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Sample records for hydrogen-deuterium exchange studies

  1. 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…

  2. Combining size-exclusion chromatography with differential hydrogen-deuterium exchange to study protein conformational changes.

    PubMed

    Makarov, Alexey A; Helmy, Roy

    2016-01-29

    Methods for protein characterization are being actively developed based on the growing importance of protein therapies and applications. The goal of this study was to demonstrate the use of size-exclusion chromatography (SEC) in combination with differential hydrogen-deuterium exchange (HDX) to compare protein global conformational changes at different solution conditions. Using chaotropic mobile phase additive, differential HDX was used to detect a number of solvent accessible labile protons of protein on-column at pH and temperature conditions which provided unrestricted intrinsic H/D exchange (all-or-nothing approach). Varying SEC on-column conditions allowed for protein conformational changes to be observed. Temperature and pressure were independently studied with regards to their effect on the proteins' (insulin, cytochrome C, ubiquitin, and myoglobin) conformational changes in the solution. The obtained ΔHDX profiles revealed protein conformational changes in solution under varied conditions manifested as the difference in the number of protons exchanged to deuterons, or vice-versa. The approach described in this manuscript could prove useful for protein batch-to-batch comparisons, for optimization of chemical reactions with enzyme as catalyst or for protein chemical modification reactions. PMID:26763301

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

    PubMed

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

    2014-08-12

    An efficient laboratory experiment has been developed for undergraduate students to conduct hydrogen-deuterium (H-D) exchange of resorcinol by electrophilic aromatic substitution using D2O and a catalytic amount of H2SO4. The resulting labeled product is characterized by (1)H NMR. Students also visualize a significant kinetic isotope effect (k H/k D ≈ 3 to 4) by adding iodine tincture to solutions of unlabeled resorcinol and the H-D 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

  4. Using hydrogen/deuterium exchange mass spectrometry to study conformational changes in granulocyte colony stimulating factor upon PEGylation.

    PubMed

    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.

  5. Methods in the Study of PTEN Structure: X-Ray Crystallography and Hydrogen Deuterium Exchange Mass Spectrometry.

    PubMed

    Masson, Glenn R; Burke, John E; Williams, Roger L

    2016-01-01

    Despite its small size and deceptively simple domain organization, PTEN remains a challenging structural target due to its N- and C-terminal intrinsically disordered segments, and the conformational heterogeneity caused by phosphorylation of its C terminus. Using hydrogen/deuterium exchange mass spectrometry (HDX-MS), it is possible to probe the conformational dynamics of the disordered termini, and also to determine how PTEN binds to lipid membranes. Here, we describe how to purify recombinant, homogenously dephosphorylated PTEN from a eukaryotic system for subsequent investigation with HDX-MS or crystallography. PMID:27033079

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

    PubMed

    Ramachandran, Gayathri; Udgaonkar, Jayant B

    2013-12-10

    One of the signatures of Alzheimer's disease and tauopathies is fibrillization of the microtubule-associated protein tau. The purpose of this study was to compare the high-resolution structure of fibrils formed by two different tau four-repeat domain constructs, tau4RD and tauK18, using hydrogen-deuterium exchange coupled to mass spectrometry as a tool. While the two fibrils are found to be constructed on similar structural principles, the tauK18 fibril has a slightly more stable core. This difference in fibril core stability appears to be reflective of the mechanistic differences in the aggregation pathways of the two proteins. PMID:24256615

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

    PubMed

    De Weck, Z; Pande, J; Kägi, J H

    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 of measured by exchange retardation is considerably larger for NAD+ 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+-pyrazole, PHLDH-NAD+-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+ 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.

  8. 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

  9. 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

  10. 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

  11. 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

  12. 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

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

    2014-09-01

    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. A 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.

  13. 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.

  14. Nonuniform isotope patterns produced by collision-induced dissociation of homogeneously labeled ubiquitin: implications for spatially resolved hydrogen/deuterium exchange ESI-MS studies.

    PubMed

    Ferguson, Peter L; Konermann, Lars

    2008-06-01

    There is an ongoing debate whether collision-induced dissociation (CID) of electrosprayed proteins after solution-phase hydrogen/deuterium exchange (HDX) is a viable approach for determining spatially resolved deuteration patterns. This work explores the use of two methods, source-CID and hexapole tandem mass spectrometry (MS/MS) on a quadrupole time-of-flight (Q-TOF) mass spectrometer, for measuring the fragment deuteration levels of regioselectively labeled ubiquitin. Both methods reveal that b-ions exhibit HDX levels significantly below that of the intact protein, whereas several y'' fragments are labeled to a much greater extent. These results are consistent with earlier source-CID data (Akashi, S.; Naito, Y.; Takio, K. Anal. Chem. 1999, 71, 4974-4980). However, the measured b-ion deuteration levels are in disagreement with the known solution-phase behavior of ubiquitin. Partial agreement is observed for y''-ions. Control experiments on homogeneously labeled ubiquitin (having the same average deuteration level at every exchangeable site) result in highly nonuniform fragment HDX levels. In particular, b-ions exhibit deuteration levels significantly below that of intact ubiquitin, thereby mimicking the behavior seen for the regioselectively labeled protein. This effect is likely caused by isotope fractionation during collisional activation, facilitated by the high mobility of charge carriers (scrambling) in the gas phase. The observation that the b-ion labeling behavior is largely independent of the spatial isotope distribution within solution-phase ubiquitin invalidates these ions as reporters of the protein deuteration pattern. This work questions the common practice of interpreting any nonuniformities in fragment deuteration as being indicative of regioselective solution-phase labeling. Artifactual deuterium enrichment or depletion during collisional activation may have contributed to the current lack of consensus as to whether HDX/CID represents a potentially

  15. 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.

  16. Influence of Murchison or Allende minerals on hydrogen-deuterium exchange of amino acids.

    PubMed

    Lerner, N R

    1995-04-01

    Deuterium-enriched amino acids occur in the Murchison carbonaceous chrondrite. This meteorite underwent a period of aqueous alteration with isotopically light water. With the objective of setting limits on the conditions of aqueous alteration, the exchange of the carbon-bonded hydrogen atoms of amino acids with D2O has been studied from 295 to 380 K as a function of time and meteorite/heavy water ratio. The amount of Murchison or Allende dust present has a significant effect on the rate and amount of hydrogen-deuterium exchange observed. At elevated temperatures, the alpha-hydrogens of all the amino acids studied were found to exchange with deuterium. In glycine and aspartic acid, this process resulted in total exchange of the carbon-bonded hydrogen. A completely deuterated isotopomer of alanine was produced in significant quantities only when the rock/water ratio was greater than 0.5. No exchange of carbon-bonded hydrogens was observed in the case of amino acids which do not possess an alpha-hydrogen atom. The rates of H/D exchange for amino acids observed here did not correspond to deuterium enrichment of the amino acids in the Murchison meteorite. These results suggest that H/D exchange with water had a negligible effect on the observed deuterium enrichment of amino acids found in Murchison and that the temperature at which the amino acids were exposed to liquid water was close to 273 K.

  17. Hydrogen--deuterium exchange in KD2PO4

    SciTech Connect

    Kucheyev, S O; Felter, T E; Siekhaus, W J; Nelson, A J; Hamza, A V

    2003-11-04

    Depth profiles of {sup 1}H and {sup 2}D in rapidly-grown KD{sub 2x}H{sub 2(1-x)}PO{sub 4} (DKDP) single crystals are studied by elastic recoil detection analysis. Results show that, at ambient conditions, deuteration in the first {approx} 500 nm from the sample surface significantly decreases within the first several days after D{sub 2}O surface polishing. This effect is attributed to the deuterium-hydrogen exchange. The effective diffusion coefficient of this process is strongly dependent on both the degree of deuteration and sample growth conditions. Physical mechanisms of the D/H exchange are discussed.

  18. 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.

  19. Changes in protein structure monitored by use of gas‐phase hydrogen/deuterium exchange

    PubMed Central

    Beeston, Helen S.; Ault, James R.; Pringle, Steven D.; Brown, Jeffery M.

    2015-01-01

    The study of protein conformation by solution‐phase hydrogen/deuterium exchange (HDX) coupled to MS is well documented. This involves monitoring the exchange of backbone amide protons with deuterium and provides details concerning the protein's tertiary structure. However, undesired back‐exchange during post‐HDX analyses can be difficult to control. Here, gas‐phase HDX‐MS, during which labile hydrogens on amino acid side chains are exchanged in sub‐millisecond time scales, has been employed to probe changes within protein structures. Addition of the solvent 2,2,2‐trifluoroethanol to a protein in solution can affect the structure of the protein, resulting in an increase in secondary and/or tertiary structure which is detected using circular dichroism. Using a Synapt G2‐S ESI‐mass spectrometer modified to allow deuterated ammonia into the transfer ion guide (situated between the ion mobility cell and the TOF analyser), gas‐phase HDX‐MS is shown to reflect minor structural changes experienced by the proteins β‐lactoglobulin and ubiquitin, as observed by the reduction in the level of deuterium incorporation. Additionally, the use of gas‐phase HDX‐MS to distinguish between co‐populated proteins conformers within a solution is demonstrated with the disordered protein calmodulin; the gas‐phase HDX‐MS results correspond directly with complementary data obtained by use of ion mobility spectrometry‐MS. PMID:25603979

  20. Hydrogen-Deuterium exchange monitored by ATR-FTIR spectroscopy

    NASA Astrophysics Data System (ADS)

    Poe, Brent; Del Vecchio, Alessandro; Cestelli Guidi, Mariangela

    2016-04-01

    Measuring the extent of isotopic exchange is a common means for the determination of self-diffusion coefficients in any type of medium (gas, liquid, amorphous solid, crystalline solid). For rapidly diffusing species such as hydrogen in condensed phases, real time methods involving vibrational spectroscopy can be used by taking advantage of the large relative mass difference between 1H and 2H, resulting in large differences in the band positions of their vibrational modes. We demonstrate rapid isotopic exchange between D2O liquid and H2O vapor using ATR (attenuated total reflectance) in a FTIR spectrometer. Over the course of a few minutes several spectra were acquired of a D2O droplet mounted on a diamond crystal. The progressive exchange reaction between the liquid phase and H2O from the atmosphere was monitored by measuring the decreasing absorbance of the D-O-D bending and O-D stretching bands and the increasing absorbance of the D-O-H and H-O-H bending and O-H stretching bands as functions of time. Our results offer some intriguing insights into the structural characteristics of water as inferred by this exchange process.

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

    PubMed

    Mysling, Simon; Salbo, Rune; Ploug, Michael; Jørgensen, Thomas J D

    2014-01-01

    Characterization of disulfide bond-containing proteins by hydrogen/deuterium exchange monitored by mass spectrometry (HDX-MS) requires reduction of the disulfide bonds under acidic and cold conditions, where the amide hydrogen exchange reaction is quenched (pH 2.5, 0 °C). The reduction typically requires a high concentration (>200 mM) of the chemical reducing agent Tris(2-carboxyethyl)phosphine (TCEP) as its reduction rate constant is decreased at low pH and temperature. Serious adverse effects on chromatographic and mass spectrometric performances have been reported when using high concentrations of TCEP. In the present study, we explore the feasibility of using electrochemical reduction as a substitute for TCEP in HDX-MS analyses. Our results demonstrate that efficient disulfide bond reduction is readily achieved by implementing an electrochemical cell into the HDX-MS workflow. We also identify some challenges in using electrochemical reduction in HDX-MS analyses and provide possible conditions to attenuate these limitations. For example, high salt concentrations hamper disulfide bond reduction, necessitating additional dilution of the sample with aqueous acidic solution at quench conditions. PMID:24251601

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

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

  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.

  4. 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

  5. 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.

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

    PubMed

    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.

  7. 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

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

    PubMed

    Jensen, Pernille Foged; Jørgensen, Thomas J D; Koefoed, Klaus; Nygaard, Frank; Sen, Jette Wagtberg

    2013-08-01

    Characterization of conformational and dynamic changes associated with protein interactions can be done by hydrogen/deuterium exchange mass spectrometry (HDX-MS) by comparing the deuterium uptake in the bound and unbound state of the proteins. Investigation of local hydrogen/deuterium exchange in heteromultimeric protein complexes poses a challenge for the method due to the increased complexity of the mixture of peptides originating from all interaction partners in the complex. Previously, interference of peptides from one interaction partner has been removed by immobilizing the intact protein on beads prior to the HDX-MS experiment. However, when studying protein complexes of more than two proteins, immobilization can possibly introduce steric limitations to the interactions. Here, we present a method based on the high affinity biotin-streptavidin interaction that allows selective capture of biotinylated proteins even under the extreme conditions for hydrogen/deuterium exchange quenching i.e. pH 2.5 and 0 °C. This biotin-streptavidin capture strategy allows hydrogen/deuterium exchange to occur in proteins in solution and enables characterization of specific proteins in heteromultimeric protein complexes without interference of peptides originating from other interaction partners in the complex. The biotin-streptavidin strategy has been successfully implemented in a model system with two recombinant monoclonal antibodies that target nonoverlapping epitopes on the human epidermal growth factor receptor (EGFR). We present a workflow for biotinylation and characterization of recombinant antibodies and demonstrate affinity capture of biotinylated antibodies under hydrogen/deuterium exchange quench conditions by the biotin-streptavidin strategy.

  9. 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

  10. Characterization of the N370S mutant of glucocerebrosidase by hydrogen/deuterium exchange mass spectrometry.

    PubMed

    Tang, Liangjie; Coales, Stephen J; Morrow, Jeffrey A; Edmunds, Tim; Hamuro, Yoshitomo

    2012-10-15

    An asparagine-to-serine substitution at residue 370 (N370S) in glucocerebrosidase (GCase) is the most prevalent mutation leading to Gaucher's disease, the most common lysosomal storage disorder. Two types of hydrogen/deuterium exchange experiment coupled with proteolysis and liquid chromatography-mass spectrometry (HDX-MS) were used to investigate the dynamic properties and unfolding stability of wt, R495H, and N370S GCases in the presence and absence of ligands. R495H GCase is used for enzyme replacement therapy and is considered to be a wt surrogate, whereas N370S is the most prevalent mutation leading to Gaucher's disease. Time-course HDX experiments of the GCases were performed under near-physiological conditions to detect the protein's local unfolding motions at a submolecular level. In guanidine-titration experiments, HDX reactions were performed with various concentrations of a chemical denaturant to provide the global stability of the proteins. The two types of experiment showed that all three purified GCases, wt, R495H, and N370S, have virtually identical local unfolding motions and global stabilities in solution. Combined with previous X-ray crystallographic studies, which showed indistinguishable backbone conformations for N370S and R495H GCase mutants and very similar melting temperatures for the wt, R495H, and N370S mutants, all three GCases are likely to have virtually identical structural and dynamic properties in solution. The guanidine-titration experiments revealed that the pharmacological chaperone, isofagomine (IFG), interacts more weakly with the N370S mutant than with the R495H GCase; this is consistent with the higher IC(50) value of IFG against N370S than against R495H. The time-course experiments showed that IFG restricts the local unfolding motions of N370S in the same way as those of R495H when the ligand saturates the proteins.

  11. 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.

  12. Identifying Zn-bound histidine residues in metalloproteins using hydrogen-deuterium exchange mass spectrometry.

    PubMed

    Dong, Jia; Callahan, Katie L; Borotto, Nicholas B; Vachet, Richard W

    2014-01-01

    In this work, we have developed a method that uses hydrogen-deuterium exchange (HDX) of C2-hydrogens of histidines coupled with mass spectrometry (MS) to identify Zn-bound histidines in metalloproteins. This method relies on differences in HDX reaction rates of Zn-bound and Zn-free His residues. Using several model peptides and proteins, we find that all Zn-bound His residues have substantially lower HDX reaction rates in the presence of the metal. The vast majority of non-Zn-binding His residues undergo no significant changes in HDX reaction rates when their reactivity is compared in the presence and absence of Zn. Using this new approach, we then determined the Zn binding site of β-2-microglobulin, a protein associated with metal-induced amyloidosis. Together, these results suggest that HDX-MS of His C2-hydrogens is a promising new method for identifying Zn-bound histidines in metalloproteins.

  13. Hydrogen deuterium exchange mass spectrometry in biopharmaceutical discovery and development - A review.

    PubMed

    Deng, Bin; Lento, Cristina; Wilson, Derek J

    2016-10-12

    Protein therapeutics have emerged as a major class of biopharmaceuticals over the past several decades, a trend that has motivated the advancement of bioanalytical technologies for protein therapeutic characterization. Hydrogen deuterium exchange mass spectrometry (HDX-MS) is a powerful and sensitive technique that can probe the higher order structure of proteins and has been used in the assessment and development of monoclonal antibodies (mAbs), antibody-drug conjugates (ADCs) and biosimilar antibodies. It has also been used to quantify protein-ligand, protein-receptor and other protein-protein interactions involved in signaling pathways. In manufacturing and development, HDX-MS can validate storage formulations and manufacturing processes for various biotherapeutics. Currently, HDX-MS is being refined to provide additional coverage, sensitivity and structural specificity and implemented on the millisecond timescale to reveal residual structure and dynamics in disordered domains and intrinsically disordered proteins. PMID:27662755

  14. 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

  15. In-ESI source hydrogen/deuterium exchange of carbohydrate ions.

    PubMed

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

    2014-03-01

    We present the investigation of hydrogen/deuterium (H/D) exchange of carbohydrates ions occurring in the electrospray ion source. The shape of the deuterium distribution was observed to be considerably dependent on the temperature of the ion transfer tube and the solvent used. If deuterated alcohol (EtOD or MeOD) or D2O/deuterated alcohol is used as an electrospray solvent, then for high temperatures (>350 °C), intensive back exchange is observed, resulting in ∼30% depth of the deuterium exchange. At low temperatures (<150 °C), the back exchange is weaker and the depth of the deuterium exchange is ∼70%. In the intermediate temperature region (∼250 °C), the deuterium distribution is unusually wide for methanol and bimodal for ethanol. The addition of 1% formic acid results in low (∼30%) depth of the deuterium exchange for any temperature in the operating region. The bimodal distribution for the ethanol can be possibly explained by the presence of differently folded gas-phase ions of carbohydrates.

  16. 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.

    2016-06-01

    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.

  17. 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.

  18. 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

  19. Microsecond pulsed hydrogen/deuterium exchange of electrosprayed ubiquitin ions stored in a linear ion trap.

    PubMed

    Rajabi, Khadijeh

    2015-02-01

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

  20. Microsecond pulsed hydrogen/deuterium exchange of electrosprayed ubiquitin ions stored in a linear ion trap.

    PubMed

    Rajabi, Khadijeh

    2015-02-01

    A pulse of D2O vapour on the order of microseconds is allowed to react with the +6 to +9 charge states of ubiquitin confined in a linear ion trap (LIT). Two envelopes of peaks are detected for the ions of ubiquitin, corresponding to the ions that exchange more quickly and more slowly. The deuterium uptake of the protonated sites on ubiquitin ions accounts for the ion population with the fast exchange. The hydrogen/deuterium exchange (HDX) kinetics of ubiquitin ions trapped in the LIT for 200 ms showed comparable structural transitions to those trapped for 300 ms. When ions are trapped for longer, i.e. up to 2000 ms, mainly the slow exchanging ion population is detected. In all experiments the +7 ions exchange the most, suggesting a short distance between the surface protonated sites and nearby charged sites, and concomitantly high accessibility of surface protonated sites towards D2O. The +6 ions are more compact than the +7 ions but have one fewer protonated site, therefore fewer surface availabilities for D2O attack. The data suggest that the +6 ions keep most of their solution-phase contacts intact while the hydrophobic core is slightly interrupted in the +7 ions, possibly due to the exposure of charged His68 that is normally buried in the hydrophobic pocket. The +8 and +9 ions have more protonated sites but are less compact than the +7 ions because of Coulombic repulsion, resulting in a larger distance between the protonated sites and the basic sites. The data indicate that the HDX mechanism of ions with the slower exchange corresponding to the second envelope of peaks is primarily governed via a relay mechanism. The results suggest that the pulsed HDX MS method is sampling a population of ubiquitin ions with a similar backbone fold to the solution. PMID:25553956

  1. Conformational stability of ribonuclease T1 determined by hydrogen-deuterium exchange.

    PubMed Central

    Mullins, L. S.; Pace, C. N.; Raushel, F. M.

    1997-01-01

    The hydrogen-deuterium exchange kinetics of 37 backbone amide residues in RNase T1 have been monitored at 25, 40, 45, and 50 degrees C at pD 5.6 and at 40 and 45 degrees C at pD 6.6. The hydrogen exchange rate constants of the hydrogen-bonded residues varied over eight orders of magnitude at 25 degrees C with 13 residues showing exchange rates consistent with exchange occurring as a result of global unfolding. These residues are located in strands 2-4 of the central beta-pleated sheet. The residues located in the alpha-helix and the remaining strands of the beta-sheet exhibited exchange behaviors consistent with exchange occurring due to local structural fluctuations. For several residues at 25 degrees C, the global free energy change calculated from the hydrogen exchange data was over 2 kcal/mol greater than the free energy of unfolding determined from urea denaturation experiments. The number of residues showing this unexpected behavior was found to increase with temperature. This apparent inconsistency can be explained quantitatively if the cis-trans isomerization of the two cis prolines, Pro-39 and Pro-55, is taken into account. The cis-trans isomerization equilibrium calculated from kinetic data indicates the free energy of the unfolded state will be 2.6 kcal/mol higher at 25 degrees C when the two prolines are cis rather than trans (Mayr LM, Odefey CO, Schutkowski M, Schmid FX. 1996. Kinetic analysis of the unfolding and refolding of ribonuclease T1 by a stopped-flow double-mixing technique. Biochemistry 35: 5550-5561). The hydrogen exchange results are consistent with the most slowly exchanging hydrogens exchanging from a globally higher free energy unfolded state in which Pro-55 and Pro-39 are still predominantly in the cis conformation. When the conformational stabilities determined by hydrogen exchange are corrected for the proline isomerization equilibrium, the results are in excellent agreement with those from an analysis of urea denaturation curves

  2. pH and urea dependence of amide hydrogen-deuterium exchange rates in the beta-trefoil protein hisactophilin.

    PubMed

    Houliston, R Scott; Liu, Chengsong; Singh, Laila M R; Meiering, Elizabeth M

    2002-01-29

    Amide hydrogen/deuterium exchange rates were measured as a function of pH and urea for 37 slowly exchanging amides in the beta-trefoil protein hisactophilin. The rank order of exchange rates is generally maintained under different solution conditions, and trends in the pH and urea dependence of exchange rates are correlated with the rank order of exchange rates. The observed trends are consistent with the expected behavior for exchange of different amides via global and/or local unfolding. Analysis of the pH dependence of exchange in terms of rate constants for structural opening and closing reveals a wide range of rates in different parts of the hisactophilin structure. The slowest exchanging amides have the slowest opening and closing rates. Many of the slowest exchanging amides are located in trefoil 2, but there are also some slow exchanging amides in trefoils 1 and 3. Slow exchangers tend to be near the interface between the beta-barrel and the beta-hairpin triplet portions of this single-domain structure. The pattern of exchange behaviour in hisactophilin is similar to that observed previously in interleukin-1 beta, indicating that exchange properties may be conserved among beta-trefoil proteins. Comparisons of opening and closing rates in hisactophilin with rates obtained for other proteins reveal clear trends for opening rates; however, trends in closing rates are less apparent, perhaps due to inaccuracies in the values used for intrinsic exchange rates in the data fitting. On the basis of the pH and urea dependence of exchange rates and optical measurements of stability and folding, EX2 is the main exchange mechanism in hisactophilin, but there is also evidence for varying levels of EX1 exchange at low and high pH and high urea concentrations. Equilibrium intermediates in which subglobal portions of structure are cooperatively disrupted are not apparent from analysis of the urea dependence of exchange rates. There is, however, a strong correlation between

  3. Platform Dependencies in Bottom-up Hydrogen/Deuterium Exchange Mass Spectrometry*

    PubMed Central

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

    2013-01-01

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

  4. 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.

  5. 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.

  6. 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

  7. 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.

  8. Fragmentation of mycosporine-like amino acids by hydrogen/deuterium exchange and electrospray ionisation tandem mass spectrometry.

    PubMed

    Cardozo, Karina H M; Carvalho, Valdemir M; Pinto, Ernani; Colepicolo, Pio

    2006-01-01

    The determination and identification of mycosporine-like amino acids (MAAs) from algae remain a major challenge due to the low concentration. Mass spectrometry (MS) can make an invaluable contribution in the search and identification of MAAs because of its high sensitivity, possibility of coupling with liquid chromatography, and the availability of powerful tandem mass spectrometric techniques. However, the unequivocal determination of the presence and location of important functional groups present on the basic skeleton of the MAAs is often elusive due to their inherent instability under MS conditions. In this study, the use of hydrogen/deuterium (H/D) exchange and electrospray ionisation tandem mass spectrometry (ESI-MS/MS) for characterisation of four MAAs (palythine, asterina, palythinol and shinorine) isolated from the macroalgae Gracilaria tenuistipitata Chang et Xia was investigated. The accurate-mass confirmation of the protonated molecules was performed on a Q-TOF instrument. We demonstrate that employing deuterium labelling in ESI-MS/MS analysis provides a convenient tool for the determination of new MAAs. Although the fragmentation patterns of MAAs were discussed earlier, to our knowledge, this is the first time that mechanisms are proposed.

  9. Effects of protein-ligand interactions on hydrogen/deuterium exchange kinetics: canonical and noncanonical scenarios.

    PubMed

    Sowole, Modupeola A; Konermann, Lars

    2014-07-01

    Hydrogen/deuterium exchange (HDX) methods are widely used for monitoring protein-ligand interactions. This approach relies on the fact that ligand binding can modulate the extent of protein structural fluctuations that transiently disrupt hydrogen bonds and expose backbone amides to the solvent. It is commonly observed that ligand binding causes a reduction of HDX rates. This reduction can be restricted to elements adjacent to the binding site, but other regions can be affected as well. Qualitatively, ligand-induced HDX protection can be rationalized on the basis of two-state models that equate structural dynamics with global unfolding/refolding. Unfortunately, such models tend to be unrealistic because the dynamics of native proteins are dominated by subglobal transitions and local fluctuations. Ligand binding lowers the ground-state free energy. It is not obvious why this should necessarily be accompanied by a depletion of excited-state occupancies, which would be required for a reduction of HDX rates. Here, we propose a framework that implies that ligand binding can either slow or accelerate amide deuteration throughout the protein. These scenarios are referred to as "type 1" and "type 2", respectively. Evidence for type 1 binding is abundant in the literature, whereas the viability of type 2 interactions is less clear. Using HDX mass spectrometry (MS), we demonstrate that the oxygenation of hemoglobin (Hb) provides a dramatic example of a type 2 scenario. The observed behavior is consistent with cooperative T → R switching, where part of the intrinsic O2 binding energy is reinvested for destabilization of the ground state. This destabilization increases the Boltzmann occupancy of unfolded conformers, thereby enhancing HDX rates. Surprisingly, O2 binding to myoglobin (Mb) also induces elevated HDX rates. These Mb data reveal that type 2 behavior is not limited to cooperative multisubunit systems. Although enhanced protection from deuteration is widely

  10. Structural dynamics of soluble chloride intracellular channel protein CLIC1 examined by amide hydrogen-deuterium exchange mass spectrometry.

    PubMed

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

    2009-09-01

    Chloride intracellular channel protein 1 (CLIC1) functions as an anion channel in plasma and nuclear membranes when its soluble monomeric form converts to an integral-membrane form. The transmembrane region of CLIC1 is located in its thioredoxin-like domain 1, but the mechanism whereby the protein converts to its membrane conformation has yet to be determined. Since channel formation in membranes is enhanced at low pH (5 to 5.5), a condition that is found at the surface of membranes, the structural dynamics of soluble CLIC1 was studied at pH 7 and at pH 5.5 in the absence of membranes by amide hydrogen-deuterium exchange mass spectrometry (DXMS). Rapid hydrogen exchange data indicate that CLIC1 displays a similar core structure at these pH values. Domain 1 is less stable than the all-helical domain 2, and, while the structure of domain 1 remains intact, its conformational flexibility is further increased in an acidic environment (pH 5.5). In the absence of membrane, an acidic environment appears to prime the solution structure of CLIC1 by destabilizing domain 1 in order to lower the activation energy barrier for its conversion to the membrane-insertion conformation. The significantly enhanced H/D-exchange rates at pH 5.5 displayed by two segments (peptides 11-31 and 68-82) could be due to the protonation of acidic residues in salt bridges. One of these segments (peptide 11-31) includes part of the transmembrane region which, in the solution structure, consists of helix alpha1. This helix is intrinsically stable and is most likely retained in the membrane conformation. Strand beta2, another element of the transmembrane region, displays a propensity to form a helical structure and has putative N- and C-capping motifs, suggesting that it too most likely forms a helix in a lipid bilayer.

  11. 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.

  12. Hydrogen/Deuterium Exchange-LC-MS Approach to Characterize the Action of Heparan Sulfate C5-Epimerase

    PubMed Central

    Babu, Ponnusamy; Victor, Xylophone V.; Nelsen, Emily; Nguyen, Thao Kim Nu; Raman, Karthik; Kuberan, Balagurunathan

    2011-01-01

    Heparan sulfate (HS) proteoglycans regulate a number of biological functions in many systems. Most of the functions of HS are attributed to its unique structure, consisting of sulfated and non-sulfated domains, arising from the differential presence of iduronyl and glucuronyl residues along the polysaccharide chain. A single glucuronyl C5-epimerase enzyme acts on heparan sulfate precursor, converts glucuronyl residues into iduronyl residues and modulates subsequent biosynthetic steps in vivo. The ratios of non-sulfated epimers within the polysaccharide chain have been calculated by resolving radiolabeled GlcA-AManR and IdoA-AManR disaccharides using a tedious paper chromatography technique. Radioactive assay, based on measuring either the release or incorporation of 3H at C5 carbon of uronyl residues of 3H-labeled HS precursor substrate, has been in use over three decades to characterize the action of HS C5-epimerase. We have developed a non-radioactive assay to estimate the epimerase activity through resolving GlcA-AManR and IdoA-AManR disaccharides on HPLC in conjunction with hydrogen/deuterium exchange upon epimerization protocol-liquid chromatography mass spectrometry (DEEP-LC-MS). Utilizing this new, non-radioactive based assay, DEEP-LC-MS, we were able to determine the extent of both forward and reverse reaction on the same substrate catalyzed by C5-epimerase. Results from this study also provide insights into the action of C5-epimerase and provide an opportunity to delineate snapshots of biosynthetic events that occur during the HSPG assembly in the Golgi. PMID:21573838

  13. Conformational difference in human IgG2 disulfide isoforms revealed by hydrogen/deuterium exchange mass spectrometry.

    PubMed

    Zhang, Aming; Fang, Jing; Chou, Robert Y-T; Bondarenko, Pavel V; Zhang, Zhongqi

    2015-03-17

    Both recombinant and natural human IgG2 antibodies have several different disulfide bond isoforms, which possess different global structures, thermal stabilities, and biological activities. A detailed mapping of the structural difference among IgG2 disulfide isoforms, however, has not been established. In this work, we employed hydrogen/deuterium exchange mass spectrometry to study the conformation of three major IgG2 disulfide isoforms known as IgG2-B, IgG2-A1, and IgG2-A2 in two recombinant human IgG2 monoclonal antibodies. By comparing the protection factors between amino acid residues in isoforms B and A1 (the classical form), we successfully identified several local regions in which the IgG2-B isoform showed more solvent protection than the IgG2-A1 isoform. On the basis of three-dimensional structural models of IgG2, these identified regions were located on the Fab domains, close to the hinge, centered on the side where the two Fab arms faced each other in spatial proximity. We speculated that in the more solvent-protected B isoform, the two Fab arms were brought into contact by the nonclassical disulfide bonds, resulting in a more compact global structure. Loss of Fab domain flexibility in IgG2-B could limit its ability to access cell-surface epitopes, leading to reduced antigen binding potency. The A2 isoform was previously found to have disulfide linkages similar to those of the classical A1 isoform, but with different biophysical behaviors. Our data indicated that, compared to IgG2-A1, IgG2-A2 had less solvent protection in some heavy-chain Fab regions close the hinge, suggesting that the A2 isoform had more flexible Fab domains. PMID:25730439

  14. Direct evidence for a two-state protein unfolding transition from hydrogen-deuterium exchange, mass spectrometry, and NMR.

    PubMed Central

    Yi, Q.; Baker, D.

    1996-01-01

    We use mass spectrometry in conjunction with hydrogen-deuterium exchange and NMR to characterize the conformational dynamics of the 62-residue IgG binding domain of protein L under conditions in which the native state is marginally stable. Mass spectra of protein L after short incubations in D2O reveal the presence of two distinct populations containing different numbers of protected protons. NMR experiments indicate that protons in the hydrophobic core are protected in one population, whereas all protons are exchanged for deuterons in the other. As the exchange period is increased, molecules are transferred from the former population to the latter. The absence of molecules with a subset of the core protons protected suggests that exchange occurs in part via a highly concerted transition to an excited state in which all protons exchange rapidly with deuterons. A steady increase in the molecular weight of the population with protected protons, and variation in the exchange rates of the individual protected protons indicates the presence of an additional exchange mechanism. A simple model in which exchange results from rapid (> 10(5)/s) local fluctuations around the native state superimposed upon transitions to an unfolded excited state at approximately 0.06/s is supported by qualitative agreement between the observed mass spectra and the mass spectra simulated according to the model using NMR-derived estimates of the proton exchange rates. PMID:8762137

  15. An electrospray ms-coupled microfluidic device for sub-second hydrogen/deuterium exchange pulse-labelling reveals allosteric effects in enzyme inhibition.

    PubMed

    Rob, Tamanna; Gill, Preet Kamal; Golemi-Kotra, Dasantila; Wilson, Derek J

    2013-07-01

    In this work, we introduce an integrated, electrospray mass spectrometry-coupled microfluidic chip that supports the complete workflow for 'bottom up' hydrogen/deuterium exchange (HDX) pulse labelling experiments. HDX pulse labelling is used to measure structural changes in proteins that occur after the initiation of a reaction, most commonly folding. In the present case, we demonstrate the device on the β-lactamase enzyme TEM-1, identifying active site changes that occur upon acylation by a covalent inhibitor and subtle changes in conformational dynamics that occur away from the active site over a period of several second after the inhibitor is bound. Our results demonstrate the power of microfluidics-enabled sub-second HDX pulse labelling as a tool for studying allostery and show some intriguing correlations with mutagenesis studies.

  16. Evidence of Allosteric Enzyme Regulation via Changes in Conformational Dynamics: A Hydrogen/Deuterium Exchange Investigation of Dihydrodipicolinate Synthase.

    PubMed

    Sowole, Modupeola A; Simpson, Sarah; Skovpen, Yulia V; Palmer, David R J; Konermann, Lars

    2016-09-27

    Dihydrodipicolinate synthase is a tetrameric enzyme of the diaminopimelate pathway in bacteria and plants. The protein catalyzes the condensation of pyruvate (Pyr) and aspartate semialdehyde en route to the end product lysine (Lys). Dihydrodipicolinate synthase from Campylobacter jejuni (CjDHDPS) is allosterically inhibited by Lys. CjDHDPS is a promising antibiotic target, as highlighted by the recent development of a potent bis-lysine (bisLys) inhibitor. The mechanism whereby Lys and bisLys allosterically inhibit CjDHDPS remains poorly understood. In contrast to the case for other allosteric enzymes, crystallographically detectable conformational changes in CjDHDPS upon inhibitor binding are very minor. Also, it is difficult to envision how Pyr can access the active site; the available X-ray data seemingly imply that each turnover step requires diffusion-based mass transfer through a narrow access channel. This study employs hydrogen/deuterium exchange mass spectrometry for probing the structure and dynamics of CjDHDPS in a native solution environment. The deuteration kinetics reveal that the most dynamic protein regions are in the direct vicinity of the substrate access channel. This finding is consistent with the view that transient opening/closing fluctuations facilitate access of the substrate to the active site. Under saturating conditions, both Lys and bisLys cause dramatically reduced dynamics in the inhibitor binding region. In addition, rigidification extends to regions close to the substrate access channel. This finding strongly suggests that allosteric inhibitors interfere with conformational fluctuations that are required for CjDHDPS substrate turnover. In particular, our data imply that Lys and bisLys suppress opening/closing events of the access channel, thereby impeding diffusion of the substrate into the active site. Overall, this work illustrates why allosteric control does not have to be associated with crystallographically detectable large

  17. NMR-Based Amide Hydrogen-Deuterium Exchange Measurements for Complex Membrane Proteins: Development and Critical Evaluation

    NASA Astrophysics Data System (ADS)

    Czerski, Lech; Vinogradova, Olga; Sanders, Charles R.

    2000-01-01

    A method for measuring site-specific amide hydrogen-deuterium exchange rates for membrane proteins in bilayers is reported and evaluated. This method represents an adaptation and extension of the approach of Dempsey and co-workers (Biophys. J. 70, 1777-1788 (1996)) and is based on reconstituting 15N-labeled membrane proteins into phospholipid bilayers, followed by lyophilization and rehydration with D2O or H2O (control). Following incubation for a time t under hydrated conditions, samples are again lyophilized and then solubilized in an organic solvent system, where 1H-15N HSQC spectra are recorded. Comparison of spectra from D2O-exposed samples to spectra from control samples yields the extent of the H-D exchange which occurred in the bilayers during time t. Measurements are site specific if specific 15N labeling is used. The first part of this paper deals with the search for a suitable solvent system in which to solubilize complex membrane proteins in an amide "exchange-trapped" form for NMR quantitation of amide peak intensities. The second portion of the paper documents application of the overall procedure to measuring site-specific amide exchange rates in diacylglycerol kinase, a representative integral membrane protein. Both the potential usefulness and the significant limitations of the new method are documented.

  18. Mapping Protein-Ligand Interactions with Proteolytic Fragmentation, Hydrogen/Deuterium Exchange-Mass Spectrometry.

    PubMed

    Gallagher, Elyssia S; Hudgens, Jeffrey W

    2016-01-01

    Biological processes are the result of noncovalent, protein-ligand interactions, where the ligands range from small organic and inorganic molecules to lipids, nucleic acids, peptides, and proteins. Amide groups within proteins constantly exchange protons with water. When immersed in heavy water (D2O), mass spectrometry (MS) can measure the change of mass associated with the hydrogen to deuterium exchange (HDX). Protein-ligand interactions modify the hydrogen exchange rates of amide protons, and the measurement of the amide exchange rates can provide rich information regarding the dynamical structure of the protein-ligand complex. This chapter describes a protocol for conducting bottom-up, continuous uptake, proteolytic fragmentation HDX-MS experiments that can help identify and map the interacting peptides of a protein-ligand interface. This tutorial outlines the fundamental theory governing hydrogen exchange; provides practical information regarding the preparation of protein samples and solutions; and describes the exchange reaction, reaction quenching, enzymatic digestion, chromatographic separation, and peptide analysis by MS. Tables list representative combinations of fluidic components used by HDX-MS researchers and summarize the available HDX-MS analysis software packages. Additionally, two HDX-MS case studies are used to illustrate protein-ligand interactions involving: (1) a continuous sequence of interacting residues and (2) a set of discontinuously numbered residues, residing spatially near each other.

