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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. Hydrogen/Deuterium Exchange Study of Subtilisin Carlsberg During Prolonged Exposure to Organic Solvents

    PubMed Central

    Fasoli, Ezio; Ferrer, Amaris; Barletta, Gabriel L.

    2009-01-01

    It has been previously reported that prolonged exposure of an enzyme to organic solvents leads to substantial decrease of activity. This effect was found to be unrelated to the catalysts’ structure or their possible aggregation in organic solvents, and up to the present day the cause for activity loss remains unclear. In the present work, the structural dynamics of the serine protease subtilisin Carlsberg (SC) have been investigated during prolonged exposure to two organic solvents by following hydrogen/deuterium (H/D) exchange of mobile protons. The enzyme, after lyophilization, was incubated in organic solvents at controlled deuteriated water activity for different times and the H/D exchange was allowed to take place. The amount of deuterium exchanged was evaluated by 2H NMR, which in turn gave us a picture of the changing dynamics of our model enzyme during incubation and under different experimental conditions. Our results show that the flexibility of SC decreases during prolonged storage in 1,4-dioxane (Diox) and acetonitrile (ACN) as indicated by the observed 3- to 10-fold decrease in the apparent rate constants of exchange (k) of fast exchangeable protons (FEP) and slow exchangeable protons (SEP) in the protein. Our study also shows that SC is more flexible in ACN than in Diox (k 3−20 times higher in ACN for the FEP and SEP), suggesting that enzyme dynamics are affected by solvent physicochemical properties. Additionally, the enzyme dynamics are also affected by the method of preparation: decreased flexibility (k decreases 3- to 10-fold for FEP and SEP) is observed when the enzyme is chemically modified with poly ethylene glycol (PEGylated) or colyophilized with crown ethers. A possible relationship between activity, enantioselectivity (E), and structural dynamics is discussed, demonstrating that direct correlations, as have been attempted in the past, are hampered by the multi-variable nature and complexity of the system. PMID:18985614

  3. Combining Crystallography and Hydrogen-Deuterium Exchange to Study Galectin-Ligand Complexes.

    PubMed

    Ruiz, Federico M; Gilles, Ulrich; Lindner, Ingo; André, Sabine; Romero, Antonio; Reusch, Dietmar; Gabius, Hans-Joachim

    2015-09-21

    The physiological significance arising from translating information stored in glycans into cellular effects explains the interest in structurally defining lectin-carbohydrate recognition. The relatively small set of adhesion/growth-regulatory galectins in chicken makes this system attractive to study the origins of specificity and divergence. Cell binding by using glycosylation mutants reveals binding of the N-terminal domain of chicken galectin-8 (CG-8N) to α-2,3-sialylated and galactose-terminated glycan chains. Cocrystals with lactose and its 3'-sialylated derivative disclose Arg58 as a key contact for the carboxylic acid and differences in loop lengths to the three homodimeric chicken galectins. Monitoring hydrogen-deuterium exchange by mass spectrometry revealed an effective reduction of deuteration after ligand binding within the contact area. In addition, evidence for changes in solvent accessibility of amide protons beyond this site was obtained. Their detection, which highlights the sensor capacity of this technique, encourages systematic studies on galectins and beyond.

  4. 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 (kH/kD ≈ 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.

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

    NASA Astrophysics Data System (ADS)

    Mazur, Sharlyn J.; Weber, Daniel P.

    2017-02-01

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

  6. Monitoring allostery in D2O: a necessary control in studies using hydrogen/deuterium exchange to characterize allosteric regulation.

    PubMed

    Prasannan, Charulata B; Artigues, Antonio; Fenton, Aron W

    2011-08-01

    There is currently a renewed focus aimed at understanding allosteric mechanisms at atomic resolution. This current interest seeks to understand how both changes in protein conformations and changes in protein dynamics contribute to relaying an allosteric signal between two ligand binding sites on a protein (e.g., active and allosteric sites). Both nuclear magnetic resonance (NMR), by monitoring protein dynamics directly, and hydrogen/deuterium exchange, by monitoring solvent accessibility of backbone amides, offer insights into protein dynamics. Unfortunately, many allosteric proteins exceed the size limitations of standard NMR techniques. Although hydrogen/deuterium exchange as detected by mass spectrometry (H/DX-MS) offers an alternative evaluation method, any application of hydrogen/deuterium exchange requires that the property being measured functions in both H(2)O and D(2)O. Due to the promising future H/DX-MS has in the evaluation of allosteric mechanisms in large proteins, we demonstrate an evaluation of allosteric regulation in D(2)O. Exemplified using phenylalanine inhibition of rabbit muscle pyruvate kinase, we find that binding of the inhibitor is greatly reduced in D(2)O, but the effector continues to elicit an allosteric response.

  7. Protein structure change studied by hydrogen-deuterium exchange, functional labeling, and mass spectrometry.

    PubMed

    Englander, Joan J; Del Mar, Charyl; Li, Will; Englander, S Walter; Kim, Jack S; Stranz, David D; Hamuro, Yoshitomo; Woods, Virgil L

    2003-06-10

    An automated high-throughput, high-resolution deuterium exchange HPLC-MS method (DXMS) was used to extend previous hydrogen exchange studies on the position and energetic role of regulatory structure changes in hemoglobin. The results match earlier highly accurate but much more limited tritium exchange results, extend the analysis to the entire sequence of both hemoglobin subunits, and identify some energetically important changes. Allosterically sensitive amide hydrogens located at near amino acid resolution help to confirm the reality of local unfolding reactions and their use to evaluate resolved structure changes in terms of allosteric free energy.

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

    PubMed

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

    2014-12-01

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

  9. Mapping the interaction network of key proteins involved in histone mRNA generation - a hydrogen/deuterium exchange study

    PubMed Central

    Skrajna, Aleksandra; Yang, Xiao-cui; Tarnowski, Krzysztof; Fituch, Kinga; Marzluff, William F.; Dominski, Zbigniew; Dadlez, Michał

    2016-01-01

    Histone pre-mRNAs are cleaved at the 3′ end by a complex that contains U7 snRNP, the FLICE-Associated Huge protein (FLASH) and Histone pre-mRNA Cleavage Complex (HCC) consisting of several polyadenylation factors. Within the complex, the N-terminus of FLASH interacts with the N-terminus of the U7 snRNP protein Lsm11 and together they recruit the HCC. FLASH through its distant C-terminus independently interacts with the C-terminal SANT/Myb-like domain of Nuclear Protein, Ataxia-Telangiectasia locus (NPAT), a transcriptional co-activator required for expression of histone genes in S-phase. To gain structural information on these interactions, we used mass spectrometry to monitor hydrogen/deuterium (H/D) exchange in various regions of FLASH, Lsm11 and NPAT alone or in the presence of their respective binding partners. Our results indicate that the FLASH-interacting domain in Lsm11 is highly dynamic, while the more downstream region required for recruiting the HCC exchanges deuterium slowly and likely folds into a stable structure. In FLASH, a stable structure is adopted by the domain that interacts with Lsm11 and this domain is further stabilized by binding Lsm11. Notably, both H/D exchange experiments and in vitro binding assays demonstrate that Lsm11, in addition to interacting with the N-terminal region of FLASH, also contacts the C-terminal SANT/Myb-like domain of FLASH, the same region that binds NPAT. However, while NPAT stabilizes this domain, Lsm11 causes its partial relaxation. These competing reactions may play a role in regulating histone gene expression in vivo. PMID:26860583

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

    PubMed

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

    2017-03-17

    Gas-phase hydrogen/deuterium exchange (HDX) using D2O reagent and collision cross-section (CCS) measurements are utilized to monitor the ion conformers of the model peptide acetyl-PAAAAKAAAAKAAAAKAAAAK. The measurements are carried out on a home-built ion mobility instrument coupled to a linear ion trap mass spectrometer containing electron transfer dissociation (ETD) capabilities. ETD is utilized to obtain per-residue deuterium uptake data for select ion conformers, and a new algorithm is presented for interpreting the HDX data. Using molecular dynamics (MD) production data and a hydrogen accessibility scoring (HAS)-number of effective collisions (NEC) model, hypothetical HDX behavior is attributed to various in-silico candidate (CCS match) structures. The HAS-NEC model is applied to all candidate structures, and non-negative linear regression is employed to determine structure contributions resulting in the best match to deuterium uptake. The accuracy of the HAS-NEC model is tested with the comparison of predicted and experimental isotopic envelopes for several of the observed c-ions. It is proposed that gas-phase HDX can be utilized effectively as a second criterion (after CCS matching) for filtering suitable MD candidate structures. In this study, the second step of structure elucidation, 13 nominal structures were selected (from a pool of 300 candidate structures) and each with a population contribution proposed for these ions. Graphical Abstract ᅟ.

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

    NASA Astrophysics Data System (ADS)

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

    2017-03-01

    Gas-phase hydrogen/deuterium exchange (HDX) using D2O reagent and collision cross-section (CCS) measurements are utilized to monitor the ion conformers of the model peptide acetyl-PAAAAKAAAAKAAAAKAAAAK. The measurements are carried out on a home-built ion mobility instrument coupled to a linear ion trap mass spectrometer containing electron transfer dissociation (ETD) capabilities. ETD is utilized to obtain per-residue deuterium uptake data for select ion conformers, and a new algorithm is presented for interpreting the HDX data. Using molecular dynamics (MD) production data and a hydrogen accessibility scoring (HAS)-number of effective collisions (NEC) model, hypothetical HDX behavior is attributed to various in-silico candidate (CCS match) structures. The HAS-NEC model is applied to all candidate structures, and non-negative linear regression is employed to determine structure contributions resulting in the best match to deuterium uptake. The accuracy of the HAS-NEC model is tested with the comparison of predicted and experimental isotopic envelopes for several of the observed c-ions. It is proposed that gas-phase HDX can be utilized effectively as a second criterion (after CCS matching) for filtering suitable MD candidate structures. In this study, the second step of structure elucidation, 13 nominal structures were selected (from a pool of 300 candidate structures) and each with a population contribution proposed for these ions.

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

    PubMed

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

    2017-01-25

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

  13. An algorithm for the deconvolution of mass spectroscopic patterns in isotope labeling studies. Evaluation for the hydrogen-deuterium exchange reaction in ketones.

    PubMed

    Gruber, Christian C; Oberdorfer, Gustav; Voss, Constance V; Kremsner, Jennifer M; Kappe, C Oliver; Kroutil, Wolfgang

    2007-07-20

    An easy to use computerized algorithm for the determination of the amount of each labeled species differing in the number of incorporated isotope labels based on mass spectroscopic data is described and evaluated. Employing this algorithm, the microwave-assisted synthesis of various alpha-labeled deuterium ketones via hydrogen-deuterium exchange with deuterium oxide was optimized with respect to time, temperature, and degree of labeling. For thermally stable ketones the exchange of alpha-protons was achieved at 180 degrees C within 40-200 min. Compared to reflux conditions, the microwave-assisted protocol led to a reduction of the required reaction time from 75-94 h to 40-200 min. The alpha-labeled deuterium ketones were reduced by biocatalytic hydrogen transfer to the corresponding enantiopure chiral alcohols and the deconvolution algorithm validated by regression analysis of a mixture of labeled and unlabeled ketones/alcohols.

  14. 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

  15. Higher order structure characterization of protein therapeutics by hydrogen/deuterium exchange mass spectrometry.

    PubMed

    Huang, Richard Y-C; Chen, Guodong

    2014-10-01

    Characterization of therapeutic drugs is a crucial step in drug development in the biopharmaceutical industry. Analysis of protein therapeutics is a challenging task because of the complexities associated with large molecular size and 3D structures. Recent advances in hydrogen/deuterium-exchange mass spectrometry (HDX-MS) have provided a means to assess higher-order structure of protein therapeutics in solution. In this review, the principles and procedures of HDX-MS for protein therapeutics characterization are presented, focusing on specific applications of epitope mapping for protein-protein interactions and higher-order structure comparison studies for conformational dynamics of protein therapeutics.

  16. Hydrogen/deuterium exchange of myoglobin ions in a linear quadrupole ion trap.

    PubMed

    Mao, Dunmin; Ding, Chuanfan; Douglas, D J

    2002-01-01

    The hydrogen/deuterium (H/D) exchange of gas-phase ions of holo- and apo-myoglobin has been studied by confining the ions in a linear quadrupole ion trap with D(2)O or CD(3)OD at a pressure of several mTorr. Apo-myoglobin ions were formed by collision-induced dissociation of holo-myoglobin ions between the orifice and skimmer of the ion sampling system. The exchange takes place on a time scale of seconds. Earlier cross section measurements have shown that holo-myoglobin ions can have more compact structures than apo-myoglobin. Despite this, both holo-myoglobin and apo-myoglobin in charge states +8 to +14 are found to exchange nearly the same number of hydrogens (ca. 103) in 4 s. It is possible the ions fold or unfold to new conformations on the much longer time scale of the exchange experiment compared with the cross section measurements.

  17. [Interactions between proteins and cation exchange adsorbents analyzed by NMR and hydrogen/deuterium exchange technique].

    PubMed

    Wang, Kang; Hao, Dongxia; Qi, Shuting; Ma, Guanghui

    2014-09-01

    In silico acquirement of the accurate residue details of protein on chromatographic media is a bottleneck in protein chromatography separation and purification. Here we developed a novel approach by coupling with H/D exchange and nuclear magnetic resonance to observe hen egg white lysozyme (HEWL) unfolding behavior adsorbed on cation exchange media (SP Sepharose FF). Analysis of 1D 1H-NMR shows that protein unfolding accelerated H/D exchange rate, leading to more loss of signal of amide hydrogen owing to exposure of residues and the more unfolding of protein. Analysis of two-dimensional hydrogen-hydrogen total correlation spectroscopy shows that lysozyme lost more signals and experienced great unfolding during its adsorption on media surface. However, for several distinct fragments, the protection degrees varied, the adsorbed lysozyme lost more signal intensity and was less protected at disorder structures (coil, bend, and turn), but was comparatively more protected against exchange at secondary structure domains (α-helix, β-sheet). Finally, the binding site was determined by electrostatic calculations using computer simulation methods in conjunction with hydrogen deuterium labeled protein and NMR. This study would help deeply understand the microscopic mechanism of protein chromatography and guide the purposely design of chromatographic process and media. Moreover, it also provide an effective tool to study the protein and biomaterials interaction in other applications.

  18. 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.

