actually, I Wanted to Learn": Study-Related Knowledge Exchange on Social Networking Sites

    ERIC Educational Resources Information Center

    Wodzicki, Katrin; Schwammlein, Eva; Moskaliuk, Johannes

    2012-01-01

    Social media open up multiple options to add a new dimension to learning and knowledge processes. Particularly, social networking sites allow students to connect formal and informal learning settings. Students can find like-minded people and organize informal knowledge exchange for educational purposes. However, little is known about in which way…

  18. Study of residence-time distribution of non-Newtonian fluids in scraped-surface heat exchangers

    SciTech Connect

    Benezech, T.; Maingonnat, J.F. )

    1993-04-01

    The change of residence-time distribution in scraped-surface heat exchangers handling shear thinning fluids has been studied as a function of the speed of rotation of the shaft, the axial flow rate, the number of blades (2 or 4), the length of the heat exchanger, and the rheological parameters of the fluids. Spreading of the residence-time distribution is caused by rotational flow of the fluid. A particular value of the generalized Taylor number has been identified, which corresponds to the appearance of Taylor vortices and a change in the shape of the residence-time distribution curves. The mean rate of flow and the number of blades did not have any effect under the operating conditions used in this work. In contrast, a decrease in the ratio of the length of heat exchanger to the inside diameter of the heat-exchange surface has resulted in a spreading of the residence-time distribution in the presence of Taylor vortices. Finally, the axial dispersion coefficient determined in this work correlates, quantitatively, with the axial thermal diffusivity.

  19. "Lifepoint": a case study in using social science community identification data to guide the implementation of a needle exchange program.

    PubMed

    Somlai, A M; Kelly, J A; Otto-Salaj, L; Nelson, D

    1999-06-01

    The public health benefits of needle exchange programs (NEPs) are well known. NEPs lower risk factors for HIV transmission by providing injection drug users (IDUs) with clean syringes and needles; harm reduction materials; and referrals to drug, sexually transmitted disease, mental health, and medical treatment facilities. While exchange programs continue to be implemented, there have been few reports illustrating how social science and community assessment research can be used to guide the development of NEPs. Using the Lifepoint needle exchange program in Milwaukee as a case study, this paper shows how social science methods can be used to understand IDU culture through the community identification process, link qualitative and observational findings to program decision making, and guide the implementation and operation of a needle exchange. The community identification process showed that there were different IDU subcultures in the city indicating that the NEP would need to be tailored to meet the distinctive needs of multiple drug use networks. Ethnographic field observations and key informant and systems representative interviews resulted in a two-stage NEP planning process that included a community task force on IDUs and of the development of methods to operationalize community assessment findings into the operating plan of the NEP. This process illustrates the importance of integrating a systematic community analysis in the planning of a NEP. PMID:10407453

  20. Real-time NMR study of guanine nucleotide exchange and activation of RhoA by PDZ-RhoGEF.

    PubMed

    Gasmi-Seabrook, Geneviève M C; Marshall, Christopher B; Cheung, Melissa; Kim, Bryan; Wang, Feng; Jang, Ying Ju; Mak, Tak W; Stambolic, Vuk; Ikura, Mitsuhiko

    2010-02-19

    Small guanosine triphosphatases (GTPases) become activated when GDP is replaced by GTP at the highly conserved nucleotide binding site. This process is intrinsically very slow in most GTPases but is significantly accelerated by guanine nucleotide exchange factors (GEFs). Nucleotide exchange in small GTPases has been widely studied using spectroscopy with fluorescently tagged nucleotides. However, this method suffers from effects of the bulky fluorescent moiety covalently attached to the nucleotide. Here, we have used a newly developed real-time NMR-based assay to monitor small GTPase RhoA nucleotide exchange by probing the RhoA conformation. We compared RhoA nucleotide exchange from GDP to GTP and GTP analogues in the absence and presence of the catalytic DH-PH domain of PDZ-RhoGEF (DH-PH(PRG)). Using the non-hydrolyzable analogue guanosine-5'-O-(3-thiotriphosphate), which we found to be a reliable mimic of GTP, we obtained an intrinsic nucleotide exchange rate of 5.5 x 10(-4) min(-1). This reaction is markedly accelerated to 1179 x 10(-4) min(-1) in the presence of DH-PH(PRG) at a ratio of 1:8,000 relative to RhoA. Mutagenesis studies confirmed the importance of Arg-868 near a conserved region (CR3) of the Dbl homology (DH) domain and revealed that Glu-741 in CR1 is critical for full activity of DH-PH(PRG), together suggesting that the catalytic mechanism of PDZ-RhoGEF is similar to Tiam1. Mutation of the single RhoA (E97A) residue that contacts the pleckstrin homology (PH) domain rendered the mutant 10-fold less sensitive to the activity of DH-PH(PRG). Interestingly, this mutation does not affect RhoA activation by leukemia-associated RhoGEF (LARG), indicating that the PH domains of these two homologous GEFs may play different roles. PMID:20018869

  1. A study on the surface shape and roughness of aluminum alloy for heat exchanger using ball end milling

    NASA Astrophysics Data System (ADS)

    Lee, E.; Kim, Y.; jeong, H.; Chung, H.

    2015-09-01

    Aluminum alloy is a material with a high strength-weight ratio and excellent thermal conductivity. It neither readily corrodes nor quickly weakens at low temperatures, but can be easily recycled. Because of these features, aluminum heat exchangers are widely used in aluminum alloy. In addition, the aluminum alloy used in other areas is expected to gradually increase. As a result, researchers have been continuously studying the cutting patterns of aluminium alloy. However, such studies are fewer than those on the cutting patterns of ordinary steel. Moreover, the research on ball end milling with aluminium alloys has not received much attention. Therefore, in this study, an attempt was made to find the optimal cutting pattern among the seven cutting patterns for the machining of the commonly used aluminum alloy using ball end milling for a heat exchanger. The optimal pattern was found by comparing the different shapes and surface roughness values produced by the seven patterns.

  2. New studies of optical pumping, spin resonances, and spin exchange in mixtures of inert gases and alkali-metal vapors

    NASA Astrophysics Data System (ADS)

    Jau, Yuan-Yu

    In this thesis, we present new studies of alkali-hyperfine resonances, new optical pumping of alkali-metal atoms, and the new measurements of binary spin-exchange cross-section between alkali-metal atoms and xenon atoms. We report a large light narrowing effect of the hyperfine end-resonance signals, which was predicted from our theory and observed in our experiments. By increasing the intensity of the circularly polarized pumping beam, alkali-metal atoms are optically pumped into a state of static polarization, and trapped into the hyperfine end-state. Spin exchange between alkali-metal atoms has minimal effect on the end-resonance of the highly spin-polarized atoms. This new result will possibly benefit the design of atomic clocks and magnetometer. We also studied the pressure dependence of the atomic-clock resonance linewidth and pointed out that the linewidth was overestimated by people in the community of atomic clock. Next, we present a series study of coherent population trapping (CPT), which is a promising technique with the same or better performance compared to the traditional microwave spectroscopy. For miniature atomic clocks, CPT method is thought to be particularly advantages. From our studies, we invented a new optical-pumping method, push-pull optical pumping, which can pump atoms into nearly pure 0-0 superposition state, the superposition state of the two ground-state hyperfine sublevels with azimuthal quantum number m = 0. We believe this new invention will bring a big advantage to CPT frequency standards, the quantum state preparation for cold atoms or hot vapor, etc. We also investigated the pressure dependence of CPT excitation and the line shape of the CPT resonance theoretically and experimentally. These two properties are important for CPT applications. A theoretical study of "photon cost" of optical pumping is also presented. Finally, we switch our attention to the problem of spin exchange between alkali-metal atoms and xenon gas. This mechanism is very important to the spin-exchange optical pumping. We report the first measurements of binary spin-exchange rate at high magnetic field (9.4 tesla). We present the first calculation of the magnetic decoupling curves of the binary spin-exchange rates by using two different methods, semi-classical approach (SCA) and distorted-wave Born approximation (DWBA).

  3. Asymmetric Preorganization of Inverted Pair Residues in the Sodium-Calcium Exchanger

    PubMed Central

    Giladi, Moshe; Almagor, Lior; van Dijk, Liat; Hiller, Reuben; Man, Petr; Forest, Eric; Khananshvili, Daniel

    2016-01-01

    In analogy with many other proteins, Na+/Ca2+ exchangers (NCX) adapt an inverted twofold symmetry of repeated structural elements, while exhibiting a functional asymmetry by stabilizing an outward-facing conformation. Here, structure-based mutant analyses of the Methanococcus jannaschii Na+/Ca2+ exchanger (NCX_Mj) were performed in conjunction with HDX-MS (hydrogen/deuterium exchange mass spectrometry) to identify the structure-dynamic determinants of functional asymmetry. HDX-MS identified hallmark differences in backbone dynamics at ion-coordinating residues of apo-NCX_Mj, whereas Na+or Ca2+ binding to the respective sites induced relatively small, but specific, changes in backbone dynamics. Mutant analysis identified ion-coordinating residues affecting the catalytic capacity (kcat/Km), but not the stability of the outward-facing conformation. In contrast, distinct “noncatalytic” residues (adjacent to the ion-coordinating residues) control the stability of the outward-facing conformation, but not the catalytic capacity. The helix-breaking signature sequences (GTSLPE) on the α1 and α2 repeats (at the ion-binding core) differ in their folding/unfolding dynamics, while providing asymmetric contributions to transport activities. The present data strongly support the idea that asymmetric preorganization of the ligand-free ion-pocket predefines catalytic reorganization of ion-bound residues, where secondary interactions with adjacent residues couple the alternating access. These findings provide a structure-dynamic basis for ion-coupled alternating access in NCX and similar proteins. PMID:26876271

  4. Structure and thermodynamics of amylin dimer studied by Hamiltonian-temperature replica exchange molecular dynamics simulations.

    PubMed

    Laghaei, Rozita; Mousseau, Normand; Wei, Guanghong

    2011-03-31

    The loss of the insulin-producing β-cells in the pancreatic islets of Langerhans, responsible for type-II diabetes, is associated with islet amyloid deposits. The main component of these deposits is the amyloid fibrils formed by the 37-residue human islet amyloid polypeptide (hIAPP also known as amylin). Although the fibrils are well characterized by cross β structure, the structure of the transient oligomers formed in the early stage of aggregation remains elusive. In this study, we apply the Hamiltonian-temperature replica exchange molecular dynamics to characterize the structure and thermodynamics of a full-length hIAPP dimer in both the presence and the absence of the Cys2-Cys7 disulfide bond. We compare these results with those obtained on the monomeric and dimeric forms of rat IAPP (rIAPP) with a disulfide bridge which differ from the hIAPP by 6 amino acids in the C-terminal region, but it is unable to form fibrils. Using a coarse-grained protein force field (OPEP-the Optimized Potential for Efficient peptide structure Prediction) running for a total of 10-28 μs per system studied, we show that sequences sample α-helical structure in the N-terminal region but that the length of this secondary element is shorter and less stable for the chains without the disulfide bridge (residues 5-16 for hIAPP with the bridge vs 10-16 for hIAPP without the bridge). This α-helix is known to be an important transient stage in the formation of oligomers. In the C-terminal, the amyloidogenic region of hIAPP, β-strands are seen for residues 17-26 and 30-35. On the contrary, no significant β-sheet content in the C-terminal is observed for either the monomeric or the dimeric rIAPP. These numerical results are fully consistent with recent experimental findings that the N-terminal residues are not part of the fibril by forming α-helical structure but rather play a significant role in stabilizing the amyloidogenic region available for the fibrillation. PMID:21384830

  5. Heat exchanges in fast, high-performance liquid chromatography. A complete thermodynamic study

    SciTech Connect

    Gritti, Fabrice; Guiochon, Georges A

    2008-01-01

    The successive physical transformations of the mobile phase that take place in very high pressure liquid chromatography were studied based on the formalism of classical thermodynamics. The eluent is initially under atmospheric pressure (P{sup 0}) and at ambient temperature (T{sub ext}). In a first step, it is compressed to a high pressure (P{sub max} of the order of 1 kbar) in the pump heads of the chromatograph. In a second step, the pressurized eluent is transferred to the inlet of the chromatographic column, along which, in a third step, it is decompressed to atmospheric pressure. Both the compression and the decompression of the fluid were considered to take place under conditions that can be either adiabatic or nonadiabatic and either reversible or irreversible. Applications of the first and second principles of thermodynamics allow the determination of the heat and energy exchanged between the eluent and the external surroundings during each transformation. Experimental data were acquired using acetonitrile as the mobile phase. The true state equation, {rho}(P, T), of liquid acetonitrile was used in the theoretical calculations. A series of four different flow rates (0.55, 0.85, 1.15, and 1.45 mL/min, corresponding to inlet pressures of 357.2, 559.5, 765.1, and 972.9 bar, respectively), were applied to a 2.1 x 100 mm column packed with 1.7-{micro}m bridged ethane-silicon hybrid particles. Thermocouples were used to measure the eluent temperature before and after its passage through the column. These data provide estimates of the variation of the internal energy of the eluent. The heat lost through the external wall of the column during the eluent decompression was estimated by measuring the surface temperature of the column tube under steady state. Both the compression and the decompression of acetonitrile were found to be nonadiabatic and irreversible transformations. The results showed that, during the eluent decompression, the heat released by the friction forces serves four different purposes: (1) it increases the eluent entropy at constant temperature (for 35%); (2) it increases the temperature of the eluent (for 5%); (3) it provides heat to the laboratory atmosphere (for 5%); and (4) it provides some work inside the column (for 5%). This quantitative heat balance description accounts well for the actual performance of the new, very high pressure liquid chromatographic technique.

  6. Study of flow distribution and its improvement on the header of plate-fin heat exchanger

    NASA Astrophysics Data System (ADS)

    Wen, Jian; Li, Yanzhong

    2004-11-01

    In order to enhance the uniformity of flow distribution, an improved header configuration of plate-fin heat exchanger is put forward in this paper. Based on the analysis of the fluid flow maldistribution for the conventional header used in industry, a baffle with small holes of three different kinds of diameters is recommended to install in the header. The flow maldistribution parameter S is obtained under different header configuration. When the baffle is properly installed with an optimum length, with stagger arranged and suitably distributed holes from axial line to baffle boundary, the ratio of the maximum flow velocity to the minimum flow velocity drops from 3.44-3.04 to 1.57-1.68 for various Reynolds numbers. The numerical results indicate that the improved header configuration can effectively improve the performance. The conclusion of this paper is of great significance in the improvement of plate-fin heat exchanger.

  7. Chiral ligand exchange countercurrent chromatography: Equilibrium model study on enantioseparation of mandelic acid.

    PubMed

    Tong, Shengqiang; Shen, Mangmang; Xiong, Qing; Wang, Xiaoping; Lu, Mengxia; Yan, Jizhong

    2016-05-20

    The equilibrium model in enantioseparation of mandelic acid by chiral ligand exchange countercurrent chromatography was investigated using N-n-dodecyl-l-proline as chiral ligand and cupric ion as central metal. Important parameters, including physical partition coefficient and formation constants of binary and ternary coordination complexes in the two-phase solvent system, were determined. This equilibrium model could give an excellent prediction of distribution ratio and enantioseparation factor of the analyte in the biphasic solvent system, which was further verified by experiments. All the average relative deviations were less than 12%, indicating that the established model could provide a simple computational approach for optimization of enantioseparation conditions in chiral ligand exchange countercurrent chromatography. PMID:27102304

  8. Spectroscopic studies of Fe(III) ion-exchanged ETS-10 and ETAS-10 molecular sieves

    SciTech Connect

    Sommerfeld, D.A.; Ellis, W.R. Jr.; Eyring, E.M.

    1992-11-26

    Two new titanium silicate molecular sieves, designated ETS-10 and ETAS-10, have been ion-exchanged with Fe(III). Both products exhibit prominent EPR signals, at g = 6.0 and 4.3, that are assigned to populations of ferric iron on the surface and in the interior cavities, respectively, of the molecular sieve microcrystals. Corollary XPS measurements on these samples indicate that a substantial fraction of the surface iron is present as Fe(II). Chemical modification procedures have been explored in an effort to produce ion-exchanged materials containing no exterior iron. Acid treatment (pH 1.0) proved to be an effective means of achieving this goal in the case of ETS-10-based materials. ETAS-10-based samples do not retain their crystallinity under these conditions. 35 refs., 4 figs., 2 tabs.

  9. Micromagnetic study of exchange interaction effect on magnetization reversal mode of CoFeAl

    NASA Astrophysics Data System (ADS)

    Azizah, Umi Muflihatun Nurul; Trihandaru, Suryasatriya; Wibowo, Nur Aji

    2016-02-01

    A magnetization switching dynamics of perpendicular magnetic anisotropy material CoFeAl has been simulated. This simulation was conducted using Landau-Lifshift Gilbert equation. The used magnetic parameters are magnetic anisotropy 2.3 × 106 erg/cm3, magnetic saturation 10 kG, medium Gilbert damping 0.3 and various exchange constants in a range of (1.5 - 4.0) × 10-7 erg/cm. CoFeAl is modeled as a parallel-pipe with the dimension is 50 × 50 × 20 nm3. As a result, this simulation predicts that the chosen materials exhibit good thermal stability which is greatly affected by exchange energy. Magnetization reversal mechanism is dominated by domain wall propagation process. Moreover, the simultaneous distribution of thermal with external magnetic field on the materials reduces the writing field which reaches the minimum value when exchange constant is 3.5 × 10-7 erg/cm.

  10. Magneto-optical indicator film study of the hybrid exchange spring formation and evolution processes

    NASA Astrophysics Data System (ADS)

    Nikitenko, V. I.; Gornakov, V. S.; Kabanov, Yu. P.; Shapiro, A. J.; Shull, R. D.; Chien, C. L.; Jiang, J. S.; Bader, S. D.

    2003-03-01

    The elementary events of the remagnetization processes in nanocomposite magnetic bilayers were investigated using iron-garnet indicator films with in-plane anisotropy. We have observed hybrid domain walls consisting of both ferromagnetic and antiferromagnetic sections perpendicular to the interface. The external magnetic field shifts only the ferromagnetic part of the domain walls. This leads to the formation of a hybrid exchange spin spring parallel to the interface. The processes of spring nucleation and untwisting occur at different locations. With the field oriented antiparallel to the macroscopic unidirectional anisotropy, remagnetization of the soft ferromagnet layer in the hard/soft nanocomposite starts by the formation of an exchange spring consisting of micrometer-scale sub-domains with opposite direction spin twisting. A rotating magnetic field (smaller than some critical value) creates firstly a single-chiral spin spiral; this spiral then loses stability, incoherently untwists and gradually inverts its chirality with increasing field rotation. Untwisting of the hybrid exchange spring at higher fields leads to the creation of unusual hybrid non-180° domain walls. The initial (ground) state of the bilayer with such noncollinear magnetized domains is not restored after stopping the field rotation and returning it to zero. The revealed phenomena are attributed to the influence of the dispersion in the unidirectional anisotropy induced by magnetization frustration in the interface and bilayer crystal lattice defects.

  11. Advantages of Chemical Exchange-Sensitive Spin-Lock (CESL) Over Saturation Transfer (CEST) for Hydroxyl- and Amine-Water Proton Exchange Studies

    PubMed Central

    Jin, Tao; Kim, Seong-Gi

    2014-01-01

    The chemical exchange (CE) rate of endogenous hydroxyl and amine protons with water is often comparable to the difference in their chemical shifts. These intermediate exchange (IMEX) processes have been imaged by the CE saturation transfer (CEST) approach with low-power and long-duration irradiation. However, its sensitivity is not optimal, and more importantly, the signal is contaminated by slow magnetization transfer processes. Here, the property of CEST signals is compared to a CE-sensitive spin-locking (CESL) technique irradiating at the labile proton frequency. Firstly, using a higher power and shorter irradiation in CE-MRI yields i) increasing selectivity to faster chemical exchange rates by higher sensitivity to faster exchanges and less sensitivity to slower CE and magnetization transfer processes, and ii) decreasing in vivo asymmetric magnetization transfer contrast measured at ±15 ppm. The sensitivity gain of CESL over CEST is higher for a higher-power and shorter irradiation. Unlike CESL, CEST signals oscillate at a very high power and short irradiation. Secondly, time-dependent CEST and CESL signals are well modeled by analytical solutions of CE-MRI with asymmetric population approximation (CEAPA), which can be used for quantitative CE-MRI, and validated by simulations of Bloch-McConnell equations and phantom experiments. Lastly, in vivo amine-water proton exchange contrast measured at 2.5 ppm with ω1 of 500 Hz is 18% higher in sensitivity for CESL than CEST at 9.4 T. Overall, CESL provides better exchange rate selectivity and sensitivity than CEST; therefore, CESL is more suitable for CE-MRI of IMEX protons. PMID:25199631

  12. Oxygen-17 nuclear magnetic resonance kinetic study of water exchange on the lanthanide(III) aqua ions

    SciTech Connect

    Cossy, C.; Helm, L.; Merbach, A.E.