  19. Polarized Fourier transform infrared spectroscopy of bacteriorhodopsin. Transmembrane alpha helices are resistant to hydrogen/deuterium exchange

    SciTech Connect

    Earnest, T.N.; Herzfeld, J.; Rothschild, K.J. )

    1990-12-01

    The secondary structure of bacteriorhodopsin has been investigated by polarized Fourier transform infrared spectroscopy combined with hydrogen/deuterium exchange, isotope labeling and resolution enhancement methods. Oriented films of purple membrane were measured at low temperature after exposure to H2O or D2O. Resolution enhancement techniques and isotopic labeling of the Schiff base were used to assign peaks in the amide I region of the spectrum. alpha-helical structure, which exhibits strong infrared dichroism, undergoes little H/D exchange, even after 48 h of D2O exposure. In contrast, non-alpha-helical structure, which exhibits little dichroism, undergoes rapid H/D exchange. A band at 1,640 cm-1, which has previously been assigned to beta-sheet structure, is found to be due in part to the C = N stretching vibration of protonated Schiff base of the retinylidene chromophore. We conclude that the membrane spanning regions of bR consist predominantly of alpha-helical structure whereas most beta-type structure is located in surface regions directly accessible to water.

  20. 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.

  1. 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).

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

    PubMed

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

    2016-04-29

    An experimental setup for the speciation of compounds by hydrogen/deuterium exchange (HDX) with atmospheric pressure ionization while performing chromatographic separation is presented. The proposed experimental setup combines the high performance supercritical fluid chromatography (SFC) system that can be readily used as an inlet for mass spectrometry (MS) and atmospheric pressure photo ionization (APPI) or atmospheric pressure chemical ionization (APCI) HDX. This combination overcomes the limitation of an approach using conventional liquid chromatography (LC) by minimizing the amount of deuterium solvents used for separation. In the SFC separation, supercritical CO2 was used as a major component of the mobile phase, and methanol was used as a minor co-solvent. By using deuterated methanol (CH3OD), AP HDX was achieved during SFC separation. To prove the concept, thirty one nitrogen- and/or oxygen-containing standard compounds were analyzed by SFC-AP HDX MS. The compounds were successfully speciated from the obtained SFC-MS spectra. The exchange ions were observed with as low as 1% of CH3OD in the mobile phase, and separation could be performed within approximately 20min using approximately 0.24 mL of CH3OD. The results showed that SFC separation and APPI/APCI HDX could be successfully performed using the suggested method. PMID:27020885

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

    PubMed

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

    2016-04-29

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

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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

  9. Preparation and hydrogen-deuterium exchange of alkyl and hydride bis(trimethylsilyl)amido derivatives of the actinide elements

    SciTech Connect

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

    1981-09-01

    The monomeric, hydrocarbon-soluble monohydrides and monodeuterides of the actinide metals (thorium or uranium) of the type HM[N(SiMe3)2]3 have been prepared for this research. Their reaction chemistry, n-BuLi followed by MeBr yields MeM[N(SiMe3)2]3 and borane in tetrahydrofuran yields BH4M[N(SiMe3)2]3, suggests that the hydrogen atom is hydridic. Pyrolysis of the hydrides yields the novel, four-membered ring metallocycle [(Me3Si)2N]2MCH2Si(Me)2NSiMe3 where M is Th or U. In conclusion, these metallocycles are the key intermediates in the hydrogen-deuterium exchange reaction that yields {[(CD3)3Si]2N}3MD.

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

    PubMed

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

    2014-06-01

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

  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. 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.

  13. 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. PMID:26898203

  14. Different conformational dynamics of PDZ1 and PDZ2 in full-length EBP50 analyzed by hydrogen/deuterium exchange mass spectrometry.

    PubMed

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

    2015-08-01

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

  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.

  16. Hydrogen/Deuterium Exchange and Molecular Dynamics Analysis of Amyloid Fibrils Formed by a D69K Charge-Pair Mutant of Human Apolipoprotein C-II.

    PubMed

    Mao, Yu; Zlatic, Courtney O; Griffin, Michael D W; Howlett, Geoffrey J; Todorova, Nevena; Yarovsky, Irene; Gooley, Paul R

    2015-08-11

    Plasma apolipoproteins form amphipathic α helices in lipid environments but in the lipid-free state show a high propensity to form β structure and self-associate into amyloid fibrils. The widespread occurrence of apolipoproteins in amyloid plaques suggests disease-related roles, specifically in atherosclerosis. To reconcile the dual abilities of apolipoproteins to form either α helices or cross-β sheet structures, we examined fibrils formed by human apolipoprotein C-II (apoC-II). A structural model for apoC-II fibrils shows a cross-β core with parallel β strands, including a buried K30-D69 charge pair. We investigated the effect of abolishing this charge pair in mutant D69K apoC-II. Fluorescence studies indicated more rapid fibril formation and less solvent accessibility of tryptophan (W26) in D69K apoC-II fibrils than in wild-type (WT) fibrils. X-ray diffraction data of aligned D69K apoC-II fibrils yielded a typical cross-β structure with increased β sheet spacing compared to that of WT fibrils. Hydrogen/deuterium (H/D) exchange patterns were similar for D69K apoC-II fibrils compared to WT fibrils, albeit with an overall reduction in the level of slow H/D exchange, particularly around residues 29-32. Molecular dynamics simulations indicated reduced β strand content for a model D69K apoC-II tetramer compared to the WT tetramer and confirmed an expansion of the cross-β spacing that contributed to the formation of a stable charge pair between K69 and E27. The results highlight the importance of charge-pair interactions within the apoC-II fibril core, which together with numerous salt bridges in the flexible connecting loop play a major role in the ability of lipid-free apoC-II to form stable cross-β fibrils.

  17. Two-Site Evaluation of the Repeatability and Precision of an Automated Dual-Column Hydrogen/Deuterium Exchange Mass Spectrometry Platform.

    PubMed

    Cummins, David J; Espada, Alfonso; Novick, Scott J; Molina-Martin, Manuel; Stites, Ryan E; Espinosa, Juan Felix; Broughton, Howard; Goswami, Devrishi; Pascal, Bruce D; Dodge, Jeffrey A; Chalmers, Michael J; Griffin, Patrick R

    2016-06-21

    Hydrogen/deuterium exchange coupled with mass spectrometry (HDX-MS) is an information-rich biophysical method for the characterization of protein dynamics. Successful applications of differential HDX-MS include the characterization of protein-ligand binding. A single differential HDX-MS data set (protein ± ligand) is often comprised of more than 40 individual HDX-MS experiments. To eliminate laborious manual processing of samples, and to minimize random and gross errors, automated systems for HDX-MS analysis have become routine in many laboratories. However, an automated system, while less prone to random errors introduced by human operators, may have systematic errors that go unnoticed without proper detection. Although the application of automated (and manual) HDX-MS has become common, there are only a handful of studies reporting the systematic evaluation of the performance of HDX-MS experiments, and no reports have been published describing a cross-site comparison of HDX-MS experiments. Here, we describe an automated HDX-MS platform that operates with a parallel, two-trap, two-column configuration that has been installed in two remote laboratories. To understand the performance of the system both within and between laboratories, we have designed and completed a test-retest repeatability study for differential HDX-MS experiments implemented at each of two laboratories, one in Florida and the other in Spain. This study provided sufficient data to do both within and between laboratory variability assessments. Initial results revealed a systematic run-order effect within one of the two systems. Therefore, the study was repeated, and this time the conclusion was that the experimental conditions were successfully replicated with minimal systematic error. PMID:27224086

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

    PubMed Central

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

    2009-01-01

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

  20. 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.

  1. 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.

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

    PubMed

    Seger, Signe T; Breinholt, Jens; Faber, Johan H; Andersen, Mette D; Wiberg, Charlotte; Schjødt, Christine B; Rand, Kasper D

    2015-06-16

    Human growth hormone (hGH), and its receptor interaction, is essential for cell growth. To stabilize a flexible loop between helices 3 and 4, while retaining affinity for the hGH receptor, we have engineered a new hGH variant (Q84C/Y143C). Here, we employ hydrogen-deuterium exchange mass spectrometry (HDX-MS) to map the impact of the new disulfide bond on the conformational dynamics of this new hGH variant. Compared to wild type hGH, the variant exhibits reduced loop dynamics, indicating a stabilizing effect of the introduced disulfide bond. Furthermore, the disulfide bond exhibits longer ranging effects, stabilizing a short α-helix quite distant from the mutation sites, but also rendering a part of the α-helical hGH core slightly more dynamic. In the regions where the hGH variant exhibits a different deuterium uptake than the wild type protein, electron transfer dissociation (ETD) fragmentation has been used to pinpoint the residues responsible for the observed differences (HDX-ETD). Finally, by use of surface plasmon resonance (SPR) measurements, we show that the new disulfide bond does not compromise receptor affinity. Our work highlight the analytical potential of HDX-ETD combined with functional assays to guide protein engineering. PMID:25978680

  4. Hydrogen/Deuterium Exchange Kinetics Demonstrate Long Range Allosteric Effects of Thumb Site 2 Inhibitors of Hepatitis C Viral RNA-dependent RNA Polymerase.

    PubMed

    Deredge, Daniel; Li, Jiawen; Johnson, Kenneth A; Wintrode, Patrick L

    2016-05-01

    New nonnucleoside analogs are being developed as part of a multi-drug regimen to treat hepatitis C viral infections. Particularly promising are inhibitors that bind to the surface of the thumb domain of the viral RNA-dependent RNA polymerase (NS5B). Numerous crystal structures have been solved showing small molecule non-nucleoside inhibitors bound to the hepatitis C viral polymerase, but these structures alone do not define the mechanism of inhibition. Our prior kinetic analysis showed that nonnucleoside inhibitors binding to thumb site-2 (NNI2) do not block initiation or elongation of RNA synthesis; rather, they block the transition from the initiation to elongation, which is thought to proceed with significant structural rearrangement of the enzyme-RNA complex. Here we have mapped the effect of three NNI2 inhibitors on the conformational dynamics of the enzyme using hydrogen/deuterium exchange kinetics. All three inhibitors rigidify an extensive allosteric network extending >40 Å from the binding site, thus providing a structural rationale for the observed disruption of the transition from distributive initiation to processive elongation. The two more potent inhibitors also suppress slow cooperative unfolding in the fingers extension-thumb interface and primer grip, which may contribute their stronger inhibition. These results establish that NNI2 inhibitors act through long range allosteric effects, reveal important conformational changes underlying normal polymerase function, and point the way to the design of more effective allosteric inhibitors that exploit this new information. PMID:27006396

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

    PubMed Central

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

    2016-01-01

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

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

    PubMed Central

    2015-01-01

    Phage display (PD) is frequently used to discover peptides capable of binding to biological protein targets. The structural characterization of peptide–protein complexes is often challenging due to their low binding affinities and high structural flexibility. Here, we investigate the use of hydrogen/deuterium exchange mass spectrometry (HDX-MS) to characterize interactions of low affinity peptides with their cognate protein targets. The HDX-MS workflow was optimized to accurately detect low-affinity peptide–protein interactions by use of ion mobility, electron transfer dissociation, nonbinding control peptides, and statistical analysis of replicate data. We show that HDX-MS can identify regions in the two epigenetic regulator proteins KDM4C and KDM1A that are perturbed through weak interactions with PD-identified peptides. Two peptides cause reduced HDX on opposite sides of the active site of KDM4C, indicating distinct binding modes. In contrast, the perturbation site of another PD-selected peptide inhibiting the function of KDM1A maps to a GST-tag. Our results demonstrate that HDX-MS can validate and map weak peptide–protein interactions and pave the way for understanding and optimizing the binding of peptide scaffolds identified through PD and similar ligand discovery approaches. PMID:25325890

  7. 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

  8. Hydrogen-deuterium exchange mass spectrometry reveals the interaction of Fenna-Matthews-Olson protein and chlorosome CsmA protein

    PubMed Central

    Huang, Richard Y-C.; Wen, Jianzhong; Blankenship, Robert E.; Gross, Michael L.

    2011-01-01

    In green-sulfur bacterial photosynthesis, excitation energy absorbed by a peripheral antenna structure known as the chlorosome is sequentially transferred through a baseplate protein to the Fenna-Matthews-Olson (FMO) antenna protein and into the reaction center, which is embedded in the cytoplasmic membrane. The molecular details of the optimized photosystem architecture required for efficient energy transfer are only partially understood. We address here the question of how the baseplate interacts with the FMO protein by applying hydrogen/deuterium exchange coupled with enzymatic digestion and mass spectrometry analysis to reveal the binding interface of the FMO antenna protein and the CsmA baseplate protein. Several regions on the FMO protein, represented by peptides consisting of 123-129, 140-149, 150-162, 191-208 and 224-232, show significant decreases of deuterium uptake after CsmA binding. The results indicate that the CsmA protein interacts with the Bchl a #1 side of the FMO protein. A global picture including peptide-level details for the architecture of the photosystem from green sulfur bacteria can now be drawn. PMID:22142245

  9. Liquid chromatography/quadrupole time-of-flight mass spectrometry in combination with online hydrogen/deuterium exchange technique for structural elucidation of phase I metabolites of iso-phenylcyclopentylamine in rat bile.

    PubMed

    Liu, Xiaoxue; Wang, Suilou; Ding, Li; Chen, Xiaoping; Shen, Wenbin; Dong, Xin; Yun, Changhong; Lin, Hongda

    2014-10-01

    MS/MS experiment and accurate mass measurement are powerful tools in metabolite identification. However, sometimes these data do not provide enough information to assign an unambiguous structure to a metabolite. In combination with MS techniques, hydrogen/deuterium (H/D) exchange can provide additional information for structural elucidation by determination of the number of exchangeable hydrogen atoms in a structure. In this study, the principal phase I metabolites of iso-phenylcyclopentylamine in rat bile were identified by high-performance liquid chromatography with electrospray ionization quadrupole time-of-flight mass spectrometry (ESI-Q-TOF-MS). Since N-oxidation may occur because of the existence of the primary amino group in the structure, it was difficult to differentiate the hydroxylated metabolites from N-oxides by ESI-Q-TOF-MS alone. Therefore, online H/D exchange technique was applied to solve this problem. Finally, 25 phase I metabolites were detected and structurally described, in which 11 were confirmed to be N-oxides. This study demonstrated the effectiveness of high-resolution mass spectrometry in combination with an online H/D exchange technique in rapid identification of drug metabolites, especially in discriminating hydroxylated metabolites from N-oxides.

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

    PubMed

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

    2014-06-01

    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.

  11. 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

  12. Is the pre-Tg DSC endotherm observed with solid state proteins associated with the protein internal dynamics? Investigation of bovine serum albumin by solid state hydrogen/deuterium exchange.

    PubMed

    Mizuno, Masayasu; Pikal, Michael J

    2013-10-01

    DSC thermograms of solid state pure proteins often show a distinct endotherm at a temperature far below the glass transition temperature of the system (Tg). We hypothesized this endotherm represents enthalpy recovery associated with an internal mobility transition of the protein molecule. Although the existence of an internal transition has been postulated, whether this endotherm is associated with such a transition has not previously been discussed. The purpose of this study was to investigate the origin of the pre-Tg endotherm in lyophilized bovine serum albumin (BSA). Due to strong glass behavior, the system Tg was determined by extrapolating Tg data of disaccharide/BSA formulations to zero saccharide. A small pre-Tg endotherm around 40-60 °C was observed in amorphous BSA equilibrated at 11%RH. The apparent activation energy suggested the endotherm was "α-mobility"-related. A solid state hydrogen/deuterium exchange study using FTIR was conducted over a temperature range spanning the endotherm. We found a fast phase, followed by essentially a plateau level which is highly temperature dependent in the 40-60 °C range, suggesting enhanced internal protein motion as the system passes through the temperature range of the endotherm. These results suggest the pre-Tg endotherm is associated with a protein internal mobility transition.

  13. First-principles study of temperature-dependent diffusion coefficients: Hydrogen, deuterium, and tritium in α-Ti

    NASA Astrophysics Data System (ADS)

    Lu, Yong; Zhang, Ping

    2013-05-01

    We report the prediction of temperature-dependent diffusion coefficients of interstitial hydrogen, deuterium, and tritium atoms in α-Ti using transition state theory. The microscopic parameters in the pre-factor and activation energy of the impurity diffusion coefficients are obtained from first-principles total energy and phonon calculations including the full coupling between the vibrational modes of the diffusing atom with the host lattice. The dual occupancy case of impurity atom in the hcp matrix is considered, and four diffusion paths are combined to obtain the final diffusion coefficients. The calculated diffusion parameters show good agreement with experiments. Our numerical results indicate that the diffusions of deuterium and tritium atoms are slower than that of the hydrogen atom at temperatures above 425 K and 390 K, respectively.

  14. Comparative hydrogen-deuterium exchange for a mesophilic vs thermophilic dihydrofolate reductase at 25 °C: identification of a single active site region with enhanced flexibility in the mesophilic protein.

    PubMed

    Oyeyemi, Olayinka A; Sours, Kevin M; Lee, Thomas; Kohen, Amnon; Resing, Katheryn A; Ahn, Natalie G; Klinman, Judith P

    2011-09-27

    The technique of hydrogen-deuterium exchange coupled to mass spectrometry (HDX-MS) has been applied to a mesophilic (E. coli) dihydrofolate reductase under conditions that allow direct comparison to a thermophilic (B. stearothermophilus) ortholog, Ec-DHFR and Bs-DHFR, respectively. The analysis of hydrogen-deuterium exchange patterns within proteolytically derived peptides allows spatial resolution, while requiring a series of controls to compare orthologous proteins with only ca. 40% sequence identity. These controls include the determination of primary structure effects on intrinsic rate constants for HDX as well as the use of existing 3-dimensional structures to evaluate the distance of each backbone amide hydrogen to the protein surface. Only a single peptide from the Ec-DHFR is found to be substantially more flexible than the Bs-DHFR at 25 °C in a region located within the protein interior at the intersection of the cofactor and substrate-binding sites. The surrounding regions of the enzyme are either unchanged or more flexible in the thermophilic DHFR from B. stearothermophilus. The region with increased flexibility in Ec-DHFR corresponds to one of two regions previously proposed to control the enthalpic barrier for hydride transfer in Bs-DHFR [Oyeyemi et al. (2010) Proc. Natl. Acad. Sci. U.S.A. 107, 10074]. PMID:21859100

  15. 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

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

    PubMed

    Gershon, P D

    2010-12-15

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

  17. Controlling hydrogen scrambling in multiply charged protein ions during collisional activation: implications for top-down hydrogen/deuterium exchange MS utilizing collisional activation in the gas phase.

    PubMed

    Abzalimov, Rinat R; Kaltashov, Igor A

    2010-02-01

    Hydrogen exchange in solution combined with ion fragmentation in the gas phase followed by MS detection emerged in recent years as a powerful tool to study higher order protein structure and dynamics. However, a certain type of ion chemistry in the gas phase, namely, internal rearrangement of labile hydrogen atoms (the so-called hydrogen scrambling), is often cited as a factor limiting the utility of this experimental technique. Although several studies have been carried out to elucidate the roles played by various factors in the occurrence and the extent of hydrogen scrambling, there is still no consensus as to what experimental protocol should be followed to avoid or minimize it. In this study we employ fragmentation of mass-selected subpopulations of protein ions to assess the extent of internal proton mobility prior to dissociation. A unique advantage of tandem MS is that it not only provides a means to map the deuterium content of protein ions whose overall levels of isotope incorporation can be precisely defined by controlling the mass selection window, but also correlates this spatial isotope distribution with such global characteristic as the protein ion charge state. Hydrogen scrambling does not occur when the charge state of the precursor protein ions selected for fragmentation is high. Fragment ions derived from both N- and C-terminal parts of the protein are equally unaffected by scrambling. However, spatial distribution of deuterium atoms obtained by fragmenting low-charge-density protein ions is consistent with a very high degree of scrambling prior to the dissociation events. The extent of hydrogen scrambling is also high when multistage fragmentation is used to probe deuterium incorporation locally. Taken together, the experimental results provide a coherent picture of intramolecular processes occurring prior to the dissociation event and provide guidance for the design of experiments whose outcome is unaffected by hydrogen scrambling.

  18. Hydrogen-deuterium exchange of diborane in superacid solution through diboranonium (B sub 2 H sub 7 sup + ) and diboranium (B sub 2 H sub 5 sup + ) ions

    SciTech Connect

    Olah, G.A.; Aniszfeld, R.; Surya Prakash, G.K.; Williams, R.E.; Lammertsma, K.; Guener, O.F.

    1988-11-09

    The slow proton/deuterium exchange of B{sub 2}H{sub 6} in the superacidic FSO{sub 3}D SbF{sub 5}/SO{sub 2}ClF medium at low temperature involving the corresponding isotopomeric diboranonium ions B{sub 2}H{sub 7}{sup +} is reported here. The structure of the B{sub 2}H{sub 7}{sup +} ion has also been probed by ab inito theoretical calculations. The H/D exchange is rationalized by the pathway that deuteriation occurs exclusively on an unbridged (terminal B-H) bond resulting in a B{sub 2}H{sub 6}D{sup +} ion which is expected to undergo polytopol (bond-to-bond) rearrangement scrambling all hydrogens and deuteriums followed by proton loss leading to the exchanged product. 18 references.

  19. "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

  20. Protonated hydronium dication, H/sub 4/O/sup 2 +/. Hydrogen-deuterium exchange of D/sub 2/H/sup 17/O/sup +/ in HF:SbF/sub 5/ and DH/sub 2//sup 17/O/sup +/ in DF:SbF/sub 5/ and theoretical calculations

    SciTech Connect

    Olah, G.A.; Prakash, G.K.S.; Barzaghi, M.; Lammertsma, K.; von R. Schleyer, P.; Pople, J.A.

    1986-03-05

    Isotopic hydronium ions D/sub 2/H/sup 17/O/sup +/ and DH/sub 2//sup 17/O/sup +/ in 1:1 (molar) HF:SbF/sub 5//SO/sub 2/ and DF:SbF/sub 2/SO/sub 2/ solutions, respectively, at -15/sup 0/C undergo slow hydrogen-deuterium exchange as monitored by /sup 17/O NMR spectroscopy. The rate of such exchange increases with the increase in the acidity of the fluoroantimonic acid medium (1:2 molar composition). The previously observed lack of exchange of isotopic hydronium ions in the somewhat weaker Magic Acid, FSO/sub 3/H:SbF/sub 5/, medium (H/sub 0/ approx. -21.5) suggests that in the stronger HF:SbF/sub 5/ medium (H/sub 0/ approx. -25 to -28), the exchange occurs through the intermediacy of protonated hydronium dication. Consequently, the structure and stability of protonated hydronium dication has been probed by ab initio theory. The T/sub d/ symmetry structure was found to be the minimum energy structure at the HF/6.31G* level. At the HF/6.31G* level this structure is thermodynamically unstable (dissociation preferred by 59.2 kcal/mol), it seems to have significant kinetic stability (deprotonation barrier 39.4 kcal/mol). 20 references, 1 table.

  1. Metabolite identification of artemether by data-dependent accurate mass spectrometric analysis using an LTQ-Orbitrap hybrid mass spectrometer in combination with the online hydrogen/deuterium exchange technique.

    PubMed

    Liu, Tian; Du, Fuying; Zhu, Fanping; Xing, Jie

    2011-11-15

    Artemether (ARM), the O-methyl ether prodrug of dihydroartemisinin (DHA), is a first-line antimalarial drug used in areas of multi-drug resistance. Artemisinin drugs can be metabolized extensively in vivo and this seems related to their autoinduction pharmacokinetics. In the present study, the metabolite identification of ARM was performed by the generic data-dependent accurate mass spectrometric analysis, using high-resolution (HR) liquid chromatography/electrospray ionization mass spectrometry (LC/ESI-MS) and tandem mass spectrometry (MS/MS) LTQ-Orbitrap hybrid mass spectrometer in conjunction with online hydrogen (H)/deuterium (D) exchange for rapid structural characterization. The LC separation was improved allowing the separation of ARM parent drugs and their metabolites from their diastereomers. A total of 77 phase I metabolites of ARM were identified in rat liver microsomal incubates and rat urine, including dihydroartemisinin and artemisinin. In rat bile, 12 phase II metabolites were found. Accurate mass data were obtained in both full scan and HR-MS/MS mode to support assignments of metabolite structures. Online H/D exchange LC/HR-ESI-MS experiments provided additional evidence in differentiating dihydroxylated deoxy-ARM from mono-hydroxylated ARM. The results showed the main phase I metabolites of artemether are hydroxylated, dehydro, demethylated and deoxy products, and they will undergo subsequent phase II glucuronidation processes. Most metabolites were reported for the first time. This study also demonstrated the effectiveness of high-resolution mass spectrometry in combination with an online H/D exchange LC/HR-MS(n) technique in rapid identification of drug metabolites. PMID:22006394

  2. Speed of sound in solid molecular hydrogen-deuterium: Quantum Molecular Dynamics Approximation

    NASA Astrophysics Data System (ADS)

    Guerrero, Carlo Luis; Perlado, Jose Manuel

    2016-05-01

    Uniformity of the solid layer is one of the critical points for an efficient ignition of the Deuterium-Tritium (DT) target. During the compression process this layer, perturbations grow as the Rayleigh-Taylor instability. Knowing the mechanical properties of this layer and its thermo-mechanical limits is necessary if we want to control or to minimize these instabilities. In this work we have used a simplified approach, replacing the DT ice system with a mixture of hydrogen-deuterium (HD) because beta decay of tritium complicates the analysis in the former case. Through simulation with ab initio methods we have calculated the elastic constants, the bulk modulus and sound velocity for hydrogen isotopes in solid molecular state. In this work we present the results for hydrogen-deuterium mixtures 50%-50%, at 15 K and with a compression which covers the range of 1 to 15 GPa. This system is interesting for study the early stages of the dynamic compression and provides conditions that are close to the manufacture of DT target in inertial confinement fusion. Discontinuities in the curve that have been observed on pure hydrogen, which are associated with phase transitions and the phase hysteresis.

  3. Electron Scattering Experiments with Polarized Hydrogen/Deuterium Internal Targets

    SciTech Connect

    van Buuren, L.D.; 97-01 Collaboration

    2000-12-31

    A high-density polarized hydrogen/deuterium internal gas target is presented. The target is based on a setup previously used in electron scattering experiments with tensor-polarized deuterium. To increase the target thickness, new state-of-the-art permanent sextupole magnets and a more powerful pumping system were installed together with a longer (60 cm) and colder ({approximately}70 K) cylindrical storage cell. Electro-nuclear spin observables were measured by scattering longitudinally polarized electrons stored in the AmPS ring (NIFHEF) from the target gas. The product of electron beam and target polarization was determined from the known e{prime}p (quasi) elastic asymmetries. A target thickness of 1.1 {times} 10{sup 14} atoms/cm{sup 2} was achieved which with typical beam currents of 110 mA corresponds to a luminosity of about 7.5 {times} 10{sup 31} cm{sup {minus}2}s{sup {minus}1}. Target and beam polarizations up to 0.7 and 0.65, respectively, were obtained.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. A very light and thin liquid hydrogen/deuterium heat pipe target for COSY experiments

    NASA Astrophysics Data System (ADS)

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

    2005-07-01

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

  9. Mapping the structure of folding cores in TIM barrel proteins by hydrogen exchange mass spectrometry: the roles of motif and sequence for the indole-3-glycerol phosphate synthase from Sulfolobus solfataricus.

    PubMed

    Gu, Zhenyu; Zitzewitz, Jill A; Matthews, C Robert

    2007-04-27

    To test the roles of motif and amino acid sequence in the folding mechanisms of TIM barrel proteins, hydrogen-deuterium exchange was used to explore the structure of the stable folding intermediates for the of indole-3-glycerol phosphate synthase from Sulfolobus solfataricus (sIGPS). Previous studies of the urea denaturation of sIGPS revealed the presence of an intermediate that is highly populated at approximately 4.5 M urea and contains approximately 50% of the secondary structure of the native (N) state. Kinetic studies showed that this apparent equilibrium intermediate is actually comprised of two thermodynamically distinct species, I(a) and I(b). To probe the location of the secondary structure in this pair of stable on-pathway intermediates, the equilibrium unfolding process of sIGPS was monitored by hydrogen-deuterium exchange mass spectrometry. The intact protein and pepsin-digested fragments were studied at various concentrations of urea by electrospray and matrix-assisted laser desorption ionization time-of-flight mass spectrometry, respectively. Intact sIGPS strongly protects at least 54 amide protons from hydrogen-deuterium exchange in the intermediate states, demonstrating the presence of stable folded cores. When the protection patterns and the exchange mechanisms for the peptides are considered with the proposed folding mechanism, the results can be interpreted to define the structural boundaries of I(a) and I(b). Comparison of these results with previous hydrogen-deuterium exchange studies on another TIM barrel protein of low sequence identify, alpha-tryptophan synthase (alphaTS), indicates that the thermodynamic states corresponding to the folding intermediates are better conserved than their structures. Although the TIM barrel motif appears to define the basic features of the folding free energy surface, the structures of the partially folded states that appear during the folding reaction depend on the amino acid sequence. Markedly, the good

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

    NASA Astrophysics Data System (ADS)

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

    2001-12-01

    The performance of a high-density polarized hydrogen/deuterium gas target internal to a medium-energy electron storage ring is presented. Compared to our previous electron scattering experiments with tensor-polarized deuterium at NIKHEF (Zhou et al., Nucl. Instr. and Meth. A 378 (1996) 40; Ferro-Luzzi et al., Phys. Rev. Lett. 77 (1996) 2630; Van den Brand et al., Phys. Rev. Lett. 78 (1997) 1235; Bouwhuis et al., Phys. Rev. Lett. 82 (1999) 687; Zhou et al., Phys. Rev. Lett. 82 (1999) 687) the target figure of merit, ( polarization) 2× luminosity, was improved by more than an order of magnitude. The target density was increased by upgrading the flux of nuclear-polarized atoms injected into the storage cell and by using a longer (60 cm) and colder (˜70 K) storage cell. A maximal target thickness of 1.2 (1.1)±0.1×10 14 nuclei/ cm2 was achieved with deuterium (hydrogen). With typical beam currents of 110 mA, this corresponds to a luminosity of about 8.4 (7.8)±0.8×10 31e- nuclei cm -2 s-1. By reducing the molecular background and using a stronger target guide field, a higher polarization was achieved. The target was used in combination with a 720 MeV polarized electron beam stored in the AmPS ring (NIKHEF) to measure spin observables in electron-proton and electron-deuteron scattering. Scattered electrons were detected in a large acceptance magnetic spectrometer. Ejected hadrons were detected in a single time-of-flight scintillator array. The product of beam and target vector polarization, PePt, was determined from the known spin-correlation parameters of e' p quasi-elastic (or elastic) scattering. With the deuterium (hydrogen) target, values up to PePt=0.49±0.03 (0.32±0.03) were obtained with an electron beam polarization of Pe=0.62±0.04 (0.56±0.03) as measured with a Compton backscattering polarimeter (Passchier et al., Nucl. Instr. and Meth. A 414 (1998) 4988). From this, we deduce a cell-averaged target polarization of Pt=0.78±0.07 (0.58±0.07), including

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

    PubMed

    Cho, Kyu Taek; Mench, Matthew M

    2012-03-28

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

  12. Stainless-Steel Ball-Milling Method for Hydro-/Deutero-genation using H2O/D2O as a Hydrogen/Deuterium Source.

    PubMed

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

    2015-11-01

    A one-pot continuous-flow method for hydrogen (deuterium) generation and subsequent hydrogenation (deuterogenation) was developed using a stainless-steel (SUS304)-mediated ball-milling approach. SUS304, especially zero-valent Cr and Ni as constituents of the SUS304, and mechanochemical processing played crucial roles in the development of the reactions. PMID:26493945

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

    PubMed

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

    2015-02-17

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

  14. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

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

  16. 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.

  17. The hydrogen exchange core and protein folding.

    PubMed Central

    Li, R.; Woodward, C.

    1999-01-01

    A database of hydrogen-deuterium exchange results has been compiled for proteins for which there are published rates of out-exchange in the native state, protection against exchange during folding, and out-exchange in partially folded forms. The question of whether the slow exchange core is the folding core (Woodward C, 1993, Trends Biochem Sci 18:359-360) is reexamined in a detailed comparison of the specific amide protons (NHs) and the elements of secondary structure on which they are located. For each pulsed exchange or competition experiment, probe NHs are shown explicitly; the large number and broad distribution of probe NHs support the validity of comparing out-exchange with pulsed-exchange/competition experiments. There is a strong tendency for the same elements of secondary structure to carry NHs most protected in the native state, NHs first protected during folding, and NHs most protected in partially folded species. There is not a one-to-one correspondence of individual NHs. Proteins for which there are published data for native state out-exchange and theta values are also reviewed. The elements of secondary structure containing the slowest exchanging NHs in native proteins tend to contain side chains with high theta values or be connected to a turn/loop with high theta values. A definition for a protein core is proposed, and the implications for protein folding are discussed. Apparently, during folding and in the native state, nonlocal interactions between core sequences are favored more than other possible nonlocal interactions. Other studies of partially folded bovine pancreatic trypsin inhibitor (Barbar E, Barany G, Woodward C, 1995, Biochemistry 34:11423-11434; Barber E, Hare M, Daragan V, Barany G, Woodward C, 1998, Biochemistry 37:7822-7833), suggest that developing cores have site-specific energy barriers between microstates, one disordered, and the other(s) more ordered. PMID:10452602

  18. 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.

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

    PubMed

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

    2015-07-01

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

  20. 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.

  1. 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.

  2. 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.

  3. Exchange of deeply trapped and interstitial hydrogen in silicon

    SciTech Connect

    Tuttle, B.; Van de Walle, C.G.; Adams, J.B.

    1999-02-01

    Using {ital ab initio} density-functional calculations, we examine possible exchange mechanisms between an interstitial hydrogen atom and a deeply bound H at a silicon-hydrogen bond. We determine a low-energy pathway for exchange, which involves an intermediate, metastable {equivalent_to}SiH{sub 2} complex with both hydrogen atoms strongly bound to the silicon atom. The energy barrier for the exchange process is E{sub ex}{lt}0.2 eV, consistent with observations of hydrogen-deuterium exchange in a-Si:H(D) films. {copyright} {ital 1999} {ital The American Physical Society}

  4. Multinuclear NMR study of the structure of the Fv fragment of anti-dansyl mouse IgG2a antibody

    SciTech Connect

    Takahashi, Hideo; Odaka, Asano; Matsunaga, Chigusa; Kato, Koichi; Shimada, Ichio; Arata, Yoji ); Kawaminami, Shunro )

    1991-07-02

    A multinuclear NMR study is reported of Fv, which is a minimum antigen-binding unit of immunoglobulin. Fv has been prepared by clostripain digestion of a mouse anti-dansyl IgG2a monoclonal antibody that lacks the entire C{sub H}1 domain. A variety of Fv analogues labeled with {sup 2}H in the aromatic rings and with {sup 13}C and/or {sup 15}N in the peptide bonds have been prepared and used for multinuclear NMR analyses of Fv spectra of Fv sensitively reflect the antigen binding and can be used along with {sup 1}H and {sup 13}C spectral data for the structural analyses of antigen-antibody interactions. Hydrogen-deuterium exchange of the amide protons has been folowed in the absence and presence of DNS-Lys by using the {sup 1}H-{sup 15}N shift correlation spectra. Use of the {beta}-shift observed for the carbonyl carbon resonances has also been helpful in following the hydrogen-deuterium exchange. On the basis of the NMR data obtained, the static and dynamic structure of the Fv fragment in the absence and presence of DNS-Lys has been discussed.

  5. Hydrogen bond stabilities in membrane-reconstituted alamethicin from amide-resolved hydrogen-exchange measurements.

    PubMed Central

    Dempsey, C E; Handcock, L J

    1996-01-01

    Amide-resolved hydrogen-deuterium exchange-rate constants were measured for backbone amides of alamethicin reconstituted in dioleoylphosphatidylcholine vesicles by an exchange-trapping method combined with high-resolution nuclear magnetic resonance spectroscopy. In vesicles containing alamethicin at molar ratios between 1:20 and 1:100 relative to lipid, the exchange-rate constants increased with increasing volume of the D20 buffer in which the vesicles were suspended, indicating that exchange under these conditions is dominated by partitioning of the peptide into the aqueous phase. This was supported by observation of a linear relationship between the exchange-rate constants for amides in membrane-reconstituted alamethicin and those for amides in alamethicin dissolved directly into D2O buffer. Significant protection of amides from exchange with D2O buffer in membrane-reconstituted alamethicin is interpreted in terms of stabilization by helical hydrogen bonding. Under conditions in which amide exchange occurred by partitioning of the peptide into solution, only lower limits for hydrogen-bond stabilities in the membrane were determined; all the potentially hydrogen-bonded amides of alamethicin are at least 1000-fold exchange protected in the membrane-bound state. When partitioning of alamethicin into the aqueous phase was suppressed by hydration of reconstituted vesicles in a limiting volume of water [D2O:dioleoylphosphatidylcholine:alamethicin; 220:1:0.05; (M:M:M)], the exchange-protection factors exhibited helical periodicity with highly exchange-protected, and less well-protected, amides on the nonpolar and polar helix faces, respectively. The exchange data indicate that, under the conditions studied, alamethicin adopts a stable helical structure in DOPC bilayers in which all the potentially hydrogen-bonded amides are stabilized by helical hydrogen bonds. The protection factors define the orientation of the peptide helix with respect to an aqueous phase, which is

  6. 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

  7. 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.

  8. Hydrogenation vs. H-D isotope scrambling during the conversion of ethylene with hydrogen/deuterium catalyzed by platinum under single-collision conditions.

    PubMed

    Dong, Yujung; Ebrahimi, Maryam; Tillekaratne, Aashani; Simonovis, Juan Pablo; Zaera, Francisco

    2016-07-28

    The catalytic hydrogenation of olefins promoted by transition metals, represented here by the conversion of ethylene with platinum, was studied under a unique regime representing pressures in the mTorr range and single-collision conditions. Isotope labeling was used to follow the concurrent H-D exchange steps that occur during this conversion. Multiple isotope substitutions were observed in the resulting ethane products, reflecting the operability of the reversible stepwise mechanism proposed a long time ago by Horiuti and Polanyi. In fact, the ethane isotopologue distributions obtained in these experiments reflect a much higher probability for the dehydrogenation of ethyl intermediates back to the olefin, relative to the hydrogenation to ethane, than typically seen in this catalysis. In addition, a second mechanistic pathway was clearly identified, responsible for most of the dideuteroethane produced. Based on the dependence of the rates of formation of each isotopologue on the fluxes of deuterium and ethylene, it is argued that this second route may be a "reverse" Eley-Rideal step between gas-phase ethylene and two deuterium atoms adsorbed on adjacent sites of the platinum surface. The clear identification of this second pathway is new, and was possible thanks to our ability to explore a new single-collision intermediate pressure regime. PMID:27373226

  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. Experimental study of ocean-atmosphere exchanges

    SciTech Connect

    Eymard, L.; Weill, A.; Planton, S.