  19. Regio-Selective Intramolecular Hydrogen/Deuterium Exchange in Gas-Phase Electron Transfer Dissociation

    NASA Astrophysics Data System (ADS)

    Hamuro, Yoshitomo

    2017-02-01

    Protein backbone amide hydrogen/deuterium exchange mass spectrometry (HDX-MS) typically utilizes enzymatic digestion after the exchange reaction and before MS analysis to improve data resolution. Gas-phase fragmentation of a peptic fragment prior to MS analysis is a promising technique to further increase the resolution. The biggest technical challenge for this method is elimination of intramolecular hydrogen/deuterium exchange (scrambling) in the gas phase. The scrambling obscures the location of deuterium. Jørgensen's group pioneered a method to minimize the scrambling in gas-phase electron capture/transfer dissociation. Despite active investigation, the mechanism of hydrogen scrambling is not well-understood. The difficulty stems from the fact that the degree of hydrogen scrambling depends on instruments, various parameters of mass analysis, and peptide analyzed. In most hydrogen scrambling investigations, the hydrogen scrambling is measured by the percentage of scrambling in a whole molecule. This paper demonstrates that the degree of intramolecular hydrogen/deuterium exchange depends on the nature of exchangeable hydrogen sites. The deuterium on Tyr amide of neurotensin (9-13), Arg-Pro-Tyr-Ile-Leu, migrated significantly faster than that on Ile or Leu amides, indicating the loss of deuterium from the original sites is not mere randomization of hydrogen and deuterium but more site-specific phenomena. This more precise approach may help understand the mechanism of intramolecular hydrogen exchange and provide higher confidence for the parameter optimization to eliminate intramolecular hydrogen/deuterium exchange during gas-phase fragmentation.

  20. Analysis of Agonist and Antagonist Effects on Thyroid Hormone Receptor Conformation by Hydrogen/Deuterium Exchange

    PubMed Central

    Figueira, A. C. M.; Saidemberg, D. M.; Souza, P. C. T.; Martínez, L.; Scanlan, T. S.; Baxter, J. D.; Skaf, M. S.; Palma, M. S.; Webb, P.; Polikarpov, I.

    2011-01-01

    Thyroid hormone receptors (TRs) are ligand-gated transcription factors with critical roles in development and metabolism. Although x-ray structures of TR ligand-binding domains (LBDs) with agonists are available, comparable structures without ligand (apo-TR) or with antagonists are not. It remains important to understand apo-LBD conformation and the way that it rearranges with ligands to develop better TR pharmaceuticals. In this study, we conducted hydrogen/deuterium exchange on TR LBDs with or without agonist (T3) or antagonist (NH3). Both ligands reduce deuterium incorporation into LBD amide hydrogens, implying tighter overall folding of the domain. As predicted, mass spectroscopic analysis of individual proteolytic peptides after hydrogen/deuterium exchange reveals that ligand increases the degree of solvent protection of regions close to the buried ligand-binding pocket. However, there is also extensive ligand protection of other regions, including the dimer surface at H10–H11, providing evidence for allosteric communication between the ligand-binding pocket and distant interaction surfaces. Surprisingly, C-terminal activation helix H12, which is known to alter position with ligand, remains relatively protected from solvent in all conditions suggesting that it is packed against the LBD irrespective of the presence or type of ligand. T3, but not NH3, increases accessibility of the upper part of H3–H5 to solvent, and we propose that TR H12 interacts with this region in apo-TR and that this interaction is blocked by T3 but not NH3. We present data from site-directed mutagenesis experiments and molecular dynamics simulations that lend support to this structural model of apo-TR and its ligand-dependent conformational changes. PMID:21106879

  1. 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.

  2. Ion mobility spectrometry-hydrogen deuterium exchange mass spectrometry of anions: part 1. Peptides to proteins.

    PubMed

    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.

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

    SciTech Connect

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

    2009-09-20

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

  4. 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.

  5. 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

  6. 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.

  7. Photoactivation of rhodopsin causes an increased hydrogen-deuterium exchange of buried peptide groups.

    PubMed Central

    Rath, P; DeGrip, W J; Rothschild, K J

    1998-01-01

    A key step in visual transduction is the light-induced conformational changes of rhodopsin that lead to binding and activation of the G-protein transducin. In order to explore the nature of these conformational changes, time-resolved Fourier transform infrared spectroscopy was used to measure the kinetics of hydrogen/deuterium exchange in rhodopsin upon photoexcitation. The extent of hydrogen/deuterium exchange of backbone peptide groups can be monitored by measuring the integrated intensity of the amide II and amide II' bands. When rhodopsin films are exposed to D2O in the dark for long periods, the amide II band retains at least 60% of its integrated intensity, reflecting a core of backbone peptide groups that are resistant to H/D exchange. Upon photoactivation, rhodopsin in the presence of D2O exhibits a new phase of H/D exchange which at 10 degrees C consists of fast (time constant approximately 30 min) and slow (approximately 11 h) components. These results indicate that photoactivation causes buried portions of the rhodopsin backbone structure to become more accessible. PMID:9449322

  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

    2013-08-06

    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. Isomerization and Oxidation in the Complementarity-Determining Regions of a Monoclonal Antibody: A Study of the Modification-Structure-Function Correlations by Hydrogen-Deuterium Exchange Mass Spectrometry.

    PubMed

    Yan, Yuetian; Wei, Hui; Fu, Ya; Jusuf, Sutjano; Zeng, Ming; Ludwig, Richard; Krystek, Stanley R; Chen, Guodong; Tao, Li; Das, Tapan K

    2016-02-16

    Chemical modifications can potentially change monoclonal antibody's (mAb) local or global conformation and therefore impact their efficacy as therapeutic drugs. Modifications in the complementarity-determining regions (CDRs) are especially important because they can impair the binding affinity of an antibody for its target and therefore drug potency as a result. In order to understand the impact on mAb attributes induced by specific chemical modifications within the CDR, hydrogen-deuterium exchange mass spectrometry (HDX MS) was used to interrogate the conformational impact of Asp isomerization and Met oxidation in the CDRs of a model monoclonal antibody (mAb1). Our results indicate that despite their proximity to each other, Asp54 isomerization and Met56 oxidation in CDR2 in the heavy chain of mAb1 result in opposing conformational impacts on the local and nearby regions, leading directly to different alterations on antibody-antigen binding affinity. This study revealed direct evidence of local and global conformational changes caused by two of the most common degradation pathways in the CDRs of a mAb and identified correlations between chemical modification, structure, and function of the therapeutic monoclonal antibody.

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

    PubMed

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

    2015-01-01

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

  11. Hydrogen/deuterium exchange of hydrophobic peptides in model membranes by electrospray ionization mass spectrometry.

    PubMed

    Hansen, Raino K; Broadhurst, R William; Skelton, Paul C; Arkin, Isaiah T

    2002-12-01

    We demonstrate here that the hydrogen/deuterium solvent exchange (HDX) properties of the transmembrane fragment of the M2 protein of Influenza A (M2-TM) incorporated into lipid vesicles or detergent micelles can be studied with straightforward electrospray (ESI) and nanospray mass spectrometry (MS) configurations provided that key factors, including sample preparation techniques, are optimized. Small unilamellar vesicle preparations were obtained by solubilizing dimyristoyl phosphatidylcholine (DMPC) and the M2-TM peptide in aqueous solution with n-octyl-beta-D-glycopyranoside, followed by dialysis to remove the detergent. Electron microscopy experiments revealed that subsequent concentration by centrifugation introduced large multilamellar aggregates that were not compatible with ESI-MS. By contrast, a lyophilization-based concentration procedure, followed by thawing above the liquid crystal transition temperature of the lipid component, maintained the liposome size profile and yielded excellent ion fluxes in both ESI-MS and nano-ESI-MS. Using these methods the global HDX profile of M2-TM in aqueous DMPC vesicles was compared with that in methanol, demonstrating that several amide sites were protected from exchange by the lipid membrane. We also show that hydrophobic peptides can be detected by ESI-MS in the presence of a large molar excess of the detergent Triton X-100. The rate of HDX of M2-TM in Triton X-100 micelles was faster than that in DMPC vesicles but slower than when the peptide had been denatured in methanol. These results indicate that the accessibility of backbone amide sites to the solvent can be profoundly affected by membrane protein structure and dynamics, as well as the properties of model bilayer systems.

  12. New developments in protein structure-function analysis by MS and use of hydrogen-deuterium exchange microfluidics.

    PubMed

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

    2011-10-01

    The study of protein structure and function has evolved to become a leading discipline in the biophysical sciences. Although it is not yet possible to determine 3D protein structures from MS data alone, multiple MS-based techniques can be combined to obtain structural and functional data that are complementary to classical protein structure information obtained from NMR or X-ray crystallography. Monitoring gas-phase interactions of noncovalent complexes yields information on binding constants, complex stability, and the nature of interactions. Ion mobility MS and chemical crosslinking strategies can be applied to probe the architecture of macromolecular assemblies and protein-ligand complexes. MS analysis of hydrogen-deuterium exchange can be used to determine the localization of secondary structure elements, binding sites and conformational dynamics of proteins in solution. This minireview focuses first on new strategies that combine these techniques to gain insights into protein structure and function. Using one such strategy, we then demonstrate how a novel hydrogen-deuterium exchange microfluidics tool can be used online with an ESI mass spectrometer to monitor regional accessibility in a peptide, as exemplified with amyloid-β peptide 1-40.

  13. The kinetics of the hydrogen/deuterium exchange of epidermal growth factor receptor ligands.

    PubMed

    Iloro, Ibon; Narváez, Daniel; Guillén, Nancy; Camacho, Carlos M; Guillén, Lalisse; Cora, Elsa; Pastrana-Ríos, Belinda

    2008-05-15

    Five highly homologous epidermal growth factor receptor ligands were studied by mass spectral analysis, hydrogen/deuterium (H/D) exchange via attenuated total reflectance Fourier transform-infrared spectroscopy, and two-dimensional correlation analysis. These studies were performed to determine the order of events during the exchange process, the extent of H/D exchange, and associated kinetics of exchange for a comparative analysis of these ligands. Furthermore, the secondary structure composition of amphiregulin (AR) and heparin-binding-epidermal growth factor (HB-EGF) was determined. All ligands were found to have similar contributions of 3(10)-helix and random coil with varying contributions of beta-sheets and beta-turns. The extent of exchange was 40%, 65%, 55%, 65%, and 98% for EGF, transforming growth factor-alpha (TGF-alpha), AR, HB-EGF, and epiregulin (ER), respectively. The rate constants were determined and classified as fast, intermediate, and slow: for EGF the 0.20 min(-1) (Tyr), 0.09 min(-1) (Arg, beta-turns), and 1.88 x 10(-3) min(-1) (beta-sheets and 3(10)-helix); and for TGF-alpha 0.91 min(-1) (Tyr), 0.27 min(-1) (Arg, beta-turns), and 1.41 x 10(-4) min(-1) (beta-sheets). The time constants for AR 0.47 min(-1) (Tyr), 0.04 min(-1) (Arg), and 1.00 x 10(-4) min(-1) (buried 3(10)-helix, beta-turns, and beta-sheets); for HB-EGF 0.89 min(-1) (Tyr), 0.14 min(-1) (Arg and 3(10)-helix), and 1.00 x 10(-3) min(-1) (buried 3(10)-helix, beta-sheets, and beta-turns); and for epiregulin 0.16 min(-1) (Tyr), 0.03 min(-1) (Arg), and 1.00 x 10(-4) min(-1) (3(10)-helix and beta-sheets). These results provide essential information toward understanding secondary structure, H/D exchange kinetics, and solvation of these epidermal growth factor receptor ligands in their unbound state.

  14. Gas chromatography mass spectrometry study of hydrogen deuterium exchange reactions of volatile hydrides of As, Sb, Bi, Ge and Sn in aqueous media

    NASA Astrophysics Data System (ADS)

    D'Ulivo, Alessandro; Mester, Zoltan; Meija, Juris; Sturgeon, Ralph E.

    2006-07-01

    The H-D exchange processes in MH n or MD n hydrides (M = As, Sb, Bi, n = 3; M = Ge, Sn, n = 4) taking place when they are in contact with H 2O or D 2O solution at different pH or pD values (interval of pH = [0,13]) have been investigated using gas chromatography-mass spectrometry (GC-MS). MH n or MD n compounds were injected into the headspace of reaction vials (4-12 ml) containing 1-2 ml of buffered solution maintained under stirring or shaking conditions. The isotopic composition of the gaseous phase hydrides/deuterides was determined at regular intervals in the range of time 0-15 min. The MH n or MD n compounds were synthesized in separate vials and their purity was checked separately before injection into the reaction vials. The mass spectra were deconvoluted in order to estimate the relative abundance of each species formed following the H-D exchange process (AsH nD 3- n , SbH nD 3- n, BiH nD 3- n, n = 0-3; GeH nD 4- n, SnH nD 4- n, n = 0-4) and the relative abundance of H and D. In the investigated pH (or pD) interval arsanes and stibanes undergo H-D exchange in alkaline media for pH > 7. No H-D exchange was detected for the other hydrides, where the prevailing process is their decomposition in the aqueous phase. A reaction model, based on the formation of protonated or deprotonated intermediates is proposed for H-D exchange of MH n or MD n compounds placed in contact with H 2O or D 2O at different pH or pD values. The H-D exchange in the already formed hydrides can be source of the interference in mechanistic studies on hydride formation performed using labeled reagents; no H-D exchange was detected within the following pH intervals that can be considered free from interference: arsanes pH = [0,7), stibanes pH = [0,7), bismuthanes, germanes and stannanes pH = [0,13].

  15. Evidence for a bound water molecule next to the retinal Schiff base in bacteriorhodopsin and rhodopsin: a resonance Raman study of the Schiff base hydrogen/deuterium exchange.

    PubMed Central

    Deng, H.; Huang, L.; Callender, R.; Ebrey, T.

    1994-01-01

    The retinal chromophores of both rhodopsin and bacteriorhodopsin are bound to their apoproteins via a protonated Schiff base. We have employed continuous-flow resonance Raman experiments on both pigments to determine that the exchange of a deuteron on the Schiff base with a proton is very fast, with half-times of 6.9 +/- 0.9 and 1.3 +/- 0.3 ms for rhodopsin and bacteriorhodopsin, respectively. When these results are analyzed using standard hydrogen-deuteron exchange mechanisms, i.e., acid-, base-, or water-catalyzed schemes, it is found that none of these can explain the experimental results. Because the exchange rates are found to be independent of pH, the deuterium-hydrogen exchange can not be hydroxyl (or acid-)-catalyzed. Moreover, the deuterium-hydrogen exchange of the retinal Schiff base cannot be catalyzed by water acting as a base because in that case the estimated exchange rate is predicted to be orders of magnitude slower than that observed. The relatively slow calculated exchange rates are essentially due to the high pKa values of the Schiff base in both rhodopsin (pKa > 17) and bacteriorhodopsin (pKa approximately 13.5). We have also measured the deuterium-hydrogen exchange of a protonated Schiff base model compound in aqueous solution. Its exchange characteristics, in contrast to the Schiff bases of the pigments, is pH-dependent and consistent with the standard base-catalyzed schemes. Remarkably, the water-catalyzed exchange, which has a half-time of 16 +/- 2 ms and which dominates at pH 3.0 and below, is slower than the exchange rate of the Schiff base in rhodopsin and bacteriorhodopsin. Thus, there are two anomalous results, the inconsistency of the observed hydrogen exchange rates of retinal Schiff base in the two pigments with those predicted from the standard exchange schemes and the enhancement of the rate of hydrogen exchange in the two proteins over the model Schiff base in aqueous solution. We suggest that these results are explained by the

  16. 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.