    1988-06-01

    A variable-temperature /sup 17/O NMR study of aqueous lanthanide solutions is reported. Chemical shift measurements on 0.3 m Ln(ClO/sub 4/)/sub 3//2 m HClO/sub 4/ solutions of 12 paramagnetic lanthanide ions are consistent with a constant hydration number along the series. This observation is reinforced by spectrophotometric measurements in acidified Nd(ClO/sub 4/)/sub 3/ solutions. A critical review of the previously published results on this topic suggests that the hydration number is nine for all lanthanide ions. The study was made on high-field NMR spectrometers, extending the accessible kinetic NMR window toward larger rate constants. By a combination of the chemical shifts and the longitudinal and the transverse relaxation rates, the water exchange activation parameters were obtained for six heavy lanthanide ions. The exchange rate constants calculated at 298.15 K are 5.0 /times/ 10/sup 8/ s/sup /minus/1/ for Tb/sup 3+/, 3.9 /times/ 10/sup 8/ s/sup /minus/1/ for Dy/sup 3+/, 1.9 /times/ 10/sup 8/ s/sup /minus/1/ for Ho/sup 3+/, 1.2 /times/ 10/sup 8/ s/sup /minus/1/ for Er/sup 3+/, 8.1 /times/ 10/sup 7/ s/sup /minus/1/ for Tm/sup 3+/, and 4.1 /times/ 10/sup 7/ s/sup /minus/1/ for Yb/sup 3+/. Unsuccessful attempts were made to study the water exchange on Nd/sup 3+/ and Eu/sup 3+/. The regular decrease of the k/sup 298/ value with ionic radius and the fairly constant negative activation entropies are interpreted as grounds for a similar exchange mechanism for the six ions successfully kinetically characterized. 45 references, 5 figures, 4 tables.

  13. Theoretical and computational studies of renewable energy materials: Room temperature ionic liquids and proton exchange membranes

    NASA Astrophysics Data System (ADS)

    Feng, Shulu

    2011-12-01

    Two kinds of renewable energy materials, room temperature ionic liquids (RTILs) and proton exchange membranes (PEMs), especially Nafion, are studied by computational and theoretical approaches. The ultimate purpose of the present research is to design novel materials to meet the future energy demands. To elucidate the effect of alkyl side chain length and anion on the structure and dynamics of the mixtures, molecular dynamics (MD) simulations of three RTILs/water mixtures at various water mole fractions: 1-butyl-3-methylimidazolium (BMIM+)/BF4-, 1-octyl-3-methylimidazolium (OMIM+)/BF4-, and OMIM +/Cl- are performed. Replacing the BMIM + cation with OMIM+ results in stronger aggregation of the cations as well as a slower diffusion of the anions, and replacing the BF4- anion with Cl- alters the water distribution at low water mole fractions and slows diffusion of the mixtures. Potential experimental manifestations of these behaviors in both cases are provided. Proton solvation properties and transport mechanisms are studied in hydrated Nafion, by using the self-consistent multistate empirical valence bond (SCI-MS-EVB) method. It is found that by stabilizing a more Zundel-like (H5O 2+) structure in the first solvation shells, the solvation of excess protons, as well as the proton hydration structure are both influenced by the sulfonate groups. Hydrate proton-related hydrogen bond networks are observed to be more stable than those with water alone. In order to characterize the nature of the proton transport (PT), diffusive motion, Arrhenius activation energies, and transport pathways are calculated and analyzed. Analysis of diffusive motion suggests that (1) a proton-hopping mechanism dominates the proton transport for the studied water loading levels and (2) there is an obvious degree of anti-correlation between the proton hopping and the vehicular transport. The activation energy drops rapidly with an increasing water content when the water loading level is smaller than ˜ 10 H2O/SO 3-, which is consistent with experimental observations. The sulfonate groups are also found to have influence on the proton hopping directions. The temperature and water content effects on the PT pathways are also investigated. The morphological effects on proton solvation and transport in hydrated Nafion are investigated, by using the SCI-MS-EVB method. Two of the most significant morphological models of Nafion, the lamellar model and the cylinder model, are selected. The two models exhibit distinct PT patterns, which result in different proton diffusion rates. In both models, the interaction between protons and the sulfonate groups are proven to be the key to determining PT behavior. The proton solvation structure change as a function of the distance between protons and sulfonate groups has been analyzed. It is found that the increase of water cylinder radius or water layer height leads to the presence of more protons around the sulfonate groups. Furthermore, at a lower hydration level, the increased amount of protons around the sulfonate groups consists of more Zundel-like structures, which is influenced by the distinct morphological structures of Nafion.

  14. IMPACT OF SMALL COLUMN ION EXCHANGE STREAMS ON DWPF GLASS FORMULATION MELT RATE STUDIES

    SciTech Connect

    Fox, K.; Miller, D.; Koopman, D.

    2011-04-26

    This study was undertaken to evaluate the potential impacts of the Small Column Ion Exchange (SCIX) streams - particularly the addition of Monosodium Titanate (MST) and Crystalline Silicotitanate (CST) - on the melt rate of simulated feed for the Defense Waste Processing Facility (DWPF). Additional MST was added to account for contributions from the Salt Waste Processing Facility (SWPF). The Savannah River National Laboratory (SRNL) Melt Rate Furnace (MRF) was used to evaluate four melter feed compositions: two with simulated SCIX and SWPF material and two without. The Slurry-fed Melt Rate Furnace (SMRF) was then used to compare two different feeds: one with and one without bounding concentrations of simulated SCIX and SWPF material. Analyses of the melter feed materials confirmed that they met their targeted compositions. Four feeds were tested in triplicate in the MRF. The linear melt rates were determined by using X-ray computed tomography to measure the height of the glass formed along the bottom of the beakers. The addition of the SCIX and SWPF material reduced the average measured melt rate by about 10% in MRF testing, although there was significant scatter in the data. Two feeds were tested in the SMRF. It was noted that the ground CST alone (ground CST with liquid in a bucket) was extremely difficult to resuspend during preparation of the feed with material from SCIX and SWPF. This feed was also more difficult to pump than the material without MST and CST due to settling occurring in the melter feed line, although the yield stress of both feeds was high relative to the DWPF design basis. Steady state feeding conditions were maintained for about five hours for each feed. There was a reduction in the feed and pour rates of approximately 15% when CST and MST were added to the feed, although there was significant scatter in the data. Analysis of samples collected from the SMRF pour stream showed that the composition of the glass changed as expected when MST and CST were added to the feed. These reductions in melt rate are consistent with previous studies that showed a negative impact of increased TiO{sub 2} concentrations on the rate of melting. The impact of agitating the melt pool via bubbling was not studied as part of this work, but may be of interest for further testing. It is recommended that additional melt rate testing be performed should a potential reduction in melt rate of 10-15% be considered an issue of concern, or should the anticipated composition of the glass with the addition of material from salt waste processing be modified significantly from the current projections, either due to changes in sludge batch preparation or changes in the composition or volume of SCIX and SWPF material.

  15. The Effectiveness of the Picture Exchange Communication System (PECS) for Children with Autism Spectrum Disorder (ASD): A South African Pilot Study

    ERIC Educational Resources Information Center

    Travis, Julia; Geiger, Martha

    2010-01-01

    This study investigated the effects of introducing the Picture Exchange Communication System (PECS) on the frequency of requesting and commenting and the length of verbal utterances of two children with autism spectrum disorder (ASD) who presented with some spoken language, but limited use of language in communicative exchanges. A mixed research…

  16. In situ heat exchanger tube fouling thickness measurements using ultrasonics. Final report on a laboratory feasibility study

    SciTech Connect

    Hirshman, J; Munier, R S.C.

    1980-09-01

    The growth of fouling layers on heat exchanger surfaces and the corrosion of heat exchanger materials exposed to seawater have been recognized since the beginning of OTEC research as basic problems which could render the concept uneconomical. Consequently, a significant effort has been directed toward predicting, measuring, identifying, explaining and solving potential biofouling and corrosion phenomena. To address this problem, the feasibility of establishing a practical microacoustic technique to measure fouling film thickness in situ on typical OTEC heat exchanger tasks was studied. Seven techniques were studied for this application, including velocity measurements, acoustic diffraction, acoustic interferometer, Doppler flow velocity, pulse echo, critical angle, and surface (shear) wave effects. Of these, the latter five were laboratory tested using conventional microacoustic system components in various configuratons. Only the pulse echo technique yielded promising results. On fouled aluminum plates, thin film layers of 40 ..mu..m and greater were measured using a focused 30 MHz ceramic transducer operated at 25 MHz; this represents a resolution of about 2/3 wavelength. Measurements made on the inside of fouled 1'' aluminum pipes yielded film thicknesses of 75 to 125 ..mu..m. The thinnest layer resolved was approximately 1-1/4 wavelength. The resolution of slime layer thicknesses in the magnitudes of OTEC interest (5 to 30 ..mu..m) using pulse echo microacoustics will require transducer development. In particular, a higher operating frequency (150 to 200 MHz) and advanced material construction is recommended for further research.

  17. A Good Learning Opportunity, but Is It for Me? A Study of Swedish Students' Attitudes towards Exchange Studies in Higher Education

    ERIC Educational Resources Information Center

    Ahn, Song-ee

    2014-01-01

    This article describes students' involvement and interest in exchange programmes in Swedish higher education. Law and Engineering bachelor's programmes were chosen to exemplify an over-represented and under-represented group respectively in terms of international mobility in this context. The study combines interview and survey data. The…

  18. Droplet infiltration and OM composition of intact soil structural surfaces for studying mass exchange

    NASA Astrophysics Data System (ADS)

    Leue, Martin, ,, Dr.; Gerke, PD Horst H., ,, Dr.; Godow, Sophie Ch.; Ellerbrock, PD Ruth H., ,, Dr.

    2014-05-01

    During rapid percolation through macropores with local nonequilibrium conditions water and solute mass exchange with the porous matrix and sorption of reactive components is both taken place at the surface of preferential flow paths. Aggregate surfaces can be coated by illuviated clayey particles and biopores covered by plant residues or earthworm casts. By controlling wettability and sorption properties, the organic matter (OM) of surface coatings may also affect the transport properties of structured soils. Composition of OM in wall coatings was found spatially distributed at the mm-scale; thus, it remained unclear if water absorption by the soil matrix (i.e., mass exchange) was affected by locally-distributed OM. For samples with intact aggregate surfaces and biopore walls taken at clay-illuvial subsoil horizon of Luvisols developed from Loess and glacial till, the mm-scale spatial distribution of OM composition was measured using diffuse reflectance infrared spectroscopy (DRIFT). Spectra were analysed with respect to alkyl and carboxyl functional groups in OM to obtain an estimate for its potential wettability. The infiltration dynamic of water droplets was evaluated using contact angle measurements and droplet penetration time. The potential wettability of OM differed for coatings and burrow walls and was generally lower for the Loess-derived than for the till-derived samples. The droplet infiltration times were significantly lower only for the Loess Luvisol samples. The results suggest that mass exchange between flow path and matrix can be affected by OM composition of structural surfaces among other factors such as texture, moisture, and chemical status (pH).

  19. Studies on the application of temperature-responsive ion exchange polymers with whey proteins.

    PubMed

    Maharjan, Pankaj; Campi, Eva M; De Silva, Kirthi; Woonton, Brad W; Jackson, W Roy; Hearn, Milton T W

    2016-03-18

    Several new types of temperature-responsive ion exchange resins of different polymer composition have been prepared by grafting the products from the co-polymerisation of N-phenylacrylamide, N-iso-propylacrylamide and acrylic acid derivatives onto cross-linked agarose. Analysis of the binding isotherms for these different resins obtained under batch adsorption conditions indicated that the resin based on N-iso-propylacrylamide containing 5% (w/w) N-phenylacrylamide and 5% (w/w) acrylic acid resulted in the highest adsorption capacity, Bmax, for the whey protein, bovine lactoferrin, e.g. 14mg bovine lactoferrin/mL resin at 4°C and 62mg bovine lactoferrin/mL resin at 40°C, respectively. Under dynamic loading conditions at 40°C, 94% of the loaded bovine lactoferrin on a normalised mg protein per mL resin basis was adsorbed by this new temperature-responsive ion-exchanger, and 76% was eluted by a single cycle temperature shift to 4°C without varying the composition of the 10mM sodium dihydrogen phosphate buffer, pH 6.5, or the flow rate. The binding characteristics of these different ion exchange resins with bovine lactoferrin were also compared to results obtained using other resins based on N-isopropylacrylamide but contained N-tert-butylacrylamide rather than N-phenylacrylamide, where the corresponding dynamic capture and release properties for bovine lactoferrin required different temperature conditions of 20°C and 50°C, respectively for optimal desorption/adsorption. The cationic protein, bovine lactoperoxidase, was also adsorbed and desorbed with these temperature-responsive resins under similar conditions of changing temperature, whereas the anionic protein, bovine β-lactoglobulin, was not adsorbed under this regime of temperature conditions but instead eluted in the flow-through. PMID:26905884

  20. Structure-dynamic basis of splicing-dependent regulation in tissue-specific variants of the sodium-calcium exchanger.

    PubMed

    Lee, Su Youn; Giladi, Moshe; Bohbot, Hilla; Hiller, Reuben; Chung, Ka Young; Khananshvili, Daniel

    2016-03-01

    Tissue-specific splice variants of Na(+)/Ca(2+) exchangers contain 2 Ca(2+)-binding regulatory domains (CBDs), CBD1 and CBD2. Ca(2+) interaction with CBD1 activates sodium-calcium exchangers (NCXs), and Ca(2+) binding to CBD2 alleviates Na(+)-dependent inactivation. A combination of mutually exclusive (A, B) and cassette (C-F) exons in CBD2 raises functionally diverse splice variants through unknown mechanisms. Here, the effect of exons on CBDs backbone dynamics were investigated in the 2-domain tandem (CBD12) of the brain, kidney, and cardiac splice variants by using hydrogen-deuterium exchange mass spectrometry and stopped-flow techniques. Mutually exclusive exons stabilize interdomain interactions in the apoprotein, which primarily predefines the extent of responses to Ca(2+) binding. Deuterium uptake levels were up to 20% lower in the cardiac vs. the brain CBD12, reveling that elongation of the CBD2 FG loop by cassette exons rigidifies the interdomain Ca(2+) salt bridge at the 2-domain interface, which secondarily modulates the Ca(2+)-bound states. In matching splice variants, the extent of Ca(2+)-induced rigidification correlates with decreased (up to 10-fold) Ca(2+) off rates, where the cardiac CBD12 exhibits the slowest Ca(2+) off rates. Collectively, structurally disordered/dynamic segments at mutually exclusive and cassette exons have local and distant effects on the folded structures nearby the Ca(2+) binding sites, which may serve as a structure-dynamic basis for splicing-dependent regulation of NCX.-Lee, S. Y., Giladi, M., Bohbot, H., Hiller, R., Chung, K. Y., Khananshvili, D. Structure-dynamic basis of splicing-dependent regulation in tissue-specific variants of the sodium-calcium exchanger. PMID:26644350

  1. Extraction of local hydrogen exchange data from HDX CAD MS measurements by deconvolution of isotopic distributions of fragment ions.

    PubMed

    Abzalimov, Rinat R; Kaltashov, Igor A

    2006-11-01

    Hydrogen/deuterium exchange (HDX) coupled to protein fragmentation either in solution (by means of proteolysis) or in the gas phase (using collisional activation of protein ions) and followed by mass spectral measurements of deuterium content of individual fragments has become one of the major experimental tools to probe protein structure and dynamics. One difficulty, which often arises in the course of interpretation of HDX MS data, is a need to separate deuterium contribution to the observed isotopic patterns from that of naturally occurring isotopes. Another frequently encountered problem, especially when HDX in solution is followed by protein ion fragmentation in the gas phase, is a need to determine the deuterium content of an internal protein segment based on the measured isotopic distributions of overlapping fragments. While several algorithms were developed in the past several years to address the first problem, the second one did not enjoy as much attention. Here we report a new algorithm based on a maximum entropy principle, which is capable of extracting local exchange data form the isotope distribution of overlapping fragments, as well as subtracting the background due to the presence of natural isotopes and residual deuterium in exchange buffers. The new method is tested with several proteins and appears to generate stable solutions even under unfavorable circumstances, e.g., when the resolving power of a mass analyzer is not sufficient to avoid signal interference or when the isotopic distributions of individual fragments are complex and cannot be approximated with simple binomial distributions. The latter feature makes the algorithm particularly useful when the exchange in solution is correlated or semicorrelated, paving the way to precise structural characterization of non-native protein states in solution. PMID:16934998

  2. Lead exchange into zeolite and clay minerals: A [sup 29]Si, [sub 27]Al, [sup 23]Na solid-state NMR study

    SciTech Connect

    Liang, J.J.; Sherriff, B.L. )

    1993-08-01

    Chabazite, vermiculite, montmorillonite, hectorite, and kaolinite were used to remove Pb, through ion exchange, from 0.01 M aqueous Pb(NO[sub 3])[sub 2] solutions. These minerals contained 27 (Na-chabazite), 16, 9, 9, and 0.5 wt % of Pb, respectively, after equilibration with the solutions. Ion exchange reached equilibrium within 24 h for Na-chabazite and vermiculite, but in less than 5 min for montmorillonite and hectorite. Na-chabazite took up more Pb than natural (Ca, Na)-chabazite (7 wt % Pb), whereas no such difference was observed in different cation forms of the clay minerals. Calcite impurities, associated with the clay minerals, effectively removed Pb from the aqueous solutions by the precipitation of cerussite (PbCO[sub 3]). [sup 29]Si, [sup 27]Al, and [sup 23]Na magic angle spinning (MAS) nuclear magnetic resonance (NMR), [sup 23]Na double rotation (DOR) NMR, and [sup 23]Na variable-temperature MAS NMR were used to study the ion exchange mechanisms. In Na-chabazite, cations in all three possible sites take part in the fast chemical exchange. The chemical exchange passes from the fast exchange regime to the slow regime at [minus]80 to [minus]100[degrees]C. One site contains a relatively low population of exchangeable cations. The other two more shielded sites contain most of the exchangeable cation. The exchangeable cations in chabazite and vermiculite were found to be close to the SiO[sub 4] and AlO[sub 4] tetrahedra, while those in the other clay minerals were more distant. Two sites (or groups of sites) for exchangeable cations were observed in hectorite. Lead tended to occupy the one which corresponds to the [minus]8 ppM peak on the [sup 23]Na MAS NMR spectrum. The behavior of the exchangeable cations in the interlayer sites was similar in all the clay minerals studied. 27 refs., 7 figs., 4 tabs.

  3. [A comparative study on chlorophyll content, chlorophyll fluorescence and diurnal course of leaf gas exchange of two ecotypes of banyan].

    PubMed

    Zhao, P; Sun, G; Zeng, X; Peng, S; Mo, X; Li, Y

    2000-06-01

    The morphological differences, chlorophyll contents, fluorescence and diurnal course of leaf gas exchange between terrestrial banyan and amphibious banyan were compared with pot culture. The amphibious banyan possesses well developed aerial and hydro-adventitious roots, and wider leaf with inclination of evolution toward mesophytic traits. The chlorophyll content of terrestrial banyan was higher than that of amphibious banyan. The diurnal course of leaf gas exchange indicated that net photosynthetic rate of terrestrial banyan was slightly higher than that of amphibious banyan grown in water, but much higher than that grown in soil. The amphibious banyan grown in water had the highest transpiration rate, the terrestrial banyan had a lower one, and the amphibious banyan grown in soil had the lowest. Linear regression analysis showed a positive correlation between net photosynthetic rate and stomatal conductance, implying that the stomatal conductance was dominant factor controlling the gas exchange. In this study, the term of intrinsic water use efficiency (net photosynthetic rate/stomatal conductance ratio, Intrinsic WUE) was applied to describe the photosynthesis and water properties, and the result showed that it was a more suitable measure compared to the usual WUE(net photosynthetic rate/transpiration rate). Among the three banyan plants examined, the amphibious banyan had the highest intrinsic WUE. PMID:11767625

  4. Open inquiry-based learning experiences: a case study in the context of energy exchange by thermal radiation

    NASA Astrophysics Data System (ADS)

    Pizzolato, Nicola; Fazio, Claudio; Rosario Battaglia, Onofrio

    2014-01-01

    An open inquiry (OI)-based teaching/learning experience, regarding a scientific investigation of the process of energy exchange by thermal radiation, is presented. A sample of upper secondary school physics teachers carried out this experience at the University of Palermo, Italy, in the framework of ESTABLISH, a FP7 European Project aimed at promoting and developing inquiry-based science education. The teachers had the opportunity to personally experience an OI-based learning activity, with the aim of exploring the pedagogical potentialities of this teaching approach to promote both the understanding of difficult concepts and a deeper view of scientific practices. The teachers were firstly engaged in discussions concerning real-life problematic situations, and then stimulated to design and carry out their own laboratory activities, aimed at investigating the process of energy exchange by thermal radiation. A scientific study on the energy exchange between a powered resistor and its surrounding environment, during the heating and cooling processes, was designed and performed. Here we report the phases of this experiment by following the teachers' perspective. A structured interview conducted both before and after the OI experience allowed us to analyze and point out the teachers' feedback from a pedagogical point of view. The advantages and limits of an OI-based approach to promote the development of more student-centred inquiry-oriented teaching strategies are finally discussed.