    1994-12-31

    The SOFIA/ASTEX and SEMAPHORE campaigns were performed over open ocean, near the Azores, to study the ocean-atmosphere exchanges at the local and meso-scales, with a particular insight to the spatial variability of fluxes and related processes. In both cases, the experimental strategy involved two research aircraft and an oceanographic vessel, as well as surface buoys. SOFIA/ASTEX was more particularly devoted to the study of boundary layer and cloud properties, including microphysical and radiative aspects, in the framework of the international campaign ASTEX. SEMAPHORE was aimed at the analysis of surface fluxes and interactions with the upper ocean at the mesoscale. It included an important network of ocean circulation and thermal properties, from ships, current meter moorings, current drifters, and drifting buoys. The thermal front associated with the Azores current is an important feature of the ocean circulation and was particularly investigated. The analysis of data from meteorological satellites is also an important aspect of the two campaigns.

  11. Ceramic heat-exchanger applications study

    SciTech Connect

    McFarlin, D.J.; Sgamboti, C.T.; Lessard, R.D.

    1982-10-01

    To put the potential benefits of ceramic heat exchangers (CHX) applications into quantitative perspective, several industrial cogeneration and electric utiity power generation systems were surveyed and evaluated. This study was focused on coal-based fuel fired applications, for which system performance and economic assessments were made. Seven CHX applications in the industrial cogeneration sector were selected for evaluation. These include (1) Gasified Coal-Fired Gas Turbine, (2) Pressurized Fluidized Bed Combustor (PFBC)-Gas Turbine, (3) Atmospheric Fluidized Bed Combustor (AFBC)-Gas Turbine, (4 and 5) AFBC Combined Cycle with and without reheat and (6 and 7) Indirect Coal-Fired Gas Turbine and Combined Cycle. The performance and economics of these cogeneration systems were evaluated and compared with other competing systems (both advanced and State-of-the-Art). For the electric utility power generation sector five applications utilizing a CHX were selected and evaluated; their performance and cost factors were compared to those of a reference pulverized coal-fired steam plant with flue gas desulfurization. These five applications included (1) PFBC-Combined Cycle, (2) AFBC-Combined Cycle, (3) Industrial Coal Gasifier-Combined Cycle, (4) Indirect Coal-Fired Combined Cycle, and (5) Indirect Coal-Fired Simple Cycle. Of the five CHX applications evaluated in the power generation sector, only the AFBC system showed a clear gain over the reference pulverized coal system.

  12. Isotope effects of neodymium in different ligands exchange systems studied by ion exchange displacement chromatography.

    PubMed

    Ismail, Ibrahim; Fawzy, Ahmed S; Ahmad, Mohammad I; Aly, Hisham F; Nomura, Masao; Fujii, Yasuhiko

    2013-03-01

    The isotope effects of neodymium in Nd-glycolate ligand exchange system were studied by using ion exchange chromatography. The separation coefficients of neodymium isotopes, ε's, were calculated from the observed isotopic ratios at the front and rear boundaries of the neodymium adsorption band. The values of separation coefficients of neodymium isotopes, ε's, for the Nd-glycolate ligand exchange system were compared with those of Nd-malate and Nd-citrate, which indicated that the isotope effects of neodymium as studied by the three ligands takes the following direction Malate > Citrate > Glycolate. This order agrees with the number of available sites for complexation of each ligand. The values of the plate height, HETP of Nd in Nd-ligand exchange systems were also calculated.

  13. 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.

  14. 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

  15. International Exchange as a Transformative Learning Experience: A Case Study

    ERIC Educational Resources Information Center

    Choi, Sheena; Slaubaugh, Michael; Kim, Ae-Sook

    2012-01-01

    This study examines the role of international exchange programs on the transformative learning of English-speaking students. A student exchange program at a South Korean university is used for this case study. It explores how learning experiences are translated by participants onto their perceptions about the host country. An analysis of a pre-…

  16. 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.

  17. 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

  18. Interaction of arginine with protein during refolding process probed by amide H/D exchange mass spectrometry and isothermal titration calorimetry.

    PubMed

    Zhao, Dawei; Liu, Yongdong; Zhang, Guifeng; Zhang, Chun; Li, Xiunan; Wang, Qingqing; Shi, Hong; Su, Zhiguo

    2015-01-01

    Arginine has been widely used as low molecular weight additive to promote protein refolding by suppressing aggregate formation. However, methods to investigate the role of arginine in protein refolding are often limited on protein's global conformational properties. Here, hydrogen/deuterium exchange mass spectrometry (HDX-MS) was used to study the effects of arginine on recombinant human granulocyte colony-stimulating factor (rhG-CSF) refolding at the scale of peptide mapping. It was found that deuteration levels of rhG-CSF refolded with arginine was higher than that without arginine during the whole refolding process, but they became almost the same when the refolding reached equilibrium. This phenomenon indicated that arginine could protect some amide deuterium atoms from being exchanged with hydrogen, but the protection diminished gradually along with refolding proceeding. Enzymatic digestion revealed six particular peptides of 16-47, 72-84, 84-93, 114-124, 145-153 and 154-162 were mainly responsible for the deuteration, and all of them dominantly located in protein's α-helix domain. Furthermore, thermodynamics analysis by isothermal titration calorimetry provided direct evidence that arginine could only react with denatured and partially refolded rhG-CSF. Taking all of the results together, we suggest that arginine suppresses protein aggregation by a reversible combination. At the initial refolding stage, arginine could combine with the denatured protein mainly through hydrogen bonding. Subsequently, arginine is gradually excluded from protein with protein's native conformation recovering.

  19. Effect of detergent binding on cytochrome P450 2B4 structure as analyzed by X-ray crystallography and deuterium-exchange mass spectrometry.

    PubMed

    Shah, Manish B; Jang, Hyun-Hee; Wilderman, P Ross; Lee, David; Li, Sheng; Zhang, Qinghai; Stout, C David; Halpert, James R

    2016-09-01

    Multiple crystal structures of CYP2B4 have demonstrated the binding of the detergent 5-cyclohexyl-1-pentyl-β-D-maltoside (CYMAL-5) in a peripheral pocket located adjacent to the active site. To explore the consequences of detergent binding, X-ray crystal structures of the peripheral pocket mutant CYP2B4 F202W were solved in the presence of hexaethylene glycol monooctyl ether (C8E6) and CYMAL-5. The structure in the presence of CYMAL-5 illustrated a closed conformation indistinguishable from the previously solved wild-type. In contrast, the F202W structure in the presence of C8E6 revealed a detergent molecule that coordinated the heme-iron and extended to the protein surface through the substrate access channel 2f. Despite the overall structural similarity of these detergent complexes, remarkable differences were observed in the A, A', and H helices, the F-G cassette, the C-D and β4 loop region. Hydrogen-deuterium exchange mass spectrometry (DXMS) was employed to probe these differences and to test the effect of detergents in solution. The presence of either detergent increased the H/D exchange rate across the plastic regions, and the results obtained by DXMS in solution were consistent in general with the relevant structural snapshots. The study provides insight into effect of detergent binding and the interpretation of associated conformational dynamics of CYP2B4. PMID:27280734

  20. 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.

  1. Practical and economical implementation of online H/D exchange in LC-MS.

    PubMed

    Shah, Ravi P; Garg, Amit; Putlur, Siva Prasad; Wagh, Santosh; Kumar, Vineet; Rao, Venugopala; Singh, Saranjit; Mandlekar, Sandhya; Desikan, Sridhar

    2013-11-19

    Structural elucidation is an integral part of drug discovery and development. In recent years, due to acceleration of the drug discovery and development process, there is a significant need for highly efficient methodologies for structural elucidation. In this work, we devised and standardized a simple and economical online hydrogen-deuterium exchange methodology, which can be used for structure elucidation purposes. Deuterium oxide (D2O) was infused as a postcolumn addition using the syringe pump at the time of elution of the analyte. The obtained hydrogen/deuterium (H/D) exchange spectrum of the unknown analyte was compared with the nonexchanged spectrum, and the extent of deuterium incorporation was delineated by using an algorithm to deconvolute partial H/D exchange, which confirmed the number of labile hydrogen(s) in the analyte. The procedure was standardized by optimizing flow rates of LC output, D2O infusion, sheath gas, and auxiliary gas using the model compound sulfasalazine. The robustness of the methodology was demonstrated by performing sensitivity analysis of various parameters such as concentrations of analyte, effect of matrices, concentrations of aqueous mobile phase, and types of LC modifiers. The optimized technique was also applied to chemically diverse analytes and tested on various mass spectrometers. Moreover, utility of the technique was demonstrated in the areas of impurity profiling and metabolite identification, taking pravastatin-lactone and N-oxide desloratidine, as examples.

  2. 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.

  3. 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.

  4. 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.

  5. 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 ...

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

    PubMed Central

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

    2010-01-01

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

  8. 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

    2016-07-01

    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.

  9. 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.

  10. Phosphate/sulphate exchange studies on Amberlite IRA-400.

    PubMed

    Mustafa, S; Naeem, A; Rehana, N; Hamid, A; Dilara, B

    2004-10-01

    The sorption behaviour of phosphate on strong basic anion exchanger, Amberlite IRA-400 (SO4(2-) form) is studied as a function of pH (3-11) at two different initial concentration ranges (0.161 - 0.807 mmol l(-1), 3.874 - 6.134 mmol l(-1)) at 25 degrees C. The stiochiometry of the exchange reactions is observed to be dependent upon concentration and pH of the solutions. It is suggested that the sorption of phosphate takes place initially as PO4(3-) followed by HPO4(2-)/H2PO4(-). The data obtained is explained with the help of a modified Langmuir and mass law action equations.

  11. John Locke's seed lists: a case study in botanical exchange.

    PubMed

    Harris, Stephen A; Anstey, Peter R

    2009-12-01

    This paper gives a detailed analysis of four seed lists in the journals of John Locke. These lists provide a window into a fascinating open network of botanical exchange in the early 1680s which included two of the leading botanists of the day, Pierre Magnol of Montpellier and Jacob Bobart the Younger of Oxford. The provenance and significance of the lists are assessed in relation to the relevant extant herbaria and plant catalogues from the period. The lists and associated correspondence provide the main evidence for Locke's own important, though modest contribution to early modern botany, a contribution which he would have regarded as a small part of the broader project of constructing a natural history of plants. They also provide a detailed case study of the sort of open and informal network of knowledge exchange in the early modern period that is widely recognised by historians of science, but all too rarely illustrated.

  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. 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

  14. Mass Spectrometric Approaches to Study Protein Structure and Interactions in Lyophilized Powders

    PubMed Central

    Topp, Elizabeth M.

    2015-01-01

    Amide hydrogen/deuterium exchange (ssHDX-MS) and side-chain photolytic labeling (ssPL-MS) followed by mass spectrometric analysis can be valuable for characterizing lyophilized formulations of protein therapeutics. Labeling followed by suitable proteolytic digestion allows the protein structure and interactions to be mapped with peptide-level resolution. Since the protein structural elements are stabilized by a network of chemical bonds from the main-chains and side-chains of amino acids, specific labeling of atoms in the amino acid residues provides insight into the structure and conformation of the protein. In contrast to routine methods used to study proteins in lyophilized solids (e.g., FTIR), ssHDX-MS and ssPL-MS provide quantitative and site-specific information. The extent of deuterium incorporation and kinetic parameters can be related to rapidly and slowly exchanging amide pools (Nfast, Nslow) and directly reflects the degree of protein folding and structure in lyophilized formulations. Stable photolytic labeling does not undergo back-exchange, an advantage over ssHDX-MS. Here, we provide detailed protocols for both ssHDX-MS and ssPL-MS, using myoglobin (Mb) as a model protein in lyophilized formulations containing either trehalose or sorbitol. PMID:25938927

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

    PubMed

    Xiao, Yiming; Konermann, Lars

    2015-08-01

    Gas/water interfaces (such as air bubbles or foam) are detrimental to the stability of proteins, often causing aggregation. This represents a potential problem for industrial processes, for example, the production and handling of protein drugs. Proteins possess surfactant-like properties, resulting in a high affinity for gas/water interfaces. The tendency of previously buried nonpolar residues to maximize contact with the gas phase can cause significant structural distortion. Most earlier studies in this area employed spectroscopic tools that could only provide limited information. Here we use hydrogen/deuterium exchange (HDX) mass spectrometry (MS) for probing the conformational dynamics of the model protein myoglobin (Mb) in the presence of N(2) bubbles. HDX/MS relies on the principle that unfolded and/or highly dynamic regions undergo faster deuteration than tightly folded segments. In bubble-free solution Mb displays EX2 behavior, reflecting the occurrence of short-lived excursions to partially unfolded conformers. A dramatically different behavior is seen in the presence of N(2) bubbles; EX2 dynamics still take place, but in addition the protein shows EX1 behavior. The latter results from interconversion of the native state with conformers that are globally unfolded and long-lived. These unfolded species likely correspond to Mb that is adsorbed to the surface of gas bubbles. N(2) sparging also induces aggregation. To explain the observed behavior we propose a simple model, that is, "semi-unfolded" ↔ "native" ↔ "globally unfolded" → "aggregated". This model quantitatively reproduces the experimentally observed kinetics. To the best of our knowledge, the current study marks the first exploration of surface denaturation phenomena by HDX/MS. PMID:25761782

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

    PubMed Central

    Xiao, Yiming; Konermann, Lars

    2015-01-01

    Gas/water interfaces (such as air bubbles or foam) are detrimental to the stability of proteins, often causing aggregation. This represents a potential problem for industrial processes, for example, the production and handling of protein drugs. Proteins possess surfactant-like properties, resulting in a high affinity for gas/water interfaces. The tendency of previously buried nonpolar residues to maximize contact with the gas phase can cause significant structural distortion. Most earlier studies in this area employed spectroscopic tools that could only provide limited information. Here we use hydrogen/deuterium exchange (HDX) mass spectrometry (MS) for probing the conformational dynamics of the model protein myoglobin (Mb) in the presence of N2 bubbles. HDX/MS relies on the principle that unfolded and/or highly dynamic regions undergo faster deuteration than tightly folded segments. In bubble-free solution Mb displays EX2 behavior, reflecting the occurrence of short-lived excursions to partially unfolded conformers. A dramatically different behavior is seen in the presence of N2 bubbles; EX2 dynamics still take place, but in addition the protein shows EX1 behavior. The latter results from interconversion of the native state with conformers that are globally unfolded and long-lived. These unfolded species likely correspond to Mb that is adsorbed to the surface of gas bubbles. N2 sparging also induces aggregation. To explain the observed behavior we propose a simple model, that is, “semi-unfolded” ↔ “native” ↔ “globally unfolded” → “aggregated”. This model quantitatively reproduces the experimentally observed kinetics. To the best of our knowledge, the current study marks the first exploration of surface denaturation phenomena by HDX/MS. PMID:25761782

  17. A correlation between thermal stability and structural features of staphylokinase and selected mutants: a Fourier-transform infrared study.

    PubMed

    Dornberger, U; Fandrei, D; Backmann, J; Hübner, W; Rahmelow, K; Gührs, K H; Hartmann, M; Schlott, B; Fritzsche, H

    1996-05-23

    Variants of recombinant staphylokinase (Sak) were investigated by Fourier-transform infrared spectroscopy: Sak (wild type), Sak-M26A, Sak-M26L, and Sak-G34S/R36G/R43H (Sak-B). Estimation of the secondary structure and hydrogen-deuterium exchange experiments revealed the existence of fast-exchanging and strongly solvent-exposed fractions of the helical structures in the two samples Sak and Sak-M26L. These two samples are also thermally less stable with unfolding transition temperatures of 43.7 degrees C (Sak) and 43.5 degrees C (Sak-M26L), respectively. On contrast, Sak-M26A and Sak-G34S/R36G/R43H have a slower hydrogen-deuterium exchange, have a smaller solvent-exposed portion of the helical part, and are more resistant against thermal unfolding; the transition temperatures are 51.7 degrees C and 59.3 degrees C, respectively. The secondary structure analysis was performed by two different approaches, by curve-fitting after band narrowing and by pattern recognition (factor analysis) based upon reference spectra of proteins with known crystal structure. Within the limits of the used methods, we are unable to detect significant differences in the secondary structure of the four variants of Sak. According to the results of the factor analysis, the portions of secondary structure elements were obtained to 16-20% alpha-helix, 28-30% beta-sheet, 23-27% turns, 28-30% irregular (random) and other structure. The sharp differences in the specific plasminogen-activating capacity (Sak, Sak-G34S/R36G/R43H and Sak-M26L are fully active, but Sak-M26A does not form a stable complex with plasminogen) are not reflected in the structural features revealed by the infrared spectra of this study.

  18. Cation exchange pretreatment studies for high recovery - Yuma desalting plant

    SciTech Connect

    Kaakinen, J.W.; Laverty, P.E.

    1983-10-01

    The main purpose of the High Recovery Test Program was to obtain feasibility design data for cation exchange softening to allow a greater fractional recovery of desalted product water at the YDP(Yuma Desalting Plant). Compared to the original YDP design with 70-percent desalting recovery, additional removal of calcium in the desalting feed would allow recoveries over 90 percent. Pilot plant equipment to test this process was operated at the YDTF(Yuma Desalting Test Facility) and consisted of an IX unit and an electrodialyzer to supply reject-brine regenerant for the IX experiments. Gypsum scale buildup in the resin bed could be avoided by regeneration with a high upward flow rate causing a fluidized bed. Reuse of regenerant was also beneficial. Results show that the ion exchange high recovery pretreatment process is highly feasible, and that it is technically possible to achieve high recovery in the YDP. Numerous recommendations for a plant design are given and future studies are noted.

  19. Interlayer diffusion studies of a Laves phase exchange spring superlattice

    NASA Astrophysics Data System (ADS)

    Wang, C.; Kohn, A.; Wang, S. G.; Ward, R. C. C.

    2011-03-01

    Rare earth Laves phase (RFe2) superlattice structures grown at different temperatures are studied using x-ray reflectivity (XRR), x-ray diffraction, and transmission electron microscopy. The optimized molecular beam epitaxy growth condition is matched with the XRR simulation, showing minimum diffusion/roughness at the interfaces. Electron microscopy characterization reveals that the epitaxial growth develops from initial 3D islands to a high quality superlattice structure. Under this optimum growth condition, chemical analysis by electron energy loss spectroscopy with high spatial resolution is used to study the interface. The analysis shows that the interface roughness is between 0.6 and 0.8 nm and there is no significant interlayer diffusion. The locally sharp interface found in this work explains the success of simple structural models in predicting the magnetic reversal behavior of Laves exchange spring superlattices.

  20. 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.

  1. 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.

  2. 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.

  3. Isolation and characterization of degradation products of moxidectin 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

    2012-11-01

    This study aimed to evaluate the degradation profile and pathways, and identify unknown impurities of moxidectin under stress conditions. During the experiments, moxidectin samples were stressed using acid, alkali, heat and oxidation, and chromatographic profiles were compared with known impurities given in European Pharmacopeia (EP) monograph. Moxidectin has shown good stability under heat, while reaction with alkali produced 2-epi and ∆2,3 isomers (impurities D and E in EP) by characteristic reactions of the oxahydrindene (hexahydrobenzofuran) portion of the macrocyclic lactone. Two new, previously unreported, unknown degradation products, i.e. impurity 1 and impurity 2, detected after acid hydrolysis of moxidectin (impurity 2 was also observed to a lesser extent after oxidation), were isolated from sample matrices and identified using liquid chromatography, NMR, high-resolution FT-ICR MS, and hydrogen/deuterium exchange studies. FTMS analysis showed accurate mass of molecular ion peaks for moxidectin at m/z 640.38412, impurity 1 at m/z 656.37952 and impurity 2 at m/z 611.35684, giving rise to daughter ions traceable up to the seventh levels of MS(n) experiments and supporting the proposed structures. Both unknown impurities along with moxidectin were fully characterized by (1)H, (13)C, 1D HMBC and 2D (NOESY, COSY and HSQC) NMR experiments. The interpretation of experimental data positively identified impurity 1 as 3,4-epoxy-moxidectin and impurity 2 as 23-keto-nemadectin. The identification of new impurities and correlation of their chromatographic profiles with the EP method is very useful to establish the stability profile of moxidectin and its preparations, as well as add value to the forthcoming moxidectin finished product European Pharmacopeia monographs. PMID:22986987

  4. 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.

  5. Structure and orientation of two voltage-dependent anion-selective channel isoforms. An attenuated total reflection fourier-transform infrared spectroscopy study.

    PubMed

    Abrecht, H; Goormaghtigh, E; Ruysschaert, J M; Homble, F

    2000-12-29

    Two VDAC (voltage-dependent anion-selective channel) isoforms were purified from seed cotyledons of Phaseolus vulgaris by chromatofocusing chromatography. Attenuated total reflection Fourier-transform infrared (ATR-FTIR) spectroscopy was used to study the structural properties of the two isoforms reconstituted in a mixture of asolectin and 5% stigmasterol. The IR spectra of the two VDAC isoforms were highly similar indicating 50 to 53% anti-parallel beta-sheet. The orientation of the beta-strands relative to the barrel axis was calculated from the experimentally obtained dichroic ratios of the amide I beta-sheet component and the amide II band. Comparing the IR spectra of the reconstituted VDAC isoforms with the IR spectra of the bacterial porin OmpF, for which a high resolution structure is available, provided evidence for a general structural organization of the VDAC isoforms similar to that of bacterial porins. Hydrogen-deuterium exchange measurements indicated that the exchange of the amide protons occurs to a higher extent in the two VDAC isoforms than in the OmpF porin.

  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. Phosphorylation- and nucleotide-binding-induced changes to the stability and hydrogen exchange patterns of JNK1β1 provide insight into its mechanisms of activation.

    PubMed

    Owen, Gavin R; Stoychev, Stoyan; Achilonu, Ikechukwu; Dirr, Heini W

    2014-10-23

    Many studies have characterized how changes to the stability and internal motions of a protein during activation can contribute to their catalytic function, even when structural changes cannot be observed. Here, unfolding studies and hydrogen-deuterium exchange (HX) mass spectrometry were used to investigate the changes to the stability and conformation/conformational dynamics of JNK1β1 induced by phosphorylative activation. Equivalent studies were also employed to determine the effects of nucleotide binding on both inactive and active JNK1β1 using the ATP analogue, 5'-adenylyl-imidodiphosphate (AMP-PNP). JNK1β1 phosphorylation alters HX in regions involved in catalysis and substrate binding, changes that can be ascribed to functional modifications in either structure and/or backbone flexibility. Increased HX in the hinge between the N- and C-terminal domains implied that it acquires enhanced flexibility upon phosphorylation that may be a prerequisite for interdomain closure. In combination with the finding that nucleotide binding destabilizes the kinase, the patterns of solvent protection by AMP-PNP were consistent with a novel mode of nucleotide binding to the C-terminal domain of a destabilized and open domain conformation of inactive JNK1β1. Solvent protection by AMP-PNP of both N- and C-terminal domains in active JNK1β1 revealed that the domains close around nucleotide upon phosphorylation, concomitantly stabilizing the kinase. This suggests that phosphorylation activates JNK1β1 in part by increasing hinge flexibility to facilitate interdomain closure and the creation of a functional active site. By uncovering the complex interplay that occurs between nucleotide binding and phosphorylation, we present new insight into the unique mechanisms by which JNK1β1 is regulated.

  9. Positional isotope exchange studies on enzyme using NMR spectroscopy

    SciTech Connect

    Matsunaga, T.O.

    1987-01-01

    The isotopically enriched compounds, /sup 18/O-..beta..,..gamma..-ATP and /sup 18/O bridge-labeled pyrophosphate, synthesized previously in this laboratory, were used to investigate and measure the exchange vs. turnover of substrates and products from their central complexes in four selected enzyme systems. Using hi-field /sup 31/P NMR, we were able to differentiate between /sup 18/O labeled in the bridge vs. the non-bridge positions by virtue of the isotope shift upon the phosphorus nuclei. The bridge to non-bridge scrambling of the label was quantitated and the exchange vs. turnover ratios under a variety of conditions was determined. Using the substrate inhibitor carboxycreatinine, PIX experiments with /sup 18/O-..beta..,..gamma..-ATP and creatine kinase were conducted. It was shown that carboxycreatinine and creatine kinase promoted exchange of the /sup 18/O label as determined by NMR. We have concluded that carboxycreatinine is either a substrate that catalyzes very slow turnover or it catalyzes exchange by a dissociative (SN/sub 1//sub P/) type of mechanism

  10. The Economic Aspect of the Exchange of Duplicates. Time Studies on Books. A Case Study.

    ERIC Educational Resources Information Center

    Ejlersen, Rita

    This report of a 10-month study performed at the Institut Danois des Echanges Internationaux de Publications Scientifiques et Litteraires (IDE) on its exchange program for duplicate monographs provides an analysis of the working methods and time spent on the various phases, i.e., acquisition, processing, and distribution. The major function of the…

  11. NMR studies of proton exchange kinetics in aqueous formaldehyde solutions

    NASA Astrophysics Data System (ADS)

    Rivlin, Michal; Eliav, Uzi; Navon, Gil

    2014-05-01

    Aqueous solutions of formaldehyde, formalin, are commonly used for tissue fixation and preservation. Treatment with formalin is known to shorten the tissue transverse relaxation time T2. Part of this shortening is due to the effect of formalin on the water T2. In the present work we show that the shortening of water T2 is a result of proton exchange between water and the major constituent of aqueous solutions of formaldehyde, methylene glycol. We report the observation of the signal of the hydroxyl protons of methylene glycol at 2 ppm to high frequency of the water signal that can be seen at low temperatures and at pH range of 6.0 ± 1.5 and, at conditions where it cannot be observed by the single pulse experiment, it can be detected indirectly through the water signal by the chemical exchange saturation transfer (CEST) experiment. The above finding made it possible to obtain the exchange rate between the hydroxyl protons of the methylene glycol and water in aqueous formaldehyde solutions, either using the dispersion of the spin-lattice relaxation rate in the rotating frame (1/T1ρ) or, at the slow exchange regime, from the line width hydroxyl protons of methylene glycol. The exchange rate was ∼104 s-1 at pH 7.4 and 37 °C, the activation energy, 50.2 kJ/mol and its pH dependence at 1.1 °C was fitted to: k (s-1) = 520 + 6.5 × 107[H+] + 3.0 × 109[OH-].

  12. 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

  13. 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

  14. Mössbauer study of proton-exchanged LiNbO3:Fe

    NASA Astrophysics Data System (ADS)

    Engelmann, H.; Andler, G.; Dézsi, I.

    1990-07-01

    Topotactic proton exchange (Li against H) can be achieved by treating LiBnO3 with appropriate acids. In order to investigate the effect of proton exchange on Fe-impurities we studied LiNbO3:Fe powder material treated in sulphuric acid and LiNbO3:Fe single crystals treated in benzoic acid by Mössbauer spectroscopy. During the topotactic ion exchange only the Li-ions are exchanged for protons, whereas the Fe-impurities are retained in the material.

  15. 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.

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

    PubMed

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

    2015-11-01

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

  17. 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.

  18. Effects of International Student Exchange on Pre-Service Teachers: A Quasi-Experimental Study

    ERIC Educational Resources Information Center

    Leutwyler, Bruno; Meierhans, Claudia

    2016-01-01

    This contribution provides empirical answers to the question of how teaching-specific competencies develop during participation in an international student exchange programme. The quantitative analyses of this quasi-experimental study suggest that, generally speaking, no specific developments occur during an exchange experience. These findings…

  19. In ESI-source H/D exchange under atmospheric pressure for peptides and proteins of different molecular weights from 1 to 66 kDa: the role of the temperature of the desolvating capillary on H/D exchange.

    PubMed

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

    2015-01-01

    Transition of proteins from the solution to the gas phase during electrospray ionization remains a challenging problem despite the large amount of attention it has received during the past few decades. One of the major questions relates to the extent to which proteins in the gas phase retain their condensed phase structures. We have used in-electrospray source hydrogen/deuterium exchange to determine the number of deuterium incorporations as a function of protein mass, charge state and temperature of the desolvating capillary where the reaction occurs. All experiments were performed on a Thermo LTQ FT Ultra equipped with a 7-T superconducting magnet. Ions were generated by an IonMax Electrospray ion source operated in the positive ESI mode. Deuterium exchange was performed by introducing a droplet of D2 O beneath the ESI capillary. We systematically investigated gas phase hydrogen/deuterium (H/D) exchange under atmospheric pressure for peptides and proteins of different molecular weights from 1 to 66 kDa. We observed that almost all proteins demonstrate similar exchange rates for all charge states and that these rates increase exponentially with the temperature of the desolvating capillary. We did not observe any clear correlation of the number of H/D exchanges with the value of the cross section for a corresponding charge state. We have demonstrated the possibility of performing in-ESI source H/D exchange of large proteins under atmospheric pressure. The simplicity of the experimental setup makes it a useful experimental technique that can be applied for the investigation of gas phase conformations of proteins. PMID:25601674

  20. In ESI-source H/D exchange under atmospheric pressure for peptides and proteins of different molecular weights from 1 to 66 kDa: the role of the temperature of the desolvating capillary on H/D exchange.

    PubMed

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

    2015-01-01

    Transition of proteins from the solution to the gas phase during electrospray ionization remains a challenging problem despite the large amount of attention it has received during the past few decades. One of the major questions relates to the extent to which proteins in the gas phase retain their condensed phase structures. We have used in-electrospray source hydrogen/deuterium exchange to determine the number of deuterium incorporations as a function of protein mass, charge state and temperature of the desolvating capillary where the reaction occurs. All experiments were performed on a Thermo LTQ FT Ultra equipped with a 7-T superconducting magnet. Ions were generated by an IonMax Electrospray ion source operated in the positive ESI mode. Deuterium exchange was performed by introducing a droplet of D2 O beneath the ESI capillary. We systematically investigated gas phase hydrogen/deuterium (H/D) exchange under atmospheric pressure for peptides and proteins of different molecular weights from 1 to 66 kDa. We observed that almost all proteins demonstrate similar exchange rates for all charge states and that these rates increase exponentially with the temperature of the desolvating capillary. We did not observe any clear correlation of the number of H/D exchanges with the value of the cross section for a corresponding charge state. We have demonstrated the possibility of performing in-ESI source H/D exchange of large proteins under atmospheric pressure. The simplicity of the experimental setup makes it a useful experimental technique that can be applied for the investigation of gas phase conformations of proteins.

  1. 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

  2. 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

  3. 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.

  4. 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.

  5. Study of the forced degradation behavior of prasugrel hydrochloride by liquid chromatography with mass spectrometry and liquid chromatography with NMR detection and prediction of the toxicity of the characterized degradation products.

    PubMed

    Singh, Dilip Kumar; Sahu, Archana; Handa, Tarun; Narayanam, Mallikarjun; Singh, Saranjit

    2015-09-01

    Prasugrel was subjected to forced degradation studies under conditions of hydrolysis (acid, base, and neutral), photolysis, oxidation, and thermal stress. The drug showed liability in hydrolytic as well as oxidative conditions, resulting in a total of four degradation products. In order to characterize the latter, initially mass fragmentation pathway of the drug was established with the help of mass spectrometry/time-of-flight, multiple stage mass spectrometry and hydrogen/deuterium exchange data. The degradation products were then separated on a C18 column using a stability-indicating volatile buffer method, which was later extended to liquid chromatography-mass spectrometry studies. The latter highlighted that three degradation products had the same molecular mass, while one was different. To characterize all, their mass fragmentation pathways were established in the same manner as the drug. Subsequently, liquid chromatography-nuclear magnetic resonance (NMR) spectroscopy data were collected. Proton and correlation liquid chromatography with NMR spectroscopy studies highlighted existence of diastereomeric behavior in one pair of degradation products. Lastly, toxicity prediction by computer-assisted technology (TOPKAT) and deductive estimation of risk from existing knowledge (DEREK) software were employed to assess in silico toxicity of the characterized degradation products.

  6. Fourier transform infrared spectroscopy study of the secondary structure of the gastric H+,K+-ATPase and of its membrane-associated proteolytic peptides.

    PubMed

    Raussens, V; Ruysschaert, J M; Goormaghtigh, E

    1997-01-01

    Membrane topology of the H+,K+-ATPase has been studied after proteolytic degradation of the protein by proteinase K. Proteinase K had access to either the cytoplasmic part of the protein or to both sides of the membrane. Fourier transform infrared attenuated total reflection spectroscopy indicated that membrane-associated domain of the protein represented about 55% of the native protein, meanwhile the cytoplasmic part represented only 27% of the protein. The secondary structure of the ATPase and of its membrane-associated domains was investigated by infrared spectroscopy. The secondary structure of the membrane-associated structures and of the entire protein was quite similar (alpha-helices, 35%; beta-sheets, 35%; turns, 20%; random, 15%). These data were in agreement with 10 alpha-helical transmembrane segments but suggested a participation of beta-sheet structures in the membrane-associated part of the protein. Polarized infrared spectroscopy indicated that the alpha-helices were oriented nearly perpendicular to the membrane plane. No preferential orientation could be attributed to the beta-sheets. Monitoring the amide hydrogen/deuterium exchange kinetics demonstrated that the membrane associated part of the ATPase molecule is characterized by a relatively high accessibility to the solvent, quite different from that observed for bacteriorhodopsin membrane segments.

  7. Study of a thermosyphon with a counter-flow heat exchanger

    NASA Astrophysics Data System (ADS)

    Mertol, A.; Greif, R.

    The transient and steady state heat transfer and fluid flow in a closed thermosyphon loop have been studied. The toroidal thermosyphon is heated over the lower half and cooled over the upper half by an annular, insulated counter-flow heat exchanger in which the flow rate of the coolant is kept constant. The results include the temperature distributions, velocity variations, efficiency and pressure drop across the heat exchanger. Special attention is also given to the effect of the heat exchanger on the stability of the thermosyphon.

  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. Evaluating Humidity Recovery Efficiency of Currently Available Heat and Moisture Exchangers: A Respiratory System Model Study

    PubMed Central

    Lucato, Jeanette Janaina Jaber; Adams, Alexander Bernard; Souza, Rogério; Torquato, Jamili Anbar; Carvalho, Carlos Roberto Ribeiro; Marini, John J

    2009-01-01

    OBJECTIVES: To evaluate and compare the efficiency of humidification in available heat and moisture exchanger models under conditions of varying tidal volume, respiratory rate, and flow rate. INTRODUCTION: Inspired gases are routinely preconditioned by heat and moisture exchangers to provide a heat and water content similar to that provided normally by the nose and upper airways. The absolute humidity of air retrieved from and returned to the ventilated patient is an important measurable outcome of the heat and moisture exchangers’ humidifying performance. METHODS: Eight different heat and moisture exchangers were studied using a respiratory system analog. The system included a heated chamber (acrylic glass, maintained at 37°C), a preserved swine lung, a hygrometer, circuitry and a ventilator. Humidity and temperature levels were measured using eight distinct interposed heat and moisture exchangers given different tidal volumes, respiratory frequencies and flow-rate conditions. Recovery of absolute humidity (%RAH) was calculated for each setting. RESULTS: Increasing tidal volumes led to a reduction in %RAH for all heat and moisture exchangers while no significant effect was demonstrated in the context of varying respiratory rate or inspiratory flow. CONCLUSIONS: Our data indicate that heat and moisture exchangers are more efficient when used with low tidal volume ventilation. The roles of flow and respiratory rate were of lesser importance, suggesting that their adjustment has a less significant effect on the performance of heat and moisture exchangers. PMID:19578664

  10. Study of 25 cases of exchange transfusion by reconstituted blood in hemolytic disease of newborn.

    PubMed

    Sharma, D C; Rai, Sunita; Mehra, Aakash; Kaur, M M; Sao, Satya; Gaur, Ajay; Sapra, Rahul

    2007-07-01

    This study was aimed to review and establish the practice of exchange transfusion (ET) with reconstituted blood in neonates and to observe fall of bilirubin and its comparison with related studies. Twenty-five neonates diagnosed as hemolytic disease of newborn (HDN) were selected for this study, in which exchange transfusion was carried out as one of the treatments for hyperbilirubinemia. Out of the 25 cases, 15 were of Rhesus (Rh) HDN, while ABO and other blood groups constituted 6 and 4 HDN cases respectively. First, the neonates's and mother's blood samples were subjected to relevant investigations. After that, for neonates having Rh HDN, O Rh negative cells suspended in AB plasma were given, O Rh positive cells suspended in AB plasma were given to ABO HDN; and O positive cells, which were indirect Coomb's cross-matched compatible with neonates' and mother's serum / plasma, suspended in AB plasma were given to the neonates having HDN because of other blood group antibodies. The exchange transfusion (ET) was carried out taking all aseptic precautions by Push-Pull technique with double-volume exchange transfusion method. The average post-exchange fall in serum indirect bilirubin was (52.01%) in all 25 cases, which was found to be more significant than the previous studies. Looking into the superiority of the exchange transfusion in HDN by reconstituted blood, the reconstituted blood can be modified and supplied as per the requirement and conditions.

  11. Modeling of temporal behavior of isotopic exchange between gaseous hydrogen and palladium hydride power

    SciTech Connect

    Melius, C F; Foltz, G W

    1987-01-01

    A parametric rate-equation model is described which depicts the time dependent behavior of the isotopic exchange process occurring between the solid and gas phases in gaseous hydrogen (deuterium) flows through packed-powder palladium deuteride (hydride) beds. The exchange mechanism is assumed to be rate-limited by processes taking place on the surface of the powder. The fundamental kinetic parameter of the model is the isotopic exchange probability, p, which is the probability that an isotopic exchange event occurs during a collision of a gas phase atom with the surface. Isotope effects between the gas and solid phases are explicitly included in terms of the isotope separation factor, ..cap alpha... Results of the model are compared with recent experimental measurements of isotope exchange in the ..beta..-phase hydrogen/palladium system and, using a literature value of ..cap alpha.. = 2.4, a good description of the experimental data is obtained for p approx. 10/sup -7/. In view of the importance of the isotope effects in the hydrogen/palladium system and the range of ..cap alpha.. values reported for the ..beta..-phase in the literature, the sensitivity of the model results to a variation in the value of ..cap alpha.. is examined.

  12. 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.

  13. 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…

  14. Unfolding and aggregation of monoclonal antibodies on cation exchange columns: effects of resin type, load buffer, and protein stability.

    PubMed

    Guo, Jing; Carta, Giorgio

    2015-04-01

    The chromatographic behavior of a monoclonal antibody (mAb) that exhibits a pronounced two-peak elution behavior is studied for a range of strong cation exchange resins and with varying load buffer pH and composition. Six stationary phases are considered, including two tentacle-type resins (Fractogel EMD SO3-(M) and Eshmuno S), a resin with grafted polymeric surface extenders (Nuvia S), a resin with a bimodal pore size distribution (POROS HS 50), and two macroporous resins without polymer grafts (Source 30S and UNOsphere Rapid S). The two-peak elution behavior is very pronounced for the tentacle and polymer-grafted resins and for POROS HS 50, but is essentially absent for the two macroporous resins. The extent of this behavior decreases as the buffer pH and concentration increase and, consequently, mAb binding becomes weaker. Replacing sodium with arginine as the buffer counterion, which is expected to decrease the mAb binding strength, nearly completely eliminates the two-peak behavior, while replacing sodium with tetra-n-butylammonium hydroxide, which is expected to increase the mAb binding strength, dramatically exacerbate the effect. As shown by hydrogen-deuterium exchange mass spectrometry (HX-MS), the two-peak elution behavior is related to conformational changes that occur when the mAb binds. These changes result in increased solvent exposure of specific peptides in the Fc-region for either the Fractogel or the Nuvia resin. No significant conformational changes were seen by HX-MS when the mAb was bound to the UNOsphere resin or on the Fractogel resin when arginine was used in lieu of sodium as the load buffer counterion. Experiments with two additional mAbs on the Fractogel resin show that the two-peak elution behavior is dependent on the particular antibody. Circular dichroism suggests that the propensity of different mAbs to either precipitate directly or to form stabilizing intermolecular structures upon exposure to thermal stress can be related to their

  15. A time-resolved study on the interaction of oppositely charged bicelles--implications on the charged lipid exchange kinetics.