  17. Activation of AMP-activated protein kinase revealed by hydrogen/deuterium exchange Mass Spectrometry

    PubMed Central

    Landgraf, Rachelle R.; Goswami, Devrishi; Rajamohan, Francis; Harris, Melissa S.; Calabrese, Matthew; Hoth, Lise R.; Magyar, Rachelle; Pascal, Bruce D.; Chalmers, Michael J.; Busby, Scott A.; Kurumbail, Ravi; Griffin, Patrick R.

    2013-01-01

    Summary AMP-Activated protein kinase (AMPK) monitors cellular energy, regulates genes involved in ATP synthesis and consumption, and is allosterically activated by nucleotides and synthetic ligands. Analysis of the intact enzyme by hydrogen/deuterium exchange mass spectrometry reveals conformational perturbations of AMPK in response to binding of nucleotides, cyclodextrin and a synthetic small molecule activator, A769662. Results from this analysis clearly show that binding of AMP leads to conformational changes primarily in the γ subunit of AMPK and subtle changes in the α and β subunits. In contrast, A769662 causes profound conformational changes in the glycogen binding module of the β subunit and in the kinase domain of the α subunit suggesting that the molecular binding site of latter resides between the α and β subunits. The distinct short and long-range perturbations induced upon binding of AMP and A769662 suggest fundamentally different molecular mechanisms for activation of AMPK by these two ligands. PMID:24076403

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

    PubMed Central

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

    2015-01-01

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

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

    PubMed

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

    2016-06-01

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

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

    PubMed

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

    2005-08-23

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

  1. Protein Conformation in Amorphous Solids by FTIR and by Hydrogen/Deuterium Exchange with Mass Spectrometry

    PubMed Central

    Sinha, Sandipan; Li, Yunsong; Williams, Todd D.; Topp, Elizabeth M.

    2008-01-01

    Solid-state hydrogen/deuterium exchange (ssHDX) with electrospray ionization mass spectrometry (ESI-MS) and Fourier transform infrared (FTIR) spectroscopy were used to assess protein conformation in amorphous solids. Myoglobin, lysozyme, β-lactoglobulin, ribonuclease A, E-cadherin 5, and concanavalin A were co-lyophilized with carbohydrates (trehalose, raffinose, and dextran 5000), linear polymers (polyvinyl alcohol and polyvinyl pyrrolidone) or guanidine hydrochloride (negative control). For ssHDX, samples were exposed to D2O vapor at 33% relative humidity and room temperature, and then reconstituted at low temperature (4°C) and pH 2.5 and analyzed by ESI-MS. Peptic digestion of selected proteins was used to provide region-specific information on exchange. FTIR spectra were acquired using attenuated total reflectance. FTIR and ssHDX of intact proteins showed preservation of structure by raffinose and trehalose, as indicated by FTIR band intensity and protection from exchange. ssHDX of peptic digests further indicated that these protective effects were not exerted uniformly along the protein sequence but were observed primarily in α-helical regions, a level of structural resolution not afforded by FTIR. The results thus demonstrate the utility of HDX with ESI-MS for analyzing protein conformation in amorphous solid samples. PMID:18835903

  2. 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

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

    PubMed

    Rajabi, Khadijeh

    2015-02-07

    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.

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

    PubMed

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

    2016-01-01

    Cdc42 regulates pathways related to cell division. Dysregulation of Cdc42 can lead to cancer, cardiovascular diseases and neurodegenerative diseases. GTP induced activation mechanism plays an important role in the activity and biological functions of Cdc42. P-loop, Switch I and Switch II are critical regions modulating the enzymatic activity of Cdc42. We applied amide hydrogen/deuterium exchange coupled with liquid chromatography mass spectrometry (HDXMS) to investigate the dynamic changes of apo-Cdc42 after GDP, GTP and GMP-PCP binding. The natural substrate GTP induced significant decreases of deuteration in P-loop and Switch II, moderate changes of deuteration in Switch I and significant changes of deuteration in the α7 helix, a region far away from the active site. GTP binding induced similar effects on H/D exchange to its non-hydrolysable analog, GMP-PCP. HDXMS results indicate that GTP binding blocked the solvent accessibility in the active site leading to the decrease of H/D exchange rate surrounding the active site, and further triggered a conformational change resulting in the drastic decrease of H/D exchange rate at the remote α7 helix. Comparing the deuteration levels in three activation states of apo-Cdc42, Cdc42-GDP and Cdc42-GMP-PCP, the apo-Cdc42 has the most flexible structure, which can be stabilized by guanine nucleotide binding. The rates of H/D exchange of Cdc42-GDP are between the GMP-PCP-bound and the apo form, but more closely to the GMP-PCP-bound form. Our results show that the activation of Cdc42 is a process of conformational changes involved with P-loop, Switch II and α7 helix for structural stabilization.

  5. 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

  6. Elucidation of tRNA-cytochrome c interactions through hydrogen/deuterium exchange mass spectrometry.

    PubMed

    Lo, Yi-Ting; Huang, Hung-Wei; Huang, Yi-Chuan; Chan, Jui-Fen; Hsu, Yuan-Hao Howard

    2017-02-27

    Cytochrome c (cyt c) is a mitochondrial protein responsible for transferring electrons between electron transport chain complexes III and IV. The release of cyt c from the mitochondria has been considered as a commitment step in intrinsic apoptosis. Transfer RNA (tRNA) has recently been found to interact with the released cyt c to prevent the formation of the apoptosome complex, thus preventing cell apoptosis. To understand the molecular basis of tRNA-cyt c interactions, we applied hydrogen/deuterium exchange mass spectrometry (HDXMS) to analyze the interactions between tRNA and cyt c. tRNA(Phe) binding to cyt c reduced the deuteration level of cyt c in all analyzed regions, indicating that tRNA binding blocks the solvent-accessible regions and results in the formation of a more compact conformation. Substitution of the tRNA(Phe) with the total tRNA from brewer's yeast in the HDXMS experiment significantly reduced deuteration in the N-terminus and the region 18-32 residue of cyt c, where all tRNAs are bound. To clarify the cause of binding, we used synthesized single-stranded oligonucleotides of 12-mer dA and dT to form complexes with cyt c. The exchange of the nucleotide bases between adenine and thymine did not affect the deuteration level of cyt c. However, the regions 1-10 and 65-82 showed minor decreases after unstructured dA or dT DNA binding. Collectively, these results reveal that cyt c maintains its globular structure to interact with tRNA. The region 18-32 selectively interacts with tRNA, and N-terminal 1-10 interacts with oligonucleotides electrostatically.

  7. 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

  8. Dynamic Structural Changes During Complement C3 Activation Analyzed by Hydrogen/Deuterium Exchange Mass Spectrometry

    PubMed Central

    Schuster, Michael C.; Ricklin, Daniel; Papp, Krisztián; Molnar, Kathleen S.; Coales, Stephen J.; Hamuro, Yoshitomo; Sfyroera, Georgia; Chen, Hui; Winters, Michael S.; Lambris, John D.

    2008-01-01

    Proteolytic cleavage of component C3 to C3b is a central step in the activation of complement. Whereas C3 is largely biologically inactive, C3b is directly involved in various complement activities. While the recently described crystal structures of C3 and C3b provide a molecular basis of complement activation, they do not reflect the dynamic changes that occur in solution. In addition, the available C3b structures diverge in some important aspects. Here we have utilized hydrogen/deuterium exchange coupled with mass spectrometry (HDX-MS) to investigate relative changes in the solution-phase structures of C3 and C3b. By combining two forms of mass spectrometry we could maximize the primary sequence coverage of C3b and demonstrate the feasibility of this method for large plasma proteins. While the majority of the 82 peptides that could be followed over time showed only minor alterations in HDX, we observed clear changes in solvent accessibility for 16 peptides, primarily in the α-chain (α’NT, MG6-8, CUB, TED, C345C domains). Most of these peptides could be directly linked to the structural transitions visible in the crystal structures and revealed additional information about the probability of the structural variants of C3b. In addition, a discontinuous cluster of seven peptides in the MG3, MG6, LNK and α’NT domains showed a decreased accessibility after activation to C3b. Although no gross conformational changes are detected in the crystal structure, this area may reflect a structurally flexible region in solution that contributes to C3 activation and function. PMID:18456336

  9. Identification of CRALBP ligand interactions by photoaffinity labeling, hydrogen/deuterium exchange, and structural modeling.

    PubMed

    Wu, Zhiping; Hasan, Azeem; Liu, Tianyun; Teller, David C; Crabb, John W

    2004-06-25

    Cellular retinaldehyde-binding protein (CRALBP) functions in the retinal pigment epithelium (RPE) as an acceptor of 11-cis-retinol in the isomerization step of the rod visual cycle and as a substrate carrier for 11-cis-retinol dehydrogenase. Toward a better understanding of CRALBP function, the ligand binding cavity in human recombinant CRALBP (rCRALBP) was characterized by photoaffinity labeling with 3-diazo-4-keto-11-cis-retinal and by high resolution mass spectrometric topological analyses. Eight photoaffinity-modified residues were identified in rCRALBP by liquid chromatography tandem mass spectrometry, including Tyr(179), Phe(197), Cys(198), Met(208), Lys(221), Met(222), Val(223), and Met(225). Multiple different adduct masses were found on the photolabeled residues, and the molecular identity of each modification remains unknown. Supporting the specificity of photo-labeling, 50% of the modified residues have been associate with retinoid interactions by independent analyses. In addition, topological analysis of apo- and holo-rCRALBP by hydrogen/deuterium exchange and mass spectrometry demonstrated residues 198-255 incorporate significantly less deuterium when the retinoid binding pocket is occupied with 11-cis-retinal. This hydrophobic region encompasses all but one of the photo-labeled residues. A structural model of CRALBP ligand binding domain was constructed based on the crystal structures of three homologues in the CRAL-TRIO family of lipid-binding proteins. In the model, all of the photolabeled residues line the ligand binding cavity except Met(208), which appears to reside in a flexible loop at the entrance/exit of the ligand cavity. Overall, the results expand to 12 the number of residues proposed to interact with ligand and provide further insight into CRALBP ligand and protein interactions.

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

    PubMed

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

    2009-12-15

    Accumulating evidence suggests that solution-phase conformations of small globular proteins and large molecular protein assemblies can be preserved for milliseconds after electrospray ionization. Thus, the study of proteins in the gas phase on this time scale is highly desirable. Here we demonstrate that a traveling wave ion guide (TWIG) of a Synapt mass spectrometer offers a highly suitable environment for rapid and efficient gas-phase hydrogen/deuterium exchange (HDX). Gaseous ND(3) was introduced into either the source TWIG or the TWIG located just after the ion mobility cell, such that ions underwent HDX as they passed through the ND(3) on the way to the time-of-flight analyzer. The extent of deuterium labeling could be controlled by varying the quantity of ND(3) or the speed of the traveling wave. The gas-phase HDX of model peptides corresponded to labeling of primarily fast exchanging sites due to the short labeling times (ranging from 0.1 to 10 ms). In addition to peptides, gas-phase HDX of ubiquitin, cytochrome c, lysozyme, and apomyoglobin were examined. We conclude that HDX of protein ions in a TWIG is highly sensitive to protein conformation, enables the detection of conformers present on submilliseconds time scales, and can readily be combined with ion mobility spectrometry.

  11. Quenched hydrogen-deuterium exchange NMR of a disease-relevant Aβ(1-42) amyloid polymorph

    PubMed Central

    Wälti, Marielle Aulikki; Orts, Julien; Riek, Roland

    2017-01-01

    Alzheimer’s disease is associated with the aggregation into amyloid fibrils of Aβ(1–42) and Aβ(1–40) peptides. Interestingly, these fibrils often do not obtain one single structure but rather show different morphologies, so-called polymorphs. Here, we compare quenched hydrogen-deuterium (H/D) exchange of a disease-relevant Aβ(1–42) fibril for which the 3D structure has been determined by solid-state NMR with H/D exchange previously determined on another structural polymorph. This comparison reveals secondary structural differences between the two polymorphs suggesting that the two polymorphisms can be classified as segmental polymorphs. PMID:28319116

  12. 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.

  13. Dissecting the mechanism of Epac activation via hydrogen-deuterium exchange FT-IR and structural modeling.

    PubMed

    Yu, Shaoning; Fan, Fenghui; Flores, Samuel C; Mei, Fang; Cheng, Xiaodong

    2006-12-26

    Exchange proteins directly activated by cAMP (Epac) make up a family of cAMP binding domain-containing proteins that play important roles in mediating the effects of cAMP through the activation of downstream small GTPases, Ras-proximate proteins. To delineate the mechanism of Epac activation, we probed the conformation and structural dynamics of Epac using amide hydrogen-deuterium (H-D) exchange coupled with Fourier transform infrared spectroscopy (FT-IR) and structural modeling. Our studies show that unlike that of cAMP-dependent protein kinase (PKA), the classic intracellular cAMP receptor, binding of cAMP to Epac does not induce significant changes in overall secondary structure and structural dynamics, as measured by FT-IR and the rate of H-D exchange, respectively. These results suggest that Epac activation does not involve significant changes in the amount of exposed surface areas as in the case of PKA activation, and conformational changes induced by cAMP in Epac are most likely confined to small local regions. Homology modeling and comparative structural analyses of the CBDs of Epac and PKA lead us to propose a model of Epac activation. On the basis of our model, Epac activation by cAMP employs the same underlying structural principal utilized by PKA, although the detailed structural and conformational changes associated with Epac and PKA activation are significantly different. In addition, we predict that during Epac activation the first beta-strand of the switchboard switches its conformation to a alpha-helix, which folds back to the beta-barrel core of the CBD and interacts directly with cAMP to form the base of the cAMP-binding pocket.

  14. 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

    2009-09-08

    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.

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

    NASA Astrophysics Data System (ADS)

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

    2012-04-01

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

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

    PubMed Central

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

    2013-01-01

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

  17. Determination of Histidine pKa Values in the Propeptides of Furin and Proprotein Convertase 1/3 Using Histidine Hydrogen-Deuterium Exchange Mass Spectrometry.