  5. A High-Resolution Modeling Study of the Bosphorus Strait Dynamics and Exchange Flows

    NASA Astrophysics Data System (ADS)

    Sözer, Adil; Sannino, Gianmaria; Özsoy, Emin

    2013-04-01

    An all-time modelling challenge aims to establish a sound understanding of the high energy environment of the Turkish Straits System, relating to inter-basin water and material transports and their influence on the sensitive ecosystems of the adjacent seas. As a first step in this direction, well resolved, high level, physically representative predictive models of the Bosphorus Strait exchange flow hydrodynamics are developed, adequately representing its complex topography, hydraulic controls, dissipative hydraulic jumps, mixing and turbulence mechanisms, with the application of appropriate basin boundary and initial conditions and judiciously selected numerical and physical model options. Both the ROMS and MITgcm models are used and compared for performance. Idealized and real case model results successfully reproduce observed flow features. The unique maximal exchange regime of the Bosphorus Strait, with hydraulic controls are demonstrated, although frictional effects, especially of the highly irregular lateral boundaries, are found to be extremely important, associated with mixing and entrainment and nonlinear dynamics determining the two-way fluxes as a function of sea-level changes across the strait. The intercomparison of ROMS and MITgcm results are extremely satisfactory in the basic elements of the flow, except for some small differences.

  6. Tank 241-AZ-102 SuperLig 639 Technetium Ion Exchange Eluate Evaporation Study

    SciTech Connect

    King, W.D.

    2001-02-15

    As part of the Hanford River Protection Project (RPP), the Savannah River Technology Center (SRTC) has conducted tests on the pretreatment and vitrification of a radioactive waste sample from Hanford Tank 241-AZ-102. The original, AZ-102 sample which was received at SRTC was characterized and filtered to remove entrained solids.1 The sample was then passed sequentially through ion exchange columns containing SuperLig{reg_sign} 644 and 639 resins for the removal of cesium and technetium ions (Tc removed as pertechnetate, TcO{sub 4}{sup {minus}}), respectively.2 The cesium and technetium absorbed to the resins was then eluted to give separate eluate solutions containing relatively high concentrations of Cs{sup +} and TcO{sub 4}{sup {minus}}. According to the current plant design, the decontaminated Tank 241-AZ-102 sample and the eluate solutions will be subjected to separate evaporation and vitrification processes to give low- and high-activity waste glasses, respectively. This report describes evaporation testing of the Tc eluate solution derived from ion exchange processing of the Tank 241-AZ-102 sample with SuperLig 639 resin.

  7. Factors affecting the stereospecificity and catalytic efficiency of the tryptophan synthase-catalysed exchange of the pro-2R and pro-2S protons of glycine.

    PubMed

    Milne, J J; Malthouse, J P

    1995-11-01

    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. The first- and second-order rate constants for exchange when the alpha 2 beta 2 enzyme complex is or is not saturated with glycine have been determined at pH 7.0 and 7.8. At pH 7.8 the effects of binding the allosteric effector, DL-alpha-glycerol 3-phosphate, and of removing the alpha-subunits have been examined. The beta-subunits preferentially catalyse the exchange of the pro-2R proton of glycine, but adding alpha-subunits decreases the stereospecificity of the exchange reactions. Likewise, binding of DL-alpha-glycerol 3-phosphate to the alpha 2 beta 2 enzyme complex causes a further decrease in the stereospecificity of this reaction. The stereospecificity of the second-order exchange reaction catalysed by the beta-subunits is 136-fold larger than that of the alpha 2 beta 2 enzyme complex in the presence of DL-alpha-glycerol 3-phosphate, while there is only a 5-fold decrease in the stereospecificity of the first-order exchange reaction under the same conditions. We discuss how these results relate to current theories which attempt to explain how the alpha-subunits and DL-alpha-glycerol 3-phosphate modify the catalytic properties of tryptophan synthase. PMID:7487918

  8. Higher Education Exchange, 2010

    ERIC Educational Resources Information Center

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

    2010-01-01

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

  9. Higher Education Exchange, 2005

    ERIC Educational Resources Information Center

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

    2005-01-01

    The "Higher Education Exchange" is part of a movement to strengthen higher education's democratic mission and foster a more democratic culture throughout American society. Working in this tradition, the "Higher Education Exchange" publishes case studies, analyses, news, and ideas about efforts within higher education to develop more democratic…

  10. Higher Education Exchange, 2004

    ERIC Educational Resources Information Center

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

    2004-01-01

    The Higher Education Exchange is part of a movement to strengthen higher education's democratic mission and foster a more democratic culture throughout American society. Working in this tradition, the Higher Education Exchange publishes case studies, analyses, news, and ideas about efforts within higher education to develop more democratic…

  11. Higher Education Exchange, 2007

    ERIC Educational Resources Information Center

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

    2007-01-01

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

  12. Higher Education Exchange, 2012

    ERIC Educational Resources Information Center

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

    2012-01-01

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

  13. Higher Education Exchange, 2011

    ERIC Educational Resources Information Center

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

    2011-01-01

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

  14. Hole spin polarization in the exchange field of the dilute magnetic (Ga,Mn)As semiconductor studied by means of polarized hot-electron photoluminescence spectroscopy

    NASA Astrophysics Data System (ADS)

    Sapega, V. F.; Sablina, N. I.; Panaiotti, I. E.; Averkiev, N. S.; Ploog, K. H.

    2009-07-01

    We have studied the hole spin polarization in the exchange field of ferromagnetic (Ga,Mn)As by means of polarized hot-electron photoluminescence (HPL). We found that the holes contribute to the HPL spectrum in two very different states. Most of the holes are strongly localized on Mn acceptors whose spin polarization under circularly polarized excitation is not sensitive to the exchange field arising in the ferromagnetic state below the Curie point. In contrast, the spin polarization of weakly localized or delocalized holes strongly decreases below the Curie temperature. This effect is explained by the hole spin orientation in the exchange field. The spin splitting of the weakly localized or delocalized holes in the mean exchange field is estimated Δ≃6meV (equivalent to the built-in exchange field ≃90T ).

  15. Fundamental studies on direct ammonia fuel cell employing anion exchange membrane

    NASA Astrophysics Data System (ADS)

    Suzuki, Shohei; Muroyama, Hiroki; Matsui, Toshiaki; Eguchi, Koichi

    2012-06-01

    The fundamental characteristics of direct ammonia fuel cell employing anion exchange membrane (AEM) as an electrolyte was evaluated. The fuel cells with three different anodes of Pt/C, Pt-Ru/C, and Ru/C were applied for the performance tests. The open circuit voltage (OCV) was notably lower than the ideal electromotive force of 1.17 V and significantly dependent on the electrocatalysts. The OCV achieved was in the following sequence: Pt-Ru/C > Pt/C > Ru/C. Furthermore, the ammonia permeated through the AEM by the solubility-diffusion mechanism and the formation of oxidants such as N2 and NO was detected in the cathode exhaust gas. This result indicates the oxidation of ammonia in the cathode, which will be another factor for the reduction in OCV. Note that OCV and performance continuously decreased during the consecutive I-V characteristic measurements because of the Nad poisoning over the surface of anode catalysts.

  16. Water exchange through the Betic and Rifian corridors prior to the Messinian Salinity Crisis: A model study

    NASA Astrophysics Data System (ADS)

    Vara, Alba; Topper, Robin P. M.; Meijer, Paul Th.; Kouwenhoven, Tanja J.

    2015-05-01

    Although the present-day Mediterranean-Atlantic water exchange has been extensively studied, little is known about the dynamics of the Betic and Rifian corridors that existed before the Messinian Salinity Crisis. Due to the difficulties in studying the paleogeographic evolution of these corridors, physics-based knowledge of their behavior is essential to interpret observational evidence and to relate flow structures to gateway geometries. Here we present the first systematic model study of the water exchange through these gateways. We use the parallel version of the Princeton Ocean Model (sbPOM) and a set of idealized bathymetries based on a late Tortonian paleogeography. This analysis represents a major step forward in the understanding of the behavior of the double-gateway system constituted by the Late Miocene Betic and Rifian corridors. We demonstrate that the "siphon" scenario, involving inflow of cold upwelled Atlantic water through the Rifian corridor and outflow of Mediterranean water only via the Betic corridor, is unlikely from a physics perspective. It is shown that two exchange patterns are possible depending solely on the relative depth of the corridors. The implication of this is that geological evidence for the behavior of one corridor provides information about the dimensions of the other. We show that disappearance of outflow in one corridor does not necessarily imply its closure and we establish a guideline to determine how geological evidence can be interpreted as indicating one- or two-layer flow. Based on the model results, we propose new physics-based scenarios for the time interval defined for the siphon.

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

    PubMed

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

    2014-01-01

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

  18. Leach studies on cement-solidified ion exchange resins from decontamination processes at operating nuclear power stations

    SciTech Connect

    McIsaac, C.V.; Akers, D.W.; McConnell, J.W.; Morcos, N.

    1992-01-01

    The effects of varying pH and leachant compositions on the physical stability and leachability of radionuclides and chelating agents were determined for cement-solidified decontamination ion-exchange resin wastes collected from two operating commercial light water reactors. Small scale waste-form specimens were collected during waste solidifications performed at the Brunswick Steam Electric Plant Unit 1 and at the James A. FitzPatrick Nuclear Power Station. The collected specimens were leach tested, and their compressive strength was measured in accordance with the Nuclear Regulatory Commission's Technical Position on Waste Form'' (Revision 1), from the Low-Level Waste Management Branch. Leachates from these studies were analyzed for radionuclides, selected transition metals, and chelating agents to assess the leachability of these waste form constituents. Leachants used for the study were deionized water, simulated seawater, and groundwater compositions similar to those found at Barnwell, South Carolina and Hanford, Washington. Results of this study indicate that initial leachant pH does not affect leachate pH or releases from cement-solidified decontamination ion-exchange resin waste forms. However, differences in leachant composition and the presence of chelating agents may affect the releases of radionuclides and chelating agents. In addition, results from this study indicate that the cumulative releases of radionuclides and chelating agents observed for forms that disintegrated were similar to those for forms that maintained their general physical integrity.

  19. Leach studies on cement-solidified ion exchange resins from decontamination processes at operating nuclear power stations

    SciTech Connect

    McIsaac, C.V.; Akers, D.W.; McConnell, J.W.; Morcos, N.

    1992-08-01

    The effects of varying pH and leachant compositions on the physical stability and leachability of radionuclides and chelating agents were determined for cement-solidified decontamination ion-exchange resin wastes collected from two operating commercial light water reactors. Small scale waste-form specimens were collected during waste solidifications performed at the Brunswick Steam Electric Plant Unit 1 and at the James A. FitzPatrick Nuclear Power Station. The collected specimens were leach tested, and their compressive strength was measured in accordance with the Nuclear Regulatory Commission`s ``Technical Position on Waste Form`` (Revision 1), from the Low-Level Waste Management Branch. Leachates from these studies were analyzed for radionuclides, selected transition metals, and chelating agents to assess the leachability of these waste form constituents. Leachants used for the study were deionized water, simulated seawater, and groundwater compositions similar to those found at Barnwell, South Carolina and Hanford, Washington. Results of this study indicate that initial leachant pH does not affect leachate pH or releases from cement-solidified decontamination ion-exchange resin waste forms. However, differences in leachant composition and the presence of chelating agents may affect the releases of radionuclides and chelating agents. In addition, results from this study indicate that the cumulative releases of radionuclides and chelating agents observed for forms that disintegrated were similar to those for forms that maintained their general physical integrity.

  20. An experimental study of the temperature profiles and heat transfer coefficients in a heat pipe for a heat exchanger

    NASA Astrophysics Data System (ADS)

    Larkin, B. S.

    This paper describes an experimental study of a heat pipe to be used as a component in an air-to-air heat recovery heat exchanger. The two fluids used are water and Refrigerant 22, over a temperature range from 20 C to 100 C. Temperature profiles and heat transfer coefficients are given for heat fluxes from 500 watts to 1100 watts, showing the effect of the fluid quantity used. Results were obtained for a smooth surface and for a surface with a circumferential capillary groove. The heat pipe was inclined at 5-deg to the horizontal.

  1. A three-dimensional, quantum mechanical study of exchange and charge transfer processes in the (Ar+H2) + system

    NASA Astrophysics Data System (ADS)

    Baer, Michael; Nakamura, Hiroki

    1987-10-01

    A three-dimensional quantum mechanical study of the (Ar+H2)+ system was carried out within the reactive infinite order sudden approximation. All three arrangement channels for exchange and charge transfer were treated simultaneously. Steric factors, opacity functions, angular distributions, and integral cross sections were calculated. Whenever possible, these were compared with both experimental and trajectory surface hopping (TSH) results. Whereas the fit with the TSH results was reasonable, the fit obtained with the experiment was less satisfactory. The reason for that can be attributed at least partially to the semiempirical DIM potential employed in the calculation.

  2. Multiscale study of bacterial growth: Experiments and model to understand the impact of gas exchange on global growth

    NASA Astrophysics Data System (ADS)

    Lalanne-Aulet, David; Piacentini, Adalberto; Guillot, Pierre; Marchal, Philippe; Moreau, Gilles; Colin, Annie

    2015-11-01

    Using a millifluidics and macroscale setup, we study quantitatively the impact of gas exchange on bacterial growth. In millifluidic environments, the permeability of the incubator materials allows an unlimited oxygen supply by diffusion. Moreover, the efficiency of diffusion at small scales makes the supply instantaneous in comparison with the cell division time. In hermetic closed vials, the amount of available oxygen is low. The growth curve has the same trend but is quantitatively different from the millifluidic situation. The analysis of all the data allows us to write a quantitative modeling enabling us to capture the entire growth process.

  3. Exergy destruction analysis of a vortices generator in a gas liquid finned tube heat exchanger: an experimental study

    NASA Astrophysics Data System (ADS)

    Ghazikhani, M.; Khazaee, I.; Monazzam, S. M. S.; Takdehghan, H.

    2016-01-01

    In the present work, the effect of using different shapes of vortices generator (VG) on a gas liquid finned heat exchanger is investigated experimentally with irreversibility analysis. In this project the ambient air with mass flow rates of 0.047-0.072 kg/s is forced across the finned tube heat exchanger. Hot water with constant flow rate of 240 L/h is circulated inside heat exchanger tubes with inlet temperature range of 45-73 °C. The tests are carried out on the flat finned heat exchanger and then repeated on the VG finned heat exchanger. The results show that using the vortex generator can decrease the ratio of air side irreversibility to heat transfer (ASIHR) of the heat exchanger. Also the results show that the IASIHR is >1.05 for all air mass flow rates, which means that ASIHR for the initial heat exchanger is higher than 5 % greater than that of improved heat exchanger.

  4. Kitchen Appliance Upgrades Improve Water Efficiency at DOD Exchange Facilities: Best Management Practice Case Study #11: Commercial Kitchen Equipment (Brochure)

    SciTech Connect

    Not Available

    2011-09-01

    The Exchange, formerly the Army and Air Force Exchange Service (AAFES), is a joint military activity and the U.S. Department of Defense?s (DOD) oldest and largest retailer. The Exchange is taking a leadership role in water efficiency improvements in their commercial kitchens by integrating water efficiency concepts into the organization?s overall sustainability plan and objectives.

  5. A Comparison Study of CO2 Exchange Within the Sahelian/Sudanian Zone of Africa

    NASA Astrophysics Data System (ADS)

    Soegaard, H.; Ardoe, J.

    2007-12-01

    The paper summarizes some of the major findings from CO2 flux campaigns ranging from Hapex Sahel (Niger 1992) to the presently ongoing Sudan experiment. In total four sites are selected, all with sandy soils, low annual rainfall (250-500 mm), sparse vegetation with a maximum volumetric water holding capacity of approximately 15 %. At all sites the net carbon exchange is measured by eddy covariance technique while the two major components, i.e. the soil respiration and the net carbon assimilation are estimated by combining measurements and modeling. For the soil respiration it is found that the fist rainfall events prior to the proper rainy season generate significance CO2-busts form the wet soil. In general it is found that the soil is strongly controlled by temperature and soil moisture but also available soil carbon should play a significant role. Using the annual maximum leaf area index as a proxy for the available carbon content it is found that the modeling of the soil respiration can be significantly improved . Except for the early seson peaks the maximum respiration level is around 3-4 Ýmol m-2 s-1 during the growing season decreasing to 2 Ýmol m-2 s-1 during senescence and reaching values close to zero during the dry season. For the CO2 assimilation there are large diurnal fluctuations with downward directed fluxes reaching a maximum level of -20 Ýmol m-2 s-1 and upward directed nighttime fluxes typically around 5 Ýmol m-2 s-l. The photosynthetic CO2 uptake is modeled by use of a mechanistic model based on published values of the Rubisco capacity. The combined photosynthesis /soil respiration model is used for estimating seasonal carbon budgets and to estimate the environmental control of the CO2 exchange. Besides radiation and LAI, the CO2 assimilation is found to depend on soil moisture and temperature The sensitivity analysis shows that at low soil moisture the assimilation is determined by the water stress function whereas for soil moisture contents above 8 vol. % there is only little control on the assimilation. The temperature dependence confirms that there is an optimal temperature at around 36 oC and the assimilation rate decreases for both increasing and decreasing temperature. It is finally discussed how the extent of the Sahelian/Sudanian zone makes it necessary to combine the flux station data with earth observation technique when aiming at regional estimates.

  6. Simulating forest productivity and surface-atmosphere carbon exchange in the BOREAS study region.

    PubMed

    Kimball, John S.; Thornton, Peter E.; White, Mike A.; Running, Steven W.

    1997-01-01

    A process-based, general ecosystem model (BIOME-BGC) was used to simulate daily gross primary production, maintenance and heterotrophic respiration, net primary production and net ecosystem carbon exchange of boreal aspen, jack pine and black spruce stands. Model simulations of daily net carbon exchange of the ecosystem (NEE) explained 51.7% (SE = 1.32 g C m(-2) day(-1)) of the variance in daily NEE derived from stand eddy flux measurements of CO(2) during 1994. Differences between measured and simulated results were attributed to several factors including difficulties associated with measuring nighttime CO(2) fluxes and model assumptions of site homogeneity. However, comparisons between simulations and field data improved markedly at coarser time-scales. Model simulations explained 66.1% (SE = 0.97 g C m(-2) day(-1)) of the variance in measured NEE when 5-day means of daily results were compared. Annual simulations of aboveground net primary production ranged from 0.6-2.4 Mg C ha(-1) year(-1) and were concurrent with results derived from tree increment core measurements and allometric equations. Model simulations showed that all of the sites were net sinks (0.1-4.1 Mg C ha(-1) year(-1)) of atmospheric carbon for 1994. Older conifer stands showed narrow margins between uptake of carbon by net photosynthesis and carbon release through respiration. Younger stands were more productive than older stands, primarily because of lower maintenance respiration costs. However, all sites appeared to be less productive than temperate forests. Productivity simulations were strongly linked to stand morphology and site conditions. Old jack pine and aspen stands showed decreased productivity in response to simulated low soil water contents near the end of the 1994 growing season. Compared with the aspen stand, the jack pine stand appeared better adapted to conserve soil water through lower daily evapotranspiration losses but also exhibited a narrower margin between daily net photosynthesis and respiration. Stands subjected to water stress during the growing season may exist on the edge between being annual sources or sinks for atmospheric carbon. PMID:14759832

  7. Study of frost growth on heat exchangers used as outdoor coils in air source heat pump systems

    NASA Astrophysics Data System (ADS)

    K P, Sankaranarayanan

    2011-12-01

    Scope and method of study. During winter heating operation, the outdoor coil of a heat pump acts as an evaporator and when the ambient temperature is near freezing, the moisture in the atmospheric air freezes on the coil surface. The frost growth affects the air flow and also adds resistance to heat transfer thus reducing the capacity and the efficiency of the heat pump. An experimental facility is designed and built to test a small scale heat exchanger working in frosting conditions. Tests are carried out using small scale fin-tube and microchannel heat exchanger over a range of glycol inlet temperatures, air velocities and ambient air RH. A semi-empirical frost model based on a scaling approach is developed and applied to both fin-tube heat and microchannel heat exchangers. The model is developed to handle non-uniformities in both refrigerant and air side. The frost model is integrated with a segment-by-segment heat exchanger calculation algorithm and is validated against experimental data. Frost growth model is also incorporated in a quasi-steady state system simulation algorithm. Findings and conclusions. From the experimental study it was observed that the temperature of the surface and air RH affected the rate of frost growth significantly while the air velocity did not have a great influence. It is demonstrated that a dry heat transfer correlation can be used during frost growth period by correctly accounting for frost thickness in the hydraulic diameter calculations. Ignoring the phenomenon of air redistribution was found to result in errors in the range of 20% to 50% in predicted frost thickness. Frost thickness predicted by the frost model is within 5% of the measured values for most of the cases. Frost mass accumulation predicted by the simple model is higher than the measured values due to a uniform thickness assumption in the model. An improved frost model based on 1-D finite volume discretization is also presented which improved the frost mass prediction to within 13% of measured values. The system simulation is validated against experimental results and found to match reasonable well. The discrepancy between simulation and experiments were due to the effects of system transience in the initial stages.

  8. The Experimental Study of Atmospheric Stirling Engines Using Pin-Fin Arrays' Heat Exchangers

    NASA Astrophysics Data System (ADS)

    Isshiki, Seita; Sato, Hidekazu; Konno, Shoji; Shiraishi, Hiroaki; Isshiki, Naotsugu; Fujii, Iwane; Mizui, Hiroyuki

    This paper reports experimental results on two kinds of atmospheric Stirling engines that were designed and manufactured using a pin-fin array heat exchanger for the heater and cooler (abbreviated to “pin-fin Stirling engine” hereafter). The first one is a large β type pin-fin Stirling engine with a 1.7-liter displacement volume and power piston volume. The heater consists of an aluminum circular disk with a diameter of 270mm and with large-scale pin-fin arrays carved into the surface. The maximum output reached 91W at a temperature difference of 330K, which is 36% of the scheduled value and 68% of the Kolin's cubic power law. The maximum thermal efficiency was estimated 4.2%. The second engine is an α type pin-fin Stirling engine. Glass syringes were used for the piston-cylinder system and the Ross-yoke mechanism was used for the crank mechanism. By changing temperature difference, the characteristic of output torque in the large range was measured with a precision torque detector.