    PubMed

    Yang, Po-Wei; Lin, Tsang-Lang; Hu, Yuan; Jeng, U-Ser

    2015-03-21

    Time-resolved small-angle X-ray scattering was applied to study charged lipid exchange between oppositely charged disc-shaped bicelles. The exchange of charged lipids gradually reduces the surface charge density and weakens the electrostatic attraction between the oppositely charged bicelles which form alternately stacked aggregates upon mixing. Initially, at a high surface charge density with almost no free water layer between the stacked bicelles, fast exchange kinetics dominate the exchange process. At a later stage with a lower surface charge density and a larger water gap between the stacked bicelles, slow exchange kinetics take over. The fast exchange kinetics are correlated with the close contact of the bicelles when there is almost no free water layer between the tightly bound bicelles with a charged lipid exchange time constant as short as 20-40 min. When the water gap becomes large enough to have a free water layer between the stacked bicelles, the fast lipid exchange kinetics are taken over by slow lipid exchange kinetics with time constants around 200-300 min, which are comparable to the typical time constant of lipid exchange between vesicles in aqueous solution. These two kinds of exchange mode fit well with the lipid exchange models of transient hemifusion for the fast mode and monomer exchange for the slow mode.

  16. Russian studies of the safety of anion exchange in nitric acid

    SciTech Connect

    Hyder, M.L.; Bartenev, S.A.; Lazarev, L.N.

    1997-07-01

    Synthetic ion exchange resins came into use in the Soviet Union in the 1950`s, and domestic anion exchange resins based on quaternary amine groups have long been used in the Russian nuclear industry. These resins are similar to resins used in the West, and include pyridine-based resins, as well as the more conventional aryl polymers with substituted methyl amines. (Slide 1) The sensitivity of these amines to reaction with nitric acid and other oxidants has been a concern in Russia as in the West, and numerous laboratory studies have been conducted on the reactions involved. Several incidents involving pressure or temperature excursions have provided incentives for such studies. (Slide 2) This report briefly summarizes this work. A report by the Russian authors of this paper providing greater detail is to be issued as a U.S. Dept. of Energy document. Additionally, a second report by these authors, describing new studies on anion exchange resin safety, will also be issued as a DOE report. The separation of plutonium, neptunium, etc. from other materials by ion exchange requires rather strong nitric acid (6-8 M). In some systems, such as the processing of {sup 238}Pu, intense ionizing radiation may also be present during ion exchange separation. As a result, it is necessary to consider not only thermal hydrolysis and oxidation and their effects on the resin, but also radiolysis. All of these were investigated in the Russian studies.

  17. 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…

  18. 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.

  19. 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.

  20. 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

  1. 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.

  2. 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…

  3. 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.

  4. 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

  5. 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.

  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. Fragmentation of doubly-protonated peptide ion populations labeled by H/D exchange with CD3OD

    NASA Astrophysics Data System (ADS)

    Herrmann, Kristin A.; Kuppannan, Krishna; Wysocki, Vicki H.

    2006-03-01

    Doubly-protonated bradykinin (RPPGFSPFR) and an angiotensin III analogue (RVYIFPF) were subjected to hydrogen/deuterium (H/D) exchange with CD3OD in a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer. A bimodal distribution of deuterium incorporation was present for bradykinin after H/D exchange for 90 s at a CD3OD pressure of 4 × 10-7 Torr, indicating the existence of at least two distinct populations. Bradykinin ion populations corresponding to 0-2 and 5-11 deuteriums (i.e., D0, D1, D2, D5, D6, D7, D8, D9, D10, and D11) were each monoisotopically selected and fragmented via sustained off-resonance irradiation (SORI) collision-induced dissociation (CID). The D0-D2 ion populations, which correspond to the slower exchanging population, consistently require lower SORI amplitude to achieve a similar precursor ion survival yield as the faster-reacting (D5-D11) populations. These results demonstrate that conformation/protonation motif has an effect on fragmentation efficiency for bradykinin. Also, the partitioning of the deuterium atoms into fragment ions suggests that the C-terminal arginine residue exchanges more rapidly than the N-terminal arginine. Total deuterium incorporation in the b1/y8 and b2/y7 ion pairs matches very closely the theoretical values for all ion populations studied, indicating that the ions of a complementary pair are likely formed during the same fragmentation event, or that no scrambling occurs upon SORI. Deuterium incorporation into the y1/a8 pseudo-ion pair does not closely match the expected theoretical values. The other peptide, doubly-protonated RVYIFPF, has a trimodal distribution of deuterium incorporation upon H/D exchange with CD3OD at a pressure of 1 × 10-7 Torr for 600 s, indicating at least three distinct ion populations. After 90 s of H/D exchange where at least two distinct populations are detected, the D0-D7 ion populations were monoisotopically selected and fragmented via SORI-CID over a range of SORI

  8. 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.

  9. 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.

  10. 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…

  11. 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…

  12. Folding study of Venus reveals a strong ion dependence of its yellow fluorescence under mildly acidic conditions.

    PubMed

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

    2010-02-12

    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 (15)N-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 beta-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.

  13. Conceptual study of in-tank cesium removal using an inorganic ion exchange material

    SciTech Connect

    Goheen, R.S.; Kurath, D.E.

    1996-04-01

    Presently, the Hanford Site contains approximately 230,000 m{sup 3} of mixed waste stored in 177 underground tanks. Approximately 55,000 m{sup 3} of this waste is sludge, 90,000 m{sup 3} is salt cake, and 80,000 m{sup 3} is supernate. Although the pretreatment and final disposal requirements for the waste have not been entirely defined, it is likely that some supernatant pretreatment will be required to remove {sup 137}Cs and possibly {sup 90}Sr and the transuranic components. The objective of this study was to estimate the number of HLW glass canisters resulting from the use of inorganic ion exchanger materials as in-tank pretreatment technology. The variables in the study were: number of contacts between waste and ion exchange material; ion exchange material; and decontamination requirement. This conceptual study investigates a generic in-tank Cs removal flowsheet using crystalline silico-titanates and IE-96 zeolites, and the impact of each ion exchanger on the number of glass canisters produced. In determining glass formulation, data based on current reference technology was used. Sample calculations from the worksheets and summaries of final calculated results are included at the end of this report.

  14. Student exchange for nursing students: does it raise cultural awareness'? A descriptive, qualitative study.

    PubMed

    Bohman, Doris M; Borglin, Gunilla

    2014-05-01

    With free movement for citizens within the European Union and with distant parts of our globe becoming more accessible, cultural awareness and cultural competence are becoming important skills for nurses. Internationalisation and raising awareness of other cultural contexts are essential elements in Swedish higher education, thus explaining the variety of student exchange programmes that are available. The aim of this study was to explore Swedish nursing students' perceptions of student exchange and their experiences. Data were collected through group interviews and then analysed following the principles of content analysis. Our analysis resulted in three categories: Preparing to go abroad, Reasons for going abroad and From expectation to experience. Cultural aspects and cultural awareness were emphasised as strong motivational factors, both personal and professional, behind participation in student exchange programmes. Information was also highlighted as a crucial means of reaching potential students as well as the power of knowledge through personal experience. This study highlights the importance of student exchange in expanding the individual student's personal and professional horizons. It also stresses the importance of including a transcultural nursing element in nursing curricula.

  15. 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)

  16. 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.

  17. Experimental study on corrugated cross-flow air-cooled plate heat exchangers

    SciTech Connect

    Kim, Minsung; Baik, Young-Jin; Park, Seong-Ryong; Ra, Ho-Sang; Lim, Hyug

    2010-11-15

    Experimental study on cross-flow air-cooled plate heat exchangers (PHEs) was performed. The two prototype PHEs were manufactured in a stack of single-wave plates and double-wave plates in parallel. Cooling air flows through the PHEs in a crosswise direction against internal cooling water. The heat exchanger aims to substitute open-loop cooling towers with closed-loop water circulation, which guarantees cleanliness and compactness. In this study, the prototype PHEs were tested in a laboratory scale experiments. From the tests, double-wave PHE shows approximately 50% enhanced heat transfer performance compared to single-wave PHE. However, double-wave PHE costs 30% additional pressure drop. For commercialization, a wide channel design for air flow would be essential for reliable performance. (author)

  18. 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

  19. Systematic modeling study of channel waveguide fabrication by thermal silver ion exchange.

    PubMed

    Li, Guangyu; Winick, Kim A; Griffin, Henry C; Hayden, Joseph S

    2006-03-10

    A systematic study of thermal silver ion exchange used for the fabrication of optical channel waveguides is reported in a single-alkali glass. The diffusion equilibrium and diffusion dynamics are experimentally studied, and the concentration-dependent diffusion coefficients are determined. The relationship between the fabrication conditions, i.e., time, temperature, and melt concentration, and the induced waveguide refractive index profile is established. It is demonstrated that the diffusion equation can be solved, without use of any free parameters, to predict the refractive index profiles of both planar and channel waveguides. A 1.6 cm diameter integrated optic ring resonator, with a propagation loss of 0.1 dB/cm, is fabricated in a glass by thermal silver ion exchange. The induced refractive index profile is related to the optical characteristics of the functional device. PMID:16572690

  20. 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.

  1. 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.

  2. 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.

  3. Science and Technology Policies Information Exchange System (SPINES) Feasibility Study. Science Policy Studies and Documents No. 33(1).

    ERIC Educational Resources Information Center

    Coblans, H.; And Others

    A feasibility study was made to define, within the conceptual framework and in accordance with the recommendations of the UNISIST program, the managerial, technical, legal, and financial framework for the setting up of an International Science and Technology Policies Information Exchange System (SPINES). This report describes in some detail the…

  4. A pilot study of manual chronic partial exchange transfusion in children with sickle disease.

    PubMed

    Aloni, Michel Ntetani; Lê, Phu-Quoc; Heijmans, Catherine; Huybrechts, Sophie; Devalck, Christine; Azzi, Nadira; Ngalula-Mujinga, Malou; Ferster, Alina

    2015-06-01

    Objective Red cell exchange transfusion is frequently used in the management of patients with sickle cell disease (SCD) either electively or chronically to maintain hemoglobin S (HbS) <30%. The purpose of this retrospective study was to evaluate the results of manual chronic partial exchange transfusion (MCPET) on level of Hb and HbS, on iron load and on the need for chelation, on risk of immunization, monitoring transfusion-transmitted viral infection, and clinical outcome. Methods We reviewed the long-term effect of MCPET in 10 children (six men and four women) with SCD and evaluated the iron balance during a median follow-up of 20 months (range: 6-36) in which 248 exchanges were performed. Results The pre-exchange median Hb value was 9.5 g/dl (range: 7.7-10.9 g/dl) and the median post-exchange value was 9.4 g/dl (range: 8.4-11.1 g/dl).The majority of patients reached an HbS of <50% with a median HbS value of 40.04% (range: 30-54). At start of the MCPET program, the median ferritin was 439 ng/ml (range: 80-1704 ng/ml). In the final evaluation, the median value of ferritin was 531 ng/ml (range: 84-3840 ng/ml). The annual calculated iron balance was 0. 28 ± 0.08 mg/kg/day. MCPET was well tolerated, and adverse effects were limited. Discussion MCPET in children with SCD is safe to prevent iron overload, and is effective and easy to use in our cohort. Conclusion Indication for chronic exchange blood transfusion is essential for patients with SCD with recurrent and frequent crises who do not respond to hydroxyurea. However, there is no consensual study for the period at which chronic transfusion can safely be stopped and further research in large population of patients with SCD will need to clarify this question. PMID:25133935

  5. 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…

  6. 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.

  7. Computational Studies of Water-Exchange Rates around Aqueous Mg2+ and Be2+

    SciTech Connect

    Dang, Liem X.

    2014-12-18

    The water-exchange mechanisms occurring around aqueous divalent Mg2+ and Be2+ ions were studied using molecular dynamics simulations and rate theory methods. Properties associated with the water-exchange process, such as ion-water potentials of mean force, time-dependent transmission coefficients, and rate constants, were examined along with transition rate theory and the reactive flux method, which includes the role of solvent friction. The effects of pressure on water-exchange rates and activation volumes also were studied. The simulated activation volume values and mechanism were different for Mg2+ and Be2+ because of the nature of their solvation shells. We found the agreement with experiments was improved up on solvent effects were taken into account. The Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences (BES), of the U.S. Department of Energy (DOE) funded this work. Battelle operates Pacific Northwest National Laboratory for DOE. The calculations were carried out using computer resources provided by BES.

  8. 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

  9. 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)

  10. 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

  11. 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

  12. The use of multiple AUVs in FASTNEt: a study of Ocean Shelf Exchange

    NASA Astrophysics Data System (ADS)

    Inall, Mark; Sherwin, Toby; Smeed, David; Palmer, Matthew; Porter, Marie; Dumont, Estelle

    2013-04-01

    We present early results and future plans from the £ 4.5M UK NERC-funded project FASTNEt (Fluxes Across the Sloping Topography of the North East Atlantic). The shelf edge is the controlling gateway to exchange of nutrients and carbon between oceanic and shelf waters, with impacts on global climate and on regional resources. As a result the shelf edge has been the focus of a number of studies which have improved our understanding of exchange processes. However, there are significant deficiencies in the current understanding of shelf edge exchange transport due largely to the sparseness of observations. Gliders and long-endurance AUVs look set to change this and are an important aspect of FASTNEt. We will report on the evolution of physical processes during the breakdown of seasonal stratification at the Celtic shelf edge observed by Glider pairs from June 2012 to January 2013. Glider CTD profiles have been ported realtime onto the GTS, and assimilation into UK Met Office forecast models has been trialled. We will report on 9-days of continuous Glider-based microstructure profiling made near the shelf break in June 2012, revealing the temporal variability of shelf-break generated turbulent mixing. Finally we will present plans to use long endurance AUVs to quantify the seasonal variations in the off-shelf bottom Ekman drain at the Malin Shelf edge during 2013/14.

  13. 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.

  14. Nutrient exchange and release experiment and its simulation study in lake water-sediment interface.

    PubMed

    Xue, Lian-Qing; Hao, Zhen-Chun

    2006-01-01

    The sediment distributed and insolated under lake was collected for experiments. The nutrient layer distribution conditions of sampled sediment and its physical and chemical characteristics were analyzed to simulate and assess the influence degree to lake water quality. Based on the dynamic water exchanging experiments the nutrient release process in sediment and influence mechanism to substance exchanging on water-sediment interface was studied, and the correlation between the changing content of total phosphors and total nitrogen in sediment and covered water were analyzed for setting up a simulation model. At the same time the influence degree is explained in detail. The experimental results indicated that even if clean water without nutrient contents was used for water exchangement so as to decrease pollution or prevent eutrophication, however owing to the vertical nutrient distribution in lake sediment, it will lead to the increasing release amount greatly especially when the organic nutrient contained in sediment turns into inorganic status because of isolation. Besides the release process of total phosphate (TP) and total nitrogen (TN) were modeled and each nutrient's exchanging equation at interface caused by covered water nutrient concentration changing was set up. According to the simulating prediction, TP and TN content of cover water will also sustain a steady higher level in a long period. The nutrient release amount of sediment is not only affected by the covered water concentration but also connects with accumulative time. The experiments provide the fundamental theoretical and practical basis for taking ecological restoration project. And research is helpful to prevent or restore lake eutrophication. PMID:17294663

  15. 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.

  16. Exchange integrals in magnetoelectric hexagonal ferrite (SrCo2Ti2Fe8O19): A density functional study

    NASA Astrophysics Data System (ADS)

    Feng, Min; Shao, Bin; Lu, Yuan; Zuo, Xu

    2014-05-01

    The exchange integrals in magnetoelectric hexagonal ferrite SrCo2Ti2Fe8O19 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 SrFe12O19 and those in SrCo2Ti2Fe8O19 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 SrCo2Ti2Fe8O19.

  17. Effects of hemoperfusion adsorption and/or plasma exchange in treatment of severe viral hepatitis: A comparative study

    PubMed Central

    He, Nian-Hai; Wang, Ying-Jie; Wang, Ze-Wen; Liu, Jun; Li, Jia-Jia; Liu, Guo-Dong; Wang, Yu-Ming

    2004-01-01

    AIM: Non-bioartificial liver has been applied to clinic for quite a long time, but the reported efficacy has been very different. The aim of this study was to compare the efficacy and safety of hemoperfusion adsorption, plasma exchange and plasma exchange plus hemoperfusion adsorption in treatment of severe viral hepatitis. METHODS: Seventy-five patients with severe viral hepatitis were treated with hemoperfusion adsorption therapy (24 cases), plasma exchange therapy (17 cases) and plasma exchange plus hemoperfusion adsorption therapy (34 cases). The data of liver function, renal function, blood routine test, prothrombin time (PT) and prothrombin activity (PTa) pre-and post-therapy were analyzed. RESULTS: Clinical symptoms of patients improved after treatment. The levels of aminotransferase, total bilirubin, direct bilirubin decreased significantly after 3 therapies (P < 0.05 or P < 0.01). PT, the level of total serum protein decreased significantly and PTa increased significantly after plasma exchange therapy and plasma exchange plus hemoperfusion adsorption therapy (P < 0.05 or P < 0.01). The side effects were few and mild in all patients. CONCLUSION: Three therapies were effective in the treatment of severe viral hepatitis. Plasma exchange therapy and plasma exchange plus hemoperfusion adsorption therapy are better than hemoperfusion adsorption therapy. PMID:15069730

  18. Conformation transitions of a polyelectrolyte chain: a replica-exchange Monte-Carlo study.

    PubMed

    Chi, Peng; Li, Baohui; Shi, An-Chang

    2011-08-01

    The thermodynamic behavior of a strongly charged polyelectrolyte chain immersed in a salt-free solution is studied using replica-exchange Monte-Carlo simulations. The results reveal that the chain can assume a variety of conformations, and it undergoes two phase transitions upon cooling. The first transition is identified as a continuous counterion condensation transition while the second one as a first-order coil-globule transition. In the globular state, the counterions and the charged chain segments are densely packed forming a three-dimensional Wigner crystal.

  19. 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.

  20. 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.

  1. Alkaline degradation studies of anion exchange polymers to enable new membrane designs

    NASA Astrophysics Data System (ADS)

    Nunez, Sean Andrew

    Current performance targets for anion-exchange membrane (AEM) fuel cells call for greater than 95% alkaline stability for 5000 hours at temperatures up to 120 °C. Using this target temperature of 120 °C, an incisive 1H NMR-based alkaline degradation method to identify the degradation products of n-alkyl spacer tetraalkylammonium cations in various AEM polymers and small molecule analogs. Herein, the degradation mechanisms and rates of benzyltrimethylammonium-, n-alkyl interstitial spacer- and n-alkyl terminal pendant-cations are studied on several architectures. These findings demonstrate that benzyltrimethylammonium- and n-alkyl terminal pendant cations are more labile than an n-alkyl interstitial spacer cation and conclude that Hofmann elimination is not the predominant mechanism of alkaline degradation. Additionally, the alkaline stability of an n-alkyl interstitial spacer cation is enhanced when combined with an n-alkyl terminal pendant. Interestingly, at 120 °C, an inverse trend was found in the overall alkaline stability of AEM poly(styrene) and AEM poly(phenylene oxide) samples than was previously shown at 80 °C. Successive small molecule studies suggest that at 120 °C, an anion-induced 1,4-elimination degradation mechanism may be activated on styrenic AEM polymers bearing an acidic alpha-hydrogen. In addition, an ATR-FTIR based method was developed to assess the alkaline stability of solid membranes and any added resistance to degradation that may be due to differential solubilities and phase separation. To increase the stability of anion exchange membranes, Oshima magnesate--halogen exchange was demonstrated as a method for the synthesis of new anion exchange membranes that typically fail in the presence of organolithium or Grignard reagents alone. This new chemistry, applied to non-resinous polymers for the first time, proved effective for the n-akyl interstitial spacer functionalization of poly(phenylene oxide) and poly(styrene- co

  2. [Social exchange and inference: an experimental study with the Wason selection task].

    PubMed

    Hayashi, N

    2001-04-01

    Social contract theory (Cosmides, 1989) posits that the human mind was equipped with inference faculty specialized for cheater detection. Cosmides (1989) conducted a series of experiments employing the Wason selection task to demonstrate that her social contract theory could account for the content effects reported in the literature. The purpose of this study was to investigate the possibility that the results were due to experimental artifacts. In the current experiment, the subject was given two versions of the Wason task that contained no social exchange context, but included an instruction implying him/her to look for something, together with the cassava root and the abstract versions used by Cosmides (1989). Results showed that the two versions with no social exchange context produced the same response pattern observed in the original study. It may be concluded that the subject's perception of the rule as a social contract was not necessary to obtain the original results, and that an instruction implying that he/she should look for something was sufficient.

  3. Temperature-Dependent Halogen-Exchange Activity Studies of Zeolite-Derived Aluminum Trifluoride

    SciTech Connect

    Hajime,E.; Delattre, J.; Stacy, A.

    2007-01-01

    A high-surface-area (190 m{sup 2}/g) amorphous aluminum trifluoride material ('plasma-AlF{sub 3}') was synthesized by plasma decomposition of zeolite, and its structural and reactivity properties were investigated. High-resolution transmission electron microscopy of plasma-AlF{sub 3} indicates morphological features on the nanometer-scale, whereas temperature-programmed X-ray diffraction is used to determine the phase-transition temperatures of plasma-AlF{sub 3} to {beta}- and {alpha}-AlF{sub 3}. Halogen-exchange reactivity is studied by temperature-programmed reaction (TPR) techniques using the dismutation of CCl{sub 2}F{sub 2} as a model reaction. Plasma-AlF{sub 3} is found to possess an unexpected low-temperature (>315 C) activity not observed with the well-known halogen-exchange catalyst {beta}-AlF{sub 3}. Supporting TPR studies on aluminum trifluoride hydrates are performed to correlate this new activity with an amorphous AlF{sub 3} structure, and a simple Lewis acid model is presented to explain the reactivity data.

  4. 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.

  5. In-situ Dehydration Studies of Fully K- Rb- and Cs-exchanged Natrolites

    SciTech Connect

    Y Lee; D Seoung; D Liu; M Park; S Hong; H Chen; J Bai; C Kao; T Vogt; Y Lee

    2011-12-31

    In-situ synchrotron X-ray powder diffraction studies of K-, Rb-, and Cs-exchanged natrolites between room temperature and 425 C revealed that the dehydrated phases with collapsed frameworks start to form at 175, 150, and 100 C, respectively. The degree of the framework collapse indicated by the unit-cell volume contraction depends on the size of the non-framework cation: K-exchanged natrolite undergoes an 18.8% unit-cell volume contraction when dehydrated at 175 C, whereas Rb- and Cs-exchanged natrolites show unit-cell volume contractions of 18.5 and 15.2% at 150 and 100 C, respectively. In the hydrated phases, the dehydration-induced unit-cell volume reduction diminishes as the cation size increases and reveals increasingly a negative slope as smaller cations are substituted into the pores of the natrolite structure. The thermal expansion of the unit-cell volumes of the dehydrated K-, Rb-, and Cs-phases have positive thermal expansion coefficients of 8.80 x 10{sup -5} K{sup -1}, 1.03 x 10{sup -4} K{sup 01}, and 5.06 x 10{sup -5} K{sup -1}, respectively. Rietveld structure refinements of the dehydrated phases at 400 C reveal that the framework collapses are due to an increase of the chain rotation angles, {Psi}, which narrow the channels to a more elliptical shape. Compared to their respective hydrated structures at ambient conditions, the dehydrated K-exchanged natrolite at 400 C shows a 2.2-fold increase in {Psi}, whereas the dehydrated Rb- and Cs-natrolites at 400 C reveal increases of {Psi} by ca. 3.7 and 7.3 times, respectively. The elliptical channel openings of the dehydrated K-, Rb-, to Cs-phases become larger as the cation size increases. The disordered non-framework cations in the hydrated K-, Rb-, and Cs-natrolite order during dehydration and the subsequent framework collapse. The dehydrated phases of Rb- and Cs-natrolite can be stabilized at ambient conditions.

  6. Multidimensional separations of ubiquitin conformers in the gas phase: relating ion cross sections to H/D exchange measurements.

    PubMed

    Robinson, Errol W; Williams, Evan R

    2005-09-01

    Investigating gas-phase structures of protein ions can lead to an improved understanding of intramolecular forces that play an important role in protein folding. Both hydrogen/deuterium (H/D) exchange and ion mobility spectrometry provide insight into the structures and stabilities of different gas-phase conformers, but how best to relate the results from these two methods has been hotly debated. Here, high-field asymmetric waveform ion mobility spectrometry (FAIMS) is combined with Fourier-transform ion cyclotron resonance mass spectrometry (FT/ICR MS) and is used to directly relate ubiquitin ion cross sections and H/D exchange extents. Multiple conformers can be identified using both methods. For the 9+ charge state of ubiquitin, two conformers (or unresolved populations of conformers) that have cross sections differing by 10% are resolved by FAIMS, but only one conformer is apparent using H/D exchange at short times. For the 12+ charge state, two conformers (or conformer populations) have cross sections differing by <1%, yet H/D exchange of these conformers differ significantly (6 versus 25 exchanges). These and other results show that ubiquitin ion collisional cross sections and H/D exchange distributions are not strongly correlated and that factors other than surface accessibility appear to play a significant role in determining rates and extents of H/D exchange. Conformers that are not resolved by one method could be resolved by the other, indicating that these two methods are highly complementary and that more conformations can be resolved with this combination of methods than by either method alone.

  7. 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.

  8. 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.

  9. Experimental study of an integral catalytic combustor: Heat exchanger for Stirling engines

    NASA Technical Reports Server (NTRS)

    Bulzan, D. L.

    1982-01-01

    The feasibility of using catalytic combustion with heat removal for the Stirling engine to reduce exhaust emissions and also improve heat transfer to the working fluid was studied using spaced parallel plates. An internally air-cooled heat exchanger was placed between two noble metal catalytic plates. A preheated fuel-air mixture passed between the plates and reacted on the surface of the catalyzed plates. Heat was removed from the catalytic surface by radiation and convection to the aircooled heat exchangers to control temperature and minimize thermal nitrogen oxide emissions. Test conditions were inlet combustion air temperatures from 850 to 900 K, inlet velocities of about 10 m/s, equivalence ratios from 0.5 to 0.9, and pressures from 1.3x10 to the 5th power to 2.0x10 to the 5th power Pa. Propane fuel was used for all testing. Combustion efficiencies greater than 99.5 percent were measured. Nitrogen oxide emissions ranged from 1.7 to 3.3 g NO2/kg fuel. The results demonstrate the feasibility of the concept and indicate that further investigation of the concept is warranted.

  10. 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.

  11. Seasonal carbon dioxide exchange between the regolith and atmosphere of Mars - Experimental and theoretical studies

    NASA Technical Reports Server (NTRS)

    Fanale, F. P.; Salvail, J. R.; Banerdt, W. B.; Saunders, R. S.; Johansen, L. A.

    1982-01-01

    CO2 penetration rate measurements have been made through basalt-clay soils under conditions simulating the penetration of the cap-induced seasonal CO2 pressure wave through the topmost regolith of Mars, and results suggest that existing theoretical models for the diffusion of a gas through a porous and highly adsorbing medium may be used to assess the importance of the Martian seasonal regolith-atmosphere CO2 exchange. The maximum effect of thermally driven exchange between the topmost seasonally (thermally) affected regolith and the atmosphere shows that, while this may be of greater importance than the isothermal exchange, the thermally driven exchange would be recognizable only if the pressure wave from CO2 exchanged at high latitudes did not propagate atmospherically faster than the rate at which the exchange itself occurred. This is an unreasonable assumption.

  12. Molecular Dynamics Simulation Study on Energy Exchange Between Vibration Modes of a Square Graphene Nanoflake Oscillator.

    PubMed

    Lee, Eunae; Kang, Jeong Won; Kim, Ki-Sub; Kwon, Oh-Kuen

    2016-02-01

    Superlubricity in nanoscale graphene structures has been of interest for developing graphene-based nanoelectromechanical systems, as well as for the study of basic mechanical properties. Here, we investigated the translational and rotational motions of a square graphene nanoflake with retracting motions by performing classical molecular dynamics simulations. Our results show that the kinetic energy of the translational motion was exchanged into the kinetic energy of the rotational motion. Thus, square graphene nanoflake oscillators have very low quality factors in translational motions. We discuss that square graphene nanoflakes have great potential to be a core component in nanoelectromechanical systems by detecting their motions with ultrahigh sensitivity to facilitate the development of sensor, memory, and quantum computing.

  13. Molecular Dynamics Simulation Study on Energy Exchange Between Vibration Modes of a Square Graphene Nanoflake Oscillator.

    PubMed

    Lee, Eunae; Kang, Jeong Won; Kim, Ki-Sub; Kwon, Oh-Kuen

    2016-02-01

    Superlubricity in nanoscale graphene structures has been of interest for developing graphene-based nanoelectromechanical systems, as well as for the study of basic mechanical properties. Here, we investigated the translational and rotational motions of a square graphene nanoflake with retracting motions by performing classical molecular dynamics simulations. Our results show that the kinetic energy of the translational motion was exchanged into the kinetic energy of the rotational motion. Thus, square graphene nanoflake oscillators have very low quality factors in translational motions. We discuss that square graphene nanoflakes have great potential to be a core component in nanoelectromechanical systems by detecting their motions with ultrahigh sensitivity to facilitate the development of sensor, memory, and quantum computing. PMID:27433628

  14. Heat transfer and flow studies of the liquid droplet heat exchanger

    NASA Technical Reports Server (NTRS)

    Bruckner, A. P.; Shariatmadar, A.

    1987-01-01

    This paper describes a lightweight, highly effective liquid droplet heat exchanger (LDHX) concept for thermal management in space. Heat is transferred by direct contact between fine droplets (100 to 300 micron diameter) of a low vapor pressure liquid and an inert working gas. Complete separation of the droplet and gas media in the microgravity environment is accomplished by configuring the LDHX as a vortex chamber. A quasi-one-dimensional, two-phase heat transfer model of the LDHX is developed and used to investigate the potential use of the LDHX for both heating and cooling the working gas in a 100-k W(e) Braytoan cycle. Experimental studies on a small scale LDHX chamber, using air and water as the two media, show excellent agreement with the theoretical model.

  15. Impedance study of membrane dehydration and compression in proton exchange membrane fuel cells

    NASA Astrophysics Data System (ADS)

    Le Canut, Jean-Marc; Latham, Ruth; Mérida, Walter; Harrington, David A.

    Electrochemical impedance spectroscopy (EIS) is used to measure drying and rehydration in proton exchange membrane fuel cells running under load. The hysteresis between forward and backward acquisition of polarization curves is shown to be largely due to changes in the membrane resistance. Drying tests are carried out with hydrogen and simulated reformate (hydrogen and carbon dioxide), and quasi-periodic drying and rehydration conditions are studied. The membrane hydration state is clearly linked to the high-frequency arc in the impedance spectrum, which increases in size for dry conditions indicating an increase in membrane resistance. Changes in impedance spectra as external compression is applied to the cell assembly show that EIS can separate membrane and interfacial effects, and that changes in membrane resistance dominate. Reasons for the presence of a capacitance in parallel with the membrane resistance are discussed.

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

    SciTech Connect

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

    2015-07-15

    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 mm{sup 3} Cs vapor cell with a heating temperature of 85 {sup ∘}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/Hz{sup 1/2} in a single channel. Theoretical analysis shows that fundamental sensitivity limits of this device with an active volume of 1 cm{sup 3} could approach 1 fT/Hz{sup 1/2}. 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.

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

    PubMed

    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 mm(3) 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/Hz(1/2) in a single channel. Theoretical analysis shows that fundamental sensitivity limits of this device with an active volume of 1 cm(3) could approach 1 fT/Hz(1/2). 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.

  18. 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

  19. 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.

  20. Theoretical and experimental studies of rectangular duct heat exchangers to be used in a high-altitude subsonic aircraft

    NASA Astrophysics Data System (ADS)

    Mathias, James Allen

    A unique need exists for heat exchangers that operate efficiently at an altitude of 85,000 feet. The application involves transferring heat to the low pressure ambient air at a low velocity that is in the laminar flow regime. Because it is desired that low pressure ambient air experience a small decrease in pressure, heat exchangers were examined with relatively short flowlengths and the boundary layers of the ambient air may be developing for a significant portion of the flowlength. These unique requirements of heat exchangers prompted an experimental study of compact heat exchangers made with relatively short rectangular fins that formed rectangular ducts. Compact heat exchangers made with rectangular fins were experimentally tested to determine the pressure drop of the air across the heat exchanger and the heat transfer to the air; the experiments were performed with air at Reynolds numbers between 100 and 1000. By placing the experimental apparatus in a chamber that was partially evacuated, experiments were also performed with air at a Reynolds number of approximately 250 at simulated elevated altitudes up to 83,000 feet. The results of the experiments performed at sea level and elevated altitudes compared very well. The results of the experiments that measured the pressure drop of the air determined the additional pressure drop caused by the developing boundary layers. An equation obtained from the data of the pressure drop measurements predicted the entrance length of the developing boundary layers. The Nusselt number of the air was calculated from the data of the heat transfer experiments. The Nusselt number significantly increased of the experiments performed with the boundary layers of the air developing for a significant portion of the rectangular duct. An equation was obtained that predicted the Nusselt number for compact heat exchangers with short flowlengths and with air at low Reynolds numbers. The equation that predicted the Nusselt number and the

  1. Thrombotic thrombocytopenic purpura: outcome in 24 patients with renal impairment treated with plasma exchange. Canadian Apheresis Study Group.

    PubMed

    Rock, G; Shumak, K; Kelton, J; Blanchette, V S; Buskard, N; Nair, R; Spasoff, R

    1992-10-01

    The Canadian Apheresis Study Group recently completed a randomized clinical trial involving 102 patients with thrombotic thrombocytopenic purpura (TTP), in which treatment with plasma infusion and treatment with plasma exchange were compared. Thirty-three other patients were ineligible or refused to be randomly assigned in the trial. Of the 33 patients, 24 were assessed as ineligible because they would be unable to tolerate the fluid input that would occur if they were randomly assigned to receive plasma infusion. All 24 patients had oliguria and elevated creatinine and/or blood urea nitrogen level. These 24 patients were treated with acetylsalicyclic acid, dipyridamole, and plasma exchange according to the standardized protocol defined in the trial. Blood for tests of factors possibly involved in the pathogenesis of TTP was drawn before exchange and at intervals during and after exchange. The mean platelet count before exchange was 35.5 x 10(9) per L. In 12 of the 24 patients, the platelet count reached 150 x 10(9) per L or greater by 7 days after the initiation of plasma exchange. Three patients responded partially, in that their platelet count increased to at least twice that at presentation, but remained below 150 x 10(9) per L. One patient died during the first week. Of the eight other patients who experienced treatment failure at the 7-day assessment point, six subsequently responded, four while continuing to receive plasma exchange and two after plasma exchange had been discontinued. Of the 15 patients who either responded fully or responded partially by the end of the first cycle, all survived.(ABSTRACT TRUNCATED AT 250 WORDS)

  2. Cultural Exchange: An Interdisciplinary, Whole Language, Inclusion Program for Teaching Social Studies, English, Understanding, and Tolerance.

    ERIC Educational Resources Information Center

    Klob, Michaeline; Michaels, Kimberly

    This book describes how to establish a Cultural Exchange Program in a school. The Cultural Exchange Program is a partnership between special education students and teachers, regular education students and teachers, and the community. The program involves a member of the international community visiting the school approximately once a month. Before…

  3. 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…

  4. Educational Exchanges: Essays on the Sino-American Experience. Research Papers and Policy Studies 21.

    ERIC Educational Resources Information Center

    Kallgren, Joyce K., Ed.; Simon, Denis Fred, Ed.

    The essays in this monograph (except one) were originally presented and discussed at the Conference on Sino-American Cultural and Scientific Exchanges held in Honolulu, Hawaii in February 1985. Frank Ninkovich presents some of the thoughts that characterized the U.S. approach to cultural exchanges before 1940. In her essay on the pre-World War II…

  5. 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…

  6. Low GWP Refrigerants Modelling Study for a Room Air Conditioner Having Microchannel Heat Exchangers

    SciTech Connect

    Shen, Bo; Bhandari, Mahabir S

    2016-01-01

    Microchannel heat exchangers (MHX) have found great successes in residential and commercial air conditioning applications, being compact heat exchangers, to reduce refrigerant charge and material cost. This investigation aims to extend the application of MHXs in split, room air conditioners (RAC), per fundamental heat exchanger and system modelling. For this paper, microchannel condenser and evaporator models were developed, using a segment-to-segment modelling approach. The microchannel heat exchanger models were integrated to a system design model. The system model is able to predict the performance indices, such as cooling capacity, efficiency, sensible heat ratio, etc. Using the calibrated system and heat exchanger models, we evaluated numerous low GWP (global warming potential) refrigerants. The predicted system performance indices, e.g. cooling efficiency, compressor discharge temperature, and required compressor displacement volume etc., are compared. Suitable replacements for R22 and R-410A for the room air conditioner application are recommended.

  7. 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.

  8. 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

  9. 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.

  10. Residue-specific NH exchange rates studied by NMR diffusion experiments

    NASA Astrophysics Data System (ADS)

    Brand, Torsten; Cabrita, Eurico J.; Morris, Gareth A.; Günther, Robert; Hofmann, Hans-Jörg; Berger, Stefan

    2007-07-01

    We present a novel approach to the investigation of rapid (>2 s -1) NH exchange rates in proteins, based on residue-specific diffusion measurements. 1H, 15N-DOSY-HSQC spectra are recorded in order to observe resolved amide proton signals for most residues of the protein. Human ubiquitin was used to demonstrate the proposed method. Exchange rates are derived directly from the decay data of the diffusion experiment by applying a model deduced from the assumption of a two-site exchange with water and the "pure" diffusion coefficients of water and protein. The "pure" diffusion coefficient of the protein is determined in an experiment with selective excitation of the amide protons in order to suppress the influence of magnetization transfer from water to amide protons on the decay data. For rapidly exchanging residues a comparison of our results with the exchange rates obtained in a MEXICO experiment showed good agreement. Molecular dynamics (MD) and quantum mechanical calculations were performed to find molecular parameters correlating with the exchangeability of the NH protons. The RMS fluctuations of the amide protons, obtained from the MD simulations, together with the NH coupling constants provide a bilinear model which shows a good correlation with the experimental NH exchange rates.

  11. Diffusion, relaxation, and chemical exchange in casein gels: A nuclear magnetic resonance study

    NASA Astrophysics Data System (ADS)

    Gottwald, Antje; Creamer, Lawrence K.; Hubbard, Penny L.; Callaghan, Paul T.