    PubMed

    Elferich, Johannes; Williamson, Danielle M; David, Larry L; Shinde, Ujwal

    2015-08-04

    Propeptides of proprotein convertases regulate activation of their protease domains by sensing the organellar pH within the secretory pathway. Earlier experimental work highlighted the importance of a conserved histidine residue within the propeptide of a widely studied member, furin. A subsequent evolutionary analysis found an increase in histidine content within propeptides of secreted eukaryotic proteases compared with their prokaryotic orthologs. However, furin activates in the trans-golgi network at a pH of 6.5 while a paralog, proprotein convertase 1/3, activates in secretory vesicles at a pH of 5.5. It is unclear how a conserved histidine can mediate activation at two different pH values. In this manuscript, we measured the pKa values of histidines within the propeptides of furin and proprotein convertase 1/3 using a histidine hydrogen-deuterium exchange mass spectrometry approach. The high density of histidine residues combined with an abundance of basic residues provided challenges for generation of peptide ions with unique histidine residues, which were overcome by employing ETD fragmentation. During this analysis, we found slow hydrogen-deuterium exchange in residues other than histidine at basic pH. Finally, we demonstrate that the pKa of the conserved histidine in proprotein convertase 1/3 is acid-shifted compared with furin and is consistent with its lower pH of activation.

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

    PubMed

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

    2015-05-01

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

  19. 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.

  20. 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

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

    PubMed Central

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

    2015-01-01

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

  2. Regulation of phenylalanine hydroxylase: conformational changes upon phenylalanine binding detected by hydrogen/deuterium exchange and mass spectrometry.

    PubMed

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

    2010-04-20

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

  3. 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

  4. Dynamics of the β2-adrenergic G-protein coupled receptor revealed by hydrogen-deuterium exchange

    PubMed Central

    Zhang, Xi; Chien, Ellen Y.T.; Chalmers, Michael J.; Pascal, Bruce D.; Gatchalian, Jovylyn; Stevens, Raymond C.; Griffin, Patrick R.

    2010-01-01

    To examine the molecular details of ligand activation of G-protein coupled receptor (GPCRs), emphasis has been placed on structure determination of these receptors with stabilizing ligands. Here we present the methodology for receptor dynamics characterization of the GPCR human β2 adrenergic receptor bound to the inverse agonist carazolol using the technique of amide hydrogen/deuterium exchange coupled with mass spectrometry (HDX MS). The HDX MS profile of receptor bound to carazolol is consistent with thermal parameter observations in the crystal structure and provides additional information in highly dynamic regions of the receptor and chemical modifications demonstrating the highly complementary nature of the techniques. Following optimization of HDX experimental conditions for this membrane protein, better than 89% sequence coverage was obtained for the receptor. The methodology presented paves the way for future analysis of β2AR bound to pharmacologically distinct ligands as well as analysis of other GPCR family members. PMID:20058880

  5. Gaseous anion chemistry. Hydrogen-deuterium exchange in mono- and dialcohol alkoxide ions: ionization reactions in dialcohols

    SciTech Connect

    Lloyd, J.R.; Agosta, W.C.; Field, F.H.

    1980-08-15

    The subject of this work is H-D exchange in certain gaseous anions using D/sub 2/ as the exchanging agent. The anions involved are produced from ethylene glycol, 1,3-propanediol, 1,4-butanediol, ethanol, 1-propanol, and 1-butanol. Spectra and postulated ionization reactions for these mono- and dialcohols are given. Hydrogen-deuterium exchange occurs in the (M - 1)/sup -/ and (2M - 1)/sup -/ ions of ethylene glycol, 1,3-propanediol, and 1,4-butanediol. The amount of exchange occurring is 3-8 times greater in (2M - 1)/sup -/ than in (M - 1)/sup -/. The amount of H-D exchange occurring in ethanol, 1-propanol, and 1-butanol is small or zero in the (2M - 1)/sup -/ ions and in the (M - 1)/sup -/ ion for 1-butanol (the only (M - 1)/sup -/ ion which could be examined experimentally). The amount of exchange occurring in the (2M - 1)/sup -/ and (M - 1)/sup -/ ions from ethylene glycol is not affected by the total pressure or composition of the reaction mixture in the ionization chamber of the mass spectrometer. A novel hydrogen-bridging mechanism is suggested to account for the observed exchange occurring in the dialcohols.

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

    PubMed

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

    2015-07-01

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

  7. Combining ion mobility spectrometry with hydrogen-deuterium exchange and top-down MS for peptide ion structure analysis.

    PubMed

    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 Å(2) and 471 Å(2). [M+3H](3+) ions exhibit a predominant conformer with a collision cross section of 340 Å(2) as well as an unresolved conformer (shoulder) with a collision cross section of ~367 Å(2). 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.

  8. 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).

  9. 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.

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

    PubMed Central

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

    1990-01-01

    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. PMID:2275968

  11. 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.

  12. 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.

  13. Mapping the interactions of selective biochemical probes of antibody conformation by hydrogen-deuterium exchange mass spectrometry.

    PubMed

    Leurs, Ulrike; Beck, Hermann; Bonnington, Lea; Lindner, Ingo; Pol, Ewa; Rand, Kasper Dyrberg

    2017-03-27

    Protein-based pharmaceuticals represent the fastest growing group of drugs in development in the pharmaceutical industry. One of the major challenges in the discovery, development and distribution of biopharmaceuticals is the assessment of changes in their higher-order structure due to chemical modifications. Here, we investigate the interactions of three different biochemical probes (Fabs) generated to detect conformational changes in a therapeutic IgG1 antibody (mAbX) by local hydrogen-deuterium exchange mass spectrometry (HDX-MS). We show that two of the probes target the Fc part of the antibody, while the third probe binds to the hinge region. Through HDX-ETD, we can distinguish specific binding patterns of the Fc-binding probes on mAbX at the single amino acid level. Preliminary surface plasmon resonance (SPR) experiments show that these domain-selective Fab probes are sensitive to conformational changes in distinct regions of a full-length therapeutic antibody upon oxidation.

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

    NASA Astrophysics Data System (ADS)

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

    2014-06-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2012-02-01

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

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

    PubMed

    Khakinejad, Mahdiar; Kondalaji, Samaneh Ghassabi; 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.

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

    PubMed

    Khakinejad, Mahdiar; Kondalaji, Samaneh Ghassabi; 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 Å(2) and 808 ± 2 Å(2). [M - 4H](4-) ions were comprised of more compact (Ω = 676 ± 3 Å(2)) and diffuse (i.e., more elongated, Ω = 779 ± 3 Å(2)) ion conformer types. Ions were subjected to HDX in the drift tube using D2O as the reagent gas. Collision-induced dissociation was used to fragment mobility-selected, isotopically labeled [M - 4H](4-) and [M - 5H](5-) ions into the protein subchains. Deuterium uptake levels of each chain can be explained by limited inter-chain isotopic scrambling upon collisional activation. Using nominal ion structures from MDS and a hydrogen accessibility model, the deuterium uptake for each chain was correlated to its exposed surface area. In separate experiments, the per-residue deuterium content for the protonated and deprotonated ions of the synthetic peptide KKDDDDDIIKIIK were compared. The differences in deuterium content indicated the regional HDX accessibility for cations versus anions. Using ions of similar conformational type, this comparison highlights the complementary nature of HDX data obtained from positive- and negative-ion analysis.

  18. 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.

  19. 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.

  20. Enhanced Digestion Efficiency, Peptide Ionization Efficiency, and Sequence Resolution for Protein Hydrogen/Deuterium Exchange Monitored by FT-ICR Mass Spectrometry

    PubMed Central

    Zhang, Hui-Min; Kazazic, Saša; Schaub, Tanner M.; Tipton, Jeremiah D.; Emmett, Mark R.; Marshall, Alan G.

    2009-01-01

    Solution-phase hydrogen/deuterium exchange (HDX) monitored by high-resolution FT-ICR mass spectrometry offers a rapid method to study protein conformations and protein-protein interactions. Pepsin is usually used to digest proteins in HDX and is known as lack of cleavage specificity. To improve digestion efficiency and specificity, we have optimized digestion conditions and cleavage preferences for pepsin and protease type XIII from Aspergillus saitoi. A dilution series of the proteases was used to determine the digestion efficiency for several test proteins. Protease type XIII prefers to cleave on the C-terminal end of basic amino acids and produced the highest number of fragments and the best sequence coverage compared to pepsin or protease type XVIII from Rhizhopus. Furthermore, protease type XIII exhibited much less self-digestion than pepsin, and thus is superior for HDX experiments. Many highly overlapped segments from protease type XIII and pepsin digestion, combined with high-resolution FT-ICR mass spectrometry, provide high sequence resolution (to as few as one or two amino acids) for the assignment of amide hydrogen exchange rate. Our H/D exchange results correlate well with the secondary and tertiary structure of myoglobin. Such assignments of highly overlapped fragments promise to greatly enhance the accuracy and sequence resolution for determining conformational differences resulting from ligand binding or protein-protein interactions. PMID:19551977

  1. Synthesis, spectroscopy, and hydrogen/deuterium exchange in high-spin iron(II) hydride complexes.

    PubMed

    Dugan, Thomas R; Bill, Eckhard; MacLeod, K Cory; Brennessel, William W; Holland, Patrick L

    2014-03-03

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

  2. 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.

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

    PubMed

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

    2011-05-30

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

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

    PubMed

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

    2016-11-01

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

  5. 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.

  6. Conformational Dynamics of the Bovine Mitochondrial ADP/ATP Carrier Isoform 1 Revealed by Hydrogen/Deuterium Exchange Coupled to Mass Spectrometry*

    PubMed Central

    Rey, Martial; Man, Petr; Clémençon, Benjamin; Trézéguet, Véronique; Brandolin, Gérard; Forest, Eric; Pelosi, Ludovic

    2010-01-01

    The mitochondrial adenine nucleotide carrier (Ancp) catalyzes the transport of ADP and ATP across the mitochondrial inner membrane, thus playing an essential role in cellular energy metabolism. During the transport mechanism the carrier switches between two different conformations that can be blocked by two toxins: carboxyatractyloside (CATR) and bongkrekic acid. Therefore, our understanding of the nucleotide transport mechanism can be improved by analyzing structural differences of the individual inhibited states. We have solved the three-dimensional structure of bovine carrier isoform 1 (bAnc1p) in a complex with CATR, but the structure of the carrier-bongkrekic acid complex, and thus, the detailed mechanism of transport remains unknown. Improvements in sample processing in the hydrogen/deuterium exchange technique coupled to mass spectrometry (HDX-MS) have allowed us to gain novel insights into the conformational changes undergone by bAnc1p. This paper describes the first study of bAnc1p using HDX-MS. Results obtained with the CATR-bAnc1p complex were fully in agreement with published results, thus, validating our approach. On the other hand, the HDX kinetics of the two complexes displays marked differences. The bongkrekic acid-bAnc1p complex exhibits greater accessibility to the solvent on the matrix side, whereas the CATR-bAnc1p complex is more accessible on the intermembrane side. These results are discussed with respect to the structural and biochemical data available on Ancp. PMID:20805227

  7. Effects of basic site proximity on deprotonation and hydrogen/deuterium exchange reactions for model dodecapeptide ions containing lysine and glycine

    NASA Astrophysics Data System (ADS)

    Zhang, Xin; Ewing, Nigel P.; Cassady, Carolyn J.

    1998-05-01

    The effects of basic site proximity on gas-phase deprotonation and hydrogen/deuterium (H/D) exchange reactions were investigated for three model dodecapeptide ions in a Fourier transform ion cyclotron resonance mass spectrometer. Each peptide contained four high basicity lysine (K) residues and eight low basicity glycine (G) residues; however, the ordering of the residues differed. In the deprotonation studies, `fully protonated' peptide ions, [M + 4H]4+, where M = (KGG)4, (K2G4)2, and K4G8, were reacted with reference compounds of known basicities. Reaction efficiencies were in the order: [K4G8 + 4H]4+ > [(K2G4)2 + 4H]4+ ~ [(KGG)4 + 4H]4+. The facile reaction of [K4G8 + 4H]4+ is consistent with this ion having the highest Coulomb energy. For gas-phase H/D exchange reactions with d4-methanol, [K4G8 + 4H]4+ has the fastest exchange rate and undergoes the largest number of exchanges; 22 of the 26 labile hydrogens exchanged within the timescale studied. In contrast, [(KGG)4 + 4H]4+ and [(K2G4)2 + 4H]4+ reacted more slowly, but at similar rates, with a maximum of 14 observed exchanges for both ions. Molecular dynamics calculations were conducted to gain insights into conformations. In the lowest energy structures for [(KGG)4 + 4H]4+ and [(K2G4)2 + 4H]4+, the lysine n-butylamino chains stretch out to minimize Coulomb energy; there is little or no intramolecular hydrogen bonding involving the protonated amino groups. In contrast, for [K4G8 + 4H]4+, the proximity of the basicity residues makes minimization of the Coulomb energy difficult; instead, the structure becomes more compact with stabilization of the protonated amino groups by extensive intramolecular hydrogen bonding to heteroatoms in the peptide backbone. The calculated structures suggest that, in the H/D exchange reactions, the compact conformation of [K4G8 + 4H]4+ allows stabilization of the methanolpeptide intermediate by hydrogen bonding, thus lowering the barrier to proton transfer within the complex. The

  8. 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.

  9. Detection of Lipid Induced Structural Changes of the Marburg Virus Matrix Protein VP40 Using Hydrogen/Deuterium Exchange Mass Spectrometry.

    PubMed

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

    2017-02-06

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

  10. Structural Dynamics of the Vimentin Coiled-coil Contact Regions Involved in Filament Assembly as Revealed by Hydrogen-Deuterium Exchange.

    PubMed

    Premchandar, Aiswarya; Mücke, Norbert; Poznański, Jarosław; Wedig, Tatjana; Kaus-Drobek, Magdalena; Herrmann, Harald; Dadlez, Michał

    2016-11-25

    Intermediate filaments (IF) are major constituents of the cytoskeleton of metazoan cells. They are not only responsible for the mechanical properties but also for various physiological activities in different cells and tissues. The building blocks of IFs are extended coiled-coil-forming proteins exhibiting a characteristic central α-helical domain ("rod"). The fundamental principles of the filament assembly mechanism and the network formation have been widely elucidated for the cytoplasmic IF protein vimentin. Also, a comprehensive structural model for the tetrameric complex of vimentin has been obtained by X-ray crystallography in combination with various biochemical and biophysical techniques. To extend these static data and to investigate the dynamic properties of the full-length proteins in solution during the various assembly steps, we analyzed the patterns of hydrogen-deuterium exchange in vimentin and in four variants carrying point mutations in the IF consensus motifs present at either end of the α-helical rod that cause an assembly arrest at the unit-length filament (ULF) stage. The results yielded unique insights into the structural properties of subdomains within the full-length vimentin, in particular in regions of contact in α-helical and linker segments that stabilize different oligomeric forms such as tetramers, ULFs, and mature filaments. Moreover, hydrogen-deuterium exchange analysis of the point-mutated variants directly demonstrated the active role of the IF consensus motifs in the oligomerization mechanism of tetramers during ULF formation. Ultimately, using molecular dynamics simulation procedures, we provide a structural model for the subdomain-mediated tetramer/tetramer interaction via "cross-coiling" as the first step of the assembly process.