  9. Study and development of sulfated zirconia based proton exchange fuel cell membranes

    NASA Astrophysics Data System (ADS)

    Kemp, Brittany Wilson

    With the increasing consumption of energy, fuel cells are among the most promising alternatives to fossil fuels, provided some technical challenges are overcome. Proton exchange membrane fuel cells (PEMFCs) have been investigated and improvements have been made, but the problem with NafionRTM, the main membrane for PEMFCs, has not been solved. NafionRTM restricts the membranes from operating at higher temperatures, thus preventing them from working in small electronics. The problem is to develop a novel fuel cell membrane that performs comparably to NafionRTM in PEMFCs. The membranes were fabricated by applying sulfated zirconia, via template wetting, to porous alumina membranes. The fabricated membranes showed a proton conductivity of 0.016 S/cm in comparison to the proton conductivity of Nafion RTM (0.05 S/cm). Both formic acid and methanol had a lower crossover flux through the sulfated zirconia membranes (formic acid- 2.89x10 -7 mols/cm2s and methanol-1.78x10-9 mols/cm2s) than through NafionRTM (formic acid-2.03x10 -8 mols/cm2s methanol-2.42x10-6 mols/cm 2s), indicating that a sulfated zirconia PEMFC may serve as a replacement for NafionRTM.

  10. A Field Study of How Hydraulic Conductivity Heterogeneity Influences Hyporheic Exchange

    NASA Astrophysics Data System (ADS)

    Ryan, R. J.; Boufadel, M. C.

    2006-05-01

    A conservative solute tracer experiment was conducted in Indian Creek, a small urban stream located in Philadelphia, Pennsylvania to investigate the role of bed sediment hydraulic conductivity on hyporheic (surface- subsurface) exchange. Sodium Bromide (NaBr) was used as a conservative tracer, and it was monitored in the surface water at two stations and in the upper bed sediments (shallow hyporheic zone extending from 7.5 cm to 10 cm below the streambed). The hydraulic conductivity (K) of the upper bed sediments and the lower bed sediments (10 cm to 12.5 cm below the streambed) was measured in situ. High tracer concentrations were observed in the upper layer at locations where the hydraulic conductivity of the upper layer was larger than that of the lower layer. Low concentrations in the upper layer were observed in the converse case. A statistically significant relationship between the mass retained in the upper layer and the difference of K values between layers was observed.

  11. Pulsed EPR studies of the exchangeable proton at the molybdenum center of dimethyl sulfoxide reductase.

    PubMed

    Raitsimring, Arnold M; Astashkin, Andrei V; Feng, Changjian; Enemark, John H; Nelson, Kimberly Johnson; Rajagopalan, K V

    2003-01-01

    Electron spin echo envelope modulation (ESEEM) spectroscopy has been used to determine the hyperfine ( hfi) and quadrupole ( nqi) interactions of the exchangeable deuteron (proton) at the Mo(V) site of DMSO reductase. The data obtained have been translated into structure-related parameters. It was found that isotropic hfi constant of the proton is not unique, but is distributed within a range of 26-36 MHz. From this hfi distribution, a 30 degrees -wide distribution of the OH bond orientations due to a rotation around the Mo-O bond was estimated. The angle between the axes of the nqi and anisotropic hfi tensors was found to be anomalously small in comparison with that expected from the Mo-O-D bond geometry. This peculiarity was attributed to the effect of spin density on the hydroxyl oxygen atom. The orientation of the Mo-OH fragment with respect to the g-frame was determined from the experimental orientations of the nqi and hfi tensor axes and a theoretical evaluation of the anisotropic hfi axis direction. PMID:12459903

  12. TRENTA Facility for Trade-Off Studies Between Combined Electrolysis Catalytic Exchange and Cryogenic Distillation Processes

    SciTech Connect

    Cristescu, I.; Cristescu, I.R.; Doerr, L.; Glugla, M.; Hellriegel, G.; Schaefer, P.; Welte, S.; Kveton, O.; Murdoch, D

    2005-07-15

    One of the most used methods for tritium recovery from different sources of tritiated water is based on the combination between Combined Electrolysis Catalytic Exchange (CECE) and Cryogenic Distillation (CD) processes. The development, i.e. configuration, design and performance testing of critical components, of a tritium recovery system based on the combination CECE-CD is essential for both JET and ITER. For JET, a Water Detritiation System (WDS) is not only needed to process tritiated water which has already been accumulated from operation, but also for the tritiated water which will be generated during decommissioning. For ITER, the WDS is one of the key systems to control the tritium content in the effluents streams, to recover as much tritium as possible and consequently to minimize the impact on the environment. A cryogenic distillation facility with the aim to investigate the trade-off between CECE-CD, to validate different components and mathematical modelling software is current under development at Tritium Laboratory Karlsruhe (TLK) as an extension of the existing CECE facility.

  13. Exchange-dominated eigenmodes in sub-100 nm permalloy dots: A micromagnetic study at finite temperature

    NASA Astrophysics Data System (ADS)

    Carlotti, G.; Gubbiotti, G.; Madami, M.; Tacchi, S.; Stamps, R. L.

    2014-05-01

    Micromagnetic simulations at room temperature (300 K) have been carried out in order to analyse the magnetic eigenmodes (frequency and spatial profile) in elliptical dots with sub-100 nm lateral size. Features are found that are qualitatively different from those typical of larger dots because of the dominant role played by the exchange-energy. These features can be understood most simply in terms of nodal planes defined relative to the orientation of the static magnetization. A new, generalized labeling scheme is proposed that simplifies discussion and comparison of modes from different geometries. It is shown that the lowest-frequency mode for small dots is characterized by an in-phase precession of spins, without nodal planes, but with a maximum amplitude at the edges. This mode softens at an applied switching field with magnitude comparable to the coercive field and determines specific aspects of magnetization reversal. This characteristic behavior can be relevant for optimization of microwave assisting switching as well as for maximizing interdot coupling in dense arrays of dots.

  14. Studies on biologically induced corrosion in heat exchanger systems at the Savannah River Plant, Aiken, SC

    SciTech Connect

    Pope, D.H.; Soracco, R.J.; Wilde, E.W.

    1982-07-01

    Biological fouling and corrosion of stainless steel tubes in the heat exchangers in nuclear reactors at the Savannah River Plant have caused decreased heat transfer efficiency and reduced operational life. This report addresses the microbiology and chemistry of the films present on these tubes, and the relation of this data to the corrosion of the tube material (304L stainless steel). Very few microorganisms other than bacteria were found in the biofilm. Bacteria capable of producing H/sub 2/S, organic acids, anaerobic conditions, and slime have all been isolated from these films. All of these have been implicated in corrosion processes. The most remarkable chemical finding was the inability to detect chloride in the film around areas of presumed chloride induced stress corrosion cracking. Three model systems were used to test the fouling and corrosion potential of metal specimens under a variety of environmental conditions including various biocide regimes. Using these systems, potential improvements in the use of chlorine as a biocidal agent have been observed. It was also shown that larger bacterial populations (including viable and killed cells) were associated with corroded areas as compared to noncorroded areas on the same specimen.

  15. Catalysts based on activated aluminum alloys. I. A study of copper-alumina catalysts by XPS and deuterium-hydrogen exchange

    SciTech Connect

    Yakerson, V.I.; Subbotin, A.N.; Gudkov, B.S.; Tkachenko, O.P.; Sarmurzina, R.G.

    1994-09-01

    Surface compositions and electron states of elements in copper-containing catalysts prepared by water treatment of copper-aluminum alloys activated by indium and gallium are studied by XPS. The copper contents in the surface layers of the catalysts is found to be less than that in the bulk. Fast isotopic H{sub 2}-D{sub 2} exchange at 70-200{degrees}C on reduced copper-containing samples and the absence of the exchange on copper-free samples indicate dissociative hydrogen adsorption on copper-containing active sites. The activation energy for the isotopic exchange is essentially dependent on the procedure of catalyst preparation.

  16. Influence of 8-Oxoguanosine on the Fine Structure of DNA Studied with Biasing-Potential Replica Exchange Simulations

    SciTech Connect

    Kara, Mahmut; Zacharias, Martin W.

    2013-03-05

    Chemical modification or radiation can cause DNA damage, which plays a crucial role for mutagenesis of DNA, carcinogenesis, and aging. DNA damage can also alter the fine structure of DNA that may serve as a recognition signal for DNA repair enzymes. A new, advanced sampling replica-exchange method has been developed to specifically enhance the sampling of conformational substates in duplex DNA during molecular dynamics (MD) simulations. The approach employs specific biasing potentials acting on pairs of pseudodihedral angles of the nucleic acid backbone that are added in the replica simulations to promote transitions of the most common substates of the DNA backbone. The sampled states can exchange with a reference simulation under the control of the original force field. The application to 7,8-dihydro-8oxo-guanosine, one of the most common oxidative damage in DNA indicated better convergence of sampled states during 10 ns simulations compared to 20 times longer standard MD simulations. It is well suited to study systematically the fine structure and dynamics of large nucleic acids under realistic conditions, including explicit solvent and ions. The biasing potential-replica exchange MD simulations indicated significant differences in the population of nucleic acid backbone substates in the case of 7,8-dihydro-8oxo-guanosine compared to a regular guanosine in the same sequence context. This concerns both the ratio of the B-DNA substates BI and BII associated with the backbone dihedral angles ε and z but also coupled changes in the backbone dihedral angles a and g. Such differences may play a crucial role in the initial recognition of damaged DNA by repair enzymes.

  17. Gas exchange

    MedlinePlus Videos and Cool Tools

    ... into a left and right bronchus within the lungs and further divides into smaller and smaller branches ... exchange is the delivery of oxygen from the lungs to the bloodstream, and the elimination of carbon ...

  18. HEAT EXCHANGER

    DOEpatents

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

    1962-10-23

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

  19. Study of Np(V) Sorption by Ionic Exchange on Na, K, Ca and Mg-Montmorillonite

    NASA Astrophysics Data System (ADS)

    Benedicto, A.; Begg, J.; Zhao, P.; Kersting, A. B.; Zavarin, M.

    2012-12-01

    The transport behavior of actinides in soil and ground water are highly influenced by clay minerals due to their ubiquity in the environment, reactivity and colloidal properties. Neptunium(V) has been introduced in the environment as a result of nuclear weapons testing [e.g. 1, 2] and is a radionuclide of potential interest for safety assessment of high level radioactive waste disposal because its long half-life and high toxicity [3]. Surface complexation and ionic exchange have been identified as Np(V) sorption mechanisms onto montmorillonite. At pH below 5, Np(V) sorption is mainly attributed to ionic exchange. This study examines Np(V) ion exchange on Na, K, Ca and Mg forms of montmorillonite. Experiments were carried out using 237Np concentrations between 2 x 10-8 M and 5 x 10-6 M at three different ionic strengths 0.1, 0.01 and 0.001M. The pH was maintained at 4.5. Np(V) sorption to montmorillonite homoionized with monovalent cations (Na and K) demonstrated a markedly different behavior to that observed for montmorillonite homoionized with divalent cations (Ca and Mg). Np sorption to Na and K-montmorillonite was greater than Np sorption to Ca and Mg-montmorillonite. Isotherms with Na and K-montmorillonite showed a strong dependence on ionic strength: the percentage of Np adsorbed was near zero at 0.1M ionic strength, but increased to 30% at 0.001 M ionic strength. This suggests ionic exchange is the main Np adsorption mechanism under the experimental conditions investigated. Dependence on ionic strength was not observed in the Np sorption isotherms for Ca and Mg-montmorillonite indicating a low exchange capacity between Np and divalent cations. Modeling of the sorption experimental data will allow determination of the Na+↔NpO2+ and K+↔NpO2+ ionic exchange constants on montmorillonite. References: [1] A. R. Felmy; K. J. Cantrell; S. D. Conradson, Phys. Chem. Earth 2010, 35, 292-297 [2] D. K. Smith; D. L. Finnegan; S. M. Bowen, J. Environ. Radioact. 2003, 67, (1), 35-51 [3] N. Kozai; T. Ohnuki; S. Muraoka, J. Nucl. Sci. Technol. 1993, 30, (11), 1153-1159 This work was funded by U. S. DOE Office of Biological & Environmental Sciences, Subsurface Biogeochemistry Research Program, and performed under the auspices of the U. S. Department of Energy by Lawrence Livermore National Security, LLC under Contract DE-AC52-07NA27344. A. Benedicto was supported by a Spanish Ministry of Science and Innovation 'FPI' pre-doctoral contract in CIEMAT (Spain). LLNL-ABS-570160

  20. Definition of amide protection factors for early kinetic intermediates in protein folding.

    PubMed

    Houry, W A; Sauder, J M; Roder, H; Scheraga, H A

    1998-04-14

    Hydrogen-deuterium exchange experiments have been used previously to investigate the structures of well defined states of a given protein. These include the native state, the unfolded state, and any intermediates that can be stably populated at equilibrium. More recently, the hydrogen-deuterium exchange technique has been applied in kinetic labeling experiments to probe the structures of transiently formed intermediates on the kinetic folding pathway of a given protein. From these equilibrium and nonequilibrium studies, protection factors are usually obtained. These protection factors are defined as the ratio of the rate of exchange of a given backbone amide when it is in a fully solvent-exposed state (usually obtained from model peptides) to the rate of exchange of that amide in some state of the protein or in some intermediate on the folding pathway of the protein. This definition is straightforward for the case of equilibrium studies; however, it is less clear-cut for the case of transient kinetic intermediates. To clarify the concept for the case of burst-phase intermediates, we have introduced and mathematically defined two different types of protection factors: one is P struc, which is more related to the structure of the intermediate, and the other is P app, which is more related to the stability of the intermediate. Kinetic hydrogen-deuterium exchange data from disulfide-intact ribonuclease A and from cytochrome c are discussed to explain the use and implications of these two definitions. PMID:9539731

  1. Study of the aggregation mechanism of polyglutamine peptides using replica exchange molecular dynamics simulations.

    PubMed

    Nakano, Miki; Ebina, Kuniyoshi; Tanaka, Shigenori

    2013-04-01

    Polyglutamine (polyQ, a peptide) with an abnormal repeat length is the causative agent of polyQ diseases, such as Huntington's disease. Although glutamine is a polar residue, polyQ peptides form insoluble aggregates in water, and the mechanism for this aggregation is still unclear. To elucidate the detailed mechanism for the nucleation and aggregation of polyQ peptides, replica exchange molecular dynamics simulations were performed for monomers and dimers of polyQ peptides with several chain lengths. Furthermore, to determine how the aggregation mechanism of polyQ differs from those of other peptides, we compared the results for polyQ with those of polyasparagine and polyleucine. The energy barrier between the monomeric and dimeric states of polyQ was found to be relatively low, and it was observed that polyQ dimers strongly favor the formation of antiparallel β-sheet structures. We also found a characteristic behavior of the monomeric polyQ peptide: a turn at the eighth residue is always present, even when the chain length is varied. We previously showed that a structure including more than two sets of β-turns is stable, so a long monomeric polyQ chain can act as an aggregation nucleus by forming several pairs of antiparallel β-sheet structures within a single chain. Since the aggregation of polyQ peptides has some features in common with an amyloid fibril, our results shed light on the mechanism for the aggregation of polyQ peptides as well as the mechanism for the formation of general amyloid fibrils, which cause the onset of amyloid diseases. PMID:23288093

  2. Comparison study of global and local approaches describing critical phenomena on the Polish stock exchange market

    NASA Astrophysics Data System (ADS)

    Czarnecki, Łukasz; Grech, Dariusz; Pamuła, Grzegorz

    2008-12-01

    We confront global and local methods to analyze the financial crash-like events on the Polish financial market from the critical phenomena point of view. These methods are based on the analysis of log-periodicity and the local fractal properties of financial time series in the vicinity of phase transitions (crashes). The whole history (1991-2008) of Warsaw Stock Exchange Index (WIG) describing the largest developing financial market in Europe, is analyzed in a daily time horizon. We find that crash-like events on the Polish financial market are described better by the log-divergent price model decorated with log-periodic behavior than the corresponding power-law-divergent price model. Predictions coming from log-periodicity scenario are verified for all main crashes that took place in WIG history. It is argued that crash predictions within log-periodicity model strongly depend on the amount of data taken to make a fit and therefore are likely to contain huge inaccuracies. Turning to local fractal description, we calculate the so-called local (time dependent) Hurst exponent H for the WIG time series and we find the dependence between the behavior of the local fractal properties of the WIG time series and the crashes appearance on the financial market. The latter method seems to work better than the global approach - both for developing as for developed markets. The current situation on the market, particularly related to the Fed intervention in September’07 and the situation on the market immediately after this intervention is also analyzed from the fractional Brownian motion point of view.

  3. Orientation and electronic structure of ion exchanged dye molecules on mica: An X-ray absorption study

    SciTech Connect

    Fischer, D.; Caseri, W.R.; Haehner, G.

    1998-02-15

    Dye molecules are frequently used to determine the specific surface area and the ion exchange capacity of high-surface-area materials such as mica. The organic molecules are often considered to be planar and to adsorb in a flat orientation. In the present study the authors have investigated the orientation and electronic structure of crystal violet (CV) and malachite green (MG) on muscovite mica, prepared by immersing the substrates for extended periods into aqueous solutions of the dyes of various concentrations. The K{sup +} ions of the mica surface are replaced by the organic cations via ion exchange. X-ray photoelectron spectroscopy reveals that only one amino group is involved in the interaction of CV and MG with the muscovite surface, i.e., certain resonance structures are abolished upon adsorption. With near edge X-ray absorption fine structure spectroscopy a significant tilt angle with respect to the surface was found for all investigated species. A flat orientation, as has often been proposed before, can effectively be ruled out. Hence, results are in marked contrast to the often quoted orientation and suggest that the specific surface areas determined with dyes may, in general, be overestimated.

  4. Salt-Zeolite Ion Exchange Equilibrium Studies for Complete Set of Fission Products in Molten LiCl-KCl

    SciTech Connect

    Tae-Sic Yoo; Steven M. Frank; Michael F. Simpson; Paula A. Hahn; Terry J. Battisti; Supathorn Phongikaroon

    2010-09-01

    This paper presents results on LiCl-KCl based molten salts/zeolite-A contact experiments and the associated equilibrium ion exchange model. Experiments examine the contact behaviors of various ternary salts (LiCl-KCl-YCl3, LiCl-KCl-LaCl3, and LiCl-KCl-PrCl3) and quaternary salts (LiCl-KCl-CsCl-NdCl3 and LiCl-KCl-CsCl-SrCl2) with the zeolite-A. The developed equilibrium model assumes that there are ion exchange and occlusion sites, both of which are in equilibrium with the molten salt phase. A systematic approach in estimating total occlusion capacity of the zeolite-A is developed. The parameters of the model, including the total occlusion capacity of the zeolite-A, were determined from fitting experimental data collected via multiple independent studies including the ones reported in this paper. Experiments involving ternary salts were used for estimating the parameters of the model, while those involving quaternary salts were used to validate the model.

  5. A Comprehensive Study of the Solubility, Thermochemistry, Ion Exchange, and Precipitation Kinetics of NO3 Cancrinite and NO3 Sodalite

    SciTech Connect

    Colon, Carlos F. Joyce; Navrotsky, Alexandra; Krumhansl, James L.; Nyman, May

    2003-06-01

    NO3 cancrinite and NO3 sodalite haves been found as a common sodium alumino-silicate forming in strongly caustic alkaline aqueous solutions associated with radioactive High Level Waste (HLW) stored in many underground tanks and also in nuclear waste treatment facilities such as the Savannah River Site (SRS). The precipitation of alumino-silicate phases from caustic nuclear wastes has proven to be problematic in a number of processes in waste treatment facilities including radionuclide separations (cementation of columns by aluminosilicate phases), tank emptying (aluminosilicate tank heels), and condensation of wastes in evaporators (aluminosilicate precipitates in the evaporators, providing nucleation sites for growth of critical masses of radioactive actinide salts). Therefore, in order to prevent their formation an assessment of the relative stability, formation kinetics, and the ion-exchange characteristics of these two phases in HLW solutions needs to be investigated. The goals of this project are to: (1) Develop a robust equilibrium thermodynamic framework to accurately describe and predict the formation of NO3 cancrinite and NO3 sodalite. (2) Provide a comprehensive characterization of the solid precipitation rates and mechanisms using novel spectroscopic (e.g., NMR) and thermochemical techniques in conditions encountered in HLW waste solutions. (3) Characterize the precipitation kinetics of the aluminosilicates and study the effects of temperature and fluid composition. (4) Investigate the ion exchange capacity of these zeolitic phases with respect to radionuclides and RCRA metal species.