    2005-01-01

    Water in protein/water mixtures can be described in terms of bound water and free water, by exchange between these two states, and by its exchange with appropriate sites on the protein. 1H-NMR diffusion and relaxation measurements provide insights into the mobility of these states. T2 relaxation-time dispersions (i.e., T2 relaxation times at different echo pulse spacings) reveal additional information about exchange. We present a comprehensive set of diffusion and T2 dispersion measurements on casein gels for which the protein/water ratio ranges from 0.25 to 0.5. The combination of these methods, taken in conjunction with concentration dependence, allows a good estimate of the parameters required to fit the data with Luz/Meiboom and Carver/Richards models for relaxation and chemical exchange. We compare the exchange (a) between water and protein and (b) between free water and bound water. Further, we attempt to distinguish chemical site exchange and diffusion/susceptibility exchange.

  12. X-ray diffraction study of K- and Ca-exchanged montmorillonites in CO2 atmospheres.

    PubMed

    Giesting, Paul; Guggenheim, Stephen; Koster van Groos, August F; Busch, Andreas

    2012-05-15

    Powder X-ray diffraction shows that K- and Ca-exchanged montmorillonites swell upon interacting with CO(2) at ambient temperatures, depending on their initial hydration state. K-exchanged montmorillonite swells rapidly to a maximum d(001) of ∼12.2 Å. In contrast, Ca-exchanged montmorillonite swells more slowly, but reaches a maximum d(001) of ∼15.1 Å. Reaction kinetics differ significantly between the K- and Ca-exchanged montmorillonite complexes. Expansion of K-exchanged montmorillonite samples was rapid, occurring on time scales of tens of minutes or less. The Ca-exchanged montmorillonite samples continued to expand over periods up to 42 h. Aging of both K- and Ca-exchanged montmorillonite complexes at elevated CO(2) pressure for 1-2 days resulted in greater stability when CO(2) pressure was released. The observed intercalation reactions have important consequences for carbon sequestration: (1) CO(2) absorption by swelling clays may represent a significant pathway for storage of CO(2). (2) The swelling of smectites under CO(2) pressure may have a significant impact on the permeability of caprock formations. PMID:22494460

  13. Study on the Heat-Flow Controllable Heat Exchanger-3rd report

    NASA Astrophysics Data System (ADS)

    Ishikawa, Osamu; Hamano, Masayoshi; Yanadori, Michio

    The heat-flow controllable heat exchanger for the purpose of heat recovery through the waste hot water at the bathroom and the washing room has been developed. The system is especially available at the house of cold area and the recovery heat is used to warm the suction air conducted from ventilation device. As the result of field test, it is clarified that the heat recovery rate by the system is very large. Also, the exchanger is possible to control the amount of recorery heat. Therefore, it is considered that the exchanger is applicable in the ventilation systems used the waste hot water.

  14. 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

  15. 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

  16. 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

  17. Kinetic and computational studies on Pd(I) dimer-mediated halogen exchange of aryl iodides.

    PubMed

    Kalvet, Indrek; Bonney, Karl J; Schoenebeck, Franziska

    2014-12-19

    Building on our previous discovery and reactivity explorations of the Pd(I) dimer [(PtBu3)PdBr]2-mediated halogen exchange of aryl iodides [Chem. Sci. 2013, 4, 4434], this report presents kinetic studies of this process, giving first-order kinetic dependence in the Pd(I) dimer and aryl iodide. An activation free energy barrier of ΔG(‡) = 24.9 ± 3.3 kcal/mol was experimentally determined. Extensive computational studies on the likely reaction pathway were subsequently carried out. A variety of DFT methods were assessed, ranging from dispersion-free methods to those that better account for dispersion (M06L, ωB97XD, D3-DFT). While significant discrepancies in the quantitative prediction of activation barriers were observed, all computational methods consistently predicted the analogous qualitative reactivity that is in agreement with all spectroscopic and reactivity data collected. Overall, these data provide compelling additional support of the direct reactivity of Pd(I)-Pd(I) with aryl iodides.

  18. 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.

  19. Hyporheic exchange in a karst conduit and sediment system - A laboratory analog study

    NASA Astrophysics Data System (ADS)

    Wu, Yuexia; Hunkeler, Daniel

    2013-09-01

    Karst conduits are often partly filled by clastic sediments. Flow through such sediments can have a strong impact on the fate of sediment-entrapped contaminants. In contrast to stream bed sediments, hyporheic flow in karst sediments has received little attention so far. For karst sediments, conduit bends could induce hyporheic flow, in addition to bedforms or obstacles. The main aim of this study was to investigate flow processes in a conduit-sediment system using a laboratory model resembling a siphon and numerical modeling. In the laboratory system, zones with forward and reserve flow occurred in the sediment due to the conduit bends. As demonstrated with sediment-source tracer test, entrapped solutes were generally flushed out more rapidly at a higher flow rate and steeper conduit angle. Numerical modeling assuming pressure continuity across the conduit-sediment interface reproduced the flow patterns and breakthrough curves (BTCs) well. Based on the model, the magnitude of hyporheic exchange is expected to increase linearly with the flow rate and was higher for a steeper conduit angle. However, the increase in flushing intensity was not evenly distributed throughout the sediments but occurred mainly adjacent to the conduit bends consistent with observations from tracer tests. This study confirms that conduit bends could have a strong influence on hyporheic flow in karst sediments.

  20. 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.

  1. 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.

  2. An analytical model and parametric study of electrical contact resistance in proton exchange membrane fuel cells

    NASA Astrophysics Data System (ADS)

    Wu, Zhiliang; Wang, Shuxin; Zhang, Lianhong; Hu, S. Jack

    This paper presents an analytical model of the electrical contact resistance between the carbon paper gas diffusion layers (GDLs) and the graphite bipolar plates (BPPs) in a proton exchange membrane (PEM) fuel cell. The model is developed based on the classical statistical contact theory for a PEM fuel cell, using the same probability distributions of the GDL structure and BPP surface profile as previously described in Wu et al. [Z. Wu, Y. Zhou, G. Lin, S. Wang, S.J. Hu, J. Power Sources 182 (2008) 265-269] and Zhou et al. [Y. Zhou, G. Lin, A.J. Shih, S.J. Hu, J. Power Sources 163 (2007) 777-783]. Results show that estimates of the contact resistance compare favorably with experimental data by Zhou et al. [Y. Zhou, G. Lin, A.J. Shih, S.J. Hu, J. Power Sources 163 (2007) 777-783]. Factors affecting the contact behavior are systematically studied using the analytical model, including the material properties of the two contact bodies and factors arising from the manufacturing processes. The transverse Young's modulus of chopped carbon fibers in the GDL and the surface profile of the BPP are found to be significant to the contact resistance. The factor study also sheds light on the manufacturing requirements of carbon fiber GDLs for a better contact performance in PEM fuel cells.

  3. Nuclear Magnetic Resonance Studies of Water in Perfluorinated Ion Exchange Membranes.

    NASA Astrophysics Data System (ADS)

    Chen, Rensheng

    Perfluorinated ion-exchange membranes such as NAFION (DuPont) serve as both electrolyte and separators employed in fuel cells. The presence of the water in these membranes is critical to fuel cell operation. Water molecular diffusion and charge transport across the membrane are correlated. Through the availability of water isotopically enriched in deuterium or ^ {17} O, nuclear magnetic resonance (NMR) can be employed to study molecular dynamics by utilizing quadrupolar nuclei as probes. In this thesis, Deuteron and oxygen-17 NMR measurements in NAFION-117 membranes with variable water (D_{2}O or H_ {2}^{17}O) content (3 ~18% by weight) have been carried out. Measurements were taken at variable temperature (room T down to 115 K), high pressure (up to 0.25 GPa), and on stretched samples. One of the main results concerns the observation of anisotropic molecular motion in the membrane plane, with dramatic enhancement of the anisotropy in modestly stretched membranes. Glassy behavior of the water domains at low temperature is evidenced by the specific nature of the ^{2}H NMR line shapes at 109 K. Activation energies extracted from both ^{2}H and ^ {17}O spin-lattice relaxation data exhibit a steady increase with increasing water content. Activation volumes extracted from both ^{1} H and ^{2}H T _{1} pressure dependence show a decrease with increasing water content, at room temperature. Analysis of these observations suggests a water cluster model for water organization in NAFION membranes. The relatively free water and motionally restricted (by interaction with the polymer host) water exchange each other rapidly yielding an averaged response at room T, while the hydrogen bonds become more rigid at low temperature. Deuteron and oxygen -17 NMR studies of NAFION-117 containing either deuterated methanol (CH_{3}OD) or oxygen-17 enriched methanol (CH_{3 } ^{17}OH) demonstrate that the methanol molecular motion in NAFION-117 is considerably faster than for water in NAFION

  4. Experimental studies of alunite: II. Rates of alunite-water alkali and isotope exchange

    USGS Publications Warehouse

    Stoffregen, R.E.; Rye, R.O.; Wasserman, M.D.

    1994-01-01

    Rates of alkali exchange between alunite and water have been measured in hydrothermal experiments of 1 hour to 259 days duration at 150 to 400??C. Examination of run products by scanning electron microscope indicates that the reaction takes place by dissolution-reprecipitation. This exchange is modeled with an empirical rate equation which assumes a linear decrease in mineral surface area with percent exchange (f) and a linear dependence of the rate on the square root of the affinity for the alkali exchange reaction. This equation provides a good fit of the experimental data for f = 17% to 90% and yields log rate constants which range from -6.25 moles alkali m-2s-1 at 400??C to - 11.7 moles alkali m-2s-1 at 200??C. The variation in these rates with temperature is given by the equation log k* = -8.17(1000/T(K)) + 5.54 (r2 = 0.987) which yields an activation energy of 37.4 ?? 1.5 kcal/mol. For comparison, data from O'Neil and Taylor (1967) and Merigoux (1968) modeled with a pseudo-second-order rate expression give an activation energy of 36.1 ?? 2.9 kcal/mol for alkali-feldspar water Na-K exchange. In the absence of coupled alkali exchange, oxygen isotope exchange between alunite and water also occurs by dissolution-reprecipitation but rates are one to three orders of magnitude lower than those for alkali exchange. In fine-grained alunites, significant D-H exchange occurs by hydrogen diffusion at temperatures as low as 100??C. Computed hydrogen diffusion coefficients range from -15.7 to -17.3 cm2s-1 and suggest that the activation energy for hydrogen diffusion may be as low as 6 kcal/mol. These experiments indicate that rates of alkali exchange in the relatively coarse-grained alunites typical of hydrothermal ore deposits are insignificant, and support the reliability of K-Ar age data from such samples. However, the fine-grained alunites typical of low temperature settings may be susceptible to limited alkali exchange at surficial conditions which could cause

  5. Amide Proton Solvent Protection in Amylin Fibrils Probed by Quenched Hydrogen Exchange NMR

    PubMed Central

    Alexandrescu, Andrei T.

    2013-01-01

    Amylin is an endocrine hormone that accumulates in amyloid plaques in patients with advanced type 2 diabetes. The amyloid plaques have been implicated in the destruction of pancreatic β-cells, which synthesize amylin and insulin. To better characterize the secondary structure of amylin in amyloid fibrils we assigned the NMR spectrum of the unfolded state in 95% DMSO and used a quenched hydrogen-deuterium exchange technique to look at amide proton solvent protection in the fibrils. In this technique, partially exchanged fibrils are dissolved in 95% DMSO and information about amide proton occupancy in the fibrils is determined from DMSO-denatured monomers. Hydrogen exchange lifetimes at pH 7.6 and 37°C vary between ∼5 h for the unstructured N-terminus to 600 h for amide protons in the two β-strands that form inter-molecular hydrogen bonds between amylin monomers along the length of the fibril. Based on the protection data we conclude that residues A8-H18 and I26-Y37 comprise the two β-strands in amylin fibrils. There is variation in protection within the β-strands, particularly for strand β1 where only residues F15-H18 are strongly protected. Differences in protection appear to be due to restrictions on backbone dynamics imposed by the packing of two-layers of C2-symmetry-related β-hairpins in the protofilament structure, with strand β1 positioned on the surface and β2 in the interior. PMID:23457571

  6. 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.

  7. 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

  8. 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

  9. One- and two-dimensional chemical exchange nuclear magnetic resonance studies of the creatine kinase catalyzed reaction

    SciTech Connect

    Gober, J.R.

    1988-01-01

    The equilibrium chemical exchange dynamics of the creatine kinase enzyme system were studied by one- and two-dimensional {sup 31}P NMR techniques. Pseudo-first-order reaction rate constants were measured by the saturation transfer method under an array of experimental conditions of pH and temperature. Quantitative one-dimensional spectra were collected under the same conditions in order to calculate the forward and reverse reaction rates, the K{sub eq}, the hydrogen ion stoichiometry, and the standard thermodynamic functions. The pure absorption mode in four quadrant two-dimensional chemical exchange experiment was employed so that the complete kinetic matrix showing all of the chemical exchange process could be realized.

  10. 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.

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

    PubMed

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

    2014-10-01

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

  12. 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.

  13. 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.

  14. 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.

  15. Experimental study on the adsorption of excess heparin with anion exchange resin fiber.

    PubMed

    Matsuda, K; Oka, T; Tani, T; Hanasawa, K; Yoshioka, T; Aoki, H; Endo, Y; Ishii, Y; Numa, K; Kodama, M

    1989-12-01

    Anion exchange resin fiber (Ionex) was used as a heparin adsorbent. Ionex has the adsorption capacity of 70 mg/g (weight by desiccation) for heparin, and was used in an attempt to remove the heparin from blood-perfused artificial organs, before the blood was transfused back into the patients. In the ex vivo study, the 5 systemically heparinized dogs (500 U/kg) were treated with a 35-40 g column of Ionex, by direct hemoperfusion (DHP). The concentration of heparin was significantly reduced, within 15 to 60 minutes, using the Ionex. This suggested the possibility of removing excess heparin from the living body. In in vitro, the relationship between the amount of heparin by Ionex and the blood-flow volume were evaluated. Whole blood taken from dogs was added to 5 U/ml of heparin. This was then introduced into a small column containing 0.9 g Ionex, at blood-flow rates of 0.8, 1.6, and 3.2 ml/min. A good adsorption capacity was shown at the blood-flow rate of 0.8 ml/min. One possible explanation for this is that the heparin dispersed in the blood cells gradually was passed on into the plasma and, so, did not have time to be adsorbed at the faster flow rates. PMID:2604592

  16. 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,…

  17. 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,…

  18. Influence of bond length variation on correlated static exchange potential: A case study in e--N2 scattering

    NASA Astrophysics Data System (ADS)

    Ghose, Keya Basu; Pal, Sourav

    1994-03-01

    We discuss in this note how the correlated static exchange potential changes with bond length for N2 molecule where the earlier extensive results at equilibrium exist. We have used many-body coupled cluster technique for this study. Its relevance to e--N2 scattering is also discussed.

  19. 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…

  20. 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.

  1. Spatially distributed modelling of surface water-groundwater exchanges during overbank flood events - a case study at the Garonne River

    NASA Astrophysics Data System (ADS)

    Bernard-Jannin, Léonard; Brito, David; Sun, Xiaoling; Jauch, Eduardo; Neves, Ramiro; Sauvage, Sabine; Sánchez-Pérez, José-Miguel

    2016-08-01

    Exchanges between surface water (SW) and groundwater (GW) are of considerable importance to floodplain ecosystems and biogeochemical cycles. Flood events in particular are important for riparian water budget and element exchanges and processing. However SW-GW exchanges present complex spatial and temporal patterns and modelling can provide useful knowledge about the processes involved at the scale of the reach and its adjacent floodplain. This study used a physically-based, spatially-distributed modelling approach for studying SW-GW exchanges. The modelling in this study is based on the MOHID Land model, combining the modelling of surface water flow in 2D with the Saint-Venant equation and the modelling of unsaturated groundwater flow in 3D with the Richards' equation. Overbank flow during floods was also integrated, as well as water exchanges between the two domains across the entire floodplain. Conservative transport simulations were also performed to study and validate the simulation of the mixing between surface water and groundwater. The model was applied to the well-monitored study site of Monbéqui (6.6 km²) in the Garonne floodplain (south-west France) for a five-month period and was able to represent the hydrology of the study area. Infiltration (SW to GW) and exfiltration (SW to GW) were characterised over the five-month period. Results showed that infiltration and exfiltration exhibited strong spatiotemporal variations, and infiltration from overbank flow accounted for 88% of the total simulated infiltration, corresponding to large flood periods. The results confirmed that overbank flood events played a determinant role in floodplain water budget and SW-GW exchanges compared to smaller (below bankfull) flood events. The impact of floods on water budget appeared to be similar for flood events exceeding a threshold corresponding to the five-year return period event due to the study area's topography. Simulation of overbank flow during flood events was an

  2. 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

  3. 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.

  4. Study on Fins' Effect of Boiling Flow in Millimeter Channel Heat Exchanger

    NASA Astrophysics Data System (ADS)

    Watanabe, Satoshi

    2005-11-01

    Recently, a lot of researches about compact heat exchangers with mini-channels have been carried out with the hope of obtaining a high-efficiency heat transfer, due to the higher ratio of surface area than existing heat exchangers. However, there are many uncertain phenomena in fields such as boiling flow in mini-channels. Thus, in order to understand the boiling flow in mini-channels to design high-efficiency heat exchangers, this work focused on the visualization measurement of boiling flow in a millimeter channel. A transparent acrylic channel (heat exchanger form), high-speed camera (2000 fps at 1024 x 1024 pixels), and halogen lamp (backup light) were used as the visualization system. The channel's depth is 2 mm, width is 30 mm, and length is 400 mm. In preparation for commercial use, two types of channels were experimented on: a fins type and a normal slit type (without fins). The fins are circular cylindrical obstacles (diameter is 5 mm) to promote heat transfer, set in a triangular array (distance between each center point is 10 mm). Especially in this work, boiling flow and heat transfer promotion in the millimeter channel heat exchanger with fins was evaluated using a high-speed camera.

  5. Structure and properties of metal-exchanged zeolites studied using gradient-corrected and hybrid functionals. I. Structure and energetics

    NASA Astrophysics Data System (ADS)

    Göltl, Florian; Hafner, Jürgen

    2012-02-01

    The structural and energetic properties of purely siliceous, proton-, and Cu- and Co-exchanged chabazite have been studied using periodic density-functional (DFT) calculations with both conventional gradient-corrected exchange-correlation functionals and hybrid functionals mixing exact (i.e., Hartree-Fock) and DFT exchange. Spin-polarized and fixed-moment calculations have been performed to determine the equilibrium and excited spin-configurations of the metal-exchanged chabazites. For the purely siliceous chabazite, hybrid functionals predict a slightly more accurate cell volume and lattice geometry. For isolated Al/Si substitution sites, gradient-corrected functionals predict that the lattice distortion induced by the substitution preserves the local tetrahedral symmetry, whereas hybrid functionals lead to a distorted Al coordination with two short and two long Al-O bonds. Hybrid functionals yield a stronger cation-framework binding that conventional functionals in metal-exchanged zeolites, they favor shorter cation-oxygen bonds and eventually also a higher coordination of the cation. Both types of functionals predict the same spin in the ground-state. The structural optimization of the excited spin-states shows that the formation of a high-spin configuration leads to a strong lattice relaxation and a weaker cation-framework bonding. For both Cu- and Co-exchanged chabazite, the prediction of a preferred location of the cation in a six-membered ring of the zeolite agrees with experiment, but the energy differences between possible cation locations and the lattice distortion induced by the Al/Si substitution and the bonding of the cation depends quite significantly on the choice of the functional. All functionals predict similar energy differences for excited spin states. Spin-excitations are shown to be accompanied by significant changes in the cation coordination, which are more pronounced with hybrid functionals. The consequences of electronic spectra and

  6. High magnetic exchange coupling constants: a density functional theory based study of substituted Schlenk diradicals.

    PubMed

    Latif, Iqbal A; Hansda, Shekhar; Datta, Sambhu N

    2012-08-23

    The Schlenk diradical has been known since 1915. After a detailed experimental work by Rajca, its magnetic nature has remained more or less unexplored. We have investigated by quantum chemical calculations the nature of magnetic coupling in 11 substituted Schlenk diradicals. Substitution has been considered at the fifth carbon atom of the meta-phenylene moiety. The UB3LYP method has been used to study 12 diradicals including the original one. The 6-311G(d,p) basis set has been employed for optimization of molecular geometry in both singlet and triplet states for each species. The singlet optimization has led to the optimization of the broken-symmetry structure for 10 species including the unsubstituted one. This development makes it possible to carry out further broken symmetry calculations in two ways. The triplet calculation has been done using 6-311++G(d,p) basis set and the optimized triplet geometry in both procedures. The broken symmetry calculations have used the optimized geometries of either the triplet states or the broken symmetry solutions. The first method leads to the prediction of electron paramagnetic resonance (EPR) compatible magnetic exchange coupling constant (J) in the range 517-617 cm(-1). A direct optimization of the broken symmetry geometry gives rise to a lower estimate of J, in the range of 411-525 cm(-1) and compatible with macroscopic Curie studies. The calculated J for the unsubstituted Schlenk diradical is 512 cm(-1) that can be compared with 455 cm(-1) estimated by Rajca. In both cases, introduction of groups with +M and +I effects (Ingold's notation) decreases the J value from that for the unsubstituted Schlenk diradical while -I and -M groups at the same position increases J. These trends have been explained in terms of Hammett constants, atomic spin densities, and dihedral angles.

  7. Study of exchange bias and training effect in NiCr2O4

    NASA Astrophysics Data System (ADS)

    Barman, Junmoni; Bora, Tribedi; Ravi, S.

    2015-07-01

    Single phase sample of NiCr2O4 crystallized in a tetragonal structure of I41/amd space group was prepared. Ferrimagnetic transition at TC=73 K along with a large irreversibility has been observed from the magnetization measurement. The sample exhibits exchange bias phenomenon and it is explained by considering the anisotropic exchange interaction between the ferrimagnetic and the antiferromagnetic components of magnetic moment. Presence of training effect is also observed. The exchange bias field (HEB) is found to decay exponentially with increase in temperature and however, the coercive field (HCeff) follows the empirical relation HCeff = HCeff [ 1 - T/TC']2 . The maximum experimental values of HEB and HCeff are found to be 313 Oe and 4839 Oe respectively.

  8. Syringe exchange as a social movement: a case study of harm reduction in Oakland, California.

    PubMed

    Bluthenthal, R N

    1998-04-01

    The federal ban on funding for syringe exchange programs (SEPs) has greatly hampered attempts to prevent the spread of HIV among injection drug users in the United States. State laws prohibiting the possession and/or distribution of syringes have made SEPs illegal. These factors have lent a unique social movement quality to harm reduction efforts in the United States. Using a social movement perspective, this paper explores dynamics of the implementation and defense of the syringe exchange program in Oakland, California. The advantages and disadvantages of the social movement aspects of harm reduction are discussed. PMID:9596381

  9. Syringe exchange as a social movement: a case study of harm reduction in Oakland, California.

    PubMed

    Bluthenthal, R N

    1998-04-01

    The federal ban on funding for syringe exchange programs (SEPs) has greatly hampered attempts to prevent the spread of HIV among injection drug users in the United States. State laws prohibiting the possession and/or distribution of syringes have made SEPs illegal. These factors have lent a unique social movement quality to harm reduction efforts in the United States. Using a social movement perspective, this paper explores dynamics of the implementation and defense of the syringe exchange program in Oakland, California. The advantages and disadvantages of the social movement aspects of harm reduction are discussed.

  10. Replica Exchange Molecular Dynamics Study of Dimerization in Prion Protein: Multiple Modes of Interaction and Stabilization.

    PubMed

    Chamachi, Neharika G; Chakrabarty, Suman

    2016-08-01

    The pathological forms of prions are known to be a result of misfolding, oligomerization, and aggregation of the cellular prion. While the mechanism of misfolding and aggregation in prions has been widely studied using both experimental and computational tools, the structural and energetic characterization of the dimer form have not garnered as much attention. On one hand dimerization can be the first step toward a nucleation-like pathway to aggregation, whereas on the other hand it may also increase the conformational stability preventing self-aggregation. In this work, we have used extensive all-atom replica exchange molecular dynamics simulations of both monomer and dimer forms of a mouse prion protein to understand the structural, dynamic, and thermodynamic stability of dimeric prion as compared to the monomeric form. We show that prion proteins can dimerize spontaneously being stabilized by hydrophobic interactions as well as intermolecular hydrogen bonding and salt bridge formation. We have computed the conformational free energy landscapes for both monomer and dimer forms to compare the thermodynamic stability and misfolding pathways. We observe large conformational heterogeneity among the various modes of interactions between the monomers and the strong intermolecular interactions may lead to as high as 20% β-content. The hydrophobic regions in helix-2, surrounding coil regions, terminal regions along with the natively present β-sheet region appear to actively participate in prion-prion intermolecular interactions. Dimerization seems to considerably suppress the inherent dynamic instability observed in monomeric prions, particularly because the regions of structural frustration constitute the dimer interface. Further, we demonstrate an interesting reversible coupling between the Q160-G131 interaction (which leads to inhibition of β-sheet extension) and the G131-V161 H-bond formation. PMID:27390876

  11. In vitro Studies of the Gain and Exchange of Calcium in Frog Skeletal Muscle

    PubMed Central

    Cosmos, Ethel; Harris, Eric J.

    1961-01-01

    (1) The Ca++, Na+, and K+ contents of frog sartorius muscles were found analytically after exposure to various media including some containing labeled Ca++. (2) During storage in media with 100 to 120 mM Na+ and 1 mM Ca++ both Na+ and Ca++ are gained while K+ is lost; there is a high correlation between Na+ and Ca++ gains. (3) When Ca++ gain occurs from a solution containing labeled Ca++ there is also some exchange of the original Ca++ with the labeled Ca++. The amount exchanged is considerably less (e.g. 50 per cent) than the total amount of labeled Ca++ taken up by the tissue. (4) When the external Na+ concentration is reduced to 30 mM the amount of labeled Ca++ taken up is increased. Part of the increase is attributable to a greater net gain and part to a greater degree of exchange. (5) It is pointed out that muscles which have been loaded in vitro with labeled Ca++ will not provide a valid measure of the exchangeability of the normal Ca++ content present at the time of dissection. (6) Comparison is made between results obtained using Sr89 and Ca45 as labels for the Ca++. Little, if any, difference is perceptible. PMID:13695749

  12. 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…

  13. Study Abroad; Student and Academic Exchanges; Foreign Students in China; Chinese Students Abroad: Annotated Bibliography.

    ERIC Educational Resources Information Center

    Parker, Franklin

    An annotated bibliography includes 66 items drawn from a wide variety of sources including scholarly journals, government reports, books, newspapers, and ERIC documents. While many of the cited works focus on educational exchange programs between China and Western nations since the Cultural Revolution, some of the sources deal with earlier…

  14. 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…

  15. 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…

  16. "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…

  17. 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.

  18. (13)CHD2-CEST NMR spectroscopy provides an avenue for studies of conformational exchange in high molecular weight proteins.

    PubMed

    Rennella, Enrico; Huang, Rui; Velyvis, Algirdas; Kay, Lewis E

    2015-10-01

    An NMR experiment for quantifying slow (millisecond) time-scale exchange processes involving the interconversion between visible ground state and invisible, conformationally excited state conformers is presented. The approach exploits chemical exchange saturation transfer (CEST) and makes use of (13)CHD2 methyl group probes that can be readily incorporated into otherwise highly deuterated proteins. The methodology is validated with an application to a G48A Fyn SH3 domain that exchanges between a folded conformation and a sparsely populated and transiently formed unfolded ensemble. Experiments on a number of different protein systems, including a 360 kDa half-proteasome, establish that the sensitivity of this (13)CHD2 (13)C-CEST technique can be upwards of a factor of 5 times higher than for a previously published (13)CH3 (13)C-CEST approach (Bouvignies and Kay in J Biomol NMR 53:303-310, 2012), suggesting that the methodology will be powerful for studies of conformational exchange in high molecular weight proteins.

  19. Microcalorimetric study of adsorption and disassembling of virus-like particles on anion exchange chromatography media.

    PubMed

    Yu, Mengran; Zhang, Songping; Zhang, Yan; Yang, Yanli; Ma, Guanghui; Su, Zhiguo

    2015-04-01

    Chromatographic purification of virus-like particles (VLPs) is important to the development of modern vaccines. However, disassembly of the VLPs on the solid-liquid interface during chromatography process could be a serious problem. In this study, isothermal titration calorimetric (ITC) measurements, together with chromatography experiments, were performed on the adsorption and disassembling of multi-subunits hepatitis B virus surface antigen virus-like particles (HB-VLPs). Two gigaporous ion-exchange chromatography (IEC) media, DEAE-AP-280 nm and DEAE-POROS, were used. The application of gigaporous media with high ligand density led to significantly increased irreversible disassembling of HB-VLPs and consequently low antigen activity recovery during IEC process. To elucidate the thermodynamic mechanism of the effect of ligand density on the adsorption and conformational change of VLPs, a thermodynamic model was proposed. With this model, one can obtain the intrinsic molar enthalpy changes related to the binding of VLPs and the accompanying conformational change on the liquid-solid interface during its adsorption. This model assumes that, when intact HB-VLPs interact with the IEC media, the total adsorbed proteins contain two states, the intact formation and the disassembled formation; accordingly, the apparent adsorption enthalpy, ΔappH, which can be directly measured from ITC experiments, presents the sum of three terms: (1) the intrinsic molar enthalpy change associated to the binding of intact HB-VLPs (ΔbindHintact), (2) the intrinsic molar enthalpy change associated to the binding of HB-VLPs disassembled formation (ΔbindHdis), and (3) the enthalpy change accompanying the disassembling of HB-VLPs (ΔconfHdis). The intrinsic binding of intact HB-VLPs and the disassembled HB-VLPs to both kinds of gigaporous media (each of which has three different ligand densities), were all observed to be entropically driven as indicated by positive values of

  20. Microcalorimetric study of adsorption and disassembling of virus-like particles on anion exchange chromatography media.

    PubMed

    Yu, Mengran; Zhang, Songping; Zhang, Yan; Yang, Yanli; Ma, Guanghui; Su, Zhiguo

    2015-04-01

    Chromatographic purification of virus-like particles (VLPs) is important to the development of modern vaccines. However, disassembly of the VLPs on the solid-liquid interface during chromatography process could be a serious problem. In this study, isothermal titration calorimetric (ITC) measurements, together with chromatography experiments, were performed on the adsorption and disassembling of multi-subunits hepatitis B virus surface antigen virus-like particles (HB-VLPs). Two gigaporous ion-exchange chromatography (IEC) media, DEAE-AP-280 nm and DEAE-POROS, were used. The application of gigaporous media with high ligand density led to significantly increased irreversible disassembling of HB-VLPs and consequently low antigen activity recovery during IEC process. To elucidate the thermodynamic mechanism of the effect of ligand density on the adsorption and conformational change of VLPs, a thermodynamic model was proposed. With this model, one can obtain the intrinsic molar enthalpy changes related to the binding of VLPs and the accompanying conformational change on the liquid-solid interface during its adsorption. This model assumes that, when intact HB-VLPs interact with the IEC media, the total adsorbed proteins contain two states, the intact formation and the disassembled formation; accordingly, the apparent adsorption enthalpy, ΔappH, which can be directly measured from ITC experiments, presents the sum of three terms: (1) the intrinsic molar enthalpy change associated to the binding of intact HB-VLPs (ΔbindHintact), (2) the intrinsic molar enthalpy change associated to the binding of HB-VLPs disassembled formation (ΔbindHdis), and (3) the enthalpy change accompanying the disassembling of HB-VLPs (ΔconfHdis). The intrinsic binding of intact HB-VLPs and the disassembled HB-VLPs to both kinds of gigaporous media (each of which has three different ligand densities), were all observed to be entropically driven as indicated by positive values of

  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. Factors Affecting Outcome in Acute Hypertriglyceridemic Pancreatitis Treated with Plasma Exchange: An Observational Cohort Study

    PubMed Central

    Gubensek, Jakob; Buturovic-Ponikvar, Jadranka; Romozi, Karmen; Ponikvar, Rafael

    2014-01-01

    Objectives The optimal therapy for hypertriglyceridemic acute pancreatitis, especially the role of plasma exchange (PE), is not entirely clear. The aim of our large, single-center, observational, cohort study was to analyze the factors affecting outcome in hypertriglyceridemic pancreatitis treated with PE. Methods We included 111 episodes of hypertriglyceridemic pancreatitis treated with PE, which occurred in 103 different patients. The Acute Physiology and Chronic Health Evaluation (APACHE) II score, triglycerides, delay to first PE, and PE treatment details were retrospectively obtained from the patients’ records. The main outcome measures were length of hospitalization and in-hospital mortality. Results The patients were 47±9 years old and the median APACHE II score at first PE was 4 (inter-quartile range (IQR) 2–7). There was a seasonal variation in the incidence of hypertriglyceridemic pancreatitis, and the recurrence rate was 1.6% per year. Triglycerides at presentation did not correlate with APACHE II or influence the outcome. The mean reduction in triglycerides during PE was 59% (from 44±31 to 18±15 mmol/l), which was twice the reduction observed during conservative treatment (27% daily). The median hospital stay was 16 days (IQR 10–24) and in-hospital mortality was 5%. The median delay to first PE was 35 hours (IQR 24–52), and there was no difference in mortality in the early and late PE groups (7% vs. 6%, p = 0.79). The group with citrate anticoagulation during PE had a significantly lower mortality than the group with heparin anticoagulation (1% vs. 11%, p = 0.04), and citrate was an independent predictor also in the multivariate model (p = 0.049). Conclusions PE effectively reduced serum triglycerides faster than could be expected with conservative treatment. The delay in PE therapy did not influence survival. We found that citrate anticoagulation during PE was associated with reduced mortality, which should be confirmed in a

  3. The Electrochemical Noise Study of TA10 Heat Exchanger Tubes in the Tri-effect Continuous Evaporation and Crystallization Device

    NASA Astrophysics Data System (ADS)

    Chen, Bing; Ruan, Ying-Hao; Jiang, Nan

    2016-05-01

    According to the tube process conditions of a TA10 heat exchanger, which is working in a chemical plant, the paper analyzes the possible factors of corrosion, identify the main influencing factors of the corrosion failure of heat exchanger were temperature, pH value, and the concentration of Aluminum Chloride Hexahydrate. Using the orthogonal test and electrochemical noise measurement technique to study the influence of three factors on TA10 alloy. The results show that the TA10 alloy has no obvious corrosion in the range of experimental study. The result of the range analysis determines the temperature and pH value are the main factors influencing the noise resistance Rn, the value of the noise resistance Rn increases with the rise of the temperature. When the temperature is 90□, the pH value is 2, the noise resistance Rn of the TA10 alloy specimen is largest.

  4. 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.

  5. Moessbauer spectroscopy and catalytic studies on iron-exchanged, silicon-substituted Y-zeolite

    SciTech Connect

    Aparicio, L.M.; Dumesic, J.A.; Fang, S.; Long, M.A.; Ulla, M.A.; Millman, W.S.; Hall, W.K.

    1987-04-01

    Iron-exchanged zeolites with Si/Al ratios ranging from 2.49 to 8.88 were characterized by Moessbauer spectroscopy and studied for the decomposition of N/sub 2/O. Moessbauer spectra were collected at room temperature after pretreatments in H/sub 2/ and O/sub 2/ at 700 K, and after exposure of the samples to CO or H/sub 2/O. Nitrous oxide decomposition activities were determined at 800 K under a N/sub 2/O partial pressure of 3.5 kPa. Moessbauer spectra collected after pretreatment in H/sub 2/ showed that silicon-substituted Fe-Y had a larger fraction of iron cations in sites I', II', and/or II than conventional Fe-Y, in which most iron cations were in site I. The silicon-substituted Fe-Y catalysts had higher turnover frequencies for the decomposition of N/sub 2/O than conventional Fe-Y. Moessbauer spectra collected after pretreatment in O/sub 2/ showed that a fraction of the iron cations in silicon-substituted Fe-Y was more difficult to oxidize to Fe/sup 3 +/ than the iron in conventional Fe-Y. Moessbauer spectra collected after pretreatment in O/sub 2/ showed that a fraction of the iron cations in silicon-substituted Fe-Y was more difficult to oxidize to Fe/sup 3 +/ than the iron in conventional Fe-Y. This result suggests that pairs of iron cations in close proximity are needed for the oxidation process to occur readily. Finally, exposure of the zeolites to CO or H/sub 2/O produced Moessbauer spectroscopy doublets due to iron cations associated with adsorbate molecules. These doublets indicate that ferrous cations at sites I', II', and/or II serve as adsorption centers for H/sub 2/O, the adsorption process increasing the coordination of the ferrous cations, and that ferrous cations at site II can serve as adsorption centers for CO as well. 22 references.

  6. Two-state vs. multistate protein unfolding studied by optical melting and hydrogen exchange.

    PubMed Central

    Mayne, L.; Englander, S. W.

    2000-01-01

    A direct conflict between the stabilization free energy parameters of cytochrome c determined by optical methods and by hydrogen exchange (HX) is quantitatively explained when the partially folded intermediates seen by HX are taken into account. The results support the previous HX measurements of intermediate populations, show how intermediates can elude the standard melting analysis, and illustrate how they confuse the analysis when they are significantly populated within the melting transition region. PMID:11106159

  7. Planning and conducting an international seismic data exchange experiment at the center for seismic studies

    NASA Astrophysics Data System (ADS)

    Romney, C.; Huszar, L.; Frazier, G. A.; Campanella, A.; Tiberio, M. A.

    1986-01-01

    This report covers preparations for and the conduct of an international seismic data exchange experiment sponsored by the Group of Scientific Experts, U.N. Conference on Disarmament. Seismic data reports from 37 countries were transmitted over circuits of the WMO/GTS. The data were analyzed at centers in Washington, Moscow and Stockholm and epicenter lists were broadcast to participants. The experiment tested a number of aspects of a proposed nuclear test monitoring system.

  8. 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.

  9. Results from the US/USSR exchange for heat load material studies of simulated tokamak disruptions

    SciTech Connect

    Gahl, J.M.; Crawford, J.F.; McDonald, J.M.; McGrath, R.T.; Zakharov, A.; Tserevitinov, S.; Barabash, V.; Guseva, M.

    1992-08-01

    This paper presents recent results from exchange I.2 of the US/USSR Exchange Program of Cooperation for Magnetic Confinement Fusion. Previous results from this exchange demonstrated much lower than expected ablation of graphites when the graphites were exposed to disruption like heat fluxes delivered by plasma gun sources. This lower than expected ablation has been accounted for by the ``vapor shielding`` effect. Vapor shielding occurs when material is ablated from the surface of the graphite target early in the plasma pulse. This ablated material then shields the surface of the target from the rest of the incoming plasma pulse. Vapor shielding has been inferred from diagnostics and ablation data at all participating laboratories, and clear evidence of the effect has been found by laser interferometry at Kurchatov (Troitsk) in the 2MK-200 machine. Recent results from Kurchatov on the 2MK-200 and MKT experiments continue to indicate that the erosion of graphite exposed to disruption like heat fluxes is much lower than expected. Work from the University of New Mexico on the PLAIDS experiment confirms earlier important work conducted on the VIKA experiment at Efremov. This is particularly interesting in that PLAIDS and VIA have very similar plasma pulse characteristics.

  10. Results from the US/USSR exchange for heat load material studies of simulated tokamak disruptions

    NASA Astrophysics Data System (ADS)

    Gahl, J. M.; Crawford, J. F.; McDonald, J. M.; McGrath, R. T.; Zakharov, A.