  11. 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.

  12. 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.

  13. A Residue Resolved Bayesian Approach to Quantitative Interpretation of Hydrogen Deuterium Exchange from Mass Spectrometry: Application to Characterizing Protein-Ligand Interactions.

    PubMed

    Saltzberg, Daniel John; Broughton, Howard B; Pellarin, Riccardo; Chalmers, Michael J; Espada, Alfonso; Dodge, Jeffrey A; Pascal, Bruce D; Griffin, Patrick R; Humblet, Christine; Sali, Andrej

    2016-11-03

    Characterization of interactions between proteins and other molecules is crucial for understanding the mechanisms of action of biological systems and, thus, drug discovery. An increasingly useful approach to mapping these interactions is measurement of hydrogen/deuterium exchange (HDX) using mass spectrometry (HDX-MS), which measures the time-resolved deuterium incorporation of peptides obtained by enzymatic digestion of the protein. Comparison of exchange rates between apo- and ligand-bound conditions results in a mapping of the differential HDX (ΔHDX) of the ligand. Residue-level analysis of these data, however, must account for experimental error, sparseness and ambiguity due to overlapping peptides. Here, we propose a Bayesian method consisting of a forward model, noise model, prior probabilities, and a Monte Carlo sampling scheme. This method exploits a residue-resolved exponential rate model of HDX-MS data obtained from all peptides simultaneously, and explicitly models experimental error. The result is the best possible estimate of ΔHDX magnitude and significance for each residue given the data. We demonstrate the method by revealing richer structural interpretation of ΔHDX data on two nuclear receptors: vitamin D-receptor (VDR) and retinoic acid receptor gamma (RORγ). The method is implemented in HDX Workbench and as a standalone module of the open source Integrative Modeling Platform.

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

    NASA Astrophysics Data System (ADS)

    Hamuro, Yoshitomo

    2017-03-01

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

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

    PubMed

    Hamuro, Yoshitomo

    2017-03-01

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

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

    NASA Astrophysics Data System (ADS)

    Hamuro, Yoshitomo

    2017-01-01

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

  17. 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

  18. Hydrogen/Deuterium Exchange Reveals Distinct Agonist/Partial Agonist Receptor Dynamics within the intact Vitamin D Receptor/Retinoid X Receptor Heterodimer

    PubMed Central

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

    2010-01-01

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

  19. Hydrogen/deuterium exchange and mass spectrometric analysis of a protein containing multiple disulfide bonds: Solution structure of recombinant macrophage colony stimulating factor-beta (rhM-CSFbeta).

    PubMed

    Yan, Xuguang; Zhang, Heidi; Watson, Jeffrey; Schimerlik, Michael I; Deinzer, Max L

    2002-09-01

    Studies with the homodimeric recombinant human macrophage colony-stimulating factor beta (rhM-CSFbeta), show for the first time that a large number (9) of disulfide linkages can be reduced after amide hydrogen/deuterium (H/D) exchange, and the protein digested and analyzed successfully for the isotopic composition by electrospray mass spectrometry. Analysis of amide H/D after exchange-in shows that in solution the conserved four-helix bundle of (rhM-CSFbeta) has fast and moderately fast exchangeable sections of amide hydrogens in the alphaA helix, and mostly slow exchanging sections of amide hydrogens in the alphaB, alphaC, and alphaD helices. Most of the amide hydrogens in the loop between the beta1 and beta4 sheets exhibited fast or moderately fast exchange, whereas in the amino acid 63-67 loop, located at the interface of the two subunits, the exchange was slow. Solvent accessibility as measured by H/D exchange showed a better correlation with the average depth of amide residues calculated from reported X-ray crystallographic data for rhM-CSFalpha than with the average B-factor. The rates of H/D exchange in rhM-CSFbeta appear to correlate well with the exposed surface calculated for each amino acid residue in the crystal structure except for the alphaD helix. Fast hydrogen isotope exchange throughout the segment amino acids 150-221 present in rhM-CSFbeta, but not rhM-CSFalpha, provides evidence that the carboxy-terminal region is unstructured. It is, therefore, proposed that the anomalous behavior of the alphaD helix is due to interaction of the carboxy-terminal tail with this helical segment.

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

    PubMed

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

    2014-06-02

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

  1. Distinct interaction modes of an AKAP bound to two regulatory subunit isoforms of protein kinase A revealed by amide hydrogen/deuterium exchange.

    PubMed

    Burns-Hamuro, Lora L; Hamuro, Yoshitomo; Kim, Jack S; Sigala, Paul; Fayos, Rosa; Stranz, David D; Jennings, Patricia A; Taylor, Susan S; Woods, Virgil L

    2005-12-01

    The structure of an AKAP docked to the dimerization/docking (D/D) domain of the type II (RIIalpha) isoform of protein kinase A (PKA) has been well characterized, but there currently is no detailed structural information of an AKAP docked to the type I (RIalpha) isoform. Dual-specific AKAP2 (D-AKAP2) binds in the nanomolar range to both isoforms and provided us with an opportunity to characterize the isoform-selective nature of AKAP binding using a common docked ligand. Hydrogen/deuterium (H/D) exchange combined with mass spectrometry (DXMS) was used to probe backbone structural changes of an alpha-helical A-kinase binding (AKB) motif from D-AKAP2 docked to both RIalpha and RIIalpha D/D domains. The region of protection upon complex formation and the magnitude of protection from H/D exchange were determined for both interacting partners in each complex. The backbone of the AKB ligand was more protected when bound to RIalpha compared to RIIalpha, suggesting an increased helical stabilization of the docked AKB ligand. This combined with a broader region of backbone protection induced by the AKAP on the docking surface of RIalpha indicated that there were more binding constraints for the AKB ligand when bound to RIalpha. This was in contrast to RIIalpha, which has a preformed, localized binding surface. These distinct modes of AKAP binding may contribute to the more discriminating nature of the RIalpha AKAP-docking surface. DXMS provides valuable structural information for understanding binding specificity in the absence of a high-resolution structure, and can readily be applied to other protein-ligand and protein-protein interactions.

  2. 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

  3. Epitope mapping of inhibitory antibodies targeting the C2 domain of coagulation factor VIII by hydrogen-deuterium exchange mass spectrometry

    PubMed Central

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

    2014-01-01

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

  4. Hydrogen-deuterium exchange induced by an electric field in α-Al2O3 single crystals

    NASA Astrophysics Data System (ADS)

    Ramírez, R.; Colera, I.; Gonz&Ález, R.; Savoini, B.; Chen, Y.

    Hydrogen and deuterium are observed in α-Al2O3 crystals in the form of OH- and OD- radicals, respectively, which absorb in the infrared region. Infrared-absorption measurements were used to monitor diffusion of deuterons and protons in α-Al2O3 single crystals under the application of a moderate electric field parallel to the crystallographic c-axis, in the temperature range of 973-1333K. A linear dependence of the percent of exchange with both annealing time and applied voltage is observed, indicating that ionic conduction was taking place. The activation energy for the H+ ↔; D+ exchange was determined to be 2.4 eV, less than half the value obtained by pure thermal means, suggesting that under the application of an electric field the deuteron (proton) diffusion mechanism is different.

  5. Structural differences between Abeta(1-40) intermediate oligomers and fibrils elucidated by proteolytic fragmentation and hydrogen/deuterium exchange.

    PubMed

    Zhang, Aming; Qi, Wei; Good, Theresa A; Fernandez, Erik J

    2009-02-01

    The aggregation of amyloid-beta protein (Abeta) in vivo is a critical pathological event in Alzheimer's disease. Although more and more evidence shows that the intermediate oligomers are the primary neurotoxic species in Alzheimer's disease, the particular structural features responsible for the toxicity of these intermediates are poorly understood. We measured the peptide level solvent accessibility of multiple Abeta(1-40) aggregated states using hydrogen exchange detected by mass spectrometry. A gradual reduction in solvent accessibility, spreading from the C-terminal region to the N-terminal region was observed with ever more aggregated states of Abeta peptide. The observed hydrogen exchange protection begins with reporter peptides 20-34 and 35-40 in low molecular weight oligomers found in fresh samples and culminates with increasing solvent protection of reporter peptide 1-16 in long time aged fibrillar species. The more solvent exposed structure of intermediate oligomers in the N-termini relative to well-developed fibrils provides a novel explanation for the structure-dependent neurotoxicity of soluble oligomers reported previously.

  6. 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.

  7. Folding of apomyoglobin: Analysis of transient intermediate structure during refolding using quick hydrogen deuterium exchange and NMR.

    PubMed

    Nishimura, Chiaki

    2017-01-01

    The structures of apomyoglobin folding intermediates have been widely analyzed using physical chemistry methods including fluorescence, circular dichroism, small angle X-ray scattering, NMR, mass spectrometry, and rapid mixing. So far, at least two intermediates (on sub-millisecond- and millisecond-scales) have been demonstrated for apomyoglobin folding. The combination of pH-pulse labeling and NMR is a useful tool for analyzing the kinetic intermediates at the atomic level. Its use has revealed that the latter-phase kinetic intermediate of apomyoglobin (6 ms) was composed of helices A, B, G and H, whereas the equilibrium intermediate, called the pH 4 molten-globule intermediate, was composed mainly of helices A, G and H. The improved strategy for the analysis of the kinetic intermediate was developed to include (1) the dimethyl sulfoxide method, (2) data processing with the various labeling times, and (3) a new in-house mixer. Particularly, the rapid mixing revealed that helices A and G were significantly more protected at the earlier stage (400 µs) of the intermediate (former-phase intermediate) than the other helices. Mutation studies, where each hydrophobic residue was replaced with an alanine in helices A, B, E, F, G and H, indicated that both non-native and native-like structures exist in the latter-phase folding intermediate. The N-terminal part of helix B is a weak point in the intermediate, and the docking of helix E residues to the core of the A, B, G and H helices was interrupted by a premature helix B, resulting in the accumulation of the intermediate composed of helices A, B, G and H. The prediction-based protein engineering produced important mutants: Helix F in a P88K/A90L/S92K/A94L mutant folded in the latter-phase intermediate, although helix F in the wild type does not fold even at the native state. Furthermore, in the L11G/W14G/A70L/G73W mutant, helix A did not fold but helix E did, which is similar to what was observed in the kinetic

  8. 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].

  9. 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

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

    SciTech Connect

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

    2014-02-12

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

  11. 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.

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

    PubMed

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

    2012-12-15

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

  13. "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

  14. Structural characterization of in vitro rat liver microsomal metabolites of antihistamine desloratadine using LTQ-Orbitrap hybrid mass spectrometer in combination with online hydrogen/deuterium exchange HR-LC/MS.

    PubMed

    Chen, Guodong; Daaro, Ibrahim; Pramanik, Birendra N; Piwinski, John J

    2009-02-01

    In vitro drug metabolism study is an integral part of drug discovery process. In this report, we have described the application of LTQ-Orbitrap hybrid mass spectrometer in conjunction with online hydrogen (H)/deuterium (D) exchange high resolution (HR)-LC/MS for structural characterization of in vitro rat liver microsomal metabolites of antihistamine desloratadine. Five metabolites M1--M5 have been identified, including three hydroxylated metabolites M1--M3, one N-oxide M4 and one uncommon aromatized N-oxide M5. Accurate mass data have been obtained in both full scan and MSn mode support assignments of metabolite structures with reported mass errors less than 3 ppm. Online H/D exchange HR-LC/MS experiments provide additional evidence in differentiating hydroxylated metabolites from N-oxides. This study demonstrates the effectiveness of this approach in structural characterization of drug metabolites.

  15. 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.

  16. Phonon Localization by Mass Disorder in Dense Hydrogen-Deuterium Binary Alloy

    NASA Astrophysics Data System (ADS)

    Howie, Ross T.; Magdǎu, Ioan B.; Goncharov, Alexander F.; Ackland, Graeme J.; Gregoryanz, Eugene

    2014-10-01

    Using a combination of the Raman spectroscopy and density functional theory calculations on dense hydrogen-deuterium mixtures of various concentrations, we demonstrate that, at 300 K and above 200 GPa, they transform into phase IV, forming a disordered binary alloy with six highly localized intramolecular vibrational (vibrons) and four delocalized low-frequency (<1200 cm-1) modes. Hydrogen-deuterium mixtures are unique in showing a purely mass-induced localization effect in the quantum solid: chemical bonding is isotope-independent while the mass varies by a factor of 2.

  17. Precision Measurement of the Hydrogen-Deuterium 1S-2S Isotope Shift

    SciTech Connect

    Parthey, Christian G.; Matveev, Arthur; Alnis, Janis; Pohl, Randolf; Udem, Thomas; Kolachevsky, Nikolai; Haensch, Theodor W.; Jentschura, Ulrich D.

    2010-06-11

    Measuring the hydrogen-deuterium isotope shift via two-photon spectroscopy of the 1S-2S transition, we obtain 670 994 334 606(15) Hz. This is a 10-times improvement over the previous best measurement [A. Huber et al., Phys. Rev. Lett. 80, 468 (1998)] confirming its frequency value. A calculation of the difference of the mean square charge radii of deuterium and hydrogen results in {sub d}-{sub p}=3.820 07(65) fm{sup 2}, a more than twofold improvement compared to the former value.

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

    SciTech Connect

    Gaskell, David

    2001-03-22

    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.

  19. 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.

  20. Study of H/D exchange rates to derive the strength of intramolecular hydrogen bonds in halo substituted organic building blocks: An NMR spectroscopic investigation

    NASA Astrophysics Data System (ADS)

    Mishra, Sandeep Kumar; Suryaprakash, N.

    2015-10-01

    Rates of hydrogen/deuterium (H/D) exchange determined by 1H NMR spectroscopy are utilized to derive the strength of hydrogen bonds and to monitor the electronic effects in the site-specific halogen substituted benzamides and anilines. The theoretical fitting of the time dependent variation of the integral areas of 1H NMR resonances to the first order decay function permitted the determination of H/D exchange rate constants (k) and their precise half-lives (t1/2) with high degree of reproducibility. The comparative study also permitted the unambiguous determination of relative strength of hydrogen bonds and the contribution from electronic effects on the H/D exchange rate.

  1. 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.

  2. Quantum interference effects in laser spectroscopy of muonic hydrogen, deuterium, and helium-3

    NASA Astrophysics Data System (ADS)

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

    2015-08-01

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

  3. 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

  4. 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.