  6. Comparative study on performance of a zigzag printed circuit heat exchanger with various channel shapes and configurations

    NASA Astrophysics Data System (ADS)

    Lee, Sang-Moon; Kim, Kwang-Yong

    2013-07-01

    Comparative study has been performed with various channel cross-sectional shapes and channel configurations of a zigzag printed circuit heat exchanger (PCHE), which has been considered as a heat exchanging device for the gas turbine based generation systems. Three-dimensional Reynolds-averaged Navier-Stokes equations and heat transfer equations are solved to analyze conjugate heat transfer in the zigzag channels. The shear stress transport model with a low Reynolds number wall treatment is used as a turbulence closure. The global Nusselt number, Colburn j-factor, effectiveness, and friction factor are used to estimate the thermal-hydraulic performance of the PCHE. Four different shapes of channel cross section (semicircular, rectangular, trapezoidal, and circular) and four different channel configurations are tested to determine their effects on thermal-hydraulic performance. The rectangular channel shows the best thermal performance but the worst hydraulic performance, while the circular channel shows the worst thermal performance. The Colburn j-factor and friction factor are found to be inversely proportional to the Reynolds number in cold channels, while the effectiveness and global Nusselt number are proportional to the Reynolds number.

  7. Feasibility and kinetics study on the direct bio-regeneration of perchlorate laden anion-exchange resin.

    PubMed

    Wang, Chao; Lippincott, Lee; Meng, Xiaoguang

    2008-11-01

    Anion exchange is one of the most promising treatment technologies for the removal of low levels of perchlorate. The spent anion-exchange resins, however, need to be disposed of or regenerated because they contain high contents of perchlorate. This study investigated the feasibility and kinetics of a direct bio-regeneration method. The method accomplished resin regeneration and biological perchlorate destruction concurrently, by directly contacting the spent resin with the perchlorate-reducing bacteria (PRB). The results indicated that the method was effective in regeneration of perchlorate and nitrate loaded resin and the resin could be repeatedly regenerated with the method. The regenerated resin was effective, stable, and durable in the filtration treatment of perchlorate in well water from the Saddle River area, NJ. Moreover, the method was also effective in regeneration of the spent A-530E resin, which had high perchlorate affinity and was yet very difficult for regeneration with the conventional brine desorption technique. Besides, the results further suggested that the perchlorate and nitrate desorption from the loaded resin coupling with their subsequent biological reduction could be the direct bio-regeneration mechanism. No biofilm was formed on the regenerated resin surface according to a scanning electron microscopy (SEM) analysis. PMID:18786692

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

    NASA Technical Reports Server (NTRS)

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

    2002-01-01

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

  9. First-principles studies of interlayer exchange coupling in (Ga, Cr)N-based diluted magnetic semiconductor multilayers

    NASA Astrophysics Data System (ADS)

    Luo, M.; Sun, F.; Tang, Z.

    2013-02-01

    Interlayer exchange coupling (IEC) in a series model diluted magnetic semiconductor multilayer consisting of two magnetic (Ga, Cr)N layers separated by non-doped or Mg-doped GaN non-magnetic spacers has been studied by first-principles calculations. The effects of the spacer thickness and hole doping to the IEC were studied systematically. For the GaN spacers without Mg doping, the IEC between two magnetic (Ga, Cr)N layers is always ferromagnetic and is clarified as an intrinsic character of the Ruderman-Kittle-Kasuya-Yoshida interaction based on a two-band model for a gapped system. For the Mg-doped GaN spacers, the IEC is antiferromagnetic, and the antiferromagnetic IEC is stable with increasing the spacer thickness.

  10. First-principles studies of interlayer exchange coupling in (Ga, Co)N-based diluted magnetic semiconductor multilayers

    NASA Astrophysics Data System (ADS)

    Luo, M.; Yin, H. H.; Zhu, Z. Q.

    2012-11-01

    Interlayer exchange coupling (IEC) in a series model diluted magnetic semiconductor (DMS) multilayer consisting of two magnetic (Ga, Co)N layers separated by non-doped or Mg-doped GaN non-magnetic spacers has been studied by first-principles calculations. The effects of the spacer thickness and hole doping to the IEC were studied systematically. It is observed that (1) for the GaN spacers without Mg doping, the IEC between two magnetic (Ga, Co)N layers is always ferromagnetic, which is clarified as an intrinsic character of the Ruderman-Kittle-Kasuya-Yoshida (RKKY) interaction based on a two-band model for a gapped system; and (2) for the Mg-doped GaN spacers, the IEC is tunable from ferromagnetic to antiferromagnetic by varying the spacer’s thickness and the dopant’s site.

  11. Magnetic properties of exchange biased and of unbiased oxide/permalloy thin layers: a ferromagnetic resonance and Brillouin scattering study.

    PubMed

    Zighem, F; Roussigné, Y; Chérif, S-M; Moch, P; Ben Youssef, J; Paumier, F

    2010-10-13

    Microstrip ferromagnetic resonance and Brillouin scattering are used to provide a comparative determination of the magnetic parameters of thin permalloy layers interfaced with a non-magnetic (Al(2)O(3)) or with an antiferromagnetic oxide (NiO). It results from our microstructural study that no preferential texture is favoured in the observed polycrystalline sublayers. It is shown that the perpendicular anisotropy can be monitored using an interfacial surface energy term which is practically independent of the nature of the interface. In the interval of thicknesses investigated (5-25 nm) the saturation magnetization does not significantly differ from the reported one in bulk permalloy. In-plane uniaxial anisotropy and exchange bias anisotropy are also derived from the study of the dynamic magnetic excitations and compared with our independent evaluations using conventional magnetometry. PMID:21386581

  12. A portable hydro-thermo-mechanical loading cell for in situ small angle neutron scattering studies of proton exchange membranes.

    PubMed

    Yu, Dunji; An, Ke; Gao, Carrie Y; Heller, William T; Chen, Xu

    2013-10-01

    A portable hydro-thermo-mechanical loading cell has been designed to enable in situ small angle neutron scattering (SANS) studies of proton exchange membranes (PEMs) under immersed tensile loadings at different temperatures. The cell consists of three main parts as follows: a letter-paper-size motor-driven mechanical load frame, a SANS friendly reservoir that provides stable immersed and thermal sample conditions, and a data acquisition and control system. The ex situ tensile tests of Nafion 212 membranes demonstrated a satisfactory thermo-mechanical testing performance of the cell for either dry or immersed conditions at elevated temperatures. The in situ SANS tensile measurements on the Nafion 212 membranes immersed in D2O at 70 °C proved the feasibility and capability of the cell for small angle scattering study on deformation behaviors of PEM and other polymer materials under hydro-thermo-mechanical loading. PMID:24182171

  13. A portable hydro-thermo-mechanical loading cell for in situ small angle neutron scattering studies of proton exchange membranes

    NASA Astrophysics Data System (ADS)

    Yu, Dunji; An, Ke; Gao, Carrie Y.; Heller, William T.; Chen, Xu

    2013-10-01

    A portable hydro-thermo-mechanical loading cell has been designed to enable in situ small angle neutron scattering (SANS) studies of proton exchange membranes (PEMs) under immersed tensile loadings at different temperatures. The cell consists of three main parts as follows: a letter-paper-size motor-driven mechanical load frame, a SANS friendly reservoir that provides stable immersed and thermal sample conditions, and a data acquisition and control system. The ex situ tensile tests of Nafion 212 membranes demonstrated a satisfactory thermo-mechanical testing performance of the cell for either dry or immersed conditions at elevated temperatures. The in situ SANS tensile measurements on the Nafion 212 membranes immersed in D2O at 70 °C proved the feasibility and capability of the cell for small angle scattering study on deformation behaviors of PEM and other polymer materials under hydro-thermo-mechanical loading.

  14. Subunit exchange of lens alpha-crystallin: a fluorescence energy transfer study with the fluorescent labeled alphaA-crystallin mutant W9F as a probe.

    PubMed

    Sun, T X; Akhtar, N J; Liang, J J

    1998-07-01

    A Trp-free alphaA-crystallin mutant (W9F) was prepared by site-directed mutation. This mutant appears to be identical to the wild-type in terms of conformation (secondary and tertiary structures). W9F was labeled with a sulfhydryl-specific fluorescent probe, 2-(4'-maleimidylanilino) naphthalene-6-sulfonate (MIANS), and used in a subunit exchange between alphaA- and alphaA-crystallins as well as between alphaA- and alphaB-crystallins, studied by measurement of fluorescence resonance energy transfer. Energy transfer was observed between Trp (donor, with emission maximum at 336 nm) of wild-type alphaA- or alphaB-crystallin and MIANS (acceptor, with absorption maximum at 313 nm) of labeled W9F when subunit exchange occurred. Time-dependent decrease of Trp and increase of MIANS fluorescence were recorded. The exchange was faster at 37 degrees C than at 25 degrees C. The energy transfer efficiency was greater between homogeneous subunits (alphaA-alphaA) than between heterogeneous subunits (alphaA-alphaB). A previous exchange study with isoelectric focusing indicated a complete but slow exchange between alphaA and alphaB subunits. The present study showed that the exchange was a fast process, and the different energy transfer efficiencies between alphaA-alphaA and alphaA-alphaB indicated that alphaA- and alphaB-crystallins were not necessarily structurally equivalent. PMID:9688580

  15. Real-time HD Exchange Kinetics of Proteins from Buffered Aqueous Solution with Electrothermal Supercharging and Top-Down Tandem Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Going, Catherine C.; Xia, Zijie; Williams, Evan R.

    2016-02-01

    Electrothermal supercharging (ETS) with electrospray ionization produces highly charged protein ions from buffered aqueous solutions in which proteins have native folded structures. ETS increases the charge of ribonuclease A by 34%, whereas only a 6% increase in charge occurs for a reduced-alkylated form of this protein, which is unfolded and its structure is ~66% random coil in this solution. These results indicate that protein denaturation that occurs in the ESI droplets is the primary mechanism for ETS. ETS does not affect the extent of solution-phase hydrogen-deuterium exchange (HDX) that occurs for four proteins that have significantly different structures in solution, consistent with a droplet lifetime that is considerably shorter than observable rates of HDX. Rate constants for HDX of ubiquitin are obtained with a spatial resolution of ~1.3 residues with ETS and electron transfer dissociation of the 10+ charge-state using a single capillary containing a few μL of protein solution in which HDX continuously occurs. HDX protection at individual residues with ETS HDX is similar to that with reagent supercharging HDX and with solution-phase NMR, indicating that the high spray potentials required to induce ETS do not lead to HD scrambling.

  16. Real-time HD Exchange Kinetics of Proteins from Buffered Aqueous Solution with Electrothermal Supercharging and Top-Down Tandem Mass Spectrometry.

    PubMed

    Going, Catherine C; Xia, Zijie; Williams, Evan R

    2016-06-01

    Electrothermal supercharging (ETS) with electrospray ionization produces highly charged protein ions from buffered aqueous solutions in which proteins have native folded structures. ETS increases the charge of ribonuclease A by 34%, whereas only a 6% increase in charge occurs for a reduced-alkylated form of this protein, which is unfolded and its structure is ~66% random coil in this solution. These results indicate that protein denaturation that occurs in the ESI droplets is the primary mechanism for ETS. ETS does not affect the extent of solution-phase hydrogen-deuterium exchange (HDX) that occurs for four proteins that have significantly different structures in solution, consistent with a droplet lifetime that is considerably shorter than observable rates of HDX. Rate constants for HDX of ubiquitin are obtained with a spatial resolution of ~1.3 residues with ETS and electron transfer dissociation of the 10+ charge-state using a single capillary containing a few μL of protein solution in which HDX continuously occurs. HDX protection at individual residues with ETS HDX is similar to that with reagent supercharging HDX and with solution-phase NMR, indicating that the high spray potentials required to induce ETS do not lead to HD scrambling. Graphical Abstract ᅟ. PMID:26919868

  17. A new approach to measuring protein backbone protection with high spatial resolution using H/D exchange and electron capture dissociation

    PubMed Central

    Abzalimov, Rinat R.; Bobst, Cedric E.; Kaltashov, Igor A.

    2013-01-01

    Inadequate spatial resolution remains one of the most serious limitations of hydrogen/deuterium exchange mass spectrometry (HDX MS), especially when applied to larger proteins (over 30 kDa). Supplementing proteolytic fragmentation of the protein in solution with ion dissociation in the gas phase has been used successfully by several groups to obtain near-residue level resolution. However, the restrictions imposed by the LC/MS/MS mode of operation on the data acquisition time frame makes it difficult in many cases to obtain signal-to-noise ratio adequate for reliable assignment of the backbone amide protection levels at individual residues. This restriction is lifted in the present work by eliminating the LC separation step from the workflow and taking advantage of the high resolving power and dynamic range of a Fourier transform ion cyclotron resonance mass spectrometer (FT ICR MS). A residue-level resolution is demonstrated for a peptic fragment of a 37 kDa recombinant protein (N-lobe of human serum transferrin) using electron-capture dissociation as an ion fragmentation tool. The absence of hydrogen scrambling in the gas phase prior to ion dissociation is verified using redundant HDX MS data generated by FT ICR MS. The backbone protection pattern generated by direct HDX MS/MS is in excellent agreement with the known crystal structure of the protein, but also provides information on conformational dynamics, which is not available from the static X-ray structure. PMID:23978257

  18. Studying temporal and spatial variations of groundwater-surface water exchange flux for the Slootbeek (Belgium) using the LPML method

    NASA Astrophysics Data System (ADS)

    Anibas, Christian; Schneideweind, Uwe; Vandersteen, Gerd; Huysmans, Marijke; Batelaan, Okke

    2015-04-01

    Knowledge of groundwater-surface water interaction is important for the assessment of water resources and for the investigation of fate and transport of contaminants and nutrients. In streams and rivers exchange fluxes of water are sensitive to local and regional factors such as riverbed hydraulic conductivity and hydraulic gradients. Field monitoring in time and space is therefore indispensible for assessing the variability of groundwater-surface water interaction. Not only the complexity of the examined processes demand novel data processing and characterization tools, the amount of acquired data also urges for new modeling tools. These tools should be easily applicable, allow for a fast computation, and utilize the maximum amount of available data for detailed analysis, including uncertainties. Such analytical tools should be combined with modern field equipment, data processing tools, geographical information systems and geostatistics for best results. A simple and cost effective methodology to estimate groundwater-surface water interaction is the use of temperature as an environmental tracer (ANDERSON, 2005). LPML (VANDERSTEEN et al., 2014) is one of the most advanced analytical 1D coupled water flow and heat transport models, combining a local polynomial method with a maximum likelihood estimator. It is flexible, fast and able to create time series of exchange fluxes, as well as model quality and parameter uncertainty. LPML determines frequency response functions from measured temperature time series and an analytical model, and applies a non-linear optimization technique. With this tool the variability of groundwater-surface water interaction of the Belgian stream Slootbeek was assessed. Multilevel temperature sensors were placed in seven locations to obtain temperature-time series. Located at the streambed top and at six depths below, several months worth of data was collected and analyzed. Results identified a high spatial and temporal variability of vertical exchange fluxes for the investigated stream section. Fluxes ranged from strong exfiltration of -450 mm/d to infiltration fluxes of 110 mm/d. Events of high stream stages strongly influenced groundwater-surface water interaction, changing the normally gaining reach into a losing one. Measurements of vertical hydraulic gradients were used for validation. It was possible to relate the flow system of Slootbeek to earlier studies performed in the catchment (e.g. ANIBAS et al., 2009) to further advance the understanding of the regional groundwater flow system. These results show that the presented LPML methodology is flexible, fast and able to create reliable time series of groundwater-surface water interaction and their uncertainties. References ANDERSON, M.P. (2005): Heat as a Groundwater Tracer. Ground Water 43 (6): 951-968. ANIBAS, C., FLECKENSTEIN, J.H., VOLZE, N., BUIS, K., VERHOEVEN, R., MEIRE, P., BATELAAN, O. (2009): Transient or steady-state? Using vertical temperature profiles to quantify groundwater-surface water exchange. Hydrological Processes 23(15) 2165-2177. VANDERSTEEN, G., SCHNEIDEWIND, U., ANIBAS, C., SCHMIDT, C., SEUNTJENS, P., BATELAAN, O. (2014): Determining groundwater-surface water exchange from temperature time series: Combining a local polynomial method with a maximum likelihood estimator. Water Resour. Res. DOI: 10.1002/2014wr015994.

  19. Short-Term Faculty-Led Study Abroad Programs Enhance Cultural Exchange and Self-Awareness

    ERIC Educational Resources Information Center

    Gaia, A. Celeste

    2015-01-01

    Though many experts argue that semester or year abroad study is the optimal path, short-term programs meet the needs of students who would not otherwise study abroad and can be effective at increasing intercultural competency. The present study describes one type of short-term program--the embedded faculty-led model--and provides evidence that…

  20. Exploring Knowledge Exchange between Senior and Future Leaders: A Grounded-Theory Study

    ERIC Educational Resources Information Center

    Gonzaga, Stephanie Young

    2009-01-01

    A grounded theory study examined senior leaders methods of knowledge sharing with junior leaders in a small commercial mortgage company. The study was designed to develop an emergent theory to explain the cultural elements that influenced the methods leaders used to transfer knowledge to junior people. The study identified a systemic value of…

  1. Exploring Knowledge Exchange between Senior and Future Leaders: A Grounded-Theory Study

    ERIC Educational Resources Information Center

    Gonzaga, Stephanie Young

    2009-01-01

    A grounded theory study examined senior leaders methods of knowledge sharing with junior leaders in a small commercial mortgage company. The study was designed to develop an emergent theory to explain the cultural elements that influenced the methods leaders used to transfer knowledge to junior people. The study identified a systemic value of

  2. Mass transport studies in conventional and microfabricated free convection proton exchange membrane fuel cells

    NASA Astrophysics Data System (ADS)

    Modroukas, Dean

    This thesis presents the design, modeling and testing of both conventional and non-conventional free convection proton exchange membrane fuel cells (PEMFC) which are particularly attractive for low power (<100W), man portable applications. As part of this investigation, experimental data coupled with computational simulations has provided a deeper understanding into the mechanisms that limit operability. In particular, the low temperatures of operation (<50°C) and lack of forced air convection generate high levels of saturation within the cell thereby reducing the available catalytic sites. A 2-D, single- and two-phase computational model for an open-cathode, free convection PEMFC was developed. The two-phase modeling has provided significant insight into the mass transport limitations caused primarily by liquid water flooding while the single phase simulations present an upper limit in performance assuming product water exists only in vapor form. A set of parametric experiments were performed using conventional gas diffusion media (GDM) along with numerous 1cm2 stainless steel grid-based current collectors having open area ratios of 10%, 25% and 50%. These experiments provided a data set that was used to "tune" and validate the model. Single cell polarization data experienced limiting currents ranging from 190mA/cm2 to 600mA/cm 2 at operating cell temperatures of 38°C-45°C, depending on the open area ratio. The two-phase model captured the effect of current collector porosity as well as the increase in limiting current associated with rising cell temperature. Once validated, the model was used with confidence as a design tool for MEMS-based tailored mass transfer media (TMTM) that provide more advanced functionality than customary GDM. They were based on a microfabricated hydrophobic silicon mesh comprised of square pores with discrete zones made to be hydrophilic using a carbon-polyethylene oxide treatment. The TMTM were engineered to localize the removal of liquid water and allow saturation free transport of the gas phases to and from the catalyst layer. The hydrophilic zone spacing distance was varied (1250mum and 2500mum) while keeping the overall wetting to non-wetting area ratio at 12.5%. The TMTM were tested using conventional catalyst on membrane assemblies at low temperatures (ambient and 32.5°C) and were shown to efficiently segregate water and provide unobstructed reactant gas paths to the cell. The ability to control the wetting characteristics of these structures and provided enhanced evaporation to the surroundings has resulted in significant increases in steady state limiting current densities compared to untreated silicon structures (the latter of which delivered 100mA/cm2 and 133mA/cm 2 at 26.6°C and 33.1°C, respectively). Liquid water transport within the catalyst layer has been shown to be a function of the hydrophilic spacing where the TMTM having a hydrophilic separation distance of 1250mum delivered higher limiting current densities (148.9mA/cm2 and 250mA/cm2 for ambient and 32.5°C) than the larger separation distance of 2500mum (134mA/cm2 and 175mA/cm2 for ambient and 32.5°C). Limiting current performance improvements between the treated and untreated substrates ranged from 34-50% at ambient temperature to 32-88% at the 32.5°C operating temperature. In summary, the work presented herein will not only advance the state of the art in miniaturizing PEMFC's using MEMS technology but it will also open up a path for a more scientific approach to understanding multi-phase transport within porous fuel cell layers and interfaces.

  3. Science exchanges

    NASA Astrophysics Data System (ADS)

    Richman, Barbara T.

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

  4. Perpendicular exchange bias behaviors of CoPt/IrMn and CoPt/FeMn bilayers: A comparative study

    SciTech Connect

    Tsai, C. Y.; Lin, K. F.; Hsu, Jen-Hwa

    2015-05-07

    In this study, FeMn was introduced as an antiferromagnetic (AFM) layer to couple with a single-layered Co{sub 49}Pt{sub 51} alloy thin film, and it was compared with a Co{sub 49}Pt{sub 51}/IrMn bilayer system in exchange bias (EB) effect, to explore the mechanism of spontaneous perpendicular exchange bias (PEB), which has been recently observed in CoPt/IrMn bilayers. Bilayers of CoPt/IrMn and CoPt/FeMn were prepared under the same conditions by sputtering at room temperature without any inducing field. Although PEB was observed in as-grown CoPt/FeMn bilayers, the loop shape and PEB behavior were found to exhibit different characteristics from those of CoPt/IrMn bilayers. The CoPt (5 nm)/FeMn (10 nm) bilayer has a sheared loop that is similar to a double-shifted loop and a much lower squareness ratio (SQR = 0.52) and exchange bias field (H{sub e} = 180 Oe) than the CoPt (5 nm)/IrMn (10 nm) system, which has a rectangular loop shape and a high SQR of 0.97 and large H{sub e} of 290 Oe. The two systems present entirely different dependences of PEB on the thickness of the AFM layer. CoPt/IrMn exhibits behavior that is typical of most EB systems, but for CoPt/FeMn, this dependence is more complicated with an unusual peak at an AFM layer thickness of 10 nm. Based on the dissimilar loop shapes and dependences of PEB on AFM thickness, the mechanisms of the spontaneously established PEB in these two systems are considered to differ. Investigations of cross-sectional transmission electron microscopy revealed no apparent difference between the interfacial microstructures of the two systems. X-ray diffraction studies demonstrated the 〈111〉 texture of both systems. Therefore, different interfacial spin configurations may be responsible for the dissimilar PEB behaviors in these two FM/AFM bilayer systems.