    This paper presents recent results from exchange I.2 of the US/USSR Exchange Program of Cooperation for Magnetic Confinement Fusion. Previous results from this exchange demonstrated much lower than expected ablation of graphites when the graphites were exposed to disruption like heat fluxes delivered by plasma gun sources. This lower than expected ablation has been accounted for by the 'vapor shielding' effect. Vapor shielding occurs when material is ablated from the surface of the graphite target early in the plasma pulse. This ablated material then shields the surface of the target from the rest of the incoming plasma pulse. Vapor shielding has been inferred from diagnostics and ablation data at all participating laboratories, and clear evidence of the effect has been found by laser interferometry at Kurchatov (Troitsk) in the 2MK-200 machine. Recent results from Kurchatov on the 2MK-200 and MKT experiments continue to indicate that the erosion of graphite exposed to disruption like heat fluxes is much lower than expected. Work from the University of New Mexico on the PLAIDS experiment confirms earlier important work conducted on the VIKA experiment at Efremov. This is particularly interesting in that PLAIDS and VIA have very similar plasma pulse characteristics.

  11. Results from the US/USSR exchange for heat load material studies of simulated tokamak disruptions

    SciTech Connect

    Gahl, J.M.; Crawford, J.F. ); McDonald, J.M.; McGrath, R.T. ); Zakharov, A. ); Tserevitinov, S. ); Barabash, V. ); Guseva, M. (Gosudarstvennyj Komitet po Ispol'zovaniy

    1992-01-01

    This paper presents recent results from exchange I.2 of the US/USSR Exchange Program of Cooperation for Magnetic Confinement Fusion. Previous results from this exchange demonstrated much lower than expected ablation of graphites when the graphites were exposed to disruption like heat fluxes delivered by plasma gun sources. This lower than expected ablation has been accounted for by the vapor shielding'' effect. Vapor shielding occurs when material is ablated from the surface of the graphite target early in the plasma pulse. This ablated material then shields the surface of the target from the rest of the incoming plasma pulse. Vapor shielding has been inferred from diagnostics and ablation data at all participating laboratories, and clear evidence of the effect has been found by laser interferometry at Kurchatov (Troitsk) in the 2MK-200 machine. Recent results from Kurchatov on the 2MK-200 and MKT experiments continue to indicate that the erosion of graphite exposed to disruption like heat fluxes is much lower than expected. Work from the University of New Mexico on the PLAIDS experiment confirms earlier important work conducted on the VIKA experiment at Efremov. This is particularly interesting in that PLAIDS and VIA have very similar plasma pulse characteristics.

  12. Atom exchange between aqueous Fe(II) and goethite: an Fe isotope tracer study.

    PubMed

    Handler, Robert M; Beard, Brian L; Johnson, Clark M; Scherer, Michelle M

    2009-02-15

    The reaction of aqueous Fe(II) with Fe(III) oxides is a complex process, comprising sorption, electron transfer, and in some cases, reductive dissolution and transformation to secondary minerals. To better understand the dynamics of these reactions, we measured the extent and rate of Fe isotope exchange between aqueous Fe(II) and goethite using a 57Fe isotope tracer approach. We observed near-complete exchange of Fe atoms between the aqueous phase and goethite nanorods over a 30-day time period. Despite direct isotopic evidence for extensive mixing between the aqueous and goethite Fe, no phase transformation was observed, nor did the size or shape of the goethite rods change appreciably. High-resolution transmission electron microscopy images, however, appear to indicate that some recrystallization of the goethite particles may have occurred. Near-complete exchange of Fe between aqueous Fe(II) and goethite, coupled with negligible change in the goethite mineralogy and morphology, suggests a mechanism of coupled growth (via sorption and electron transfer) and dissolution at separate crystallographic goethite sites. We propose that sorption and dissolution sites are linked via conduction through the bulk crystal, as was recently demonstrated for hematite. Extensive mixing between aqueous Fe(II) and goethite, a relatively stable iron oxide, has significant implications for heavy metal sequestration and release (e.g., arsenic and uranium), as well as reduction of soil and groundwater contaminants.

  13. 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…

  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

  15. Trip time comparison of conventional and exchange container mode for solid waste collection a case study of Ilorin, Nigeria.

    PubMed

    Aremu, A S; Vijay, Ritesh; Adeleke, O O

    2013-01-01

    The use of hauled container system for municipal solid waste collection and transportation often results in socio-economic and environmental impacts which are linearly related to trip time. In this study, trip times for the conventional and exchange container mode of solid waste collection by the hauled container system were evaluated. A trip time model was developed for this evaluation through field studies. The model was applied on ten trips to collect solid waste bins and its transportation to disposal site in the city of Ilorin, Nigeria. The results of the model for both modes were compared and Showed that at 5 % significance level,.the trip time for the conventional mode was greater than the trip time for the exchange container mode. Also, the exchange container mode resulted in haul distance reduction by 3 to 15% and trip time reduction by 2.5 to 13 %. This reduction could help in improving logistics and also reduce the negative, impacts associated with collection operation.

  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. Thermodynamic study of the interaction between linear plasmid DNA and an anion exchange support under linear and overloaded conditions.

    PubMed

    Aguilar, P A; Twarda, A; Sousa, F; Dias-Cabral, A C

    2014-11-01

    Anion-exchange chromatography has been successfully used in plasmid DNA (pDNA) purification. However, pDNA adsorption mechanism using this method is still not completely understood, and the prediction of the separation behavior is generally unreliable. Flow microcalorimetry (FMC) has proven its ability to provide an improved understanding of the driving forces and mechanisms involved in the adsorption process of biomolecules onto several chromatographic systems. Thus, using FMC, this study aims to understand the adsorption mechanism of linear pDNA (pVAX1-LacZ) onto the anion-exchange support Fast Flow (FF) Q-Sepharose. Static binding capacity studies have shown that the mechanism of pDNA adsorption onto Q-Sepharose follows a Langmuir isotherm. FMC experiments resulted in thermograms that comprised endothermic and exothermic heats. Endothermic heat major contributor was suggested to be the desolvation process. Exothermic heats were related to the interaction between pDNA and Q-Sepharose primary and secondary adsorption. Furthermore, FMC revealed that the overall adsorption process is exothermic, as expected for an anion-exchange interaction. Nevertheless, there are evidences of the presence of nonspecific effects, such as reorientation and electrostatic repulsive forces. PMID:25465014

  18. 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.…

  19. 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.…

  20. Higher Education Exchange, 2008

    ERIC Educational Resources Information Center

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

    2008-01-01

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

  1. 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…

  2. 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…

  3. 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.…

  4. Ion exchange and dehydration experimental studies of clinoptilolite: Implications to zeolite dating

    SciTech Connect

    WoldeGabriel, G.

    1995-02-01

    Variable effects were noted on the argon (Ar) and potassium (K) contents of clinoptilolite fractions used in ion-exchange and dehydration experiments. The K contents of clinoptilolite fractions were differently affected during cation exchange with Ca-, Cs-, K-, and Na-chloride solutions. Ar was generally less affected during these experiments, except for a Na-clinoptitolite fraction exchanged for five days. Loss of Ar during organic heavy-liquid treatment and cleaning using acetone and deionized water does occur, as indicated by comparing the amounts of radiogenic Ar of treated and untreated fractions. Moreover, a regular decrease in radiogenic Ar contents was noted in clinoptilolite fractions during dehydration experiments at different temperatures for 16 hours. Comparable losses do not occur from saturated samples that were heated in 100 C for more than five months. Water appears to play a vital role in stabilizing the clinoptilolite framework structure and in the retention of Ar. The radiogenic Ar depletion pattern noted in clinoptilolite fractions dehydrated in unsaturated environment at different temperatures is similar to variations in the amount of radiogenic Ar observed in clinoptilolite samples from the unsaturated zone of an altered tuff. These results can be used to evaluate the extent of zeolitic water (and hence Ar) retention in unsaturated geologic settings. The utility of alkali zeolites (e.g., phillipsite, clinoptilolite, and mordenite) from low-temperature, open-hydrologic alteration as potential dateable minerals was evaluated using the K/Ar method as part of the Yucca Mountain Site Characterization Project, which is evaluating Yucca Mountain, Nevada, as a potential high-level radioactive waste repository site.

  5. 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. 14 mg bovine lactoferrin/mL resin at 4 °C and 62 mg 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.

  6. 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).

  7. Study of the Heat-Transfer Processes of Tubular Elements of Ground Heat Exchangers

    NASA Astrophysics Data System (ADS)

    Kusaiynov, K.; Shuyushbayeva, N. N.; Shaimerdenova, K. M.; Nurgalieva, Zh. G.; Omarov, N. N.

    2015-05-01

    In this paper, consideration is given to the efficiency of utilization of the low-potential heat of the ground. Also, the advantages and distinctive features of polyethylene tubes used in vertical tubular elements of heat pumps are described. This paper gives the results of investigation of the heat transfer of tubular elements of ground heat exchangers. The dependences of the temperature distributions in the ground in the vicinity of a tube and the change in the temperature with time in dry and moist grounds are determined.

  8. 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…

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

    PubMed

    Gülbakan, Basri; Barylyuk, Konstantin; Zenobi, Renato

    2015-02-01

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

  10. 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.

  11. An XML Model of an Enhanced Data Dictionary to Facilitate the Exchange of Clinical Research Data in International Studies

    PubMed Central

    Duda, Stephany N.; Cushman, Clint; Masys, Daniel R.

    2013-01-01

    The clinical research data sets exchanged in international epidemiology research often lack the elements needed to assess their suitability for use in multi-region meta-analyses. While the missing information is generally known to local investigators, it is not contained in the files exchanged between sites. Instead, such content must be solicited by the study coordinating center though a series of lengthy phone and electronic communications: an informal process whose reproducibility and accuracy decays over time. This report describes a set of supplemental information needed to assess whether clinical research data from diverse research sites are truly comparable, and what metadata (“data about the data”) should be preserved when a data set is archived for future use. We propose a structured Extensible Markup Language (XML) model that captures this information. The authors hope this model will be a first step towards preserving the metadata associated with clinical research data sets, thereby improving the quality of international data exchange, data archiving, and merged-data research using data collected in many different countries, languages and care settings. PMID:17911757

  12. Numerical study of the influence of interfacial roughness on the exchange bias properties of ferromagnetic/antiferromagnetic bilayers

    NASA Astrophysics Data System (ADS)

    Moritz, J.; Bacher, P.; Dieny, B.

    2016-09-01

    Exchange bias and coercivity are both studied numerically in antiferromagnetic/ferromagnetic (AFM/FM) bilayers in the presence of a rough interface. The roughness is modeled by an AFM atomic mesa of variable width, in a periodic bidimensional system. Unlike the flat interface case, roughness can favor the presence of magnetic interfacial frustration or the formation of sharp magnetic domain walls pinned within the first AFM planes, inside the AFM mesa, in a Peierls potential well. We demonstrate by using athermal steepest-descent calculations that irreversible processes can occur during the hysteresis loops, when the AFM mesa width is less than half of the system period. In this case, the depinning of the domain wall from the Peierls potential well during the descending branch is not followed by its rewinding in a certain range of the AFM anisotropy. This leads to a large increase of both exchange bias and coercivity at low temperature and to an athermal training effect. When the thermal activation is taken into account by using Monte Carlo simulations, we show that a random walk of the domain wall occurs within the AFM layer. These processes induce changes in the AFM spin configuration when the system is cycled several times and produce a thermally activated training effect. Our simulations, interpreted in the context of periodic Peierls potential, provide an explanation for two important features of the exchange bias phenomenon, i.e., the thermal variation of its characteristic fields and the different contributions giving rise to the training effect (AFM bulk vs interface). More generally, the presence of interfacial atomic roughness reduces both exchange bias and coercivity with respect to the perfect interface case.

  13. A prospective randomized control study comparing classic laryngeal mask airway with Guedel's airway for tracheal tube exchange and smooth extubation

    PubMed Central

    Jain, Shruti; Nazir, Nazia; Khan, Rashid M.; Ahmed, Syed M.

    2016-01-01

    Introduction: Extubation in deep plane of anesthesia followed by Guedel's oropharyngeal airway (OPA™) insertion is a routine method to avoid hemodynamic changes associated with tracheal extubation. Exchange of endotracheal tube (ETT) with Classic laryngeal mask airway (LMA™) prior to emergence from anesthesia also serves similar purpose. We had compared the hemodynamic changes involved during this ETT/LMA™ and ETT/OPA™ exchange technique. Material and Methods: This was a randomized prospective study on ASA I and 2 patients undergoing elective surgery under general anesthesia. These patients were randomly divided into two groups i.e. OPA group and LMA group of 50 patients each. Hemodynamic parameters i.e. systolic blood pressure (SBP) and heart rate (HR) were recorded during exchange of ETT with OPA™ or LMA™. Coughing / bucking during removal of OPA™ and LMA™, and presence of post operative sore throat for both the groups were also graded and recorded. Data within the groups have been analyzed using paired “t” test while those between the groups were analyzed using unpaired “t” test. Chi square test was used to analyze grades of coughing and post operative sore throat. Results: In both groups, hemodynamic parameters rose significantly as OPA™/LMA™ was placed (P < 0.05) and then started declining. Hemodynamic parameters continued to fall in LMA group after extubation. However in OPA group, hemodynamic parameters continued to rise even after extubation and declined only when OPA™ was removed. There was no statistical significant difference between the LMA and OPA group in respect to coughing and post operative sore throat. Conclusion: LMA™ is superior to OPA™ for exchange of ETT as it provides greater hemodynamic stability. PMID:27746550

  14. Isotope Fractionation of chlorine in Aqueous System: One Study on Anion-Exchange Chromatography.

    NASA Astrophysics Data System (ADS)

    Musashi, M.; Oi, T.; Eggenkamp, H.; Van Cappellen, P.

    2001-05-01

    Stable chlorine isotopes such as 37Cl and 35Cl have been paid attention as useful tool identifying the source, and monitoring the transport process and natural fate of chlorinated organic pollutants in air and groundwater. However, it is not established yet whether any isotope effects accompany biodegradation or reductive dehalogenation of the pollutants (Clark and Fritz, 1997). Here we first present an experimental determination of isotope fractionation factor of chlorine in aqueous system by using anion-exchange chromatographic technique. Into the Cl-free anion exchange resin (Muromac, OH- form) packed in a 30 cm long pyrex glass column and controlled temperature at 25 oC, hydrochloric solution was fed with controlling the flow rate constant. Effluent from the column was recovered by an automatic fraction collector and prepared for Cl isotope analysis. The Cl isotope ratio (δ 37Cl vs. SMOC) was measured by IR-MS at the Utrecht University with precision of 0.06 per-mil. Magnitude of the factor obtained was 1.00035 at 25 oC. The result indicates that the lighter isotope (35Cl) was preferably fractionated into the resin phase, while the heavier one (37Cl) was enriched into the aqueous phase. This trend suggests that molecular structure of hydrolysis with Cl in aqueous phase may be more stable than that of Cl ionically bonding with the resin. This result may offer physico-chemical insights into behavior and fate of the pollutants.

  15. Study on the heat-flow controllable heat exchanger (2nd report): Dehumidification in the greenhouse by the ventilation type dehumidifier with heat-flow controllable heat exchanger

    SciTech Connect

    Yanadori, Michio; Hamano, Masayoshi )

    1994-07-01

    A novel ventilation type dehumidifier with heat-flow controllable heat exchanger was installed on the wall of a greenhouse. Dehumidification and heat recovery experiments were conducted. The construction of the novel dehumidifier is simpler than that of the conventional dehumidifier with a compressor. It was found that the required input for the ventilation type dehumidifier was less than that of a conventional dehumidifier with compressor.

  16. The investigation of the bitumen from ancient Greek amphora using FT ICR MS, H/D exchange and novel spectrum reduction approach.

    PubMed

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

    2016-06-01

    Recently Russian archeologists have discovered on Taman peninsula an ancient (V B.C.) Greek amphora full of dense bitumen. This is the oldest amphora in the world that contains bitumen. We report the investigation of this bitumen using ultrahigh resolution Fourier transform mass spectrometry. Also we used recently developed in-ESI source Hydrogen/Deuterium exchange approach for the structural characterization of the individual molecules and estimation of the biodegradation of the bitumen. The increase of number of the labile hydrogens compared to the non-degraded oil can serve as an additional evidence of the degradation of bitumen via oxidation. For the facilitation of the spectrum processing we have developed the special iterative spectrum reduction approach. It was observed that molecules that have only oxygen heteroatoms possess two -OH groups what is unusual for the petroleum. Based on this we suggested that the bitumen degraded during its being in amphora for 2500 years. Copyright © 2016 John Wiley & Sons, Ltd. PMID:27270866

  17. 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.

    2016-06-01

    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.

  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. 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.

  20. 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.

  1. 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.

  2. 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.

    2016-11-01

    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.

  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. Multiscale study of bacterial growth: Experiments and model to understand the impact of gas exchange on global growth.

    PubMed

    Lalanne-Aulet, David; Piacentini, Adalberto; Guillot, Pierre; Marchal, Philippe; Moreau, Gilles; Colin, Annie

    2015-01-01

    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.

  5. 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.

  6. 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

  7. 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.

  8. The Grammar of Exchange: A Comparative Study of Reciprocal Constructions Across Languages

    PubMed Central

    Majid, Asifa; Evans, Nicholas; Gaby, Alice; Levinson, Stephen C.

    2010-01-01

    Cultures are built on social exchange. Most languages have dedicated grammatical machinery for expressing this. To demonstrate that statistical methods can also be applied to grammatical meaning, we here ask whether the underlying meanings of these grammatical constructions are based on shared common concepts. To explore this, we designed video stimuli of reciprocated actions (e.g., “giving to each other”) and symmetrical states (e.g., “sitting next to each other”), and with the help of a team of linguists collected responses from 20 languages around the world. Statistical analyses revealed that many languages do, in fact, share a common conceptual core for reciprocal meanings but that this is not a universally expressed concept. The recurrent pattern of conceptual packaging found across languages is compatible with the view that there is a shared non-linguistic understanding of reciprocation. But, nevertheless, there are considerable differences between languages in the exact extensional patterns, highlighting that even in the domain of grammar semantics is highly language-specific. PMID:21713188

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. Influence of 8-Oxoguanosine on the Fine Structure of DNA Studied with Biasing-Potential Replica Exchange Simulations

    PubMed Central

    Kara, Mahmut; Zacharias, Martin

    2013-01-01

    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 ζ but also coupled changes in the backbone dihedral angles α and γ. Such differences may play a crucial role in the initial recognition of damaged DNA by repair enzymes. PMID:23473492

  14. A Study on a Performance of Water-Spray-Type Ice Thermal Energy Storage Vessel with Vertical Heat Exchanger Plates

    NASA Astrophysics Data System (ADS)

    Yoshimura, Kenji; Sasaguchi, Kengo; Fukuda, Toshihito; Koyama, Shigeru

    A system with a water-embedded-trpe ice storage vessel is widely used because of its simple structure and compactness. However, the water-embedded-type ice storage vessel has a disadvantage, that is, the solidification rate is very small. The use of falling water film seems to be one of promising ways for solving this disadvantage. We have found in a previous study that the use of the falling water film is very effective, especially for high initial water temperatures. In the present study, we eexamined the performance of a faling-water-film-type ice thermal energy storage vessel with pratical size, having vertical heat exchanger plates. The ice making performance coefficient, η, increases with time, and it becomes am aximum value of 2.5, after that, it decreases gradually. In order to make ice efficiently, it is necessary to set a flow rate of refrigerant properly and to adjust a difference between the evaporating temperature of refrigerant and the freezing point of water so that the refrigerant evaporates in the heat exchanger plates overall.

  15. 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

  16. Heat exchanger

    SciTech Connect

    Drury, C.R.

    1988-02-02

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

  17. 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.

  18. 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.

  19. Experimental and numerical study of nanofluid in heat exchanger fitted by modified twisted tape: exergy analysis and ANN prediction model

    NASA Astrophysics Data System (ADS)

    Maddah, Heydar; Ghasemi, Nahid; Keyvani, Bahram; Cheraghali, Ramin

    2016-09-01

    Present study provides an experimental investigation of the exergetic efficiency due to the flow and heat transfer of nanofluids in different geometries and flow regimes of the double pipe heat exchangers. The experiments with different Geometrical Progression Ratio (GPR) of twists as the new modified twisted tapes and different nanofluid concentration were performed under similar operation condition. Pitch length of the proposed twisted tapes and consequently the twist ratios changed along the twists with respect to the Geometrical Progression Ratio (GPR) whether reducer (RGPR < 1) or increaser (IGPR > 1). Regarding the experimental data, utilization of RGPR twists together with nanofluids tends to increase exergetic efficiency. Since the Prediction of exergetic efficiency from experimental process is complex and time consuming, artificial neural networks for identification of the relationship, which may exist between the thermal and flow parameters and exergetic efficiency, have been utilized. The network input consists of five parameters (Re,Pr ,φ, Tr, GPR) that crucially dominate the heat transfer process. The results proved that the introduced ANN model is reliable and capable in proposing a proper development plan for a heat exchanger and/or to determine the optimal plan of operation for heat transfer process.

  20. 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.

  1. 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.

  2. The Canopy Horizontal Array Turbulence Study (CHATS): Influence of canopy density and atmospheric stability on turbulent exchange

    NASA Astrophysics Data System (ADS)

    Patton, E. G.

    2011-12-01

    Understanding the micrometeorology within and above forest canopies is of great interest for many environmental applications such as weather and climate forecasting as well as for vegetation-atmosphere scalar exchanges. Within a canopy, both the ground and the vegetation can act as scalar sources/sinks, where the distribution of canopy sources/sinks depends on the amount and state of the canopy foliage. For deciduous trees, the foliage evolves across a seasonal cycle from bare limbs in winter (no photosynthesis and an open canopy) to rapid growth in spring (increasing photosynthesis and canopy density), to maturity in summer (more constant photosynthesis and canopy density), to senescence and leaf-drop in fall (decreasing photosynthesis and canopy density). Thus a broad spectrum of different conditions occurs through the year, thereby imposing height and seasonal dependence on dynamical and scalar fluxes. The Canopy Horizontal Array Turbulence Study (CHATS) took place in 2007 focusing on a 10 m tall deciduous walnut orchard in Dixon, California (USA). High spatial resolution micrometeorological measurements were deployed aiming to establish the influence of seasonality (prior to, and follwing leaf-out) on canopy exchange. This talk will discuss the sensitivity of velocity, temperature and humidity fields within and above the deciduous walnut orchard at CHATS to the canopy evolution and atmospheric stability.

  3. An example of demographic anthropology, the study of matrimonial exchanges--endogamy, choice of spouse and preferential marriage.

    PubMed

    Cazes, Marie-Hélène

    2006-09-01

    The development of demographic studies in anthropology is directly linked to the success of population genetics. The anthropodemographic or anthropogenetic approach is thus underpinned by questions of genetics. While demographers focus on population dynamics and renewal in quantitative terms, population geneticists refer not to individuals but to the sets of genes carried by individuals in a population. Their aim is to detect the factors and processes which influence the genetic evolution of a group, i.e. which modify gene frequencies from one generation to the next. Among them are the factors which affect modes of reproduction. To illustrate the association of these three approaches, i.e. demographic, anthropological and genetic, I use here the example of matrimonial exchanges--which lie at the heart of the population renewal process--among the Dogon of Boni, a Malian ethnic group living in the southern Sahel. We can see how successive analyses--starting with endogamy at macroscopic level and moving down to the individual with choice of spouse and preferential marriage-- combining both quantitative and qualitative approaches, can be used to obtain a detailed description of matrimonial exchanges which shed light upon and complement the three different viewpoints.

  4. Design study of a coal-fired thermionic (THX) topped power plant. Volume IV. Thermionic heat exchanger design and costing

    SciTech Connect

    Dick, R.S.; Britt, E.J.

    1980-10-15

    This volume deals with the details of how thermionic conversion works, and how it is used in a coal-fired furnace to achieve power plant efficiencies of 45%, and overall costs of 36.3 mills/kWh. A review of the fundamental technical aspects of thermionic conversion is given. The overall Thermionic Heat Exchanger (THX) design, the heat pipe design, and the interaction of the heat pipes with the furnace are presented. Also, the operational characteristics of thermionic converters are described. Details on the computer program used to perform the parametric study are given. The overall program flow is reviewed along with the specifics of how the THX subroutine designed the converter to match the conditions imposed. Also, input costs and variables effecting the THX's performance are detailed. The efficiencies of the various power plants studied are given as a function of the air preheat temperature, size of the power plant, and thermionic level of performance.

  5. Cross-border data exchange - a case study on international collaboration gone wrong

    NASA Astrophysics Data System (ADS)

    Yanko-Hombach, Valentina

    2016-04-01

    The subject of ethics in science has become a hot topic recently (Gleick, 2011). As publication pressure on researchers increases and use of the internet allows faster turn-around, the quality of the peer review process has suffered. This presentation describes one case of scientific ethics violation in which the editors of a high-ranking scientific journal improperly permitted publication of a paper that was based upon unethical acquisition of data and failed to acknowledge scientific collaboration and exchange of intellectual property. We will present "Case description" and "Ethical issues" with a hope that our experience draws attention to important ethical issues in international collaborative research, and prevents such misconduct in the future. Since international research involves cooperation and coordination among many people in different disciplines and institutions across national borders, ethical standards should promote values that are essential to integrity and collaborative work, including trust, accountability, mutual respect, and fairness. One lesson to be learned is not to engage in collaboration without a written agreement stating clearly who is responsible for what and how the results of collaborative research are to be shared. This is especially important in cases of international collaborations, particularly those involving smaller or developing nations who often do not have the high-tech facilities of developed nations. There is also need to establish clear regulations regarding co-authorship on papers in which intellectual property and significant financial investment was made to allow the research to proceed. As such, a system of ethics to guide the practice of science from data collection to publication and beyond is timely and much needed to protect the integrity of scientific collaboration. It will keep science moving forward by validating research findings and confirming or raising questions about results. References Benos, D. J., Fabres

  6. Manitoba Exchange.

    ERIC Educational Resources Information Center

    Coss, Maurice

    Planning ideas and follow-up activities are described for a reciprocal exchange program between groups of 5th and 6th grade students in Manitoba who are "twinned" with another school in the province. Emphasis is on providing learning experiences which help students become familiar with the economic activity in the area, with the local government…

  7. 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.

  8. 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.

  9. Experimental study of the influence of cold heat exchanger geometry on the performance of a co-axial pulse tube cooler

    NASA Astrophysics Data System (ADS)

    Pang, Xiaomin; Dai, Wei; Wang, Xiaotao; Vanapalli, S.; Luo, Ercang

    2016-09-01

    Improving the performance of the pulse tube cooler is one of the important objectives of the current studies. Besides the phase shifters and regenerators, heat exchangers also play an important role in determining the system efficiency and cooling capacity. A series of experiments on a 10 W @ 77 K class co-axial type pulse tube cooler with different cold heat exchanger geometries are presented in this paper. The cold heat exchangers are made from a copper block with radial slots, cut through using electrical discharge machining. Different slot widths varying from 0.12 mm to 0.4 mm and different slot numbers varying from around 20-60 are investigated, while the length of cold heat exchangers are kept the same. The cold heat exchanger geometry is classified into three groups, namely, constant heat transfer area, constant porosity and constant slot width. The study reveals that a large channel width of 0.4 mm (about ten times the thermal penetration depth of helium gas at 77 K, 100 Hz and 3.5 MPa) shows poor performance, the other results show complicated interaction effects between slot width and slot number. These systematic comparison experiments provide a useful reference for selecting a cold heat exchanger geometry in a practical cooler.

  10. 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

    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.

  11. Synthesis and application of a novel GTP phosphonamide photoaffinity reagent: Study of exchangeable GTP-binding domain on tubulin

    SciTech Connect

    Chavan, A.J.

    1989-01-01

    The regulatory role played by nucleotides in various biochemical processes has been the topic of study for several years. This has led to the identification of several regulatory proteins which require guanosine triphosphate (GTP), a nucleotide, for their action. The G-protein family utilizes GTP and displays many common features in the mechanism of their action. Chapter 1 is an overview of several GTP-binding proteins including G-proteins. Tubulin, a structural protein also requires GTP for its assembly/disassembly process. The nature of interaction of GTP with tubulin, particularly at the exchangeable GTP-binding site has been under investigation for several years. Chapter 2 presents an overview of the structure of tubulin, and the studies leading up to the present understanding of the GTP-tubulin interaction. To study the exchangeable GTP-binding domain on tubulin which would complement the other techniques, and reagents used, the author synthesized a novel GTP phosphonamide photoaffinity reagent. Chapter 3 describes the synthesis of {sup 125}I-APTG (36). He utilized {sup 125}I-APTG to establish that it could act as a mimic to GTP. Using the combination of anion-exclusion chromatography, gel-filtration and reverse-phase HPLC techniques he isolated residues 65-79 on the {beta}-chain as the major peptide in the GTP-binding domain. He also isolate residues 65-79 and 353-370 on the {alpha}-chain as minor peptides supporting the hypothesis that the phosphate region is in close proximity of the {alpha}-subunit.

  12. 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…

  13. Comprehensive kinetic studies of acidic oil continuous esterification by cation-exchange resin in fixed bed reactors.

    PubMed

    Cheng, Yu; Feng, Yaohui; Ren, Yanbiao; Liu, Xuan; Gao, Aoran; He, Benqiao; Yan, Feng; Li, Jianxin

    2012-06-01

    Biodiesel produced by esterification from molar ratio of methanol to free fatty acid (FFA) as 25:1 in presence of triglyceride was carried out with cation-exchange resin as a heterogeneous catalyst in three different scales of fixed bed reactors from minireactor (6.8 mm × 110 mm) to pilot scale reactor (70 mm × 1260 mm) at 338 K. The kinetic study of esterification was undertaken in terms of pseudo-homogeneous mechanism and performed as a first order reaction with elimination of the solid-liquid internal and external mass transfer resistances. Moreover, a kinetic model of FFA esterification was developed to illustrate the relationship between the FFA conversion and the catalyst bed height of fixed bed reactor. The model was also suitable for various resins in fixed bed reactor. The theoretical predictions were in agreement with the experimental data with root mean square (RMS) errors <10.

  14. Comparative study of glycated hemoglobin by ion exchange chromatography and affinity binding nycocard reader in type 2 diabetes mellitus.

    PubMed

    Gautam, N; Dubey, R K; Jayan, A; Nepaune, Y; Padmavathi, P; Chaudhary, S; Jha, S K; Sinha, A K

    2014-12-01

    The aim of this study was to compare the level of glycated hemoglobin (HbA1c) in type 2 Diabetes Mellitus (DM) patients by two different methods namely Ion Exchange Chromatography and Affinity Binding Nycocard Reader. This is a cross-sectional study conducted on confirmed type 2 diabetes mellitus patients (n = 100) who visited Out Patients Department of the Universal College of Medical Sciences Teaching hospital, Bhairahawa, Nepal from November 2012 to March 2013. The diagnosis of diabetes mellitus was done on the basis of their fasting (164.46 ± 45.33 mg/dl) and random (187.93 ± 78.02 mg/dl) serum glucose level along with clinical history highly suggestive of type 2 DM. The HbA1c values of (7.8 ± 1.9%) and (8.0 ± 2.2%) were found in DM patients as estimated by those two different methods respectively. The highest frequency was observed in HbA1c > 8.0% indicating maximum cases were under very poor glycemic control. However, there were no significant differences observed in HbA1c value showing both methods are comparable in nature and can be used in lab for ease of estimation. The significant raised in HbA1c indicates complications associated with DM and monitoring of therapy become hard for those patients. Despite having standard reference method for HbA1c determination, the availability of report at the time of the patient visit can be made easy by using Nycocard Reader and Ion Exchange Chromatography techniques without any delay in communicating glycemic control, clinical decision-making and changes in treatment regimen.

  15. 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.

  16. 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…

  17. 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;

  18. 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)

  19. 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.

  20. Hydrogen-exchange labeling study of the allosteric R-state to T-state equilibrium in methemoglobin

    NASA Astrophysics Data System (ADS)

    McKinnie, R. E.; Englander, J. J.; Englander, S. W.

    1991-12-01

    Hydrogen-exchange labeling methods can be used to identify functionally important changes at positions all through a protein structure, can monitor the effect at these positions of structure changes anywhere in the protein, and can quantify these effects in terms of change in structural-stabilization free energy. These methods were used to study effects at two widely separated positions in human methemoglobin (metHb). The results show that the observed changes in hydrogen-exchange behavior reflect changes in the global R-state to T-state equilibrium, and specifically that stabilizing salt links at the α-chain N-terminus and the β-chain C-terminus are reformed in the R-T transition. The strong allosteric effector, inositol hexaphosphate (IHP), switches R-state methemoglobin to the T-state, but achieves a T/R equilibrium constant of only ≈ 3 (at pH=6.5, 0°C). Addition of the weaker effector, bezafibrate (Bzf), promotes this transition by an additional 0.7 kcal (T/R shifts to ≈ 12). Bzf alone is insufficient to cause the transition, indicating that R/T is 10 or more in stripped metHb under these conditions. However, R/T is small enough, not more than 103, to be reversed by the differential (T versus R) binding energy of IHP. The R-T transition caused by IHP and Bzf acting together can be reversed by some covalent modifications that sever the stabilizing salt links at the chain termini and thus favor transition back to the R-state.

  1. Study of Total Detection Efficiency (η) of Charge Exchange Analyzer (CXA) in TVD Tokamak

    NASA Astrophysics Data System (ADS)

    Kazemi, M.; Habibi, M.; Tafreshi, M.

    2013-02-01

    Diagnostic devices detection efficiency consist of many parameters. Contribution of each part in main detection efficiency need to study all aspect of devices and experimentally researches. In this paper experimental results and theoretical study merged to figure out the total detection efficiency of CXA. Most important primary parameters has been recognized (stripping foil thickness, incident energy, etc.) and effect of these parameters in related part studied. For CXA of TVD tokamak total detection efficiency presented and shown for 3 keV this parameter equal to .09 and stripping efficiency is equal 1.1 approximately. Choosing appropriate system for stripping of neutral beam is the most important factor in CXA diagnostic devices specially for high energy beams.

  2. 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…

  3. 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…

  4. 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

    ... HUMAN SERVICES Food and Drug Administration 21 CFR Chapter I Regulatory New Drug Review: Solutions for... Administration (FDA) is announcing a meeting entitled ``Regulatory New Drug Review: Solutions for Study Data... Planning & Informatics, Center for Drug Evaluation and Research, Food and Drug Administration, 10903...

  5. 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...

  6. 75 FR 77636 - Public Information Exchange on EPA Nanomaterial Case Studies

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-12-13

    ...: Nanoscale Titanium Dioxide in Water Treatment and in Topical Sunscreen [External Review Draft] (U.S... Dioxide in Water Treatment and in Topical Sunscreen ( http://cfpub.epa.gov/ncea/cfm/recordisplay.cfm?deid... Nanomaterial Case Studies: Nanoscale Titanium Dioxide in Water Treatment and in Topical Sunscreen...

  7. 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.

  8. Social Studies Now. This Halloween, Exchange the Hysterical for the Historical.

    ERIC Educational Resources Information Center

    Lindquist, Tarry

    1996-01-01

    A social studies wax museum can teach elementary students facts as they celebrate Halloween. A primary activity has students determine historic scenes to include in the wax museum, practice their poses, and put on a Halloween show. An intermediate activity has students research historic events, interpret information, create backdrops and props,…

  9. 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…

  10. Exchanging Ideas on Evaluation: Evaluating an Initial Management Skills Course: A Case Study.

    ERIC Educational Resources Information Center

    Lyman, Pat

    1979-01-01

    Describes an evaluation study of an interpersonal effectiveness management course for first-level supervisors. The evaluator collected information using graduate appraisal of course content, skill retention, measures, significant incident techniques, analysis of work products/records, appraisal of instructor, observation checklists, and…

  11. Temperature data assimilation for hyporheic exchange: numerical studies and sandbox experiments

    NASA Astrophysics Data System (ADS)

    Ju, L.; Zeng, L.; Wu, L.

    2015-12-01

    Due to the temperature difference between groundwater and surface water (GW-SW), heat can be used as an ideal tracer in hyporheic zone. To quantify GW-SW interactions, existing methods are mainly based on the analytical solution of one-dimensional heat transport equation. However, the assumptions therein are usually violated in practical applications. Furthermore, there are relatively limited experimental sandbox studies regarding heat tracer for complicated GW-SW interactions. In this study, we developed a data assimilation method to quantify the GW-SW interaction in the presence of heterogeneous river bed. A numerical simulator was used to solve the groundwater and heat transport equation. Then the ensemble Kalman filter (EnKF) was employed to assimilate the temperature data to quantify the unknown interactions (velocity field) between GW-SW and heterogeneous hydraulic conductivity field. The validity of this method was verified by both numerical simulation and sandbox experiment for different scenarios.

  12. Studies on a frustrated Heisenberg spin chain with alternating ferromagnetic and antiferromagnetic exchanges.

    PubMed

    Sahoo, Shaon; Durga Prasad Goli, V M L; Sen, Diptiman; Ramasesha, S

    2014-07-01

    We study Heisenberg spin-1/2 and spin-1 chains with alternating ferromagnetic (J(F)(1)) and antiferromagnetic (J(A)(1)) nearest-neighbor interactions and a ferromagnetic next-nearest-neighbor interaction (J(F)(2)). In this model frustration is present due to the non-zero J(F)(2). The model with site spin s behaves like a Haldane spin chain, with site spin 2s in the limit of vanishing J(F)(2)and large J(F)(1)/J(A)(1). We show that the exact ground state of the model can be found along a line in the parameter space. For fixed J(F)(1), the phase diagram in the space of J(A)(1)-J(F)(2) is determined using numerical techniques complemented by analytical calculations. A number of quantities, including the structure factor, energy gap, entanglement entropy and zero temperature magnetization, are studied to understand the complete phase diagram. An interesting and potentially important feature of this model is that it can exhibit a macroscopic magnetization jump in the presence of a magnetic field; we study this using an effective Hamiltonian. PMID:24935169

  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

    2016-02-18

    Of central importance in chemistry and biology, enolate chemistry is an attractive topic to elaborate on possible contributions of anion-π interactions to catalysis. To demonstrate the existence of such contributions, experimental evidence for the stabilization of not only anions but also anionic intermediates and transition states on π-acidic aromatic surfaces is decisive. To tackle this challenge for enolate chemistry with maximal precision and minimal uncertainty, malonate dilactones are covalently positioned on the π-acidic surface of naphthalenediimides (NDIs). Their presence is directly visible in the upfield shifts of the α-protons in the (1) H NMR spectra. The reactivity of these protons on π-acidic surfaces is measured by hydrogen-deuterium (H-D) exchange for 11 different examples, excluding controls. The velocity of H-D exchange increases with π acidity (NDI core substituents: SO2 R>SOR>H>OR>OR/NR2 >SR>NR2 ). The H-D exchange kinetics vary with the structure of the enolate (malonates>methylmalonates, dilactones>dithiolactones). Moreover, they depend on the distance to the π surface (bridge length: 11-13 atoms). Most importantly, H-D exchange depends strongly on the chirality of the π surface (chiral sulfoxides as core substituents; the crystal structure of the enantiopure (R,R,P)-macrocycle is reported). For maximal π acidity, transition-state stabilizations up to -18.8 kJ mol(-1) are obtained for H-D exchange. The Brønsted acidity of the enols increases strongly with π acidity of the aromatic surface, the lowest measured pKa =10.9 calculates to a ΔpKa =-5.5. Corresponding to the deprotonation of arginine residues in neutral water, considered as "impossible" in biology, the found enolate-π interactions are very important. The strong dependence of enolate stabilization on the unprecedented seven-component π-acidity gradient over almost 1 eV demonstrates quantitatively that such important anion-π activities can be expected only from

  14. Water, hydrogen, deuterium, carbon, carbon-13, and oxygen-18 content of selected lunar material

    USGS Publications Warehouse

    Friedman, I.; O'Neil, J.R.; Adami, L.H.; Gleason, J.D.; Hardcastle, K.