  5. A critical compilation of experimental data on spectral lines and energy levels of hydrogen, deuterium, and tritium

    NASA Astrophysics Data System (ADS)

    Kramida, A. E.

    2010-11-01

    For more than 50 years, Charlotte Moore's compilation of atomic energy levels and its subsequent revisions have been the standard source of reference data for the spectra of hydrogen and its isotopes. In those publications, theoretical data based on quantum-electrodynamic calculations have been given. This reflects the fact that the theory of the hydrogen spectrum has been perfected to an extent far exceeding the capabilities of the best measurements. However, rapid advances in the techniques of laser spectroscopy and optical frequency metrology have recently put experiments on a par with theory in terms of precision. This calls for construction of new comprehensive data sets for H, D, and T that summarize the latest experimental work and can be directly compared with the modern theoretical reference data. The present work compiles several tens of recent measurements of the hydrogen, deuterium, and tritium fine and hyperfine structure intervals and presents sets of energy levels and Ritz wavelengths derived from those measurements. Data exist for the fine structure of energy levels of hydrogen and deuterium up to principal quantum number n = 12. For higher lying levels, there are many observed lines with unresolved fine structure. From those observations, level centers (centers of the fine structure) are derived by a least-squares optimization, and Ritz wavelengths of series with upper levels up to n = 40 are obtained. For tritium, the n = 2 and 3 energy level intervals are derived from experimental observations.

  6. Epitope mapping by epitope excision, hydrogen/deuterium exchange, and peptide-panning techniques combined with in silico analysis.

    PubMed

    Clementi, Nicola; Mancini, Nicasio; Criscuolo, Elena; Cappelletti, Francesca; Clementi, Massimo; Burioni, Roberto

    2014-01-01

    The fine characterization of protective B cell epitopes plays a pivotal role in the development of novel vaccines. The development of epitope-based vaccines, in fact, cannot be possible without a clear definition of the antigenic regions involved in the binding between the protective antibody (Ab) and its molecular target. To achieve this result, different epitope-mapping approaches have been widely described (Clementi et al. Drug Discov Today 18(9-10):464-471, 2013). Nowadays, the best way to characterize an Ab bound region is still the resolution of Ab-antigen (Ag) co-crystal structure. Unfortunately, the crystallization approaches are not always feasible. However, different experimental strategies aimed to predict Ab-Ag interaction and followed by in silico analysis of the results may be good surrogate approaches to achieve this result. Here, we review few experimental techniques followed by the use of "basic" informatics tools for the analysis of the results.

  7. Analysis of proton exchange kinetics with time-dependent exchange rate.

    PubMed

    Rutkowska-Wlodarczyk, Izabela; Kierdaszuk, Borys; Wlodarczyk, Jakub

    2010-04-01

    Mass spectrometry is used to probe the kinetics of hydrogen-deuterium exchange in lysozyme in pH 5, 6 and 7.4. An analysis based on a Verhulst growth model is proposed and effectively applied to the kinetics of the hydrogen exchange. The data are described by a power-like function which is based on a time-dependence of the exchange rate. Experimental data ranging over many time scales is considered and accurate fits of a power-like function are obtained. Results of fittings show correlation between faster hydrogen-deuterium exchange and increase of pH. Furthermore a model is presented that discriminates between easily exchangeable hydrogens (located in close proximity to the protein surface) and those protected from the exchange (located in the protein interior). A possible interpretation of the model and its biological significance are discussed.

  8. 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.

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

    PubMed

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

    2006-09-21

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

  10. Radiation Studies with Argentine Ion Exchange Material

    SciTech Connect

    Crawford, C.L.

    2002-06-28

    A recent technology exchange between Argentina Nuclear Energy Commission (CNEA) and the US Department of Energy involved vitrification studies of ion exchange resins. Details of the spent ion exchange resins currently stored at two Argentine nuclear power plants, Atucha I and Embalse, have been presented in earlier reports. The present study examines irradiation of simulant samples of ion exchange resins.

  11. 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

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

    PubMed

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

    2013-04-01

    Dimethylsulfoxide (DMSO)-quenched hydrogen/deuterium (H/D)-exchange is a powerful method to characterize the H/D-exchange behaviors of proteins and protein assemblies, and it is potentially useful for investigating non-protected fast-exchanging amide protons in the unfolded state. However, the method has not been used for studies on fully unfolded proteins in a concentrated denaturant or protein solutions at high salt concentrations. In all of the current DMSO-quenched H/D-exchange studies of proteins so far reported, lyophilization was used to remove D2 O from the protein solution, and the lyophilized protein was dissolved in the DMSO solution to quench the H/D exchange reactions and to measure the amide proton signals by two-dimensional nuclear magnetic resonance (2D NMR) spectra. The denaturants or salts remaining after lyophilization thus prevent the measurement of good NMR spectra. In this article, we report that the use of spin desalting columns is a very effective alternative to lyophilization for the medium exchange from the D2 O buffer to the DMSO solution. We show that the medium exchange by a spin desalting column takes only about 10 min in contrast to an overnight length of time required for lyophilization, and that the use of spin desalting columns has made it possible to monitor the H/D-exchange behavior of a fully unfolded protein in a concentrated denaturant. We report the results of unfolded ubiquitin in 6.0M guanidinium chloride.

  13. 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.

  14. 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.

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

    PubMed

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

    2016-04-01

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

  16. 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.

  17. Improving real-time measurement of H/D exchange using a FTIR biospectroscopic probe.

    PubMed

    Carmona, Pedro; Rodríguez-Casado, Arantxa; Molina, Marina

    2009-02-01

    We describe the improvement of a novel approach to investigating hydrogen/deuterium (H/D) exchange kinetics in biomolecules using transmission infrared spectroscopy. The method makes use of a Fourier transform infrared spectrometer coupled with a microdialysis flow cell to determine exchange rates of labile hydrogens. With this cell system, the monitoring of exchange reactions has been studied here as a function of some cell characteristics such as: (a) dialysis membrane surface contacting both the H(2)O and D(2)O compartments; (b) molecular cutoff of dialysis membrane; and (c) distance between the cell-filling holes. The best improvement has been obtained by increasing the dialysis membrane surface followed by increase of molecular cutoff. However, not significant differences were found using various distances between filling holes. The fastest exchange rate which can be measured with the cell system used here is found to be k = 0.41 +/- 0.02 min(-1), that is, about threefold greater than the one got in a previous work. This microdialysis flow cell has been used here for the study of H/D exchange in nucleic acids with subsequent structural analysis by 2D correlation spectroscopy.

  18. 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

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

    PubMed

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

    2014-04-01

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

  20. Method for decomposing observed line shapes resulting from multiple causes - Application to plasma charge-exchange-neutral spectra

    NASA Technical Reports Server (NTRS)

    Patch, R. W.

    1979-01-01

    A method is given for decomposing the widths of observed spectral lines resulting from unresolved line splitting, additive kinetic processes of different types, instrumental broadening (slit function), Doppler broadening, etc. all superimposed. The second moments are used as measures of the various widths involved. The method is not applicable if dispersion type (Lorentz) broadening occurs. Application is made to plasma charge-exchange-neutral spectra of hydrogen, deuterium, and helium.

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

    ERIC Educational Resources Information Center

    Ahn, Song-ee

    2011-01-01

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

  2. Experimental Study of Perpendicular Exchange Spring Media

    NASA Astrophysics Data System (ADS)

    Berger, Andreas; Supper, Natacha; Lengsfield, Byron; Margulies, David; Moser, Andreas; Fullerton, Eric

    2007-03-01

    We have investigated the magnetic reversal and recording properties of perpendicular exchange spring media. These structures, which combine a soft and a hard layer material^1, have recently been proposed as suitable candidates for advanced perpendicular magnetic recording^2. Previous studies^3 have also shown that the magnetization reversal can be tuned by means of a suitable coupling layer. In our study, we have investigated structures that consist of two magnetic layers having different HK-values and being separated by a coupling layer of adjustable thickness. Similar to the results of our previous work on longitudinal exchange spring media^4, we find that there is an optimum coupling layer thickness, at which the magnetic reversal field is minimized. We also observe in our magnetometry experiments that the most robust parameter to quantify this improved magnetization reversal is the closure field HS. The anticipated writability improvements for exchange spring media with optimal interlayer coupling strength are corroborated by detailed recording studies. [1] E.E. Fullerton et al., Phys. Rev. B 58, 12193 (1998); [2] R. Victora et al., IEEE Trans. MAG 41, 537 (2005); [3] K.C. Schuermann et al., J Appl. Phys. 99, 08Q904 (2006); [4] N. Supper et al., IEEE Trans. MAG 41, 3238 (2005)

  3. Exchange bias studied with polarized neutron reflectivity

    SciTech Connect

    te Velthuis, S. G. E.

    2000-01-05

    The role of Polarized Neutron Reflectivity (PNR) for studying natural and synthetic exchange biased systems is illustrated. For a partially oxidized thin film of Co, cycling of the magnetic field causes a considerable reduction of the bias, which the onset of diffuse neutron scattering shows to be due to the loosening of the ferromagnetic domains. On the other hand, PNR measurements of a model exchange bias junction consisting of an n-layered Fe/Cr antiferromagnetic (AF) superlattice coupled with an m-layered Fe/Cr ferromagnetic (F) superlattice confirm the predicted collinear magnetization in the two superlattices. The two magnetized states of the F (along or opposite to the bias field) differ only in the relative orientation of the F and adjacent AF layer. The possibility of reading clearly the magnetic state at the interface pinpoints the commanding role that PNR is having in solving this intriguing problem.

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

    PubMed

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

    2015-12-15

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

  5. 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.

  6. 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.

  7. 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.

  8. Design study of plastic film heat exchanger

    NASA Astrophysics Data System (ADS)

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

    1986-02-01

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

  9. 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.

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

    PubMed Central

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

    2012-01-01

    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. PMID:25685410

  11. 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.

  12. 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.

  13. 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.

  14. Regulation of phenylalanine hydroxylase: conformational changes upon phosphorylation detected by H/D exchange and mass spectrometry.

    PubMed

    Li, Jun; Fitzpatrick, Paul F

    2013-07-15

    The enzyme phenylalanine hydroxylase catalyzes the hydroxylation of excess phenylalanine in the liver to tyrosine. The enzyme is regulated allosterically by phenylalanine and by phosphorylation of Ser16. Hydrogen/deuterium exchange monitored by mass spectrometry has been used to gain insight into any structural change upon phosphorylation. Peptides in both the catalytic and regulatory domains show increased deuterium incorporation into the phosphorylated protein. Deuterium is incorporated into fewer peptides than when the enzyme is activated by phenylalanine, and the incorporation is slower. This establishes that the conformational change upon phosphorylation of phenylalanine hydroxylase is different from and less extensive than that upon phenylalanine activation.

  15. Protein Structure-Function Correlation in Living Human Red Blood Cells Probed by Isotope Exchange-based Mass Spectrometry.

    PubMed

    Narayanan, Sreekala; Mitra, Gopa; Muralidharan, Monita; Mathew, Boby; Mandal, Amit K

    2015-12-01

    To gain insight into the underlying mechanisms of various biological events, it is important to study the structure-function correlation of proteins within cells. Structural probes used in spectroscopic tools to investigate protein conformation are similar across all proteins. Therefore, structural studies are restricted to purified proteins in vitro and these findings are extrapolated in cells to correlate their functions in vivo. However, due to cellular complexity, in vivo and in vitro environments are radically different. Here, we show a novel way to monitor the structural transition of human hemoglobin upon oxygen binding in living red blood cells (RBCs), using hydrogen/deuterium exchange-based mass spectrometry (H/DX-MS). Exploiting permeability of D2O across cell membrane, the isotope exchange of polypeptide backbone amide hydrogens of hemoglobin was carried out inside RBCs and monitored using matrix-assisted laser desorption ionization mass spectrometry (MALDI-MS). To explore the conformational transition associated with oxygenation of hemoglobin in vivo, the isotope exchange kinetics was simplified using the method of initial rates. RBC might be considered as an in vivo system of pure hemoglobin. Thus, as a proof-of-concept, the observed results were correlated with structural transition of hemoglobin associated with its function established in vitro. This is the first report on structural changes of a protein upon ligand binding in its endogenous environment. The proposed method might be applicable to proteins in their native state, irrespective of location, concentration, and size. The present in-cell approach opens a new avenue to unravel a plethora of biological processes like ligand binding, folding, and post-translational modification of proteins in living cells.

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

    PubMed

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

    2017-02-20

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

  17. 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.

  18. 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

  19. Gas exchange in the filamentous cyanobacterium Nostoc punctiforme strain ATCC 29133 and Its hydrogenase-deficient mutant strain NHM5.

    PubMed

    Lindberg, Pia; Lindblad, Peter; Cournac, Laurent

    2004-04-01

    Nostoc punctiforme ATCC 29133 is a nitrogen-fixing, heterocystous cyanobacterium of symbiotic origin. During nitrogen fixation, it produces molecular hydrogen (H(2)), which is recaptured by an uptake hydrogenase. Gas exchange in cultures of N. punctiforme ATCC 29133 and its hydrogenase-free mutant strain NHM5 was studied. Exchange of O(2), CO(2), N(2), and H(2) was followed simultaneously with a mass spectrometer in cultures grown under nitrogen-fixing conditions. Isotopic tracing was used to separate evolution and uptake of CO(2) and O(2). The amount of H(2) produced per molecule of N(2) fixed was found to vary with light conditions, high light giving a greater increase in H(2) production than N(2) fixation. The ratio under low light and high light was approximately 1.4 and 6.1 molecules of H(2) produced per molecule of N(2) fixed, respectively. Incubation under high light for a longer time, until the culture was depleted of CO(2), caused a decrease in the nitrogen fixation rate. At the same time, hydrogen production in the hydrogenase-deficient strain was increased from an initial rate of approximately 6 micro mol (mg of chlorophyll a)(-1) h(-1) to 9 micro mol (mg of chlorophyll a)(-1) h(-1) after about 50 min. A light-stimulated hydrogen-deuterium exchange activity stemming from the nitrogenase was observed in the two strains. The present findings are important for understanding this nitrogenase-based system, aiming at photobiological hydrogen production, as we have identified the conditions under which the energy flow through the nitrogenase can be directed towards hydrogen production rather than nitrogen fixation.

  20. 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.

  1. 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.

  2. Protein hydrogen exchange studied by the fragment separation method.

    PubMed

    Englander, J J; Rogero, J R; Englander, S W

    1985-05-15

    The potential of hydrogen-exchange studies for providing detailed information on protein structure and structural dynamics has not yet been realized, largely because of the continuing inability to correlate measured exchange behavior with the parts of a protein that generate that behavior. J. Rosa and F. M. Richards (1979, J. Mol. Biol. 133, 399-416) pioneered a promising approach to this problem in which tritium label at exchangeable proton sites can be located by fragmenting the protein, separating the fragments, and measuring the label carried by each fragment. However, severe losses of tritium label during the fragment separation steps have so far rendered the results ambiguous. This paper describes methods that minimize losses of tritium label during the fragment separation steps and correct for losses that do occur so that the label can be unambiguously located and even quantified. Steps that promote adequate fragment isolation are also described.