  5. FAST TRACK COMMUNICATION: Study of low-energy resonant metastability exchange in argon by a pulsed merging beam technique

    NASA Astrophysics Data System (ADS)

    Grucker, J.; Baudon, J.; Perales, F.; Dutier, G.; Vassilev, G.; Bocvarski, V.; Ducloy, M.

    2008-01-01

    The resonant metastability exchange process in low-energy collinear collisions between metastable argon atoms (Ar* 3P2) polarized in spin (M = +2) and ground-state Ar atoms from a nozzle beam is studied by means of a time-of-flight technique. A wide range of metastable atom velocities in the laboratory frame (275 m s-1 down to 50 m s-1) is obtained by use of a Zeeman slower, the counter-propagating laser beam of which is locked in frequency onto the 3P2-3D3 closed transition (λ = 811.5 nm). The accessible centre-of-mass energy range (8-27 meV) has not been explored so far, to our knowledge. Calculations based upon existing interatomic potentials of 2g and 2u symmetries are in reasonable agreement with experiment.

  6. An sup 17 O NMR study on oxygen exchange in YBa sub 2 Cu sub 3 O sub 7-x

    SciTech Connect

    Ramli, E.; Ganja, E.A.; Reven, L.; Oldfield, E.; Rauchfuss, T.B. )

    1990-06-01

    This study evaluated the effect of reaction conditions on the extent and uniformity of {sup 17}O-labeled YBa{sub 2}Cu{sub 3}O{sub 7-x}. It was shown by {sup 17}O NMR spectroscopy and high-resolution SIMS that statistical {sup 17}O-enrichment is achieved at high temperatures by synthesis from oxides under an {sup 17}O{sub 2} atmosphere, or by direct {sup 17}O{sub 2} exchange of preformed YBa{sub 2}Cu{sub 3}O{sub 7-x}. Nonuniform enrichment can be achieved at low temperatures and with the use of short reaction times. An {sup 17}O{sub 2} circulator is described which proved useful for handling, purifying, and recovering the labeled oxygen.

  7. Neutralizing positive charges at the surface of a protein lowers its rate of amide hydrogen exchange without altering its structure or increasing its thermostability.

    PubMed

    Shaw, Bryan F; Arthanari, Haribabu; Narovlyansky, Max; Durazo, Armando; Frueh, Dominique P; Pollastri, Michael P; Lee, Andrew; Bilgicer, Basar; Gygi, Steven P; Wagner, Gerhard; Whitesides, George M

    2010-12-15

    This paper combines two techniques--mass spectrometry and protein charge ladders--to examine the relationship between the surface charge and hydrophobicity of a representative globular protein (bovine carbonic anhydrase II; BCA II) and its rate of amide hydrogen-deuterium (H/D) exchange. Mass spectrometric analysis indicated that the sequential acetylation of surface lysine-ε-NH3(+) groups--a type of modification that increases the net negative charge and hydrophobicity of the surface of BCA II without affecting its secondary or tertiary structure--resulted in a linear decrease in the aggregate rate of amide H/D exchange at pD 7.4, 15 °C. According to analysis with MS, the acetylation of each additional lysine generated between 1.4 and 0.9 additional hydrogens that are protected from H/D exchange during the 2 h exchange experiment at 15 °C, pD 7.4. NMR spectroscopy demonstrated that none of the hydrogen atoms which became protected upon acetylation were located on the side chain of the acetylated lysine residues (i.e., lys-ε-NHCOCH3) but were instead located on amide NHCO moieties in the backbone. The decrease in rate of exchange associated with acetylation paralleled a decrease in thermostability: the most slowly exchanging rungs of the charge ladder were the least thermostable (as measured by differential scanning calorimetry). This observation--that faster rates of exchange are associated with slower rates of denaturation--is contrary to the usual assumptions in protein chemistry. The fact that the rates of H/D exchange were similar for perbutyrated BCA II (e.g., [lys-ε-NHCO(CH2)2CH3]18) and peracetylated BCA II (e.g., [lys-ε-NHCOCH3]18) suggests that the electrostatic charge is more important than the hydrophobicity of surface groups in determining the rate of H/D exchange. These electrostatic effects on the kinetics of H/D exchange could complicate (or aid) the interpretation of experiments in which H/D exchange methods are used to probe the structural effects of non-isoelectric perturbations to proteins (i.e., phosphorylation, acetylation, or the binding of the protein to an oligonucleotide or to another charged ligand or protein). PMID:21090618

  8. An Ethnographic Study of Elementary Teachers', Paraprofessionals', and Students' Language Exchanges during Reading

    ERIC Educational Resources Information Center

    Aaron-Stanton, Desiree

    2014-01-01

    This ethnographic study of language shows the importance of educators' appropriate use of linguistic, nonlinguistic, and paralinguistic communication techniques when working with elementary students within two classrooms who have behavioral and emotional disorders. This study focused on communication techniques used by teachers and…

  9. Cross-cultural exchange: How students can frustrate the aims of study abroad programmes

    NASA Astrophysics Data System (ADS)

    Barnes, Leslie R.

    1982-09-01

    Readily accepting that study abroad programmes may have as many differing forms and aims as there are participating institutions, and that by no means all programmes include academic content in their goals, I would nevertheless maintain: 1. that a sociological perspective is as necessary as the hitherto predominantly psychological approach in obtaining a balanced assessment of study abroad programmes;

  10. An Ethnographic Study of Elementary Teachers', Paraprofessionals', and Students' Language Exchanges during Reading

    ERIC Educational Resources Information Center

    Aaron-Stanton, Desiree

    2014-01-01

    This ethnographic study of language shows the importance of educators' appropriate use of linguistic, nonlinguistic, and paralinguistic communication techniques when working with elementary students within two classrooms who have behavioral and emotional disorders. This study focused on communication techniques used by teachers and

  11. Web-based documentation system with exchange of DICOM RT for multicenter clinical studies in particle therapy

    NASA Astrophysics Data System (ADS)

    Kessel, Kerstin A.; Bougatf, Nina; Bohn, Christian; Engelmann, Uwe; Oetzel, Dieter; Bendl, Rolf; Debus, Jürgen; Combs, Stephanie E.

    2012-02-01

    Conducting clinical studies is rather difficult because of the large variety of voluminous datasets, different documentation styles, and various information systems, especially in radiation oncology. In this paper, we describe our development of a web-based documentation system with first approaches of automatic statistical analyses for transnational and multicenter clinical studies in particle therapy. It is possible to have immediate access to all patient information and exchange, store, process, and visualize text data, all types of DICOM images, especially DICOM RT, and any other multimedia data. Accessing the documentation system and submitting clinical data is possible for internal and external users (e.g. referring physicians from abroad, who are seeking the new technique of particle therapy for their patients). Thereby, security and privacy protection is ensured with the encrypted https protocol, client certificates, and an application gateway. Furthermore, all data can be pseudonymized. Integrated into the existing hospital environment, patient data is imported via various interfaces over HL7-messages and DICOM. Several further features replace manual input wherever possible and ensure data quality and entirety. With a form generator, studies can be individually designed to fit specific needs. By including all treated patients (also non-study patients), we gain the possibility for overall large-scale, retrospective analyses. Having recently begun documentation of our first six clinical studies, it has become apparent that the benefits lie in the simplification of research work, better study analyses quality and ultimately, the improvement of treatment concepts by evaluating the effectiveness of particle therapy.

  12. Prospects for HERMES-spin structure studies at HERA

    SciTech Connect

    Jackson, H.E.

    1994-12-31

    HERMES (HERA Measurement of Spin), is a second generation experiment to study the spin structure of the nucleon by using polarized internal gas targets in the HERA 35-GeV electron storage ring. Scattered electrons and coincident hadrons will be detected in an open geometry spectrometer which will include particle identification. Measurements are planned for each of the inclusive structure functions, g{sub 1},(x), g{sub 2}(x), b{sub 1}(x) and A(x), as well as the study of semi-inclusive pion and kaon asymmetries. Targets of hydrogen, deuterium and {sup 3}He will be studied. The accuracy of data for the inclusive structure functions will equal or exceed that of current experiments. The semi-inclusive asymmetries will provide a unique and sensitive probe of the flavor dependence of quark helicity distributions and properties of the quark sea. Monte Carlo simulations of HERMES data for experiment asymmetries and polarized structure functions are discussed.

  13. Modification of acid sites in ZSM-5 by ion-exchange: An in-situ FTIR study

    NASA Astrophysics Data System (ADS)

    Wu, Weiqiang; Weitz, Eric

    2014-10-01

    A study of the acid sites in Mn+-ZSM-5 zeolites (Mn+ = H+, Al3+, Ca2+, and Ba2+), synthesized by ion-exchange from the NH4+ form, has been carried out using X-ray diffraction, 27Al MAS NMR, and in-situ FTIR spectroscopy. X-ray diffraction data indicate that the crystalline structure of ZSM-5 is maintained on ion-exchange. 27Al MAS NMR spectroscopy confirms that Lewis acid sites in all of the Mn+-ZSM-5 zeolites are mainly located on the tetrahedral aluminum atoms in the zeolite framework. However, octahedral extra-framework aluminum is another source of Lewis acid sites in H+-ZSM-5 and Al3+-ZSM-5. Brønsted acid sites are identified as originating from the hydroxyl groups that bridge Al and Si atoms. The acid sites in Mn+-ZSM-5 have been characterized by in-situ FTIR spectroscopy with pyridine as the probe molecule. FTIR spectroscopy demonstrated that the number of accessible acid sites and ratio of Lewis to Brønsted acid sites in Mn+-ZSM-5 can be effectively modified by ion-exchange. The number of acid sites in Mn+-ZSM-5 increases in the same order as the acidity of cations with Ba2+ < Ca2+ < NH4+ < Al3+ < H+. Though the strength of both Lewis and Brønsted acid sites is virtually identical for all Mn+-ZSM-5 zeolites, the ratio of Brønsted to Lewis acid sites varies as a result of the loaded cation. In addition, modification of acid sites in Mn+-ZMS-5 by loading different cations is discussed in terms of the accessibility of the surface of the zeolite channels and the reactivity of the cations with Brønsted acid hydroxyls. We conclude that larger cations can effectively constrict the zeolite channels and impede the ability of pyridine to access acid sites on the surface of the channels.

  14. Heat exchanger

    DOEpatents

    Wolowodiuk, Walter

    1976-01-06

    A heat exchanger of the straight tube type in which different rates of thermal expansion between the straight tubes and the supply pipes furnishing fluid to those tubes do not result in tube failures. The supply pipes each contain a section which is of helical configuration.

  15. Heat exchanger

    DOEpatents

    Daman, Ernest L.; McCallister, Robert A.

    1979-01-01

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

  16. Study the adsorption of sulfates by high cross-linked polystyrene divinylbenzene anion-exchange resin

    NASA Astrophysics Data System (ADS)

    Fathy, Mahmoud; Moghny, Th. Abdel; Awadallah, Ahmed E.; El-Bellihi, Abdel-Hameed A.-A.

    2014-11-01

    In response to rising concerns about the effect of sulfate on water quality, human health, and agriculture, many jurisdictions around the world are imposing tighter regulations for sulfate discharge. This is driving the need for environmental compliance in industries like mining, metal processing, pulp and paper, sewage treatment, and chemical manufacturing. The sulfate removal from synthetic water by high cross-linked polystyrene divinylbenzene resin was studied at batch experiments in this study. The effect of pH, contact time, sulfates concentration, and adsorbent dose on the sulfate sequestration was investigated. The optimum conditions were studied on Saline water as a case study. The results showed that with increasing of the absorbent amount; contact time, and pH improve the efficiency of sulfate removal. The maximum sulfates uptake was obtained in pH and contact time 3.0 and 120 min, respectively. Also, with increasing initial concentration of sulfates in water, the efficiency of sulfate removal decreased. The obtained results in this study were matched with Freundlich isotherm and pseudo-second-order kinetic. The maximum adsorption capacity (Qm) and constant rate were found 0.318 (mg/g) and 0.21 (mg/g.min), respectively. This study also showed that in the optimum conditions, the sulfate removal efficiency from Saline water by 0.1 mg/L sulfates was 65.64 %. Eventually, high cross-linked polystyrene divinylbenzene resin is recommended as a suitable and low cost absorbent to sulfate removal from aqueous solutions.

  17. Numerical study of heat transfer in two-row heat exchangers having extended fin surfaces

    SciTech Connect

    Sheui, T.W.H.; Tsai, S.F.; Chiang, T.P.

    1999-05-28

    This paper reports on a three-dimensional study of air through two-row cylinder tubes. The analysis is intended to present a comparison of numerical and experimental data to validate the laminar flow postulation. The current study explores the influence of four perforated fin surfaces on the pressure drop and heat transfer rate. To gain further insight into the three-dimensional vortical flow structure, the authors conduct a topological study of the velocity field. Examination of the surface flow topology and the flow patterns at cross-flow plumes sheds some light on the complex interaction of the cylinder tube with the mainstream flow. This study clearly reveals a saddle point in front of the first row of cylinder tubes. Also clearly revealed by the computed solutions is a flow reversal found in the wake of the tube. The character of the critical-point-induced flow is also addressed. This study shows that the addition of perforated fins is not without deficiency. There is, in fact, a trade-off between the benefit of having an improved heat transfer and the penalty of having an increased pressure drop.

  18. LAB STUDY ON REGENERATION OF SPENT DOWEX 21K 16-20 MESH ION EXCHANGE RESIN

    SciTech Connect

    DUNCAN, J.B.

    2007-01-24

    Currently the effort to remove chromate from groundwater in the 100K and 100H Areas uses DOWEX 21K 16-20. This report addresses the procedure and results of a laboratory study for regeneration of the spent resin by sodium hydroxide, sulfuric acid, or sodium sulfate to determine if onsite regeneration by the Effluent Treatment Facility is a feasible option.

  19. Student Exchange Program Advances Foreign Language Study at Crow High School.

    ERIC Educational Resources Information Center

    Kelsh, Bruce

    1982-01-01

    Oregon's low requirements for foreign language instruction at the secondary school level have caused Oregon students to place well below the national average in foreign language preparation, according to this report. The Oregon Governor's Commission on Foreign Language and International Studies, created in 1980, recommended substantial increases…

  20. Infrared and neutron scattering studies of ethene adsorbed onto partially exchanged zinc A zeolite

    SciTech Connect

    Howard, J.; Nicol, J.M.; Eckert, J.

    1984-08-01

    Infrared and inelastic neutron scattering studies of ethene adsorbed onto ZnNaA zeolite show that the adsorbed molecule occupies a single adsorption site. The C-H streching modes are not observed in the infrared data but are seen as a broad band in the neutron spectrum. Some low frequency adsorbate-adsorbent modes are assigned.

  1. A Longitudinal Study of Teachers' Professional Development through an International Exchange

    ERIC Educational Resources Information Center

    Purves, Ross; Jackson, Anita; Shaughnessy, Julie

    2005-01-01

    The Teachers' International Professional Development (TIPD) Programme was launched by the British Council in 2000 in response to a Government Green Paper on teacher training. This provides opportunities for teachers to participate in international study visits to gain first-hand experience of good practice. As part of this programme, eighteen…

  2. Toward a Checklist for Exchange and Interpretation of Data froma Toxicology Study

    EPA Science Inventory

    With the advent of toxicogenomics came the need to share data across interdisciplinary teams and to deposit data associated with publications into public data repositories. Within a single institution, many variables associated with a study are standardized, for instance diet, an...

  3. Cultural Exchange and the Implementation of Evidence-Based Practices: Two Case Studies

    ERIC Educational Resources Information Center

    Palinkas, Lawrence A.; Aarons, Gregory A.; Chorpita, Bruce F.; Hoagwood, Kimberly; Landsverk, John; Weisz, John R.

    2009-01-01

    Objective: The dynamics of interactions between evidence-based intervention (EBI) developers and trainers and organizations and providers that deliver the EBI was examined in two case studies, a statewide randomized effectiveness trial of an EBI to reduce child neglect and a randomized trial of EBIs for depression, anxiety, and conduct problems in…

  4. Foreign Exchange: School Leaders Find Tangible Benefits in Their Overseas Educational Study Missions

    ERIC Educational Resources Information Center

    Brzozowski, Carol

    2004-01-01

    Collier's lesson in universal educational experiences versus culture, illustrates the eye-opening experience of a few dozen U.S. school leaders who each year travel abroad on organized educational study missions. They are doing so in an effort to build bridges, share the perspective of the United States' educational system, learn about global…

  5. Mutagenicity of inhalation anaesthetics studied by the sister chromatid exchange test in lymphocytes of patients and operating room personnel.

    PubMed

    Husum, B

    1987-06-01

    Retrospective studies have indicated that operating room personnel may have increased risks of spontaneous abortion, congenital malformations in offspring, and cancer (Cohen et al 1980, Buring et al 1985). Occupational exposure to waste anaesthetic gases may be responsible for these possible adverse health effects, but a cause-effect relationship has never been proved. Induction of changes in the DNA in the chromosomes leading to mutations may play a role in teratogenicity and carcinogenicity. Along with an increasing concern in society regarding occupational diseases and working and living environment in general, cytogenetic methods have been developed for rapid detection of potential mutagenicity in vitro of chemical agents. One such method is the SCE test, which is based on examination of sister chromatid exchanges (SCEs), i.e. exchanges of chromatid-segments between the two chromatids in a chromosome, during cell replication. SCEs are not mutations, but an increased frequency of SCE is a sensitive indicator of exposure to agents that are capable of producing damage to the DNA and thus possibly mutations. In vitro tests like the SCE test are very useful for evaluation of specific chemical agents, which may be added to the culture in known concentrations. In studies of possible hazards from chemical agents in the working or living environment, the exposure is often poorly defined. Also, biotransformation may be different in different species, and the duration and the level of the exposure may play a role. Examination of SCEs is, therefore, increasingly performed directly on human lymphocytes from peripheral blood. Thus, although the examination of SCEs is still performed in vitro, the exposure has taken place in vivo. Increased SCE levels are then regarded as a non-specific indicator that the donor has been exposed to potentially mutagenic agents in the environment. The author and his associates used the SCE test to investigate the possible mutagenicity of anaesthetic gases after exposure in vivo. From extensive methodologic studies of possible confounding factors it was concluded that each of the factors sex, age, and smoking habits contributed significantly to the interpersonal variation of SCE frequencies, whereas use of oral contraceptives did not influence the SCE rates. The potential mutagenicity of inhalation anaesthetics was studied after exposure in vivo in two settings: (1) Acute exposure to anaesthetic concentrations, and (2) Chronic occupational exposure to trace concentrations.(ABSTRACT TRUNCATED AT 400 WORDS) PMID:3297512

  6. Synchronous brain activity during cooperative exchange depends on gender of partner: A fNIRS-based hyperscanning study.

    PubMed

    Cheng, Xiaojun; Li, Xianchun; Hu, Yi

    2015-06-01

    Previous studies have shown that brain activity between partners is synchronized during cooperative exchange. Whether this neural synchronization depends on the gender of partner (i.e., opposite or same to the participant) is open to be explored. In current study, we used functional near-infrared spectroscopy (fNIRS) based hyperscanning to study cooperation in a two-person game (female-female, female-male, and male-male) while assaying brain-to-brain interactions. Cooperation was greater in male-male pairs than in female-female pairs, with intermediate cooperation levels for female-male pairs. More importantly, in dyads with partners with opposite gender (female-male pairs), we found significant task-related cross-brain coherence in frontal regions (i.e., frontopolar cortex, orbitofrontal cortex, and left dorsolateral prefrontal cortex) whereas the cooperation in same gender dyads (female-female pairs and male-male pairs) was not associated with such synchronization. Moreover, the changes of such interbrain coherence across task blocks were significantly correlated with change in degree of cooperation only in mixed-sex dyads. These findings suggested that different neural processes underlie cooperation between mixed-sex and same-sex dyadic interactions. PMID:25691124

  7. Decomposition Pathways of Tetraalkylammonium Hydroxides: Experimental and DFT Studies and Their Implications for Alkaline Exchange Fuel Cell Membranes

    SciTech Connect

    Pivovar, B. S.; Edson, J. B.; Macomber, C. S.; Long, H.; Boncella, J. M.

    2012-01-01

    The mechanism of the thermal decomposition of a series of alkyl trimethyl ammonium hydroxides ([RMe{sub 3}N][OH], R = Et, n-Pr, i-Bu, PhCH{sub 2}, Me{sub 3}CCH{sub 2}) was studied using TGA, evolved gas analysis and NMR spectroscopy due to the importance of these and related ions in anion exchange fuel cell membranes. Isotopic labeling with deuterium showed that deprotonation of the methyl groups of the ammonium ions by deuteroxide establishes a rapid equilibrium between the tetraalkyl ammonium ions and the nitrogen ylide species and water that scrambles the deuterium with the proton on the methyl groups. The products of the thermal decomposition when R = Et, n-Pr, i-Bu are predominately olefins arising from Hoffmann elimination, while the neopentyl substituted ammonium ion gives only neopentyl trimethyl amine and methanol, the products of S{sub N}2 attack of hydroxide on the methyl groups. DFT studies of these reactions confirm the relative activation barriers that are observed in the experimental decomposition studies.