    1970-01-01

    The water content of the breccia is 150 to 455 ppm, with a ??D from -580 to -870 per mil. Hydrogen gas content is 40 to 53 ppm with a ??D of -830 to -970 per mil. The CO2 is 290 to 418 ppm with S 13C = + 2.3 to + 5.1 per mil and ??18O = 14.2 to 19.1 per mil. Non-CO2 carbon is 22 to 100 ppm, ??18C = -6.4 to -23.2 per mil. Lunar dust is 810 ppm H2O (D = 80 ppm) and 188 ppm total carbon (??13C = -17.6 per mil). The 18O analyses of whole rocks range from 5.8 to 6.2 per mil. The temperature of crystallization of type B rocks is 1100?? to 1300??C, based on the oxygen isotope fractionation between coexisting plagioclase and ilmenite.

  15. Origin of Terrestrial Water: Hydrogen/Deuterium Fractionation into Earth's Core

    NASA Astrophysics Data System (ADS)

    Wu, J.; Buseck, P. R.

    2014-12-01

    Hydrogen isotopic compositions are among the most important constraints on the origin of Earth's water. Earth's bulk water content, which is small but not negligible, is significantly greater than what the thermal gradient of the solar nebula disk would suggest for planetesimal materials condensed at one astronomical unit. The proto-solar nebula is a likely source of early Earth's water, with probable contributions from one or more of the following: water-rich planetesimals, ordinary and carbonaceous meteorites, comets, asteroids, and interplanetary dust particles. However, all of these sources have been questioned, and the proposed proto-solar nebular origin has been disputed in light of the large difference in hydrogen isotopic composition between it and terrestrial water. Current opposition to the solar nebular hypothesis is based on the critical assumption that no processes in the interior of the early Earth changed the isotopic composition of hydrogen. Nevertheless, a hypothesized hydrogenation reaction of liquid iron (2Fe + xH2 ↔ 2FeHx) during core formation likely provided a fractionation mechanism between hydrogen and deuterium (D). We propose that modern D/H ratios at Earth's surface resulted from this isotopic fractionation and that terrestrial water originated from oxidation of proto-solar hydrogen dissolved in the magma ocean in the early Earth by coexisting oxides (such as FeO). Thus, the isotopic composition of water on Earth can be mainly explained by internal terrestrial processes.

  16. Nuclear microanalysis of the human amnion: A study of ionic cellular exchanges

    NASA Astrophysics Data System (ADS)

    Razafindrabe, L.; Moretto, Ph.; Llabador, Y.; Simonoff, M.; Bara, M.; Guiet-Bara, A.

    1995-09-01

    The epithelial cells of the human amniotic membrane have been extensively studied by electrophysiologists with the aim of elucidating the mechanisms of transmembrane ionic transfers. In order to provide complementary information about this model, nuclear microanalysis was performed using the CENBG ion microbeam. Quantitative mapping of the human amnion was carried out and the distributions of most mono- and divalent ions involved in cellular pathways (Na +, Mg 2+, Cl -, Ca 2+) were determined. The ionic cellular content was also compared, before and after incubation in a Hanks' physiological fluid and the resultant ions transfers were determined. The aim of this paper is to expose the advances of this experimental model, more particularly after the development of simulation programs which improved the accuracy of PIXE analysis in the measurement of low energy X-rays emitters. Statistically significant results can now be extracted and can be explained taking into account the results of previous electrophysiological experiments.

  17. Do moisture exchangers prevent patient contamination of ventilators? A microbiological study comparing two different humidifying devices.

    PubMed

    Stånge, K; Bygdeman, S

    1980-12-01

    Fifteen tracheostomized and mechanically ventilated patients in an intensive care unit for surgical patients were studied. Two types of humidifiers were used: the Cascade humidifier and the Servo humidifier. Results from bacteriological cultures of the tracheal exudates, the expiratory and inspiratory ports of the ventilator, and various parts of the Servo humidifier are presented. There was a high incidence of colonization of the trachea of the patients. When the Cascade humidifier was used, a low rate of contamination in the expiratory and inspiratory ports of the ventilator was found, while no such contamination could be demonstrated with the Servo humidifier. There was a great difference in the colonization rate of the three different parts of the Servo humidifier. The part first exposed to the gas from the patient was frequently contaminated whereas the part towards the ventilator was not contaminated et all.

  18. 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

  19. Biomimetic study of the Ca(2+)-Mg2+ and K(+)-Li+ antagonism on biologically active sites: new methodology to study potential dependent ion exchange.

    PubMed

    Paczosa-Bator, Beata; Stepien, Milena; Maj-Zurawska, Magdalena; Lewenstam, Andrzej

    2009-03-01

    Competitive divalent (magnesium and calcium) or monovalent (potassium, lithium and sodium) ion exchange and its influence on a membrane potential formation was studied at biological ligands (BL) such as adenosine triphosphate (ATP), asparagine (Asn) and glutamine (Gln) sites. The sites are dispersed electrochemically in membranes made of the conducting polymers (CPs)--poly(N-methylpyrrole) (PMPy) and poly(pyrrole) (PPy). The membranes are made sensitive to calcium and magnesium or to potassium, sodium and lithium by optimized electrodeposition and soaking procedures supported by the study of membrane topography and morphology. Distinctively different electrochemical responses, i.e. electrical potential transients or currents, are observed in the case of "antagonistic" calcium and magnesium or potassium and sodium/lithium ion pairs. Dissimilarity in the responses is ascribed to a difference between on site vs. bulk concentrations of ions, and is dictated by different transport properties of the ions, as shown by using the Nernst-Planck-Poisson (NPP) model and the diffusion-layer model (DLM). The method described allows inspecting potential-dependent competitive ion-exchange processes at the biologically active sites. It is suggested that this approach could be used as an auxiliary tool in study of potential dependent block in realistic membrane channels, such as Mg block in the N-methyl D-aspartate receptor channel (NMDA).

  20. Comparative studies of land-atmosphere energy exchange in high and low Arctic tundra ecosystems

    NASA Astrophysics Data System (ADS)

    Stiegler, Christian; Lindroth, Anders; Lund, Magnus; Tamstorf, Mikkel P.

    2013-04-01

    The energy balance of arctic terrestrial ecosystems is of crucial importance to understand future climate change in high northern latitudes. Despite a growing interest in the Arctic local measurements and observations of climate characteristics are still scarce. Therefore, we present first results of comparative short- and long-term eddy covariance and energy balance measurements of high and low Arctic terrestrial ecosystems in Greenland. The study area covers high Arctic tundra heath and fen ecosystems in Zackenberg (Northeast Greenland National Park, 74°30'N, 21°00'W) and low Arctic terrestrial ecosystems in the Kobbefjord area close to the city of Nuuk (West Greenland, 64°07'N, 51°21'W). By using a mobile eddy covariance and energy balance tower we collected data during late winter (April 2012), early summer (June/July 2012) and late summer (August 2012). Mobile eddy covariance and energy balance measurements during late winter in Zackenberg focus on the energy balance of undisturbed snow covered surfaces with variable snow depth and snow layer structure. Data collection on thin snow layers with disturbed surfaces and exposed vegetation also show the impact of Muskox cratering on the surface energy balance. Measurements during early summer in the Kobbefjord area were conducted on characteristic bare soils with scattered cushion plants, on grasslands with sedge vegetation and on shrub vegetation up to 100 cm in height. Late summer measurements of energy balance and eddy covariance in the Zackenberg valley focus on transect measurements of energy balance components and active layer thickness of adjacent high arctic fen and heath ecosystems. In addition to the short-term mobile measurements we use and analyse data sets from permanent stations monitoring eddy covariance and energy balance on heath and fen sites in both high and low Arctic environments. Long-term measurements provide continuous data since early April 2012 and in this study we compare our mobile

  1. Non-intrusive optical study of gas and its exchange in human maxillary sinuses

    NASA Astrophysics Data System (ADS)

    Persson, L.; Andersson, M.; Svensson, T.; Cassel-Engquist, M.; Svanberg, K.; Svanberg, S.

    2007-07-01

    We demonstrate a novel non-intrusive technique based on tunable diode laser absorption spectroscopy to investigate human maxillary sinuses in vivo. The technique relies on the fact that free gases have much sharper absorption features (typical a few GHz) than the surrounding tissue. Molecular oxygen was detected at 760 nm. Volunteers have been investigated by injecting near-infrared light fibre-optically in contact with the palate inside the mouth. The multiply scattered light was detected externally by a handheld probe on and around the cheek bone. A significant signal difference in oxygen imprint was observed when comparing volunteers with widely different anamnesis regarding maxillary sinus status. Control measurements through the hand and through the cheek below the cheekbone were also performed to investigate any possible oxygen offset in the setup. These provided a consistently non-detectable signal level. The passages between the nasal cavity and the maxillary sinuses were also non-intrusively optically studied, to the best of our knowledge for the first time. These measurements provide information on the channel conductivity which may prove useful in facial sinus diagnostics. The results suggest that a clinical trial together with an ear-nose-throat (ENT) clinic should be carried out to investigate the clinical use of the new technique.

  2. Exchanges of volume, heat and freshwater through the Canadian Arctic Archipelago: a numerical study.

    NASA Astrophysics Data System (ADS)

    Grivault, Nathan; Hu, Xianmin; Myers, Paul G.

    2016-04-01

    The Canadian Arctic Archipelago (CAA) is a tangle of shallow basins interlinked by narrow straits. It is the main pathway of liquid freshwater from the Arctic Ocean to North Atlantic. It also receives runoff from the Mackenzie River and the glaciers of the different islands that composes the archipelago. This study is based on a set of numerical experiments using a regional configuration of the coupled ocean/sea-ice general circulation model NEMO. We consider a long-term hindcast (1958-2014) as well as the more recent period (2002-2014) using high resolution inter-annual forcing from Environment Canada. We used an improved mapping of runoff to ensure correct amounts of freshwater are added to the system. We evaluate the flow pathways through the CAA, as well as the transport of volume, heat and freshwater. Results are evaluated against observational sections. We also look at the variability and the dynamics driving it. Passive tracers are used to complement the analysis.

  3. Electron paramagnetic resonance studies on conformation states and metal ion exchange properties of vanadium bromoperoxidase

    SciTech Connect

    de Boer, E.; Boon, K.; Wever, R.

    1988-03-08

    An electron paramagnetic resonance (EPR) study was carried out to examine structural aspects of vanadium-containing bromoperoxidase from the brown seaweed Ascophyllum nodosum. At high pH, the reduced form of bromoperoxidase showed an apparently axially symmetric EPR signal with 16 hyperfine lines. When the pH was lowered, a new EPR spectrum was formed. When EPR spectra of the reduced enzyme were recorded in the pH range from 4.2 to 8.4, it appeared that these changes were linked to a functional group with an apparent pK/sub a/ of about 5.4. In D/sub 2/O this value for the pK/sub a/ was 5.3. It is suggested that these effects arise from protonation of histidine or aspartate/glutamate residues near the metal ion. The values for the isotropic hyperfine coupling constant of the reduced enzyme at both high and low pH are also consistent with a ligand field containing nitrogen and/or oxygen donor atoms. When reduced bromoperoxidase was dissolved in D/sub 2/O or H/sub 2//sup 17/O instead of H/sub 2//sup 16/O, vanadium (IV) hyperfine line widths were markedly affected, demonstrating that water is a ligand of the metal ion. Together with previous work these findings suggest that vanadium (IV) is not involved in catalytic turnover and confirm the model in which the vanadium (V) ion of the native enzyme only serves to bind both hydrogen peroxide and bromide. After excess vanadate was added to a homogeneous preparation of purified bromoperoxidase, the extent of vanadium bound to the protein increased from 0.5 to 1.1, with a concomitant enhancement of enzymic activity. Finally, it is demonstrated that both vanadate (VO/sub 4//sup 3 -/) and molybdate (MoO/sub 4//sup 2 -/) compete for the same site on apobromoperoxidase.

  4. 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

  5. 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

  6. First-principles studies of the Gilbert damping and exchange interactions for half-metallic Heuslers alloys

    NASA Astrophysics Data System (ADS)

    Chico, Jonathan; Keshavarz, Samara; Kvashnin, Yaroslav; Pereiro, Manuel; Di Marco, Igor; Etz, Corina; Eriksson, Olle; Bergman, Anders; Bergqvist, Lars

    2016-06-01

    Heusler alloys have been intensively studied due to the wide variety of properties that they exhibit. One of these properties is of particular interest for technological applications, i.e., the fact that some Heusler alloys are half-metallic. In the following, a systematic study of the magnetic properties of three different Heusler families Co2Mn Z ,Co2FeZ , and Mn2V Z with Z=(Al,Si,Ga,Ge) is performed. A key aspect is the determination of the Gilbert damping from first-principles calculations, with special focus on the role played by different approximations, the effect that substitutional disorder and temperature effects. Heisenberg exchange interactions and critical temperature for the alloys are also calculated as well as magnon dispersion relations for representative systems, the ferromagnetic Co2Fe Si and the ferrimagnetic Mn2V Al . Correlation effects beyond standard density-functional theory are treated using both the local spin density approximation including the Hubbard U and the local spin density approximation plus dynamical mean field theory approximation, which allows one to determine if dynamical self-energy corrections can remedy some of the inconsistencies which were previously reported for these alloys.

  7. Comprehensive Study of the Solubility, Thermochemistry, Ion Exchange, and Precipitation Kinetics of NO3 Cancrinite and NO33 Sodalite

    SciTech Connect

    Navrotsky, Alexandra; Liu, Qinyuan

    2004-12-01

    The precipitation of aluminosilicate phases from caustic nuclear wastes has proven to be problematic in a number of processes 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). In a collaboration between SNL and UCD, we have investigated why and how these phases form, and which conditions favor the formation of which phases. These studies have involved synthesis and characterization of aluminosilicate phases formed using a variety of synthesis techniques, kinetics of precipitation, structural investigations of aluminosilicate phases, thermodynamic calculations of aluminosilicate solubility, calorimetric studies of aluminosilicate precipitation, and a limited investigation of radionuclide partitioning and ion exchange processes (involving typical tank fluid chemistries and these materials). The predominant phases that are observed in the aluminosilicate precipitates from basic tanks wastes (i.e. Hanford, Savannah River Site ''SRS'' wastes) are the salt enclathrated zeolites: sodium nitrate, sodium carbonate and sodium hydroxide sodalite and cancrinite. These phases precipitate readily from the high ionic strength, highly basic solutions at ambient temperatures as well as at elevated temperatures, with or without the presence of an external Al and Si source (both are contained in the waste solutions), and upon interactions with reactive soil components such as clays.

  8. Numerical study of a novel micro-diaphragm flow channel with piezoelectric device for proton exchange membrane fuel cells

    NASA Astrophysics Data System (ADS)

    Ma, H. K.; Huang, S. H.; Chen, B. R.; Cheng, L. W.

    Previous studies have shown that the amplitude of the vibration of a piezoelectric (PZT) device produces an oscillating flow that changes the chamber volume along with a curvature variation of the diaphragm. In this study, an actuating micro-diaphragm with piezoelectric effects is utilized as an air-flow channel in proton exchange membrane fuel cell (PEMFC) systems, called PZT-PEMFC. This newly designed gas pump, with a piezoelectric actuation structure, can feed air into the system of an air-breathing PEMFC. When the actuator moves outward to increase the cathode channel volume, the air is sucked into the chamber; moving inward decreases the channel's volume and thereby compresses air into the catalyst layer and enhancing the chemical reaction. The air-standard PZT-PEMFC cycle is proposed to describe an air-breathing PZT-PEMFC. A novel design for PZT-PEMFCs has been proposed and a three-dimensional, transitional model has been successfully built to account for its major phenomena and performance. Moreover, at high frequencies, PZT actuation leads to a more stable current output, more drained water, higher sucked air, higher hydrogen consumption, and also overcomes concentration losses.

  9. Forecasting of high frequency foreign currency data using artificial neural networks. A study of intraday USD/DEM exchange rates

    SciTech Connect

    Lodhia, P.; Antonious, A.; Esat, I.

    1996-12-31

    There has been much recent interest in the application of artificial intelligence systems to real world problems. Substantial interest has been shown in their application to investment markets. Artificial Neural Networks are the most common technique here. This paper is concerned with the use of ANNs in forecasting exchange rates. Much research has been carried out in currency markets. However, many of the studies use end of day or average quotes for currencies as a basis for prediction. A growing school of thought propose that markets are non-random in the short-term and can be shown to follow patterns. This short-term time span can be described as being a period when the markets are inefficient at price adjustments. The use of intraday data is an ideal testing ground for ANNs based research. This paper aims to study the intraday forecasting of the US Dollar/German Deutschmark and to address the question of whether ANNs can make acceptable predictions. The problems of forecasting in such a complex environment will be addressed.

  10. 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.

  11. 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

  12. Coordination of Cd 2+ ions in the internal pore system of zeolite-X: A combined EXAFS and isotopic exchange study

    NASA Astrophysics Data System (ADS)

    Ahmed, I. A. M.; Young, S. D.; Mosselmans, J. F. W.; Crout, N. M. J.; Bailey, E. H.

    2009-03-01

    The effect of prolonged contact time (up to 130 days) on the immobilization of Cd by sorption to calcium exchanged zeolite-X (CaX), under environmentally relevant conditions, was studied using both isotopic exchange and extended X-ray absorption fine structure spectroscopy (EXAFS). Sorption and isotopic exchange measurements revealed time-dependent Cd sorption and indicated the movement of Cd 2+ ions into less accessible sites due to ageing. EXAFS suggested progressive fixation of Cd in the double six-ring ( D6R) unit of the CaX structure. Proportional allocation of the apparent Cd-Si bond distance to two 'end-members', across all contact times, indicated that the bond distance for labile Cd was 3.41 Å and for non-labile (or fixed) Cd was 3.47 Å.

  13. Analytical and experimental study of fluid friction and heat transfer in low Reynolds number flow heat exchangers

    NASA Astrophysics Data System (ADS)

    Muzychka, Yuri Stephan

    1999-11-01

    Analysis of fluid friction and heat transfer in low Reynolds number flow heat exchangers is undertaken. Three configurations typically utilized in compact heat exchangers are examined. These are: the plain non- circular duct of constant cross-sectional area, the offset or interrupted strip fin, and the turbulator strip. Analytical models for each of these geometries are developed by combining asymptotic solutions using simple non-linear superposition. Models for predicting the friction factor-Reynolds number product, f Re, and Nusselt number, Nu, in non-circular ducts for hydrodynamically fully developed flow (HFDF), hydrodynamically developing flow (HDF), thermally fully developed flow (TFDF), thermally developing flow (TDF), and simultaneously developing flow (SDF) are developed. Thermal and hydrodynamic entrance models are developed by combining the asymptotic solutions for small and large values of the dimensionless duct length. Through the use of a novel characteristic length, the square root of the cross-sectional flow area, scatter in the dimensionless data for fully developed laminar flows is considerably reduced. Most numerical and analytical data are predicted within +/-10% for HFDF and TFDF, +/-12% for HDF and TDF, and +/-15% for SDF for most non-circular ducts. Simple analytic models for predicting the Fanning friction factor, f, and Colburn j factor of two common enhancement devices, the offset strip fin and the turbulator strip are developed from fundamental solutions of fluid dynamics and heat transfer. Models for the offset strip fin are valid over the full range of Reynolds numbers for rectangular and other non-circular sub-channel cross- sections. Model predictions for the offset strip fin agree with published experimental data within +/-20%. Models for the turbulator strip are valid over the full Reynolds number range for both straight and curved turbulator profiles. Model predictions for the turbulator strip agree with new experimental data to

  14. 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

  15. Unidirectional Flux Balance of Monovalent Ions in Cells with Na/Na and Li/Na Exchange: Experimental and Computational Studies on Lymphoid U937 Cells.

    PubMed

    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

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. 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;…

  2. 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).

  3. 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

  4. Segmented heat exchanger

    DOEpatents

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

    2010-12-14

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

  5. FMR studies of exchange-coupled multiferroic polycrystalline Pt/BiFeO3/Ni81Fe19/Pt heterostructures

    NASA Astrophysics Data System (ADS)

    Ben Youssef, Jamal; Richy, Jérôme; Beaulieu, Nathan; Hauguel, Tony; Dekadjevi, David T.; Jay, Jean-Philippe; Spenato, David; Pogossian, Souren P.

    2016-09-01

    An experimental study of the in-plane azimuthal behaviour and frequency dependence of the ferromagnetic resonance field and the resonance linewidth as a function of BiFeO3 thickness is carried out in a polycrystalline exchange-biased BiFeO3/Ni81Fe19 system. The magnetization decrease of the Pt/BiFeO3/Ni81Fe19/Pt heterostructure with BiFeO3 thickness deduced from static measurements has been confirmed by dynamic investigations. Ferromagnetic resonance measurements have shown lower gyromagnetic ratio in a perpendicular geometry compared with that of parallel geometry. The monotonous decrease of gyromagnetic ratio in perpendicular geometry as a function of the BiFeO3 film thickness seems to be related to the spin-orbit interactions due to the neighbouring Pt film at its interface with Ni81Fe19 film. The enhancement of gyromagnetic ratio in Pt/Ni81Fe19/Pt is attributed to the Pt. The in-plane azimuthal shape of the total linewidth of the uniform mode shows isotropic behaviour that increases with BiFeO3 thickness. The study of the frequency dependence of the resonance linewidth in a broad band of 3-35 GHz has allowed the determination of intrinsic and extrinsic contributions to the relaxation as a function of BiFeO3 thickness in perpendicular geometry. In our system the magnetic relaxation is dominated by the spin-pumping mechanism due to the presence of Pt. The insertion of BiFeO3 between Pt and Ni81Fe19 attenuates the spin-pumping damping at one interface.

  6. 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.

  7. 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

  8. 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.

  9. Quantum mechanical study of the proton exchange in the ortho-para H2 conversion reaction at low temperature.

    PubMed

    Honvault, P; Jorfi, M; González-Lezana, T; Faure, A; Pagani, L

    2011-11-14

    Ortho-para H(2) conversion reactions mediated by the exchange of a H(+) proton have been investigated at very low energy for the first time by means of a time independent quantum mechanical (TIQM) approach. State-to-state probabilities and cross sections for H(+) + H(2) (v = 0, j = 0,1) processes have been calculated for a collision energy, E(c), ranging between 10(-6) eV and 0.1 eV. Differential cross sections (DCSs) for H(+) + H(2) (v = 0, j = 1) → H(+) + H(2) (v' = 0, j' = 0) for very low energies only start to develop a proper global minimum around the sideways scattering direction (θ≈ 90°) at E(c) = 10(-3) eV. Rate coefficients, a crucial information required for astrophysical models, are provided between 10 K and 100 K. The relaxation ortho-para process j = 1 → j' = 0 is found to be more efficient than the j = 0 → j' = 1 conversion at low temperatures, in line with the extremely small ratio between the ortho and para species of molecular hydrogen predicted at the temperature of interstellar cold molecular clouds. The results obtained by means of a statistical quantum mechanical (SQM) model, which has previously proved to provide an adequate description of the dynamics of the title reactions at a higher collision energy regime, have been compared with the TIQM results. A reasonable good agreement has been found with the only exception of the DCSs for the H(+) + H(2) (v = 0, j = 1) → H(+) + H(2) (v' = 0, j' = 0) process at very low energy. SQM cross sections are also slightly below the quantum results. Estimates for the rate coefficients, in good accord with the TIQM values, are a clear improvement with respect to pioneering statistical studies on the reaction.

  10. Increasing NDVI values in northern Alaska: studies that mix shrub density, spectral and CO2 exchange measurements

    NASA Astrophysics Data System (ADS)

    Anderson-Smith, A.; Lewis, A.; Sullivan, P.; Welker, J. M.

    2010-12-01

    Delineating the mechanisms and consequences of changes in tundra landscapes is central to predicting the functional ecology of Alaska in the 21st Century. Evidence has been mounting during the last decade that shrub communities are expanding in the Arctic and Normalized Difference Vegetation Index (NDVI) values which measure surface greenness are rising. Several studies have suggested that NDVI increases are being driven by increases in shrub abundance. While it is clear that NDVI has increased across vegetation types, it is not clear that NDVI values are increasing in moist acidic tundra (MAT), the most extensive vegetation type in arctic Alaska and the one most likely to be changed by global warming. The MAT is important to large mammal herbivores such as caribou which provide subsistence for indigenous people. The focus of this research was to determine what rising NDVI values actually mean in the MAT. The degree to which tundra community composition affects NDVI is still very poorly understood. In order to clarify the role of shrub encroachment per se as opposed to other functional groups in driving increases in NDVI, we measured functional group composition in moist acidic tundra in conjunction with hand-held measures of NDVI and direct CO2 exchange measurements to explicitly link spectral properties, shrub, graminoid and bryophyte density and trace gas feedbacks to atmospheric chemistry. Point frame data shows a shrub coverage of Betula nana (Dwarf Birch) and Salix pulchra (Diamond Leaf Willow) combined of 5% to 35% in MAT. Our results seem to indicate that high shrub density (>30%) corresponds to peak season NDVI values greater than .75 whereas low shrub density correspond to values below .65 (R2=.66). Furthermore, NDVI is closely correlated with canopy leaf area and greater leaf area is associated with higher rates of gross and net ecosystem CO2 uptake.

  11. Educator Exchange Resource Guide.

    ERIC Educational Resources Information Center

    Garza, Cris; Rodriguez, Victor

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

  12. Native American-Native Siberian Cultural Exchange: Ancient Tribal Connections Come to Light in Monument Valley Study Program.

    ERIC Educational Resources Information Center

    Hubbard, Pat

    1998-01-01

    Describes the 1995-97 student exchange program between the Navajo Nation in San Juan School District, Utah, and the Khanty-Mansisk region of Siberia. Similarities were found in language, string games, folk tales, sweat lodges, clan traditions, traditional arts and crafts, and stories of ancient meetings between the two peoples and use of the…

  13. The Role of Learned Societies in Knowledge Exchange and Dissemination: The Case of the Regional Studies Association, 1965-2005

    ERIC Educational Resources Information Center

    Hopkins, James

    2011-01-01

    This paper discusses the role of learned societies in knowledge exchange and dissemination. It attempts to "map" the organisations that are considered to reside under the term and discusses how they have developed through history. In doing so, it seeks to highlight that whilst several types of organisations inhabit the landscape of learned…

  14. Kinetics of oxygen exchange between bisulfite ion and water as studied by oxygen-17 nuclear magnetic resonance spectroscopy

    SciTech Connect

    Horner, D.A.

    1984-08-01

    The nuclear magnetic relaxation times of oxygen-17 have been measured in aqueous sodium bisulfite solutions in the pH range from 2.5 to 5 as a function of temperature, pH, and S(IV) concentration, at an ionic strength of 1.0 m. The rate law for oxygen exchange between bisulfite ion and water was obtained from an analysis of the data, and is consistent with oxygen exchange occurring via the reaction SO/sub 2/ + H/sub 2/O right reversible H/sup +/ + SHO/sub 3//sup -/. The value of k/sub -1/ is in agreement with relaxation measurements. Direct spectroscopic evidence was found for the existence of two isomers of bisulfite ion: one with the proton bonded to the sulfur (HSO/sub 3//sup -/) and the other with the proton bonded to an oxygen (SO/sub 3/H/sup -/). (The symbol SHO/sub 3//sup -/ in the above chemical equation refers to both isomeric forms of bisulfite ion.) The relative amounts of the two isomers were determined as a function of temperature, and the rate and mechanism of oxygen exchange between the two was investigated. One of the two isomers, presumably SO/sub 3/H/sup -/, exchanges oxygens with water much more rapidly than does the other. A two-pulse sequence was developed which greatly diminished the solvent peak in the NMR spectrum.

  15. Does Study Abroad Make a Difference? An Impact Assessment of the International 4-H Youth Exchange Program.

    ERIC Educational Resources Information Center

    Boyd, Barry L.; Giebler, Christie; Hince, Matthew; Liu, Yaru; Mehta, Neha; Rash, Ryan; Rowald, Jennifer; Saldana, Carlos; Yanta, Yvonne

    2001-01-01

    A survey of 28 participants in the International 4-H Youth Exchange program, 16 family members/ friends, and 60 extension agents indicated that participants expanded awareness of global issues, developed cultural sensitivity, and increased community involvement. Barriers such as money and lack of program knowledge can be overcome by seeking…

  16. Knowledge Exchange between Universities and the Creative Industries in the UK: A Case Study of Current Practice

    ERIC Educational Resources Information Center

    Ferguson, Morag

    2014-01-01

    The importance to the economy of knowledge exchange between universities and industry has long been recognized, and in the UK a number of initiatives are in place to support such activities. These initiatives have helped to stimulate engagement between universities and the creative industries, a sector of increasing importance to the UK economy.…

  17. Validation of a Mechanistic Model for Non-Invasive Study of Ecological Energetics in an Endangered Wading Bird with Counter-Current Heat Exchange in its Legs.

    PubMed

    Fitzpatrick, Megan J; Mathewson, Paul D; Porter, Warren P

    2015-01-01

    Mechanistic models provide a powerful, minimally invasive tool for gaining a deeper understanding of the ecology of animals across geographic space and time. In this paper, we modified and validated the accuracy of the mechanistic model Niche Mapper for simulating heat exchanges of animals with counter-current heat exchange mechanisms in their legs and animals that wade in water. We then used Niche Mapper to explore the effects of wading and counter-current heat exchange on the energy expenditures of Whooping Cranes, a long-legged wading bird. We validated model accuracy against the energy expenditure of two captive Whooping Cranes measured using the doubly-labeled water method and time energy budgets. Energy expenditure values modeled by Niche Mapper were similar to values measured by the doubly-labeled water method and values estimated from time-energy budgets. Future studies will be able to use Niche Mapper as a non-invasive tool to explore energy-based limits to the fundamental niche of Whooping Cranes and apply this knowledge to management decisions. Basic questions about the importance of counter-current exchange and wading to animal physiological tolerances can also now be explored with the model. PMID:26308207

  18. Validation of a Mechanistic Model for Non-Invasive Study of Ecological Energetics in an Endangered Wading Bird with Counter-Current Heat Exchange in its Legs

    PubMed Central

    Fitzpatrick, Megan J.; Mathewson, Paul D.; Porter, Warren P.

    2015-01-01

    Mechanistic models provide a powerful, minimally invasive tool for gaining a deeper understanding of the ecology of animals across geographic space and time. In this paper, we modified and validated the accuracy of the mechanistic model Niche Mapper for simulating heat exchanges of animals with counter-current heat exchange mechanisms in their legs and animals that wade in water. We then used Niche Mapper to explore the effects of wading and counter-current heat exchange on the energy expenditures of Whooping Cranes, a long-legged wading bird. We validated model accuracy against the energy expenditure of two captive Whooping Cranes measured using the doubly-labeled water method and time energy budgets. Energy expenditure values modeled by Niche Mapper were similar to values measured by the doubly-labeled water method and values estimated from time-energy budgets. Future studies will be able to use Niche Mapper as a non-invasive tool to explore energy-based limits to the fundamental niche of Whooping Cranes and apply this knowledge to management decisions. Basic questions about the importance of counter-current exchange and wading to animal physiological tolerances can also now be explored with the model. PMID:26308207

  19. Temperature-dependent exchange interaction in molecular magnets Cu(hfac)2L(R) studied by EPR: methodology and interpretations.

    PubMed

    Veber, Sergey L; Fedin, Matvey V; Maryunina, Ksenia Yu; Potapov, Alexey; Goldfarb, Daniella; Reijerse, Edward; Lubitz, Wolfgang; Sagdeev, Renad Z; Ovcharenko, Victor I; Bagryanskaya, Elena G

    2011-10-17

    Exchange-coupled spin triads nitroxide-copper(II)-nitroxide are the key building blocks of molecular magnets Cu(hfac)(2)L(R). These compounds exhibit thermally induced structural rearrangements and spin transitions, where the exchange interaction between spins of copper(II) ion and nitroxide radicals changes typically by 1 order of magnitude. We have shown previously that electron paramagnetic resonance (EPR) spectroscopy is sensitive to the observed magnetic anomalies and provides information on both inter- and intracluster exchange interactions. The value of intracluster exchange interaction is temperature-dependent (J(T)), that can be accessed by monitoring the effective g-factor of the spin triad as a function of temperature (g(eff)(T)). This paper describes approaches for studying the g(eff)(T) and J(T) dependences and establishes correlations between them. The experimentally obtained g(eff)(T) dependences are interpreted using three different models for the mechanism of structural rearrangements on the molecular level leading to different meanings of the J(T) function. The contributions from these mechanisms and their manifestations in X-ray, magnetic susceptibility and EPR data are discussed.

  20. Nonadiabatic exchange dynamics during adiabatic frequency sweeps

    NASA Astrophysics Data System (ADS)

    Barbara, Thomas M.

    2016-04-01

    A Bloch equation analysis that includes relaxation and exchange effects during an adiabatic frequency swept pulse is presented. For a large class of sweeps, relaxation can be incorporated using simple first order perturbation theory. For anisochronous exchange, new expressions are derived for exchange augmented rotating frame relaxation. For isochronous exchange between sites with distinct relaxation rate constants outside the extreme narrowing limit, simple criteria for adiabatic exchange are derived and demonstrate that frequency sweeps commonly in use may not be adiabatic with regard to exchange unless the exchange rates are much larger than the relaxation rates. Otherwise, accurate assessment of the sensitivity to exchange dynamics will require numerical integration of the rate equations. Examples of this situation are given for experimentally relevant parameters believed to hold for in-vivo tissue. These results are of significance in the study of exchange induced contrast in magnetic resonance imaging.

  1. Study of Twenty One Cases of Red Cell Exchange in a Tertiary Care Hospital in Southern India

    PubMed Central

    Muddegowda, Prakash H; Chezhiansubash; Lingegowda, Jyothi B; Gopal, Niranjan; Prasad, Krishna

    2016-01-01

    Introduction Red Cell Exchange (RCE) is removal of a patient’s red blood cells while replacing with donor red blood cells either manually or using automated systems. RCE is beneficial in patients with Sickle Cell Disease (SCD) either during sickling crisis or prior to major surgical procedures to bring down the sickling percentage as high sickling percentage during prolonged anaesthesia may lead to vaso-occlusive crisis. It is also employed in patients infested with malaria and babesiosis where parasitic index remain high despite medical management. RCE is also tried as an adjuvant therapy in certain poisons like nitrobenzene and carbon monoxide when first line management fails. Aim To study the effectiveness, clinical outcome, challenges and complications of RCE in various clinical scenario and to understand how this procedure can be effectively utilized in the management of patients in Indian scenario. Materials and Methods This retro prospective study was conducted in tertiary care center in southern India which analyzed 21 RCE procedures performed on patients with different clinical conditions. Of the 21 RCE performed, 18 procedures were performed on patients with case of sickle cell disease, Two procedures were performed on patients infested with severe falciparum malaria and one procedure was performed on a patient with nitrobenzene poisoning. All procedures were performed using Spectra Optia® Apheresis System - Terumo BCT. Results All the 18 patients who underwent the RCE for sickle cell anaemia were admitted for hemi-arthroplasty for avascular necrosis of the head of femur. The average initial HbS levels were between 73-85% and post RCE it was brought down to 22-29% and was achieved in a single sitting in all the cases. Among the two patients infested with severe falciparum malaria, RCE helped in reducing the infestation rate. In case of nitrobenzene poisoning, RCE helped in improvement of oxygen saturation and patient showed significant improvement

  2. Corrosive resistant heat exchanger

    DOEpatents

    Richlen, Scott L.

    1989-01-01

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

  3. Chemical exchange program analysis.

    SciTech Connect

    Waffelaert, Pascale

    2007-09-01

    As part of its EMS, Sandia performs an annual environmental aspects/impacts analysis. The purpose of this analysis is to identify the environmental aspects associated with Sandia's activities, products, and services and the potential environmental impacts associated with those aspects. Division and environmental programs established objectives and targets based on the environmental aspects associated with their operations. In 2007 the most significant aspect identified was Hazardous Materials (Use and Storage). The objective for Hazardous Materials (Use and Storage) was to improve chemical handling, storage, and on-site movement of hazardous materials. One of the targets supporting this objective was to develop an effective chemical exchange program, making a business case for it in FY07, and fully implementing a comprehensive chemical exchange program in FY08. A Chemical Exchange Program (CEP) team was formed to implement this target. The team consists of representatives from the Chemical Information System (CIS), Pollution Prevention (P2), the HWMF, Procurement and the Environmental Management System (EMS). The CEP Team performed benchmarking and conducted a life-cycle analysis of the current management of chemicals at SNL/NM and compared it to Chemical Exchange alternatives. Those alternatives are as follows: (1) Revive the 'Virtual' Chemical Exchange Program; (2) Re-implement a 'Physical' Chemical Exchange Program using a Chemical Information System; and (3) Transition to a Chemical Management Services System. The analysis and benchmarking study shows that the present management of chemicals at SNL/NM is significantly disjointed and a life-cycle or 'Cradle-to-Grave' approach to chemical management is needed. This approach must consider the purchasing and maintenance costs as well as the cost of ultimate disposal of the chemicals and materials. A chemical exchange is needed as a mechanism to re-apply chemicals on site. This will not only reduce the quantity of

  4. Composite ion exchange materials

    SciTech Connect

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

    1994-12-31

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

  5. X-ray absorption studies of the purple acid phosphatase from red kidney beans (native enzyme, metal exchanged form)

    NASA Astrophysics Data System (ADS)

    Ahlers, F.; Zippel, F.; Klabunde, T.; Krebs, B.; Löcke, R.; Witzel, H.; Nolting, H.-F.

    1995-02-01

    Purple acid phosphatase from red kidney beans (KBP) catalyzes the hydrolysis of activated phosphoric acid monoesters and contains a heterodinuclear Fe(III)Zn(II) core in its active site. Iron K-edge X-ray absorption data have been obtained for the native enzyme and for a metal exchanged derivative, where Zn(II) was substituted by Fe(III). The environment of the native enzyme consists of 2.5 O/N at 1.91 Å, 3 O/N at 2.09 Å, and 1 Zn at 4.05 Å. For the metal exchanged form we obtained 2.5 O/N at 1.94 Å, 2.5 O/N at 2.09 Å, and 1 Fe at 3.79 Å.

  6. Study of Ram-air Heat Exchangers for Reducing Turbine Cooling-air Temperature of a Supersonic Aircraft Turbojet Engine

    NASA Technical Reports Server (NTRS)

    Diaguila, Anthony J; Livingood, John N B; Eckert, Ernst R G

    1956-01-01

    The sizes and weights of the cores of heat exchangers were determined analytically for possible application for reducing turbine cooling-air temperatures of an engine designed for a Mach number of 2.5 and an altitude The sizes and weights of the cores of heat exchangers were determined analytically for possible application for reducing turbine cooling-air temperatures of an engine designed for a Mach number of 2.5 and an altitude of 70,000 feet. A compressor-bleed-air weight flow of 2.7 pounds per second was assumed for the coolant; ram air was considered as the other fluid. Pressure drops and inlet states of both fluids were prescribed, and ranges of compressor-bleed-air temperature reductions and of the ratio of compressor-bleed to ram-air weight flows were considered.