  3. Heat Exchanger Design Studies for AN Lhc Inner Triplet Upgrade

    NASA Astrophysics Data System (ADS)

    Rabehl, R. J.; Huang, Y.

    2008-03-01

    A luminosity upgrade of the CERN Large Hadron Collider (LHC) is planned to coincide with the expected end of life of the existing inner triplet quadrupole magnets. The upgraded inner triplet will have much larger heat loads to be removed from the magnets by the cryogenics system. A number of cryogenics design studies have been completed under the LHC Accelerator Research Program (LARP), including investigations of required heat exchanger characteristics to transfer this heat from the pressurized He II bath to the saturated He II system. This paper discusses heat exchangers both external to the magnet cold mass and internal to the magnet cold mass. A possible design for a heat exchanger external to the magnet cold mass is also presented.

  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. 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.

  6. Cluster variation studies of the anisotropic exchange interaction model

    NASA Astrophysics Data System (ADS)

    King, T. C.; Chen, H. H.

    The cluster variation method is applied to study critical properties of the Potts-like ferromagnetic anisotropic exchange interaction model. Phase transition temperatures, order parameter discontinuities and latent heats of the model on the triangular and the fcc lattices are determined by the triangle approximation; and those on the square and the sc lattices are determined by the square approximation.

  7. 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 ...

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

    NASA Astrophysics Data System (ADS)

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

    2016-12-01

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

  9. 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.

  10. 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

  11. Ferromagnetic resonance studies of exchange-biased Permalloy thin films

    NASA Astrophysics Data System (ADS)

    Stoecklein, W.; Parkin, S. S. P.; Scott, J. C.

    1988-10-01

    Ferromagnetic resonance (FMR) spectra of Permalloy thin films exchange-coupled to iron-manganese films are analyzed. Studies were made on bilayer, ferromagnetic-antiferromagnetic (FA) and trilayer (AFA) structures, as a function of both F and A layer thicknesses in the range 20-800 Å. Data are presented at a frequency of 9.3 GHz for both in-plane and perpendicular directions of the applied field, and at 34.1 GHz, in-plane. Analysis of these data enables extraction of the magnetization, gyromagnetic ratio, and an exchange shift due to spin-wave stiffness and perpendicular-surface anisotropy, as a function of layer thickness. The azimuthal dependence of the in-plane resonance is used to determine the magnitude of the exchange anisotropy (bias field). The magnetization and gyromagnetic ratio show little dependence on the thickness of either the F or A layer down to 50 Å, implying that the interfaces are sharp on a scale of a few lattice constants. Within this interfacial region the magnetization is reduced as a result of interaction with the antiferromagnet. We suggest that the perpendicular-surface anisotropy is created by exchange coupling to the antiferromagnet whose easy axes are not in the plane of the interface. Finally, we suggest a model for exchange anisotropy in which the antiferromagnetic domain pattern is not totally locked, but adjusts in response to the ferromagnetization. Such a model qualitatively explains the bias field exerted by the antiferromagnetic layer deposited before the ferromagnet, the field-training effect, the FMR linewidth, and the magnitude of the bias field.

  12. 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.

  13. 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.

  14. An Efficient and Inexpensive Refrigerated LC System for H/D Exchange Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Keppel, Theodore R.; Jacques, Martin E.; Young, Robert W.; Ratzlaff, Kenneth L.; Weis, David D.

    2011-08-01

    Loss of deuterium label during the LC step in amide hydrogen/deuterium exchange mass spectrometry (H/D-MS) is minimized by maintaining an acidic mobile phase pH and low temperature (pH 2.5, 0 °C). Here we detail the construction and performance of a low-cost, thermoelectrically refrigerated enclosure to house high-performance liquid chromatography (HPLC) components and cool mobile phases. Small volume heat exchangers rapidly decrease mobile phase temperature and keep the temperature stable to ±0.2 °C. Using a superficially porous reversed-phase column, we obtained excellent chromatographic performance in the separation of peptides with a median peak width of 4.4 s. Average deuterium recovery was 80.2% with an average relative precision of 0.91%.

  15. Proton Exchange in a Paramagnetic Chemical Exchange Saturation Transfer Agent from Experimental Studies and ab Initio Metadynamics Simulation.

    PubMed

    Pollet, Rodolphe; Bonnet, Célia S; Retailleau, Pascal; Durand, Philippe; Tóth, Éva

    2017-03-27

    The proton-exchange process between water and a carbamate has been studied experimentally and theoretically in a lanthanide-based paramagnetic chemical exchange saturation transfer agent endowed with potential multimodality detection capabilities (optical imaging, or T1 MRI for the Gd(III) analogue). In addition to an in-depth structural analysis by a combined approach (using X-ray crystallography, NMR, and molecular dynamics), our ab initio simulation in aqueous solution sheds light on the reaction mechanism for this proton exchange, which involves structural Grotthuss diffusion.

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

    PubMed Central

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

    2011-01-01

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

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

    PubMed

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

    2011-11-29

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

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

    PubMed

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

    2013-05-01

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

  19. Fast Reversed-Phase Liquid Chromatography to Reduce Back Exchange and Increase Throughput in H/D Exchange Monitored by FT-ICR Mass Spectrometry

    PubMed Central

    Zhang, Hui-Min; Bou-Assaf, George M.; Emmett, Mark R.; Marshall, Alan G.

    2009-01-01

    In solution-phase hydrogen/deuterium exchange (HDX), it is essential to minimize the back exchange level of H for D after the exchange has been quenched, to accurately assign protein conformation and protein-protein or protein-ligand interactions. Reversed-phase HPLC is conducted at low pH and low temperature to desalt and separate proteolytic fragments. However, back exchange averages ∼30% due to long exposure to H2O in the mobile phase. In this paper, we first show that there is no significant backbone amide hydrogen back exchange during quenching and digestion; backbone exchange occurs primarily during subsequent LC separation. We then show that a rapid reversed-phase separation reduces back exchange for HDX by at least 25%, due to dramatically reduced retention time of the peptide fragments on the column. The influence of retention time on back exchange was also evaluated. The rapid separation coupled with high resolution FT-ICR MS at 14.5T provides high amino acid sequence coverage, high sample throughput, and high reproducibility and reliability. PMID:19095461

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

    PubMed Central

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

    2015-01-01

    Distinct from template-directed biosynthesis of nucleic acids and proteins, the enzymatic synthesis of heterogeneous polysaccharides is a complex process that is difficult to study using common analytical tools. Therefore, the mode of action and processivity of those enzymes are largely unknown. Dermatan sulfate epimerase 1 (DS-epi1) is the predominant enzyme during the formation of iduronic acid residues in the glycosaminoglycan dermatan sulfate. Using recombinant DS-epi1 as a model enzyme, we describe a tandem mass spectrometry-based method to study the mode of action of polysaccharide processing enzymes. The enzyme action on the substrate was monitored by hydrogen-deuterium exchange mass spectrometry and the sequence information was then fed into mathematical models with two different assumptions of the mode of action for the enzyme: processive reducing end to non-reducing end, and processive non-reducing end to reducing end. Model data was scored by correlation to experimental data and it was found that DS-epi1 attacks its substrate on a random position, followed by a processive mode of modification towards the non-reducing end and that the substrate affinity of the enzyme is negatively affected by each additional epimerization event. It could also be shown that the smallest active substrate was the reducing end uronic acid in a tetrasaccharide and that octasaccharides and longer oligosaccharides were optimal substrates. The method of using tandem mass spectrometry to generate sequence information of the complex enzymatic products in combination with in silico modeling can be potentially applied to study the mode of action of other enzymes involved in polysaccharide biosynthesis. PMID:26900446

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

    PubMed Central

    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.

    2013-01-01

    Hydrogen/deuterium exchange mass spectrometry (HDX-MS) is an established method for the interrogation of protein conformation and dynamics. While the data analysis challenge of HDX-MS has been addressed by a number of software packages, new computational tools are needed to keep pace with the improved methods and throughput of this technique. To address these needs, we report an integrated desktop program titled HDX Workbench, which facilitates automation, management, visualization, and statistical cross-comparison of large HDX data sets. Using the software, validated data analysis can be achieved at the rate of generation. The application is available at the project home page http://hdx.florida.scripps.edu. PMID:22692830

  3. 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.

  4. TGA and DTA studies of solvent-exchanged gels

    SciTech Connect

    Leeb, K.; Durakpasa, H.; Breiter, M.W.

    1994-12-31

    Sols were prepared in the system TMOS:H{sub 2}O:SOLV:HCl with molar ratios of 1:4:3:0.0005 for SOLV = MEOH, ETOH and DMF. The gelation and aging of these sols took place in cuvettes covered by parafilm. The gels were removed from the cuvettes 14 days after gelation. Solvent exchange was carried out in each of the three solvents for a period of 14 days. Starting with fresh solvent, the exchange was repeated three times. TGA and DTA curves were taken with pieces of the original gels and of gels after the 2nd and 3rd solvent exchange. The TGA curves display a considerable weight loss in the temperature range of solvent evaporation. A small step is observed at higher temperatures if MEOH or ETOH represent the exchange solvent. The DTA curves allow a distinction what mixtures of solvents are present. The effectiveness of the solvent exchange can be evaluated.

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

    PubMed

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

    2015-01-01

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

  6. 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.

  7. Parametric performance studies on fluidized-bed heat exchangers

    NASA Astrophysics Data System (ADS)

    Stoeffler, R. C.

    1982-01-01

    The performance of single and multistage shallow fluidized beds is investigated for possible application to the recovery of heat from sources such as waste heat, and coal combustion or coal gasification. Tests are conducted to (1) investigate the effects of fouling due to liquid condensate in the gas stream on fluidized bed heat exchanger performance, (2) investigate the performance of fluidized beds which are staged using baffle plates, and (3) investigate the effects of different heat exchanger surface geometries. Work is progressing in selecting the conditions for that portion of the program involving fouling by a liquid condensate, and in modifying the fluidized bed heat exchanger facility for the fouling experiments. Preliminary tests were conducted with water vapor injection. Water vapor and glycerol vapor were chosen as the condensates. The results are summarized as follows: (1) heat exchanger performance is seriously degraded by condensation when the dew point temperature exceeds the heat exchanger wall temperature; and (2) the performance decrease occurs as a result of particle adherence to the heat exchanger surface and not as a result of particle agglomeration.

  8. 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.

  9. 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

  10. Advances and challenges in analytical characterization of biotechnology products: mass spectrometry-based approaches to study properties and behavior of protein therapeutics.

    PubMed

    Kaltashov, Igor A; Bobst, Cedric E; Abzalimov, Rinat R; Wang, Guanbo; Baykal, Burcu; Wang, Shunhai

    2012-01-01

    Biopharmaceuticals are a unique class of medicines due to their extreme structural complexity. The structure of these therapeutic proteins is critically important for their efficacy and safety, and the ability to characterize it at various levels (from sequence to conformation) is critical not only at the quality control stage, but also throughout the discovery and design stages. Biological mass spectrometry (MS) offers a variety of approaches to study structure and behavior of complex protein drugs and has already become a default tool for characterizing the covalent structure of protein therapeutics, including sequence and post-translational modifications. Recently, MS-based methods have also begun enjoying a dramatic growth in popularity as a means to provide information on higher order structure and dynamics of biotechnology products. In particular, hydrogen/deuterium exchange MS and charge state distribution analysis of protein ions in electrospray ionization (ESI) MS offer a convenient way to assess the integrity of protein conformation. Native ESI MS also allows the interactions of protein drugs with their therapeutic targets and other physiological partners to be monitored using simple model systems. MS-based methods are also applied to study pharmacokinetics of biopharmaceutical products, where they begin to rival traditional immunoassays. MS already provides valuable support to all stages of development of biopharmaceuticals, from discovery to post-approval monitoring, and its impact on the field of biopharmaceutical analysis will undoubtedly continue to grow.

  11. 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)

  12. Bench-Scale Studies with Argentine Ion Exchange Material

    SciTech Connect

    Cicero-Herman, C.A.

    2002-06-28

    The United States Department of Energy (DOE), as well as international atomic energy commission, facilities use ion exchange materials for purification of aqueous streams in the nuclear industry. Unfortunately, the use of the ion exchange materials creates a waste stream that can be very high in both organic and radioactive constituents. Therefore, disposal of the spent resins often becomes an economic problem because of the large volumes of resin produced and the relatively few technologies that are capable of economically stabilizing this waste. Vitrification of this waste stream presents a reasonable disposable alternative because of its inherent destruction capabilities, the volume reductions obtainable, and the durable product that it produces.

  13. Experimental study of energy exchanges between two coupled granular gases

    NASA Astrophysics Data System (ADS)

    Chastaing, J.-Y.; Géminard, J.-C.; Naert, A.

    2016-12-01

    We report on the energy exchanges between two granular gases of different densities coupled electromechanically by immersed blades attached to dc motors. Zeroing the energy flux between the two subsystems, we demonstrate that an immersed blade is a convenient way to assess the properties of the granular gases, provided that the dissipation in the motor is properly taken into account. In addition, when the two gases have different densities, the fluctuations of the energy flux are asymmetric, very intermittent, and with most probable zero flux. We show that, for weak coupling, the main features of the energy exchanges can be explained considering the fluctuations of the two subsystems.

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

    SciTech Connect

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

    2012-04-01

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

  15. Functional studies of split Arabidopsis Ca2+/H+ exchangers.

    PubMed

    Zhao, Jian; Connorton, James M; Guo, YingQing; Li, Xiangkai; Shigaki, Toshiro; Hirschi, Kendal D; Pittman, Jon K

    2009-12-04

    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 through the use of nonfunctional halves of CAX transporters. We demonstrate that a protein coding for an N-terminal half of an activated variant of CAX1 (sCAX1) can associate with the C-terminal half of either CAX1 or CAX3 to form a functional transporter that may exhibit unique transport properties. Using yeast split ubiquitin, in planta bimolecular fluorescence complementation, and gel shift experiments, we demonstrate a physical interaction among the half proteins. Moreover, the half-proteins both independently localized to the same yeast endomembrane. Co-expressing variants of N- and C-terminal halves of CAX1 and CAX3 in yeast suggested that the N-terminal region mediates Ca(2+) transport, whereas the C-terminal half defines salt tolerance phenotypes. Furthermore, in yeast assays, auto-inhibited CAX1 could be differentially activated by CAX split proteins. The N-terminal half of CAX1 when co-expressed with CAX1 activated Ca(2+) transport, whereas co-expressing C-terminal halves of CAX variants with CAX1 conferred salt tolerance but no apparent Ca(2+) transport. These findings demonstrate plasticity through hetero-CAX complex formation as well as a novel means to engineer CAX transport.