  8. The ESA SMOS+SOS Project: Oceanography using SMOS for innovative air-sea exchange studies

    NASA Astrophysics Data System (ADS)

    Banks, Chris; Gommenginger, Christine; Boutin, Jacqueline; Reul, Nicolas; Martin, Matthew; Ash, Ellis; Reverdin, Gilles; Donlon, Craig

    2013-04-01

    We report on the work plan of the SMOS+Surface Ocean Salinity and Synergy (SMOS+SOS) project. SMOS+SOS is funded through the Support to Science Element (STSE) component of the European Space Agency's (ESA) Earth Observation Envelope Programme. The SMOS+SOS consortium consists of four organisations namely the National Oceanography Centre (UK), the LOCEAN/IFREMER/CATDS research team (France), the Met Office (UK) and Satellite Oceanographic Consultants Ltd (UK). The end of the SMOS+SOS project will be marked by a final open workshop most likely hosted by the UK Met Office in September/October 2014. The project is concerned with demonstrating the performance and scientific value of SMOS Sea Surface Salinity (SSS) products through a number of well-defined case studies. The case studies include: Amazon/Orinoco plumes (freshwater outflow); Agulhas and Gulf Stream (strong water mass boundary); Tropical Pacific/Atlantic (strong precipitation regime); sub-tropical North Atlantic (ie SPURS; strong evaporative regime); and Equatorial Pacific (equatorial upwelling). With SMOS measuring the SSS in the top cm of the ocean, validating SMOS against in situ salinity data taken typically at a few meters depth introduces assumptions about the vertical structure of salinity in the upper ocean. To address these issues, the project will examine and quantify discrepancies between SMOS and in situ surface salinity data at various depths in different regions characterised by strong precipitation or evaporation regimes. Equally, data editing and spatio-temporal averaging play a central role in determining the quality, errors and correlations in SMOS SSS data. The project will explore various processing and spatio-temporal averaging choices to define the SMOS SSS products that best address the needs of the oceanographic and data assimilation user community. One key aspect of this project is to determine how one can achieve useful accuracy/uncertainty in SSS without jeopardising SMOS's ability to capture rapidly-varying or small scale features such as rain cells or the mesoscale variability associated with river plumes and major western boundary currents. Finally, the study explores the ability of SMOS SSS to provide insights into new oceanographic processes when used in synergy with other data. Hence, synergy with Aquarius will be used to seek evidence of the possible impact of diurnal warming on the SMOS SSS data, and to explore differences in the salinity signatures of Tropical Instability Waves observed in the Pacific with SMOS and Aquarius.

  9. Parametric study of graphite foam fins and application in heat exchangers

    NASA Astrophysics Data System (ADS)

    Collins, Michael

    This thesis focuses on the simulation and experimental studies of finned graphite foam extended surfaces to test their heat transfer characteristics and potential applications in condensers. Different fin designs were developed to conduct a parametric study on the thermal effectiveness with respect to thickness, spacing and fin offset angle. Each fin design was computationally simulated to estimate the heat transfer under specific conditions. The simulations showed that this optimal fin configuration could conduct more than 297% the amount of thermal energy as compared to straight aluminum fins. Graphite foam fins were then implemented into a simulation of the condenser system. The condenser was simulated with six different orientations of baffles to examine the incoming vapor and resulting two-phase flow patterns. The simulations showed that using both horizontal and vertical baffling provided the configuration with the highest heat transfer and minimized the bypass regions where the vapor would circumvent the graphite foam. This baffle configuration increased the amount of vapor flow through the inner graphite fins and cold water pipes, which gave this configuration the highest heat transfer. The results from experimental tests using the condenser system confirmed that using three baffles will increase performance consistent with the simulation results. The experimental data showed that the condenser using graphite foam had five times the heat transfer compared to the condenser using only aluminum fins. Incorporating baffles into the condenser using graphite foam enabled this system to conduct nearly ten times more heat transfer than the condenser system which only had aluminum fins without baffles. The results from this research indicate that graphite foam is a far superior material heat transfer enhancement material for heat transfer compared to aluminum used as an extended surface. The longitudinal and horizontal baffles incorporated into the condenser system greatly enhanced the heat transfer because of the increased interaction with the porous graphite foam fins.

  10. Microtube Strip Heat Exchanger

    SciTech Connect

    Doty, F.D.

    1990-12-27

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

  11. Attenuated total reflection infrared studies of oleate and trioctylphosphine oxide ligand adsorption and exchange reactions on CdS quantum dot films.

    PubMed

    Young, Aidan G; Al-Salim, Najeh; Green, David P; McQuillan, A James

    2008-04-15

    Ligand exchange reactions at the surface of oleate- and trioctylphosphine oxide (TOPO)-capped CdS quantum dots have been studied with attenuated total reflection infrared (ATR-IR) spectroscopy, using thin films deposited from organic solvent suspensions. The oleate and trioctylphosphine capping ligands were found to form highly ordered and densely packed monolayers on the CdS surface. Adsorbed oleate is coordinated to CdS in a chelating bidentate manner through the carboxylate functional group, while adsorbed trioctylphosphine oxide is coordinated though the P=O functional group and appears to have numerous adsorption environments on the CdS surface. Exposure of such films to aqueous solution was found to cause partial delamination of the films from the ATR prism interface which was reversible upon redrying. Ligand exchange reactions on the oleate- and trioctylphosphine-capped CdS films were studied in situ at room temperature by allowing the films to be exposed to dilute aqueous solutions of thiol-containing ligands. Oleate and trioctylphosphine oxide are both strongly adsorbed to the CdS surface, and ligand exchange with monothiol-containing ligands has been found to be highly dependent upon experimental conditions, in particular pH, where exchange is only observed at solution pH where the exchanging ligand is uncharged. This is attributed to the inability of a charged ligand to penetrate the hydrophobic polymethylene layer on the CdS surface. PMID:18312011

  12. Electrical conductivity and humidity sensing studies on synthetic organic-inorganic Poly-o-toluidine-titanium(IV)phosphate cation exchange nanocomposite

    NASA Astrophysics Data System (ADS)

    Khan, Asif Ali; Baig, Umair

    2013-01-01

    Electrically conductive Poly-o-toluidine-titanium(IV)phosphate (POT-TiP) cation exchange nanocomposite was synthesized by sol-gel mixing of organic polymer (Poly-o-toluidine) into inorganic precipitate of titanium(IV)phosphate (TiP). The material was characterized by using transmission electron microscopy (TEM), X-ray diffraction analysis (XRD), scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR). The humidity sensing response of the nanocomposite was examined. It was found that the conductivity varied according to low humidity to high humidity. The composite showed good humidity response, ion-exchange capacity and electrical conductivity. Poly-o-toludine-TiP nanocomposite was also used to study electrical conductivity under isothermal conditions in the temperature range 50-130 C. The composite was found stable under ambient conditions below 90 C in terms of DC electrical conductivity retention. These studies suggest that the cation exchange nanocomposite could be a good sensing material for humidity.

  13. Moisture exchangers do not prevent patient contamination of ventilators. A microbiological study.

    PubMed

    Bygdeman, S; von Euler, C; Nyström, B

    1984-12-01

    Thirty-three mechanically ventilated patients in an intensive care unit were studied in order to verify a claim that the Servo humidifier acts as a bacterial barrier. The Servo humidifier was used on all patients. It was changed once daily, and the connecting tubes were changed once weekly. Daily bacterial cultures were taken from the trachea of the patient as well as from the humidifier, the tubing and the ventilator. In 25 of the patients, the same bacterial strain as in the trachea of the patient could not be isolated from the outside of the humidifier, from the tubing or the ventilator. In eight patients a breakthrough of bacterial strains from the trachea through the humidifier could be demonstrated. In four of these eight patients the breakthrough strains appeared to establish themselves in the respirator environment, while in the other four they appeared only temporarily outside the humidifier. The clinical importance of the establishment of a bacterial strain in the ventilator is not clear, but it seems prudent that the introduction of the Servo humidifier should not lead to less stringent cleaning and/or disinfection routines of ventilators and tubing than before. PMID:6395607

  14. Spectroscopic study of water adsorption on Li(+), TMA(+) and HDTMA(+) exchanged montmorillonite.

    PubMed

    Pálková, Helena; Hronský, Viktor; Bizovská, Valéria; Madejová, Jana

    2015-10-01

    The potential of IR and NMR spectroscopy in characterization the interaction of water with natural and organically modified montmorillonites was introduced. Organoclays were prepared from Li-saturated montmorillonite (Li-S) and tetramethylammonium (TMA) or hexadecyltrimethylammonium (HDTMA) salts. The influence of organic cation size on the water vapour uptake was examined and a comparative study with natural clay mineral was provided. The near-IR spectra confirmed the reduced water content in TMA-S and HDTMA-S. After exposure of the samples to water vapour under various relative humidities (RH) the H2O content was determined. According to the adsorption isotherms the amount of water decreased in order Li-S>TMA-S>HDTMA-S. The intensities of the 2νOH and [Formula: see text] bands, corresponding to the vibrations of H2O, gradually increased in hydrated samples. The (13)C MAS NMR and near-IR of hydrated organoclays confirmed the presence of H2O close to the cation's headgroup. NMR signals of inner -CH2- groups in HDTMA-S were also affected by hydration: the intensity of disordered gauche conformers (31.1 ppm) overtook the intensity of ordered all-trans conformers (33.0 ppm). PMID:25989613

  15. Upper bound for the s -d exchange integral in n -(Ga,Mn)N:Si from magnetotransport studies

    NASA Astrophysics Data System (ADS)

    Adhikari, R.; Stefanowicz, W.; Faina, B.; Capuzzo, G.; Sawicki, M.; Dietl, T.; Bonanni, A.

    2015-05-01

    A series of recent magneto-optical studies pointed to contradicting values of the s -d exchange energy N0α in Mn-doped GaAs and GaN as well as in Fe-doped GaN. Here, a strong sensitivity of weak-localization phenomena to symmetry-breaking perturbations (such as spin-splitting and spin-disorder scattering) is exploited to evaluate the magnitude of N0α for n -type wurtzite (Ga,Mn)N:Si films grown by metalorganic vapor phase epitaxy. Millikelvin magnetoresistance studies and their quantitative interpretation point to N0α <40 meV, a value at least 5 times smaller than the one found with similar measurements on, e.g., n -(Zn,Mn)O. It is shown that this striking difference in the values of the s -d coupling between n -type III-V and II-VI dilute magnetic semiconductors can be explained by a theory that takes into account the acceptor character of Mn in III-V compounds.

  16. A QUANTUM MECHANICAL STUDY OF STRUCTURAL AND ELECTRONIC DILUTION EFFECTS IN PARAMAGNETIC CHEMICAL EXCHANGE SATURATION TRANSFER AGENTS

    PubMed Central

    Miller, Whelton A.; Moore, Preston B.

    2014-01-01

    We present a computational study of the effect of chemical modifications of the meta and para substituents in the coordinating pendant arm of a modified 1,4,7,10-tetraazacyclododecane-N, N’, N″, N‴-tetraamide (DOTAM) ligand on the Chemical Exchange Saturation Transfer (CEST) signal. Magnetic Resonance Imaging (MRI) is currently one of the most widely used techniques available. MRI has led to a new class of pharmaceuticals termed “imagining” or “contrast” agents. These agents usually work by incorporating lanthanide metals such as Gadolinium (Gd) and Europium (Eu). This allows the contrast agents to take advantage of the paramagnetic properties of the metals, which in turn enhances the signal detectable by MRI. The effect of simple electron-withdrawing (e.g., nitro) and electron-donating (e.g., methyl) substituents chemically attached to a modified chelate arm (pendant arm) is quantified by charge transfer interactions in the coordinated water-chelate system computed from quantum mechanics. This study attempts to reveal the origin of the substituent effect on the CEST signal and the electronic structure of the complex. We find that the extent of Charge Transfer (CT) depends on orbital orientations and overlaps. However, CT interactions occur simultaneously from all arms, which causes a dilution effect with respect to the pendant arm. PMID:25485283

  17. A QUANTUM MECHANICAL STUDY OF STRUCTURAL AND ELECTRONIC DILUTION EFFECTS IN PARAMAGNETIC CHEMICAL EXCHANGE SATURATION TRANSFER AGENTS.

    PubMed

    Miller, Whelton A; Moore, Preston B

    2014-01-01

    We present a computational study of the effect of chemical modifications of the meta and para substituents in the coordinating pendant arm of a modified 1,4,7,10-tetraazacyclododecane-N, N', N″, N‴-tetraamide (DOTAM) ligand on the Chemical Exchange Saturation Transfer (CEST) signal. Magnetic Resonance Imaging (MRI) is currently one of the most widely used techniques available. MRI has led to a new class of pharmaceuticals termed "imagining" or "contrast" agents. These agents usually work by incorporating lanthanide metals such as Gadolinium (Gd) and Europium (Eu). This allows the contrast agents to take advantage of the paramagnetic properties of the metals, which in turn enhances the signal detectable by MRI. The effect of simple electron-withdrawing (e.g., nitro) and electron-donating (e.g., methyl) substituents chemically attached to a modified chelate arm (pendant arm) is quantified by charge transfer interactions in the coordinated water-chelate system computed from quantum mechanics. This study attempts to reveal the origin of the substituent effect on the CEST signal and the electronic structure of the complex. We find that the extent of Charge Transfer (CT) depends on orbital orientations and overlaps. However, CT interactions occur simultaneously from all arms, which causes a dilution effect with respect to the pendant arm. PMID:25485283

  18. Study of Chemical Exchange on the Water-Sediment Interface in the Black Sea: New Russian Lander

    NASA Astrophysics Data System (ADS)

    Rozanov, Alexander

    2010-05-01

    Study of Chemical Exchange on the Water-Sediment Interface in the Black Sea: New Russian Lander A.G. Rozanov, A.V. Vershinin, A.V. Egorov P.P. Shirshov Institute of Oceanology of the Russian Academy of Sciences (IO RAS) Nakhimovskiy prosp. 36. Moscow. 117851. Russia. Email: rozanov@ocean.ru Key words: Black Sea, coastal bottom sediments, bottom water, pore water, chemical fluxes, lender. The results of the first applications of automatic bottom station (Lаnder IO RAS) for the study of chemical exchange at the water - sediment interface were obtained in the sediments of the north-western part of the Black Sea near Gelendzhik (The Blue Bay). Lander is equipped with bottom cameras, O2-sensors (optodes) and syringes for programmed water sampling from the cameras and outer water. Exposition of the lander for one day allows direct determination of fluxes of chemical elements through the interface between bottom water and the sediments. At the same time fluxes through the water-sediment interface were calculated from the differences in concentrations of these components in bottom water and pore water (Fick's law). Bottom sediments were presented by organogenic clays containing hydrogen sulphide under the surface. High activity of diagenetic processes has led to increased consumption of O2 by the sediments from the bottom water (130 mM/(m2 day) and high fluxes of nutrients (P: 0.8 - 2.2, Si; 1.4 - 5.0 mM/(m2 day) and metals (Mn: 0.4 - 0.6, Fe: 0.04 - 1.6 mM/(m2 day) from the sediments. The first figure in each interval was received from the Fick calculations, the second one - from the lender's data. The data obtained allow to give preference to direct measurements of fluxes (lander), compared with a calculation method, because the latter is not able to register bioturbation and other animal activity/. The first applications of the lander suggests the need for methodological improvements in both technical and with regard to chemical analytical support.

  19. Photoexcitation and ionization in carbon dioxide - Theoretical studies in the separated-channel static-exchange approximation

    NASA Technical Reports Server (NTRS)

    Padial, N.; Csanak, G.; Mckoy, B. V.; Langhoff, P. W.

    1981-01-01

    Vertical-electronic static-exchange photoexcitation and ionization cross sections are reported which provide a first approximation to the complete dipole spectrum of CO2. Separated-channel static-exchange calculations of vertical-electronic transition energies and oscillator strengths, and Stieltjes-Chebyshev moment methods were used in the development. Detailed comparisons were made of the static-exchange excitation and ionization spectra with photoabsorption, electron-impact excitation, and quantum-defect estimates of discrete transition energies and intensities, and with partial-channel photoionization cross sections obtained from fluorescence measurements and from tunable-source and (e, 2e) photoelectron spectroscopy. Results show that the separate-channel static-exchange approximation is generally satisfactory in CO2.

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

    PubMed

    Bányai, István; Farkas, Ildikó; Tóth, Imre

    2016-06-01

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

  1. Exchange integrals in magnetoelectric hexagonal ferrite (SrCo{sub 2}Ti{sub 2}Fe{sub 8}O{sub 19}): A density functional study

    SciTech Connect

    Feng, Min; Shao, Bin; Lu, Yuan; Zuo, Xu

    2014-05-07

    The exchange integrals in magnetoelectric hexagonal ferrite SrCo{sub 2}Ti{sub 2}Fe{sub 8}O{sub 19} have been calculated by using density functional theory. To get 10 inter-sublattice and 3 intra-sublattice exchange integrals, the electronic structures and total energies of 20 spin arrangements have been calculated with General Gradient Approximation (GGA) + U method. The dependence of exchange integrals on U has been studied. The comparison between the exchange integrals in SrFe{sub 12}O{sub 19} and those in SrCo{sub 2}Ti{sub 2}Fe{sub 8}O{sub 19} shows that substitution of Co and Ti decreases the most interactions involving the 12 k sites. The investigation based on our exchange integrals indicates that magnetic interaction between R and S blocks reduces significantly in SrCo{sub 2}Ti{sub 2}Fe{sub 8}O{sub 19}.

  2. Evaluation of the Efficiency of the Atraumatic Endotracheal Tube in the Pulmonary-Gas Exchange: an Experimental Study

    PubMed Central

    Antonelli, Raíssa Quaiatti; Moreira, Marcos Mello; Martins, Luiz Claudio; Negro, Maíra Soliani Del; Baldasso, Tiago Antonio; Tincani, Alfio José

    2015-01-01

    OBJECTIVE Mechanical ventilation is frequently necessary, in which case the use of an endotracheal tube is mandatory. The tube has an inflatable balloon in its distal extremity, whose aim is, among other functions, an efficient arterialization. However, serious injuries in the place of contact of the balloon with the trachea can be frequent. Some studies point out that balloons with permanent pressure may reduce this complication. Nevertheless, air scape, expressed by the inspiratory (IV) and expiratory volume (EV) variation (Δ IV-EV), may occur, possibly leading to hypoxemia. Thus, the goal of this study was to verify the efficiency of a modified endotracheal tube on arterializations compared to the traditional endotracheal tube. METHODS The modified endotracheal tube presents intermittent insufflation, with three drillings in the internal region of the cuff, allowing for insufflation in the inspiratory phase of the mechanical ventilation. Three animals were used for the control group, with a cuff pressure of 30 cmH2O, and seven pigs had the modified endotracheal tube. Each animal was kept under mechanical ventilation (FIO2=0.21) for 6 hours. Arterial and venous gases were measured every three hours (T0; T3; T6). RESULTS The gases confirmed the lack of hypoxia between the Groups, with a difference in the ΔIV-EV at T0 (P=0.0486). CONCLUSIONS In this study, the lack of hypoxia showed the efficiency of the modified endotracheal tube. However, new studies are necessary, particularly in diseased lungs, in order to evaluate the real efficiency of the mentioned device on the pulmonary gas exchange. PMID:26934410

  3. A longitudinal study of the moderating role of extraversion: leader-member exchange, performance, and turnover during new executive development.

    PubMed

    Bauer, Talya N; Erdogan, Berrin; Liden, Robert C; Wayne, Sandy J

    2006-03-01

    Identifying factors that help or hinder new executives in "getting up to speed" quickly and remaining with an organization is vital to maximizing the effectiveness of executive development. The current study extends past research by examining extraversion as a moderator of relationships between leader-member exchange (LMX) and performance, turnover intentions, and actual turnover for an executive sample. The sample consisted of 116 new executives who were surveyed prior to starting their employment and at 3 months postentry. A total of 67 senior executives rated these new executives in terms of overall performance at 6 months postentry. Turnover data were gathered from company records 3 1/2 years later. Hierarchical regression results showed that LMX was not related to performance or turnover intentions for those high in extraversion; but for individuals low in extraversion, there was a relation between LMX, performance, and turnover intentions. Furthermore, survival analyses showed that LMX was only related to turnover-hazard rate for individuals low in extraversion. PMID:16551185

  4. Study of acetylene poisoning of Pt cathode on proton exchange membrane fuel cell spatial performance using a segmented cell system

    NASA Astrophysics Data System (ADS)

    Reshetenko, Tatyana V.; St-Pierre, Jean

    2015-08-01

    Acetylene is a welding fuel and precursor for organic synthesis, which requires considering it to be a possible air pollutant. In this work, the spatial performance of a proton exchange membrane fuel cell exposed to 300 ppm C2H2 and different operating currents was studied with a segmented cell system. The injection of C2H2 resulted in a cell performance decrease and redistribution of segments' currents depending on the operating conditions. Performance loss was 20-50 mV at 0.1-0.2 A cm-2 and was accompanied by a rapid redistribution of localized currents. Acetylene exposure at 0.4-1.0 A cm-2 led to a sharp voltage decrease to 0.07-0.13 V and significant changes in current distribution during a transition period, when the cell reached a voltage of 0.55-0.6 V. A recovery of the cell voltage was observed after stopping the C2H2 injection. Spatial electrochemical impedance spectroscopy (EIS) data showed different segments' behavior at low and high currents. It was assumed that acetylene oxidation occurs at high cell voltage, while it reduces at low cell potential. A detailed analysis of the current density distribution, its correlation with EIS data and possible C2H2 oxidation/reduction mechanisms are presented and discussed.