  7. Theoretical studies of the effective exchange interactions and photoinduced magnetism in manganese and copper di(4-pyridyl)carbene complexes

    NASA Astrophysics Data System (ADS)

    Takano, Yu; Soda, Tomohisa; Kitagawa, Yasutaka; Yoshioka, Yasunori; Yamaguchi, Kizashi

    1999-02-01

    UHF, UMP n ( n=2,4), UCC and DFT (UBLYP and UB3LYP) calculations using several basis sets were performed in order to elucidate the sign and magnitudes of the effective exchange interactions ( Jab) of models of 1:1 complex of Mn(hfac) 2 or Cu(hfac) 2 with (4-pryidyl)methylene. The Jab value between Mn(II) and divalent carbon (:C) through 4-pyridyl group by the UMP and UCCSD(T)/triple-zeta basis set was antiferromagnetic, while it was ferromagnetic between Cu(II) and :C. This is wholly consistent with the experiments. The signs of Jab values are explained by mechanisms of spin-exchange couplings through the configuration interaction pictures.

  8. Grazing incidence small angle X-ray scattering study of silver nanoparticles in ion-exchanged glasses

    NASA Astrophysics Data System (ADS)

    Cheng, Weidong; Wu, Zhaojun; Gu, Xiaohua; Xing, Xueqing; Mo, Guang; Wu, Zhonghua

    2015-05-01

    The size and distribution of silver nanoparticles in ion-exchanged silicate glass induced by thermal treatments in air at different temperatures were investigated by means of grazing incidence small angle X-ray scattering technique, X-ray diffraction and optical absorption spectra. Silver-sodium ion exchange of soda-lime silicate glasses was done at 350 °C for 240 min, then the samples were treated by thermal annealing in air at different temperatures 400, 500 and 550 °C, respectively, for 1 h. After the annealing treatment above 400 °C for 1 h, smaller Ag nanoparticles occurred, together with bigger ones. Both dissolution of smaller Ag nanoparticles and diffusion of larger ones are discussed in these stages of annealing in this contribution.

  9. Full cell study of Diels Alder poly(phenylene) anion and cation exchange membranes in vanadium redox flow batteries

    DOE PAGES

    Pezeshki, Alan M.; Fujimoto, Cy; Sun, Che -Nan; Mench, Matthew M.; Zawodzinski, Thomas A.; Tang, Z. J.

    2015-11-14

    In this paper, we report on the performance of Diels Alder poly(phenylene) membranes in vanadium redox flow batteries. The membranes were functionalized with quaternary ammonium groups to form an anion exchange membrane (QDAPP) and with sulfonic acid groups to form a cation exchange membrane (SDAPP). Both membrane classes showed similar conductivities in the battery environment, suggesting that the ion conduction mechanism in the material is not strongly affected by the moieties along the polymer backbone. The resistance to vanadium permeation in QDAPP was not improved relative to SDAPP, further suggesting that the polarity of the functional groups do not playmore » a significant role in the membrane materials tested. Both QDAPP and SDAPP outperformed Nafion membranes in cycling tests, with both achieving voltage efficiencies above 85% while maintaining 95% coulombic efficiency while at a current density of 200 mA/cm2.« less

  10. Experimental studies of influence of the turbulent flow structure on temperature distribution in a compact heat exchanger

    NASA Astrophysics Data System (ADS)

    Perepelitsa, B. V.

    2008-12-01

    Results of experimental investigation of temperature distribution over the surface of a complex heat exchanger (the Frenkel packing type) are presented. Measurements were carried out in the air flow between two sheets with triangular corrugations directed at 90° to each other. Measurements were carried out by the microthermocouples glued on the heated outer surface. The effect of Reynolds numbers, a gap between corrugated sheets, and substitution of one corrugated sheet by the smooth one on temperature distribution over the heat exchanger surface in the turbulent air flow is analysed. According to the performed experiments, there is a significant effect of a gap and applied perturbations on the type of temperature distribution over the perimeter of a heated cell.

  11. Full cell study of Diels Alder poly(phenylene) anion and cation exchange membranes in vanadium redox flow batteries

    SciTech Connect

    Pezeshki, Alan M.; Fujimoto, Cy; Sun, Che -Nan; Mench, Matthew M.; Zawodzinski, Thomas A.; Tang, Z. J.

    2015-11-14

    In this paper, we report on the performance of Diels Alder poly(phenylene) membranes in vanadium redox flow batteries. The membranes were functionalized with quaternary ammonium groups to form an anion exchange membrane (QDAPP) and with sulfonic acid groups to form a cation exchange membrane (SDAPP). Both membrane classes showed similar conductivities in the battery environment, suggesting that the ion conduction mechanism in the material is not strongly affected by the moieties along the polymer backbone. The resistance to vanadium permeation in QDAPP was not improved relative to SDAPP, further suggesting that the polarity of the functional groups do not play a significant role in the membrane materials tested. Both QDAPP and SDAPP outperformed Nafion membranes in cycling tests, with both achieving voltage efficiencies above 85% while maintaining 95% coulombic efficiency while at a current density of 200 mA/cm2.

  12. Evaluation of the effect of transcytolemmal water exchange analysis for therapeutic response assessment using DCE-MRI: a comparison study.

    PubMed

    Wang, Chunhao; Subashi, Ergys; Liang, Xiao; Yin, Fang-Fang; Chang, Zheng

    2016-07-01

    This study compares the shutter-speed (SS) and the Tofts models as used in assessing therapeutic response in a longitudinal DCE-MRI experiment. Sixteen nu/nu mice with implanted colorectal adenocarcinoma cell line (LS-174T) were randomly assigned into treatment/control groups (n  =  8/group) and received bevacizumab/saline twice weekly (Day1/Day4/Day8). All mice were scanned at one pre- (Day0) and two post-treatment (Day2/Day9) time points using a high spatiotemporal resolution DCE-MRI pulse sequence. The CA extravasation rate constant [Formula: see text] from the Tofts/SS model and the mean intracellular water residence time [Formula: see text] from the SS model were analyzed. A biological subvolume (BV) within the tumor was identified based on the [Formula: see text] intensity distribution, and the SS model parameters within the BV ([Formula: see text] and [Formula: see text]) were analyzed. It is found that [Formula: see text] and [Formula: see text] have a similar spatial distribution in the tumor volume. The Bayesian information criterion results show that the SS model was a better fit for all scans. At Day9, the treatment group had significantly higher tumor mean [Formula: see text] (p  =  0.021), [Formula: see text] (p  =  0.021) and [Formula: see text] (p  = 0.045). When BV from transcytolemmal water exchange analysis was adopted, the treatment group had higher mean [Formula: see text] at both Day2 (p  =  0.038) and Day9 (p  =  0.007). Additionally, at Day9, the treatment group had higher mean [Formula: see text] (p  =  0.045) and higher [Formula: see text] spatial heterogeneity indices (Rényi dimensions) d 1 (p  = 0.010) and d 2 (p  = 0.021). When mean [Formula: see text] and its coefficient of variation (CV) were used to separate treatment/control group samples using supporting vector machine, the accuracy of treatment/control classification was 68.8% at Day2 and 87.5% at Day9; in contrast, the

  13. Theoretical and experimental study of the effectiveness of the 5-pyrimidyl-tetrazolate bridging ligand in mediating magnetic exchange interactions.

    PubMed

    Mota, Antonio J; Rodríguez-Diéguez, A; Palacios, M A; Herrera, J M; Luneau, Dominique; Colacio, Enrique

    2010-10-01

    The 5-pyrimidyl-tetrazolate anion (pmtz) has six basic nitrogen atoms and, consequently, can exhibit a variety of bridging coordination modes. This ligand reacts with either copper(II) and nickel(II) ions in the presence of bi- and tridentate amines to afford the following pmtz-bridged complexes: [Cu(4)(μ-pmtz)(4)(tmda)(4)](ClO(4))(4) (1) (tmda = N,N,N',N'-tetramethylethylenediamine), [Cu(2)(μ-pmtz)(tren)(2)](ClO(4))(3) (2) (tren = tris(2-aminoethyl)amine), [Ni(2)(μ-pmtz)(tren)(2)](ClO(4))(3) (3), and [Ni(2)(μ-pmtz)(2)(ampa)(2)](n)(SCN)(2n) (ampa = bis(3-aminopropyl)amine) (4). The structure and bridging coordination mode of these complexes depend on the stereoelectronic preferences of the metal ion and the coordination properties of the polyamine (denticity and relative disposition of the donor atoms). Thus, complex 1 is a square tetranuclear compound where the ligand adopts an asymmetric k(2)N(1),N(7):k(2)N(4),N(11) bis(chelating)/bridging mode. Complexes 2 and 3 are dinuclear species. In the former the pmtz exhibits a novel k-N(1):k-N(4) imidazolyl/bridging mode whereas the latter shows a symmetric k(2)N(1),N(7):k(2)N(4),N(11) bis(chelating)/bridging mode. Complex 4 exhibits, however, a linear chain structure where the pmtz ligand connects neighboring nickel(II) atoms by using a tridentate k(2)N(1),N(7):kN(3) chelating/bridging mode. Variable-temperature magnetic susceptibility studies reveal that complexes 1-4 show weak to moderate antiferromagnetic (AF) coupling between the metal ions through the pmtz ligand with J = -14.1 cm(-1) for 1, J = -31.1 cm(-1) for 2, J = -4.09 cm(-1) for 3, and J = -8.7 cm(-1) for 4. The magneto-structural results, as well as DFT theoretical calculations carried out on the experimental geometries and model complexes, demonstrate, first, that the magnitude of the AF interaction observed for imidazolyl pmtz-bridged complexes mainly depends on the Cu-N-C angle (the greater the Cu-N-C angle, the stronger is the AF interaction) and

  14. Feature- and Face-Exchange illusions: new insights and applications for the study of the binding problem

    PubMed Central

    Shapiro, Arthur G.; Caplovitz, Gideon P.; Dixon, Erica L.

    2014-01-01

    The binding problem is a longstanding issue in vision science: i.e., how are humans able to maintain a relatively stable representation of objects and features even though the visual system processes many aspects of the world separately and in parallel? We previously investigated this issue with a variant of the bounce-pass paradigm, which consists of two rectangular bars moving in opposite directions; if the bars are identical and never overlap, the motion could equally be interpreted as bouncing or passing. Although bars of different colors should be seen as passing each other (since the colors provide more information about the bars' paths), we found “Feature Exchange”: observers reported the paradoxical perception that the bars appear to bounce off of each other and exchange colors. Here we extend our previous findings with three demonstrations. “Peripheral Feature-Exchange” consists of two colored bars that physically bounce (they continually meet in the middle of the monitor and return to the sides). When viewed in the periphery, the bars appear to stream past each other even though this percept relies on the exchange of features and contradicts the information provided by the color of the bars. In “Face-Exchange” two different faces physically pass each other. When fixating centrally, observers typically report the perception of bouncing faces that swap features, indicating that the Feature Exchange effect can occur even with complex objects. In “Face-Go-Round,” one face repeatedly moves from left to right on the top of the monitor, and the other from right to left at the bottom of the monitor. Observers typically perceive the faces moving in a circle—a percept that contradicts information provided by the identity of the faces. We suggest that Feature Exchange and the paradigms used to elicit it can be useful for the investigation of the binding problem as well as other contemporary issues of interest to vision science. PMID:25360096

  15. Experimental study and numerical simulation of flow and heat transfer performance on an offset plate-fin heat exchanger

    NASA Astrophysics Data System (ADS)

    Du, Juan; Qian, Zuo-Qin; Dai, Zhong-yuan

    2016-09-01

    An experimental investigation of heat transfer and pressure drop characteristics of an offset plate-fin heat exchanger for cooling of lubricant oil is conducted. The empirical correlations for j-factor and f-factor are obtained by evaluating the experimental data with a modified Wilson plot method. A numerical simulation is performed and the comparison between numerical results and experimental data are presented and discussed. The results show that the simulation results are consistent with experimental data.

  16. Flax pond ecosystem study: exchanges of CO/sub 2/ between a salt marsh and the atmosphere

    SciTech Connect

    Houghton, R.A.; Woodwell, G.M.

    1980-12-01

    Profiles of CO/sub 2/ concentration, windspeed, and temperature were used in the aerodynamic flux technique to calculate the CO/sub 2/ exchange between a Long Island salt marsh and the atmosphere. Uptake of CO/sub 2/ by the marsh during hours of sunlight and release during the night occurred during all times of the year. The rates of CO/sub 2/ exchange were highest during midsummer, 2.3 g CO/sub 2/.m/sup -2/.h/sup -1/ averaged over the daylight hours of July, and 1.3 g CO/sub 2/.m/sup -2/.h/sup -1/ for both uptake and release. The net 24-h exchange rates followed Spartina growth and senescence during the summer and fall, and photosynthesis of benthic algae during late winter and spring. There was a net uptake of Co/sub 2/ over 24 h by the marsh during all seasons except autumn. The net annual flow of carbon was from the atmosphere to Flax Pond (approx. = 300 g C.m/sup -2/.yr/sup -1/ averaged over the entire marsh ecosystem). This flux was larger than the net exchange of carbon between the marsh and either uplands, sediments, or coastal waters. The net uptake of CO/sub 2/ during summer was less than the net productivity of the vascular plants, indicating that some of the CO/sub 2/ assimilated by the plants came from heterotrophic respiration within the marsh. Nevertheless, respiration by the plants was by far the largest source of CO/sub 2/ from the marsh surface. Nighttime respiration of the ecosystem released a total of approx. = 510 g C.m/sup -2/.yr/sup -1/ to the atmosphere.

  17. Hydrogen Exchange Mass Spectrometry of Related Proteins with Divergent Sequences: A Comparative Study of HIV-1 Nef Allelic Variants

    NASA Astrophysics Data System (ADS)

    Wales, Thomas E.; Poe, Jerrod A.; Emert-Sedlak, Lori; Morgan, Christopher R.; Smithgall, Thomas E.; Engen, John R.

    2016-06-01

    Hydrogen exchange mass spectrometry can be used to compare the conformation and dynamics of proteins that are similar in tertiary structure. If relative deuterium levels are measured, differences in sequence, deuterium forward- and back-exchange, peptide retention time, and protease digestion patterns all complicate the data analysis. We illustrate what can be learned from such data sets by analyzing five variants (Consensus G2E, SF2, NL4-3, ELI, and LTNP4) of the HIV-1 Nef protein, both alone and when bound to the human Hck SH3 domain. Regions with similar sequence could be compared between variants. Although much of the hydrogen exchange features were preserved across the five proteins, the kinetics of Nef binding to Hck SH3 were not the same. These observations may be related to biological function, particularly for ELI Nef where we also observed an impaired ability to downregulate CD4 surface presentation. The data illustrate some of the caveats that must be considered for comparison experiments and provide a framework for investigations of other protein relatives, families, and superfamilies with HX MS.

  18. High ionic strength narrows the population of sites participating in protein ion-exchange adsorption: A single-molecule study

    PubMed Central

    Kisley, Lydia; Chen, Jixin; Mansur, Andrea P.; Dominguez-Medina, Sergio; Kulla, Eliona; Kang, Marci; Shuang, Bo; Kourentzi, Katerina; Poongavanam, Mohan-Vivekanandan; Dhamane, Sagar; Willson, Richard C.; Landes, Christy F.

    2014-01-01

    The retention and elution of proteins in ion-exchange chromatography is routinely controlled by adjusting the mobile phase salt concentration. It has repeatedly been observed, as judged from adsorption isotherms, that the apparent heterogeneity of adsorption is lower at more-eluting, higher ionic strength. Here, we present an investigation into the mechanism of this phenomenon using a single-molecule, super-resolution imaging technique called motion-blur Points Accumulation for Imaging in Nanoscale Topography (mbPAINT). We observed that the number of functional adsorption sites was smaller at high ionic strength and that these sites had reduced desorption kinetic heterogeneity, and thus narrower predicted elution profiles, for the anion-exchange adsorption of α-lactalbumin on an agarose-supported, clustered-charge ligand stationary phase. Explanations for the narrowing of the functional population such as inter-protein interactions and protein or support structural changes were investigated through kinetic analysis, circular dichroism spectroscopy, and microscopy of agarose microbeads, respectively. The results suggest the reduction of heterogeneity is due to both electrostatic screening between the protein and ligand and tuning the steric availability within the agarose support. Overall, we have shown that single molecule spectroscopy can aid in understanding the influence of ionic strength on the population of functional adsorbent sites participating in the ion-exchange chromatographic separation of proteins. PMID:24751557

  19. Metal-complex formation in continuous-flow ligand-exchange reactors studied by electrospray mass spectrometry.

    PubMed

    Krabbe, J G; de Boer, A R; van der Zwan, G; Lingeman, H; Niessen, W M A; Irth, H

    2007-04-01

    Electrospray ionization mass spectrometry was used to investigate complex formation of different metal complexes in a continuous-flow ligand-exchange reactor. A computer program was developed based on normal equilibrium calculations to predict the formation of various metal-ligand complexes. Corresponding to these calculations, infusion electrospray mass spectrometric experiments were performed to investigate the actual complex formation in solution. The data clearly show good correlation between the theoretically calculated formation of metal-ligand complexes and the experimental mass spectrometric data. Moreover, the approach demonstrates that the influence of the pH can be investigated using a similar approach. Indirectly, these infusion experiments provide information on relative binding constants of different ligands towards a metal-ion. To demonstrate this, a continuous-flow ligand-exchange detection system with mass spectrometric detection was developed. Injection of ligands, with different affinity for the metal-ion, into the reactor shows good correlation between binding constants and the response in the ligand-exchange detection system. Additional information on the introduced ligand, and the complexes formed after introduction of the ligand, can be obtained from interpretation of the mass spectra.

  20. Hydrogen Exchange Mass Spectrometry.

    PubMed

    Mayne, Leland

    2016-01-01

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

  1. Trust and Transitions in Modes of Exchange

    ERIC Educational Resources Information Center

    Cheshire, Coye; Gerbasi, Alexandra; Cook, Karen S.

    2010-01-01

    In this study, we investigate the relationship between uncertainty and trust in exogenous shifts in modes of social exchange (i.e., those that are not initiated by the individuals in a given exchange system). We explore how transitions from a high uncertainty environment (reciprocal exchange) to lower-uncertainty environments (nonbinding or…

  2. Neighbourhood Book Exchanges: Localising Information Practices

    ERIC Educational Resources Information Center

    Webster, Tenny; Gollner, Kathleen; Nathan, Lisa

    2015-01-01

    Introduction: Through this paper we report on an exploratory study into the design and use of neighbourhood book exchanges in North America. We identify dominant media framings of these book exchanges in North America, along with claims made concerning the influence of the exchanges. We compare the media claims with insights from interviews with…

  3. Spectroscopic and magnetic studies of erbium(III)-TEMPO complex as a potential single-molecule magnet: Interplay of the crystal-field and exchange coupling effects

    NASA Astrophysics Data System (ADS)

    Karbowiak, Mirosław; Rudowicz, Czesław; Nakamura, Takeshi; Murakami, Rina; Ishida, Takayuki

    2016-10-01

    Crystallographic, spectroscopic, and magnetic studies of three-center systems: lanthanoid-Ln3+ ions doubly-coordinated by TEMPO (2,2,6,6-tetramethylpiperidin-1-oxyl) radicals [Ln-TEMPO2] are reported. The temperature dependence of alternating-current magnetic susceptibility indicates the single-molecule-magnet behavior of Er-TEMPO2, exhibiting relatively slow magnetization relaxation. Well-resolved absorption spectra were obtained only for Er-TEMPO2. Other samples yielded spectra not amenable for meaningful interpretation. The crystal-field parameters (CFPs) determined from the measured Er3+-energy levels served as starting CFPs for fitting the direct-current magnetic susceptibility result. Compatibility of the so-determined and fine-tuned CFPs, and interplay between crystal-field-related effects and exchange-coupling effects are considered. Exchange couplings in Ln-TEMPO2 appear antiferromagnetic and unexpectedly large.

  4. Nuclear magnetic resonance studies of trypsin inhibitors isolated from seeds of Cucurbitaceae plants

    SciTech Connect

    Sobczyk, K.; Markley, J.L.

    1986-05-01

    Two-dimensional NMR techniques were used to assign individual protons in two trypsin inhibitors isolated from squash seeds (Cucurbita maxima and C. pepo). The assignments of /sup 1/H NMR signals from these unusually small proteins (29 amino acid residues) were based entirely on the sequences of the proteins plus the analysis of data from two-dimensional /sup 1/H)/sup 1/H) chemical shift correlation spectroscopy (COSY), relayed COSY, and nuclear Overhauser effect spectroscopy (NOESY). The pH dependence (pH range 1 to 12) of NMR chemical shifts has been analyzed in detail. The complex pH titration profiles exhibited by the /sup 1/H peaks of His-25 and Tyr-27 may be interpreted in terms of side-chain interactions between these residues. The protons of Gly-26 demonstrate a well-resolved AB spin system. These results suggest that this region of the protein has restricted conformational freedom. The kinetics of amide hydrogen/deuterium exchange were measured as a function of pH. The exchange rate for all amide hydrogens is governed by acid/base catalysis.

  5. Preliminary studies on the heat exchanger option for S-CO{sub 2} power conversion cycle coupled to water cooled SMR

    SciTech Connect

    Ahn, Y.; Lee, J.; Lee, J. I.

    2012-07-01

    For more than a half century, the steam Rankine cycle had been the major power conversion cycle for a nuclear power plant. However, as the interest on the next generation reactors grows, a variety of alternative power conversion systems have been studied. Among them, the S-CO{sub 2} cycle (Supercritical carbon dioxide Brayton cycle) is considered as a promising candidate due to several benefits such as 1) Relatively high thermal efficiency at relatively low turbine inlet temperature, 2) High efficiency with simple lay-out 3) Compactness of turbo-machineries. 4) Compactness of total cycle combined with PCHE (Printed Circuit Heat Exchanger). According to the conventional classification of heat exchangers (HE), there are three kind of HE, 1) Tubular HEs, 2) Plate-type HEs, 3) Extended surface HEs. So far, the researcher has mostly assumed PCHE type HE for the S-CO{sub 2} cycle due to its compactness with reasonably low pressure drop. However, PCHE is currently one of the most expensive components in the cycle, which can have a negative effect on the economics of the cycle. Therefore, an alternative for the HE should be seriously investigated. By comparing the operating condition (pressure and temperature) there are three kind of HE in the S-CO{sub 2} cycle, 1) IHX (Intermediate Heat exchanger) 2) Recuperator and 3) Pre-cooler. In each heat exchanger, hot side and cold side coolants are different, i.e. reactor coolant to S-CO{sub 2} (IHX), S-CO{sub 2} to S-CO{sub 2}(Recuperator), S-CO{sub 2} to water (Pre-cooler). By considering all the attributes mentioned above, all existing types of heat exchangers are compared to find a possible alternative to PCHE. The comparing factors are 1) Size(volume), 2) Cost. Plate fin type HEs are considered to be the most competitive heat exchanger regarding the size and the cost after some improvements on the design limit are made. (authors)

  6. Magnetization dynamics in an exchange-coupled NiFe/CoFe bilayer studied by x-ray detected ferromagnetic resonance

    NASA Astrophysics Data System (ADS)

    Stenning, G. B. G.; Shelford, L. R.; Cavill, S. A.; Hoffmann, F.; Haertinger, M.; Hesjedal, T.; Woltersdorf, G.; Bowden, G. J.; Gregory, S. A.; Back, C. H.; de Groot, P. A. J.; van der Laan, G.

    2015-01-01

    Exchange-coupled hard and soft magnetic layers find extensive use in data storage applications, for which their dynamical response has great importance. With bulk techniques, such as ferromagnetic resonance (FMR), it is difficult to access the behaviour and precise influence of each individual layer. By contrast, the synchrotron radiation-based technique of x-ray detected ferromagnetic resonance (XFMR) allows element-specific and phase-resolved FMR measurements in the frequency range 0.5-11 GHz. Here, we report the study of the magnetization dynamics of an exchange-coupled Ni0.81Fe0.19 (43.5 nm)/Co0.5Fe0.5 (30 nm) bilayer system using magnetometry and vector network analyser FMR, combined with XFMR at the Ni and Co L2 x-ray absorption edges. The epitaxially grown bilayer exhibits two principal resonances denoted as the acoustic and optical modes. FMR experiments show that the Kittel curves of the two layers cannot be taken in isolation, but that their modelling needs to account for an interlayer exchange coupling. The angular dependence of FMR indicates a collective effect for the modes of the magnetically hard CoFe and soft NiFe layer. The XFMR precessional scans show that the acoustic mode is dominated by the Ni signal with the Co and Ni magnetization precessing in phase, whereas the optical mode is dominated by the Co signal with the Co and Ni magnetization precessing in anti-phase. The response of the Co signal at the Ni resonance, and vice versa, show induced changes in both amplitude and phase, which can be ascribed to the interface exchange coupling. An interesting aspect of phase-resolved XFMR is the ability to distinguish between static and dynamic exchange coupling. The element-specific precessional scans of the NiFe/CoFe bilayer clearly have the signature of static exchange coupling, in which the effective field in one layer is aligned along the magnetization direction of the other layer.

  7. Kinetics of Hg(II) exchange between organic ligands, goethite, and natural organic matter studied with an enriched stable isotope approach.

    PubMed

    Jiskra, Martin; Saile, Damian; Wiederhold, Jan G; Bourdon, Bernard; Björn, Erik; Kretzschmar, Ruben

    2014-11-18

    The mobility and bioavailability of toxic Hg(II) in the environment strongly depends on its interactions with natural organic matter (NOM) and mineral surfaces. Using an enriched stable isotope approach, we investigated the exchange of Hg(II) between dissolved species (inorganically complexed or cysteine-, EDTA-, or NOM-bound) and solid-bound Hg(II) (carboxyl-/thiol-resin or goethite) over 30 days under constant conditions (pH, Hg and ligand concentrations). The Hg(II)-exchange was initially fast, followed by a slower phase, and depended on the properties of the dissolved ligands and sorbents. The results were described by a kinetic model allowing the simultaneous determination of adsorption and desorption rate coefficients. The time scales required to reach equilibrium with the carboxyl-resin varied greatly from 1.2 days for Hg(OH)2 to 16 days for Hg(II)-cysteine complexes and approximately 250 days for EDTA-bound Hg(II). Other experiments could not be described by an equilibrium model, suggesting that a significant fraction of total-bound Hg was present in a non-exchangeable form (thiol-resin and NOM: 53-58%; goethite: 22-29%). Based on the slow and incomplete exchange of Hg(II) described in this study, we suggest that kinetic effects must be considered to a greater extent in the assessment of the fate of Hg in the environment and the design of experimental studies, for example, for stability constant determination or metal isotope fractionation during sorption.

  8. Woven heat exchanger

    DOEpatents

    Piscitella, Roger R.

    1987-01-01

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

  9. Woven heat exchanger

    DOEpatents

    Piscitella, Roger R.

    1987-05-05

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

  10. Serial replica exchange.

    PubMed

    Hagen, Morten; Kim, Byungchan; Liu, Pu; Friesner, Richard A; Berne, B J

    2007-02-15

    Parallel tempering (or the replica exchange method (REM)) is a powerful method for speeding up the sampling of conformational states of systems with rough energy landscapes, like proteins, where stable conformational states can be separated by large energy barriers. The usual implementation of the REM is performed on local computer clusters (or parallel processors) where the different replicas must be run synchronously. Here, we present serial replica exchange (SREM), a method that is equivalent to the standard REM in terms of efficiency yet runs asynchronously on a distributed network of computers. A second advantage is the method's greatly enhanced fault tolerance, which enables the study of biological systems on worldwide distributed computing environments, such as Folding@Home. For proof of concept, we apply the SREM to a single alanine dipeptide molecule in explicit water. We show that the SREM reproduces the thermodynamic and structural properties determined by the REM.

  11. Serial Replica Exchange

    PubMed Central

    Hagen, Morten; Kim, Byungchan; Liu, Pu; Friesner, Richard A.; Berne, B. J.

    2009-01-01

    Parallel tempering (or the replica exchange method (REM)) is a powerful method for speeding up the sampling of conformational states of systems with rough energy landscapes, like proteins, where stable conformational states can be separated by large energy barriers. The usual implementation of the REM is performed on local computer clusters (or parallel processors) where the different replicas must be run synchronously. Here, we present serial replica exchange (SREM), a method that is equivalent to the standard REM in terms of efficiency yet runs asynchronously on a distributed network of computers. A second advantage is the method’s greatly enhanced fault tolerance, which enables the study of biological systems on worldwide distributed computing environments, such as Folding@Home.1 For proof of concept, we apply the SREM to a single alanine dipeptide molecule in explicit water. We show that the SREM reproduces the thermodynamic and structural properties determined by the REM. PMID:17249714

  12. Ferromagnetic resonance study of the misalignment between anisotropy axes in exchange-biased NiFe/FeMn/Co trilayers

    NASA Astrophysics Data System (ADS)

    Barreto, P. G.; Sousa, M. A.; Pelegrini, F.; Alayo, W.; Litterst, F. J.; Baggio-Saitovitch, E.

    2014-05-01

    Exchange-biased NiFe/FeMn/Co trilayers were grown by dc magnetron sputtering and analyzed by in-plane ferromagnetic resonance using Q-band microwaves. The experiments revealed that distinct Co and NiFe resonance modes were excited by the microwave field. A misalignment between the anisotropy axes of the magnetic layers was deduced from the angular variations of the resonance fields, which also showed the effects of uniaxial and unidirectional anisotropies. A phenomenological model was used to fit the experimental results taking also into account a rotatable anisotropy field associated to the domain structure of the FeMn layer and the magnetic history of the films.

  13. Woven heat exchanger

    DOEpatents

    Piscitella, R.R.

    1984-07-16

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

  14. Evaluation of the effect of transcytolemmal water exchange analysis for therapeutic response assessment using DCE-MRI: a comparison study

    NASA Astrophysics Data System (ADS)

    Wang, Chunhao; Subashi, Ergys; Liang, Xiao; Yin, Fang-Fang; Chang, Zheng

    2016-07-01

    This study compares the shutter-speed (SS) and the Tofts models as used in assessing therapeutic response in a longitudinal DCE-MRI experiment. Sixteen nu/nu mice with implanted colorectal adenocarcinoma cell line (LS-174T) were randomly assigned into treatment/control groups (n  =  8/group) and received bevacizumab/saline twice weekly (Day1/Day4/Day8). All mice were scanned at one pre- (Day0) and two post-treatment (Day2/Day9) time points using a high spatiotemporal resolution DCE-MRI pulse sequence. The CA extravasation rate constant K\\text{T}\\text{trans}/K\\text{S}\\text{trans} from the Tofts/SS model and the mean intracellular water residence time {τ\\text{i}} from the SS model were analyzed. A biological subvolume (BV) within the tumor was identified based on the {τ\\text{i}} intensity distribution, and the SS model parameters within the BV (K\\text{S,BV}\\text{trans} and {τ\\text{i,BV}} ) were analyzed. It is found that K\\text{S}\\text{trans} and K\\text{T}\\text{trans} have a similar spatial distribution in the tumor volume. The Bayesian information criterion results show that the SS model was a better fit for all scans. At Day9, the treatment group had significantly higher tumor mean K\\text{T}\\text{trans} (p  =  0.021), K\\text{S}\\text{trans} (p  =  0.021) and {τ\\text{i}} (p  = 0.045). When BV from transcytolemmal water exchange analysis was adopted, the treatment group had higher mean K\\text{S,BV}\\text{trans} at both Day2 (p  =  0.038) and Day9 (p  =  0.007). Additionally, at Day9, the treatment group had higher mean {τ\\text{i,BV}} (p  =  0.045) and higher K\\text{S,BV}\\text{trans} spatial heterogeneity indices (Rényi dimensions) d 1 (p  = 0.010) and d 2 (p  = 0.021). When mean K\\text{S,BV}\\text{trans} and its coefficient of variation (CV) were used to separate treatment/control group samples using supporting vector machine, the accuracy of treatment/control classification was

  15. Escherichia coli Single-Stranded DNA-Binding Protein: NanoESI-MS Studies of Salt-Modulated Subunit Exchange and DNA Binding Transactions

    NASA Astrophysics Data System (ADS)

    Mason, Claire E.; Jergic, Slobodan; Lo, Allen T. Y.; Wang, Yao; Dixon, Nicholas E.; Beck, Jennifer L.

    2013-02-01

    Single-stranded DNA-binding proteins (SSBs) are ubiquitous oligomeric proteins that bind with very high affinity to single-stranded DNA and have a variety of essential roles in DNA metabolism. Nanoelectrospray ionization mass spectrometry (nanoESI-MS) was used to monitor subunit exchange in full-length and truncated forms of the homotetrameric SSB from Escherichia coli. Subunit exchange in the native protein was found to occur slowly over a period of hours, but was significantly more rapid in a truncated variant of SSB from which the eight C-terminal residues were deleted. This effect is proposed to result from C-terminus mediated stabilization of the SSB tetramer, in which the C-termini interact with the DNA-binding cores of adjacent subunits. NanoESI-MS was also used to examine DNA binding to the SSB tetramer. Binding of single-stranded oligonucleotides [one molecule of (dT)70, one molecule of (dT)35, or two molecules of (dT)35] was found to prevent SSB subunit exchange. Transfer of SSB tetramers between discrete oligonucleotides was also observed and is consistent with predictions from solution-phase studies, suggesting that SSB-DNA complexes can be reliably analyzed by ESI mass spectrometry.

  16. Studies on the exchange interactions in R 2Fe 14B, R 2Fe 14C and R 2Co 14B by molecular field theory

    NASA Astrophysics Data System (ADS)

    Zhang, G. W.; Feng, Y. P.; Ong, C. K.

    1997-08-01

    The intra- and inter-sublattice exchange interactions in three series of permanent magnetic materials (R 2Fe 14B, R 2Fe 14C and R 2Co 14B, R = rare earth elements) have been studied on the basis of molecular field theory. The effective exchange coupling constant ( JCoCo) of Co sublattices in R 2Co 14B is about 16.61 × 10 -22J, which is nearly three times the values ( JFeFe) of Fe sublattices in both R 2Fe 14B and R 2Fe 14C. The effective exchange coupling constants ( JRT) between rare earth (R) and transition metal (T) are not constant across the series but dependent on the nature of R atoms, which is different from the usual assumption that the JRT are constant across the series due to the similarities of band structures for all R atoms. The molecular fields acting on the rare earth ions are also calculated. The maximum molecular fields are found for R = Sm in each series.

  17. Capture and isotopic exchange method for water and hydrogen isotopes on zeolite catalysts up to technical scale for pre-study of processing highly tritiated water

    SciTech Connect

    Michling, R.; Braun, A.; Cristescu, I.; Dittrich, H.; Gramlich, N.; Lohr, N.; Glugla, M.; Shu, W.; Willms, S.

    2015-03-15

    Highly tritiated water (HTW) may be generated at ITER by various processes and, due to the excessive radio toxicity, the self-radiolysis and the exceedingly corrosive property of HTW, a potential hazard is associated with its storage and process. Therefore, the capture and exchange method for HTW utilizing Molecular Sieve Beds (MSB) was investigated in view of adsorption capacity, isotopic exchange performance and process parameters. For the MSB, different types of zeolite were selected. All zeolite materials were additionally coated with platinum. The following work comprised the selection of the most efficient zeolite candidate based on detailed parametric studies during the H{sub 2}/D{sub 2}O laboratory scale exchange experiments (about 25 g zeolite per bed) at the Tritium Laboratory Karlsruhe (TLK). For the zeolite, characterization analytical techniques such as Infrared Spectroscopy, Thermogravimetry and online mass spectrometry were implemented. Followed by further investigation of the selected zeolite catalyst under full technical operation, a MSB (about 22 kg zeolite) was processed with hydrogen flow rates up to 60 mol*h{sup -1} and deuterated water loads up to 1.6 kg in view of later ITER processing of arising HTW. (authors)

  18. Experimental and theoretical study of anion-exchange preparative chromatography for neptunium: the first application to thorium(IV) and its equilibrium and kinetics.

    PubMed

    Yamamura, Tomoo; Miyakoshi, Takeshi; Shiokawa, Yoshinobu; Mitsugashira, Toshiaki

    2007-10-26

    In order to study equilibrium and kinetic parameters in anion-exchange chromatography for preparatory purpose, a quantitative model for nonlinear anion-exchange chromatography in porous media was constructed, by paying special attention to interstitial length along void structure (cm) distinguished from apparent length (cm*). Langmuir-type adsorption isotherm for thorium(IV), as a natural substitution for neptunium(IV), in 6 mol dm(-3) nitric acid to anion-exchanger MSA-1 (200-400 mesh) was investigated in batch-wise and chromatographic experiments. The equilibrium parameters determined by batch-wise experiments determined as k=2.4x10(2) mol(-1) dm3 s(-1) and s0=0.5 mol dm(-3) agrees very well with the values of k=222 mol(-1) dm3 s(-1) and s0=0.5 mol dm(-3) derived from fitting by the numerical calculation. Kinetic parameters of ks and D affect band profile similarly, thereby maximum value of each parameter was evaluated as ks=1.3 mol(-1) dm3 s(-1) and D=9x10(-4) cm2 s(-1) by the numerical calculations.

  19. Solvation of exchangeable Cu/sup 2 +/ cations by primary alcohols in montmorillonite clay studied by electron spin resonance and electron spin echo modulation spectroscopies

    SciTech Connect

    Brown, D.R.; Kevan, L.

    1988-04-07

    A montmorillonite clay (STx-1), with Mg/sup 2 +/ as the major exchangeable cation and Cu/sup 2 +/ exchanged into 5% of the Mg/sup 2 +/ sites, is used to study the interaction between the exchangeable cations and adsorbed primary alcohols, methanol, ethanol, and 1-propanol, in the clay interlayer region. Electron spin resonance (ESR) shows that, on saturation of the clay with methanol, a freely rotating Cu/sup 2 +/ center is formed in the clay interlayer. Electron spin echo modulation (ESEM) spectroscopy indicates that the center is a four-coordinate Cu/sup 2 +/ solvate, in which the methanol ligands are in a square-planar configuration. On adsorption of ethanol into the interlayer region, a rotationally restricted Cu/sup 2 +/ center is detected. ESEM again indicates a four-coordinate, square-planar solvate, and ESR of oriented clay films reveals that the major symmetry axis of the ethanol-solvated Cu/sup 2 +/ center is perpendicular to the plane of the clay lattice. Similar ESP data are reported for 1-propanol-saturated montmorillonite, and a four-coordinate, square-planar Cu/sup 2 +/ solvate, similar to that described for ethanol, is proposed.

  20. Stock Exchange

    ERIC Educational Resources Information Center

    Silverman, Jerry Stuart

    1974-01-01

    Using play money, students buy and sell six types of stock certificates at prices determined periodically by tossing three dice; all students participate as investors, brokers, or banker. In addition to gaining practice on computational skills in a motivational game, students study the real stock market concurrently. (SD)