  5. Cation exchange capacity (Qv) estimation in shaly sand reservoirs: case studies in the Junggar Basin, northwest China

    NASA Astrophysics Data System (ADS)

    Wang, Liang; Mao, Zhi-Qiang; Sun, Zhong-Chun; Luo, Xing-Ping; Deng, Ren-Shuang; Zhang, Ya-Hui; Ren, Bing

    2015-10-01

    Cation exchange capacity (Qv) is a key parameter in resistivity-based water saturation models of shaly sand reservoirs, and the accuracy of Qv calculation is crucial to the prediction of saturations of oil and gas. In this study, a theoretical expression of Qv in terms of shaly sand permeability (Kshaly-sand), total porosity (ϕt), and salinity of formation water (S) is deduced based on the capillary tube model and the physics volume model. Meanwhile, the classical Schlumberger-Doll research (SDR) model has been introduced to estimate Kshaly-sand. On this basis, a novel technique to estimate Qv from nuclear magnetic resonance (NMR) logs is proposed, and the corresponding model is also established, whose model parameters are calibrated by laboratory Qv and NMR measurements of 15 core samples from the Toutunhe formation of the Junggar Basin, northwest China. Based on the experimental data sets, this technique can be extended to reservoir conditions to estimate continuous Qv along the intervals. The processing results of field examples illustrate that the Qv calculated from field NMR logs are consistent with the analyzed results, with the absolute errors within the scope of  ±0.1 mmol cm-3 for the majority of core samples.

  6. Language and Development in Multilingual Settings: A Case Study of Knowledge Exchange and Teacher Education in South Africa

    NASA Astrophysics Data System (ADS)

    Rassool, Naz; Edwards, Viv; Bloch, Carole

    2006-12-01

    The quality of a country's human-resource base can be said to determine its level of success in social and economic development. This study focuses on some␣of the major human-resource development issues that surround the implementation of South Africa's policy of multilingualism in education. It begins by discussing the relationship between knowledge, language, and human-resource, social and economic development within the global cultural economy. It then considers the situation in South Africa and, in particular, the implications of that country's colonial and neo-colonial past for attempts to implement the new policy. Drawing on the linguistic-diversity-in-education debate in the United Kingdom of the past three decades, it assesses the first phase of an in-service teacher-education programme that was carried out at the Project for Alternative Education in South Africa (PRAESA) based at the University of Cape Town. The authors identify key short- and long-term issues related to knowledge exchange in education in multilingual societies, especially concerning the use of African languages as mediums for teaching and learning.

  7. A modeling study of water and salt exchange for a micro-tidal, stratified northern Gulf of Mexico estuary

    NASA Astrophysics Data System (ADS)

    Kim, Choong-Ki; Park, Kyeong

    2012-08-01

    A three-dimensional hydrodynamic model is applied to the Mobile Bay system to study water and salt exchange with the northern Gulf of Mexico via Main Pass (MP) and eastern Mississippi Sound via Pass-aux-Herons (PaH). On average, more water leaves the Bay through MP than through PaH, and the Bay gains salt through MP and loses about the same amount through PaH. However, the volume discharge rate Qf and salt transport rate FS vary greatly in response to wind and river discharge with the range of variation 1-2 orders of magnitude larger than the corresponding mean. Stratification plays a key role for salt transport through MP. During periods of large river discharge, the landward shear dispersive transport FE peaking during equatorial tides and the landward tidal oscillatory transport FT peaking during tropic tides, respectively, balance the seaward advective transport QfS0. During periods of relatively weak stratification, FS at MP is almost entirely determined by QfS0 and its variability is well correlated with north-south (along-estuary) wind, associated with the barotropic (water level) adjustment. At the shallow, weakly stratified PaH, FS is almost identical to QfS0, and Qf is well correlated with east-west wind, with the correlation becoming stronger during the dry period.

  8. Synthesis of transport layers with controlled anisotropy and application thereof to study proton exchange membrane fuel cell performance

    NASA Astrophysics Data System (ADS)

    Todd, Devin; Mérida, Walter

    2016-04-01

    We report on a novel method for the synthesis of fibre-based proton exchange membrane (PEM) fuel cell porous transport layers (PTLs) with controllable fibre alignment. We also report the first application of such layers as diagnostics tools to probe the effect of within-plane PTL anisotropy upon PEM fuel cell performance. These structures are realized via adaptation of electrospinning technology. Electrospun layers with progressive anisotropy magnitude are produced and evaluated. This novel approach is distinguished from the state-of-the-art because an equivalent study using commercially available materials is impossible due to lack of structurally similar substrates with different anisotropies. The anisotropy is visualized via scanning electron microscopy, and quantified using electrical resistivity. The capacity is demonstrated to achieve fibre alignment, and the associated impact on transport properties. A framework is presented for assessing the in-situ performance, whereby transport layer orientation versus bipolar plate flow-field geometry is manipulated. While an effect upon the commercial baseline cannot be discerned, electrospun transport layers with greater anisotropy magnitude suggest greater sensitivity to orientation; where greater performance is obtained with fibres cross-aligned to flow-field channels. Our approach of electrospun transport enables deterministic structures by which fuel cell performance can be explained and optimized.

  9. Unidirectional Flux Balance of Monovalent Ions in Cells with Na/Na and Li/Na Exchange: Experimental and Computational Studies on Lymphoid U937 Cells

    PubMed Central

    Vereninov, Igor A.; Yurinskaya, Valentina E.; Model, Michael A.; Vereninov, Alexey A.

    2016-01-01

    Monovalent ion traffic across the cell membrane occurs via various pathways. Evaluation of individual fluxes in whole cell is hampered by their strong interdependence. This difficulty can be overcome by computational analysis of the whole cell flux balance. However, the previous computational studies disregarded ion movement of the self-exchange type. We have taken this exchange into account. The developed software allows determination of unidirectional fluxes of all monovalent ions via the major pathways both under the balanced state and during transient processes. We show how the problem of finding the rate coefficients can be solved by measurement of monovalent ion concentrations and some of the fluxes. Interdependence of fluxes due to the mandatory conditions of electroneutrality and osmotic balance and due to specific effects can be discriminated, enabling one to identify specific changes in ion transfer machinery under varied conditions. To test the effectiveness of the developed approach we made use of the fact that Li/Na exchange is known to be an analogue of the coupled Na/Na exchange. Thus, we compared the predicted and experimental data obtained on U937 cells under varied Li+ concentrations and following inhibition of the sodium pump with ouabain. We found that the coupled Na/Na exchange in U937 cells comprises a significant portion of the entire Na+ turnover. The data showed that the loading of the sodium pump by Li/Na exchange involved in the secondary active Li+ transport at 1–10 mM external Li+ is small. This result may be extrapolated to similar Li+ and Na+ flux relationships in erythrocytes and other cells in patients treated with Li+ in therapeutic doses. The developed computational approach is applicable for studying various cells and can be useful in education for demonstrating the effects of individual transporters and channels on ion gradients, cell water content and membrane potential. PMID:27159324

  10. A Study of Medical Graduates of the WICHE Student Exchange Programs Showing the Relation of That Group to the Medical Manpower of the Sending States.

    ERIC Educational Resources Information Center

    Western Interstate Commission for Higher Education, Boulder, CO.

    The medical graduates from the Western Interstate Commission for Higher Education (WICHE) Student Exchange Programs (SEP) are studied in their relation to the medical manpower of the sending states. Participating schools were: University of California (Los Angeles, Irvine, and San Francisco branches); Loma Linda University; Stanford University;…

  11. A patient-specific study of type-B aortic dissection: evaluation of true-false lumen blood exchange

    PubMed Central

    2013-01-01

    Background Aortic dissection is a severe pathological condition in which blood penetrates between layers of the aortic wall and creates a duplicate channel – the false lumen. This considerable change on the aortic morphology alters hemodynamic features dramatically and, in the case of rupture, induces markedly high rates of morbidity and mortality. Methods In this study, we establish a patient-specific computational model and simulate the pulsatile blood flow within the dissected aorta. The k-ω SST turbulence model is employed to represent the flow and finite volume method is applied for numerical solutions. Our emphasis is on flow exchange between true and false lumen during the cardiac cycle and on quantifying the flow across specific passages. Loading distributions including pressure and wall shear stress have also been investigated and results of direct simulations are compared with solutions employing appropriate turbulence models. Results Our results indicate that (i) high velocities occur at the periphery of the entries; (ii) for the case studied, approximately 40% of the blood flow passes the false lumen during a heartbeat cycle; (iii) higher pressures are found at the outer wall of the dissection, which may induce further dilation of the pseudo-lumen; (iv) highest wall shear stresses occur around the entries, perhaps indicating the vulnerability of this region to further splitting; and (v) laminar simulations with adequately fine mesh resolutions, especially refined near the walls, can capture similar flow patterns to the (coarser mesh) turbulent results, although the absolute magnitudes computed are in general smaller. Conclusions The patient-specific model of aortic dissection provides detailed flow information of blood transport within the true and false lumen and quantifies the loading distributions over the aorta and dissection walls. This contributes to evaluating potential thrombotic behavior in the false lumen and is pivotal in guiding endovascular intervention. Moreover, as a computational study, mesh requirements to successfully evaluate the hemodynamic parameters have been proposed. PMID:23829346

  12. HK97 maturation studied by crystallography and H/2H exchange reveals the structural basis for exothermic particle transitions

    PubMed Central

    Gertsman, Ilya; Komives, Elizabeth A.; Johnson, John E.

    2010-01-01

    HK97 is an exceptionally amenable system for characterizing major conformational changes associated with capsid maturation in dsDNA bacteriophage. HK97 undergoes a capsid expansion of ~20%, accompanied by major subunit rearrangements during genome packaging. A previous 3.44 resolution crystal structure of the mature capsid, Head II, and Cryo-EM studies of other intermediate expansion forms of HK97 suggested that primarily rigid body movements facilitated the maturation process. We recently reported a 3.65 resolution structure of the pre-expanded particle form, Prohead II, and found that the capsid subunits undergo significant refolding and twisting of the tertiary structure to accommodate expansion. The Prohead II study focused on the major twisting motions in the P-domain, and refolding of the spine helix during the transition. Here we extend the crystallographic comparison between Prohead II and Head II, characterizing the refolding events occurring in each of the four major domains of the capsid subunit and their effect on quaternary structure stabilization. In addition, H/2H exchange coupled to mass spectrometry, was used to characterize the structural dynamics of three distinct capsid intermediates, Prohead II, EI, and the nearly mature Head I. Differences in solvent accessibilities of the 7 quasi-equivalent capsid subunits were observed in P-II, attributed to differences in secondary and quaternary structure. Nearly all differences in solvent accessibility among subunits disappear after the first transition to Expansion Intermediate (EI). We show that most of the refolding is coupled to this transformation, an event associated with the transition from asymmetric to symmetric hexamers. PMID:20093122

  13. 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

    2016-02-01

    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 strong enough π acids. PMID:26662724

  14. Exchange bias and perpendicular anisotropy study of ultrathin Pt-Co-Pt-IrMn multilayers sputtered on float glass

    NASA Astrophysics Data System (ADS)

    Laval, M.; Lüders, U.; Bobo, J. F.

    2007-09-01

    We have prepared ultrathin Pt-Co-Pt-IrMn polycrystalline multilayers on float-glass substrates by DC magnetron sputtering. We have determined the optimal set of thickness for both Pt layers, the Co layer and the IrMn biasing layer so that these samples exhibit at the same time out-of-plane magnetic anisotropy and exchange bias. Kerr microscopy domain structure imaging evidences an increase of nucleation rate accompanied with inhomogeneous magnetic behavior in the case of exchange-biased films compared to Pt-Co-Pt trilayers. Polar hysteresis loops are measured in obliquely applied magnetic field conditions, allowing us to determine both perpendicular anisotropy effective constant Keff and exchange-bias coupling JE, which are significantly different from the ones determined by standard switching field measurements.

  15. STUDIES OF X-RAY PRODUCTION FOLLOWING CHARGE EXCHANGE RECOMBINATION BETWEEN HIGHLY CHARGED IONS AND NEUTRAL ATOMS AND MOLECULES

    SciTech Connect

    Brown, G V; Beiersdorfer, P; Chen, H; Clementson, J; Frankel, M; Gu, M F; Kelley, R L; Kilbourne, C A; Porter, F S; Thorn, D B; Wargelin, B J

    2008-08-28

    We have used microcalorimeters built by the NASA/Goddard Space Flight Center and the Lawrence Livermore National Laboratory Electron Beam Ion Trap to measure X-ray emission produced by charge exchange reactions between highly charged ions colliding with neutral helium, hydrogen, and nitrogen gas. Our measurements show the spectral dependence on neutral species and also show the distinct differences between spectra produced by charge exchange reactions and those produced by direct impact excitation. These results are part of an ongoing experimental investigation at the LLNL EBIT facility of charge exchange spectral signatures and can be used to interpret X-ray spectra produced by a variety of laboratory and celestial sources including cometary and planetary atmospheres, the Earth's magnetosheath, the heliosphere, and tokamaks.

  16. High-productivity membrane adsorbers: Polymer surface-modification studies for ion-exchange and affinity bioseparations

    NASA Astrophysics Data System (ADS)

    Chenette, Heather C. S.

    This dissertation centers on the surface-modification of macroporous membranes to make them selective adsorbers for different proteins, and the analysis of the performance of these membranes relative to existing technology. The common approach used in these studies, which is using membrane technology for chromatographic applications and using atom transfer radical polymerization (ATRP) as a surface modification technique, will be introduced and supported by a brief review in Chapter 1. The specific approaches to address the unique challenges and motivations of each study system are given in the introduction sections of the respective dissertation chapters. Chapter 2 describes my work to develop cation-exchange membranes. I discuss the polymer growth kinetics and characterization of the membrane surface. I also present an analysis of productivity, which measures the mass of protein that can bind to the stationary phase per volume of stationary phase adsorbing material per time. Surprisingly and despite its importance, this performance measure was not described in previous literature. Because of the significantly shorter residence time necessary for binding to occur, the productivity of these cation-exchange membrane adsorbers (300 mg/mL/min) is nearly two orders of magnitude higher than the productivity of a commercial resin product (4 mg/mL/min). My work studying membrane adsorbers for affinity separations was built on the productivity potential of this approach, as articulated in the conclusion of Chapter 2. Chapter 3 focuses on the chemical formulation work to incorporate glycoligands into the backbone of polymer tentacles grown from the surface of the same membrane stationary phase. Emphasis is given to characterizing and testing the working formulation for ligand incorporation, and details about how I arrived at this formulation are given in Appendix B. The plant protein, or lectin, Concanavalin A (conA) was used as the target protein. The carbohydrate affinity membrane adsorbers were found to have a static binding capacity for con A (6.0 mg/mL) that is nearly the same as the typical dextran-based separation media used in practice. Binding under dynamic conditions was tested using flow rates of 0.1-1.0 mL/min. No bound lectin was observed for the higher flow rate. The first Damkohler number was used to assess whether adsorption kinetics or mass transport contributed the limitation to conA binding. Analyses indicate that this system is not limited by the accessibility of the binding sites, but by the inherently low rate of adsorption of conA onto the glycopolymer. The research described in Chapter 4 focuses on reaction chemistry experiments to incorporate a phosphonate-based polymer in the membrane platform to develop a new class of affinity adsorbers that function based on their affinity for Arginine (Arg) amino acid residues. The hypothesis was that benzyl phosphonate-containing functional polymers would form strong complexes with Arg-rich proteins as a result of multivalent binding. Introducing a new class of affinity membranes for purification of Arg-rich and Arg-tagged proteins may have an impact similar to the introduction of immobilized metal ion affinity chromatography (IMAC), which would be a significant achievement. Using Arg-tags would overcome some of the associated drawbacks of using metal ions in IMAC. Additionally, some cell penetrating peptides are said to be Arg-rich, and this would be a convenient feature to exploit for their isolation and purification. Lysozyme was used as a model Arg-rich protein. The affinity membranes show a static binding capacity of 3 mg/mL. (Abstract shortened by UMI.)

  17. Amide hydrogen exchange in HIV-1 subtype B and C proteases--insights into reduced drug susceptibility and dimer stability.

    PubMed

    Naicker, Previn; Stoychev, Stoyan; Dirr, Heini W; Sayed, Yasien

    2014-12-01

    Since its identification, HIV has continued to have a detrimental impact on the lives of millions of people throughout the world. The protease of HIV is a major target in antiviral treatment. The South African HIV-1 subtype C (C-SA) protease displays weaker binding affinity for some clinically approved protease inhibitors in comparison with the HIV-1 subtype B protease. The heavy HIV burden in sub-Saharan Africa, where subtype C HIV-1 predominates, makes this disparity a topic of great interest. In light of this, the enzyme activity and affinity of protease inhibitors for the subtype B and C-SA proteases were determined. The relative vitality, indicating the selective advantage of polymorphisms, of the C-SA protease relative to the subtype B protease in the presence of ritonavir and darunavir was four- and tenfold greater, respectively. Dynamic differences that contribute to the reduced drug susceptibility of the C-SA protease were investigated by performing hydrogen-deuterium exchange/mass spectrometry (HDX/MS) on unbound subtype B and C-SA proteases. The reduced propensity to form the E35-R57 salt bridge, and alterations in the hydrophobic core of the C-SA protease, are proposed to affect the anchoring of the flexible flaps, resulting in an increased proportion of the fully open flap conformation. HDX/MS data suggested that the N-terminus of both proteases is less stable than the C-terminus of the proteases, thus explaining the increased efficacy of dimerization inhibitors targeted toward the C-terminus of HIV proteases. As far as we are aware, this is the first report on assessment of HIV protease dynamics using HDX/MS. PMID:25283307

  18. Ion exchange phenomena

    SciTech Connect

    Bourg, I.C.; Sposito, G.

    2011-05-01

    Ion exchange phenomena involve the population of readily exchangeable ions, the subset of adsorbed solutes that balance the intrinsic surface charge and can be readily replaced by major background electrolyte ions (Sposito, 2008). These phenomena have occupied a central place in soil chemistry research since Way (1850) first showed that potassium uptake by soils resulted in the release of an equal quantity of moles of charge of calcium and magnesium. Ion exchange phenomena are now routinely modeled in studies of soil formation (White et al., 2005), soil reclamation (Kopittke et al., 2006), soil fertilitization (Agbenin and Yakubu, 2006), colloidal dispersion/flocculation (Charlet and Tournassat, 2005), the mechanics of argillaceous media (Gajo and Loret, 2007), aquitard pore water chemistry (Tournassat et al., 2008), and groundwater (Timms and Hendry, 2007; McNab et al., 2009) and contaminant hydrology (Chatterjee et al., 2008; van Oploo et al., 2008; Serrano et al., 2009).

  19. Study of plate-fin heat exchanger and cold plate for the active thermal control system of Space Station

    NASA Technical Reports Server (NTRS)

    Chyu, MING-C.

    1992-01-01

    Plate-fin heat exchangers will be employed in the Active Thermal Control System of Space Station Freedom. During ground testing of prototypic heat exchangers, certain anomalous behaviors have been observed. Diagnosis has been conducted to determine the cause of the observed behaviors, including a scrutiny of temperature, pressure, and flow rate test data, and verification calculations based on such data and more data collected during the ambient and thermal/vacuum tests participated by the author. The test data of a plate-fin cold plate have been also analyzed. Recommendation was made with regard to further tests providing more useful information of the cold plate performance.

  20. Out-of-hours GPs and palliative care-a qualitative study exploring information exchange and communication issues

    PubMed Central

    2010-01-01

    Background Out-of-hours general practitioners (GPs) cover the community over a significant proportion of a given week, and palliative care patients are seen as a priority. Little is known about how well these GPs feel supported in their line of work and whether communication exchanges work well for the proportion of their patients who have palliative care needs. For this study, GPs who provide out-of-hours care were interviewed in order to explore factors that they identified as detrimental or beneficial for good communication between themselves, patients, relatives and other professionals, specifically to palliative care encounters. Methods Nine GPs were interviewed using face-to-face semi-structured interviews. All nine GPs worked regular out-of-hours sessions. Data from transcripts was analysed using Interpretative Phenomenological Analysis. Results A predominant theme expressed by GPs related to constraints within the system provided by the local private company owned out-of-hours provider. A strong feeling of 'being alone out there' emerged, with some GPs more willing to call for help than others, and others expressing their concern at access to pharmacies and medication being very inconsistent. Out-of-hours GPs felt left alone on occasion, unable to access daytime services and not knowing who to call for advice. Information hand-over systems from in-hours to out-of-hours with regard to palliative care were felt to be inadequate. Out-of-hours doctors interviewed felt left out of the care loop; handover sheets from specialist palliative care providers were a rarity. Conclusions Out-of-hours services need to be mindful of the needs of the GPs they employ, in particular relating to the palliative care they provide in this setting. Other healthcare professionals should aim to keep their local out-of-hours service informed about palliative care patients they may be called to see. PMID:20704741