  16. Comprehensive Peptide Ion Structure Studies Using Ion Mobility Techniques: Part 1. An Advanced Protocol for Molecular Dynamics Simulations and Collision Cross-Section Calculation

    NASA Astrophysics Data System (ADS)

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

    2017-02-01

    Collision cross-section (CCS) measurements with a linear drift tube have been utilized to study the gas-phase conformers of a model peptide (acetyl-PAAAAKAAAAKAAAAKAAAAK). Extensive molecular dynamics (MD) simulations have been conducted to derive an advanced protocol for the generation of a comprehensive pool of in-silico structures; both higher energy and more thermodynamically stable structures are included to provide an unbiased sampling of conformational space. MD simulations at 300 K are applied to the in-silico structures to more accurately describe the gas-phase transport properties of the ion conformers including their dynamics. Different methods used previously for trajectory method (TM) CCS calculation employing the Mobcal software [1] are evaluated. A new method for accurate CCS calculation is proposed based on clustering and data mining techniques. CCS values are calculated for all in-silico structures, and those with matching CCS values are chosen as candidate structures. With this approach, more than 300 candidate structures with significant structural variation are produced; although no final gas-phase structure is proposed here, in a second installment of this work, gas-phase hydrogen deuterium exchange data will be utilized as a second criterion to select among these structures as well as to propose relative populations for these ion conformers. Here the need to increase conformer diversity and accurate CCS calculation is demonstrated and the advanced methods are discussed.

  17. Comprehensive Peptide Ion Structure Studies Using Ion Mobility Techniques: Part 1. An Advanced Protocol for Molecular Dynamics Simulations and Collision Cross-Section Calculation.

    PubMed

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

    2017-02-16

    Collision cross-section (CCS) measurements with a linear drift tube have been utilized to study the gas-phase conformers of a model peptide (acetyl-PAAAAKAAAAKAAAAKAAAAK). Extensive molecular dynamics (MD) simulations have been conducted to derive an advanced protocol for the generation of a comprehensive pool of in-silico structures; both higher energy and more thermodynamically stable structures are included to provide an unbiased sampling of conformational space. MD simulations at 300 K are applied to the in-silico structures to more accurately describe the gas-phase transport properties of the ion conformers including their dynamics. Different methods used previously for trajectory method (TM) CCS calculation employing the Mobcal software [1] are evaluated. A new method for accurate CCS calculation is proposed based on clustering and data mining techniques. CCS values are calculated for all in-silico structures, and those with matching CCS values are chosen as candidate structures. With this approach, more than 300 candidate structures with significant structural variation are produced; although no final gas-phase structure is proposed here, in a second installment of this work, gas-phase hydrogen deuterium exchange data will be utilized as a second criterion to select among these structures as well as to propose relative populations for these ion conformers. Here the need to increase conformer diversity and accurate CCS calculation is demonstrated and the advanced methods are discussed. Graphical Abstract ᅟ.

  18. 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

  19. 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.

  20. Solution dynamics of the trp repressor: a study of amide proton exchange by T1 relaxation.

    PubMed

    Gryk, M R; Finucane, M D; Zheng, Z; Jardetzky, O

    1995-03-10

    The amide proton exchange rates of Escherichia coli trp repressor have been measured through their effects on the longitudinal relaxation rates of the amide protons. Three types of exchange regimes have been observed: (1) slow exchange (on a minute/hour time-scale), measurable by isotope exchange, but not by relaxation techniques in the core of the molecule; (2) relatively rapid exchange, with the rates on a T1 relaxation time-scale (seconds) in the DNA-binding region and (3) very fast exchange at the N and C termini. The results have been analyzed in terms of the two-site exchange model originally proposed by Linderstrøm-Lang, and of a three-site extension of the model. The values of the intrinsic exchange rates calculated using the two-state model agree with the values expected from the studies of Englander and co-workers for the very fast case of the chain terminals, but disagree with the literature values by two orders of magnitude in the intermediate case found in the DNA-binding region. The implication of these findings is that the "open" state of the two-state model in the DNA-binding region is not completely open and has an intrinsic exchange rate different from that of a random coil peptide. Alternatively, if the literature values of the intrinsic exchange rates are assumed to apply to the open states in all parts of the repressor molecule, two "closed" helical states have to be postulated, in slow exchange with each other, with only one of them in rapid exchange with the open state and hence with the solvent. Kinetically, the two models are indistinguishable.

  1. Kinetic studies of clavulanic acid recovery by ion exchange chromatography.

    PubMed

    Barboza, M; Almeida, R M; Hokka, C O

    2001-01-01

    Clavulanic acid (CA) is a beta-lactamase inhibitor produced by strains of Streptomyces clavuligerus. Nowadays, the combination of CA with amoxycillin is the most successful example of the use of a beta-lactam antibiotic sensitive to beta-lactamases together with an inhibitor of these enzymes. Clavulanic acid is purified from fermentation broth by a series of steps consisting mainly of two-phase separation processes such as liquid-liquid extraction, adsorption or ion-exchange chromatography, among others. Amberlite IRA 400, a strong anion-exchange resin, has a very high adsorption capacity for CA (Mayer et al. 1997). This resin can be pre-treated with NaCl (chloride cycle), to remove selectively only those anions, which are able to displace chloride from the resin or with NaOH (hydroxyl cycle), to remove all species of anions. In order to decide the best operating conditions for CA recovery by ion-exchange resins and then to construct a model of this separation process, batch experiments were conducted using Amberlite IRA 400 in the chloride cycle. These runs were carried out in a 200 ml stirred tank, at two different initial solution pH, 6.2 and 4.0; the temperature was maintained at 10 degrees C and 20 degrees C during adsorption and 30 degrees C during the desorption step. It was possible, on the basis of these batch results, to model the separation process, including the adsorption kinetics, equilibrium data and mass transfer limitations.

  2. 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.

  3. 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…

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

    PubMed

    Pan, Yan; Brown, Leonid; Konermann, Lars

    2011-12-21

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

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

    PubMed

    Guo, Jing; Carta, Giorgio

    2015-04-03

    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

  6. 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

  7. 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.

  8. FDM study of ion exchange diffusion equation in glass

    NASA Astrophysics Data System (ADS)

    Zhou, Zigang; Yang, Yongjia; Wang, Qiang; Sun, Guangchun

    2009-05-01

    Ion-exchange technique in glass was developed to fabricate gradient refractive index optical devices. In this paper, the Finite Difference Method(FDM), which is used for the solution of ion-diffusion equation, is reported. This method transforms continual diffusion equation to separate difference equation. It unitizes the matrix of MATLAB program to solve the iteration process. The collation results under square boundary condition show that it gets a more accurate numerical solution. Compared to experiment data, the relative error is less than 0.2%. Furthermore, it has simply operation and kinds of output solutions. This method can provide better results for border-proliferation of the hexagonal and the channel devices too.

  9. 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.

  10. 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.

  11. Condensing heat exchanger microbial growth and control study-phase 2

    SciTech Connect

    Marsh, R.W.; Caron, M.E.; Metselaar, C.; Steele, J.

    1993-12-31

    The Space Station Temperature and Humidity Control Condensing Heat Exchangers will be utilized to collect and remove atmospheric water vapor generated by the metabolic and hygienic activity of crew members. The porous hydrophillic coating within the heat exchangers will always be wet. Cabin air will continuously flow through the heat exchangers during system operation which makes them a potential site for microbial colonization. This paper summarizes the findings form an ongoing study which evaluates biofilm formation on wet hydrophilic coated panels compared to panels to which microbial control measures have have been applied. The control measures evaluated are an antimicrobial agent within the coating and periodic drying.

  12. 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.

  13. Cation exchange surface-mediated denaturation of an aglycosylated immunoglobulin (IgG1).

    PubMed

    Gillespie, Ron; Nguyen, Thao; Macneil, Sean; Jones, Laurie; Crampton, Shon; Vunnum, Suresh

    2012-08-17

    Cation exchange chromatography of an aglycosylated IgG1 resulted in two distinct peaks during gradient elution. The early eluting peak contained <1% high molecular weight (HMW) species, while the later peak contained 23% HMW species. Analysis by hydrogen-deuterium exchange and Fourier transform infrared spectroscopy (FTIR) indicated that aggregate formation and generation of the second peak were caused by antibody denaturation on the resin surface. Denaturation and HMW generation was increased by the use of strong cation exchange media, by increasing antibody residence time on the exchanger, or increasing temperature. Denaturation and HMW generation was reduced by increasing pH or ionic strength, by the use of preferentially excluded solutes such as citrate or glycine and controlled entirely by addition of 125 mM arginine to the process buffers. This leads to the hypothesis that denaturation and HMW generation of this antibody can be managed by reducing the strength of binding, by increasing its conformational stability, or by suppressing non-native protein-protein interactions. The glycosylated version of this antibody exhibited less than 2% denatured form, suggesting that glycosylation contributes significantly to the stability of this antibody. These findings may be helpful in managing aggregation in other antibodies, and particularly useful in developing purification processes for aglycosylated antibodies.

  14. Computing H/D-Exchange rates of single residues from data of proteolytic fragments

    PubMed Central

    2010-01-01

    Background Protein conformation and protein/protein interaction can be elucidated by solution-phase Hydrogen/Deuterium exchange (sHDX) coupled to high-resolution mass analysis of the digested protein or protein complex. In sHDX experiments mutant proteins are compared to wild-type proteins or a ligand is added to the protein and compared to the wild-type protein (or mutant). The number of deuteriums incorporated into the polypeptides generated from the protease digest of the protein is related to the solvent accessibility of amide protons within the original protein construct. Results In this work, sHDX data was collected on a 14.5 T FT-ICR MS. An algorithm was developed based on combinatorial optimization that predicts deuterium exchange with high spatial resolution based on the sHDX data of overlapping proteolytic fragments. Often the algorithm assigns deuterium exchange with single residue resolution. Conclusions With our new method it is possible to automatically determine deuterium exchange with higher spatial resolution than the level of digested fragments. PMID:20701784

  15. Solvent Influenced Fluxionality Studied by Ultrafast Chemical Exchange Spectroscopy

    NASA Astrophysics Data System (ADS)

    Ross, Matthew; Kubarych, Kevin

    2012-02-01

    Two-dimensional infrared spectroscopy (2DIR) allows unprecedentedly detailed understanding of the dynamics of chemical systems in the condensed phase. Carbonyl vibrations of small transition metal complexes report intramolecular dynamics and solvent-solute interactions due to their strong oscillator strengths and moderate environmental sensitivity. We studed the fluxional dynamics of iron pentacarbonyl (Fe(CO)5), which is unique in that it contains nearly perfectly uncoupled vibrational modes. We seek to probe the ``molecularity'' of condensed phase activated barrier crossings beyond the continuum Kramers theory picture. Using 2DIR chemical exchange spectroscopy, we show how the dynamics of Berry pseudorotation, the only significant mechanism for vibrational mode mixing on our experimental timescale, is sensitive to interactions with the environment. In a wide range of solvents, we have investigated the effects of hydrogen bonding with alcohols and friction from high viscosity alkanes. In addition, we have monitored vibrational energy redistribution as a solvation shell probe. Moreover, recently implemented mid-infrared pulse shaper based methods allow increased flexibility in experimental design, enabling experimental techniques that are not possible using passive optics.

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

    NASA Astrophysics Data System (ADS)

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

    2015-10-01

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

  17. 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

  18. 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.

  19. Study of exchange bias in NiCr2O4 nanoparticles

    NASA Astrophysics Data System (ADS)

    Singh, H.; Chakraborty, T.; Srikanth, K.; Chandra, R.; Mitra, C.; Kumar, U.

    2014-09-01

    We investigated exchange bias as a function of temperature in nanoparticles of ferrimagnetic normal spinel NiCr2O4. The studied bulk compound exhibits ferrimagnetic and canted antiferromagnetic ordering at 68 K and 30 K respectively. Sample characterization was carried out using X-Ray, Field Emission Scanning Electron Microscope (FE-SEM) and Transmission Electron Microscope (TEM) measurements. Magnetization measurements as a function of temperature has revealed interesting features. Magnetic isotherms of bulk and nanoparticle sample were also investigated at different temperatures. It was found that in nanoparticles, with decrease in temperature, exchange bias first increases, attains maximum value and then subsequently decreases. We argue that in nanoparticles, the higher exchange bias at 68 K is because of coexistence of ferrimagnetic and surface spin effect. However, the presence of glassy spin state may be the reason for decreasing exchange bias effect below Tc down to 5 K.

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

    NASA Astrophysics Data System (ADS)

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

    2014-04-01

    Spin waves are investigated in Permalloy(Ni80Fe20)/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.

  1. 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.

  2. 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…

  3. 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.

  4. The Experimental Study on Heat Transfer Characteristics of The External Heat Exchanger

    NASA Astrophysics Data System (ADS)

    Ji, X. Y.; Lu, X. F.; Yang, L.; Liu, H. Z.

    Using the external heat exchanger in large-scale CFB boilers can control combustion and heat transfer separately, make the adjustments of bed temperature and steam temperature convenient. The state of gas-solid two phase flow in the external heat exchanger is bubbling fluidized bed, but differs from the regular one as there is a directional flow in it. Consequently, the temperature distribution changes along the flow direction. In order to study the heat transfer characteristics of the water cooled tubes in the bubbling fluidized bed and ensure the uniformity of heat transfer in the external heat exchanger, a physical model was set up according to the similarity principle and at the geometric ratio of 1∶28 to an external heat exchanger of a 300MW CFB boiler. The model was connected with an electrically heated CFB test-bed which provides the circulating particles. The influencing factors and the distribution rule of the particles' heat transfer coefficient in the external heat exchanger were assessed by measuring the temperature changes of the water in the tubes and different parts of particles flow along the flow direction. At the end, an empirical correlation of particles' heat transfer coefficient in external heat exchanger was given by modifying the Veedendery empirical correlation.

  5. Human recombinant [C22A] FK506-binding protein amide hydrogen exchange rates from mass spectrometry match and extend those from NMR.

    PubMed Central

    Zhang, Z.; Li, W.; Logan, T. M.; Li, M.; Marshall, A. G.

    1997-01-01

    Hydrogen/deuterium exchange behavior of human recombinant [C22A] FK506 binding protein (C22A FKBP) has been determined by protein fragmentation, combined with electrospray Fourier transform ion cyclotron resonance mass spectrometry (MS). After a specified period of H/D exchange in solution, C22A FKBP was digested by pepsin under slow exchange conditions (pH 2.4, 0 degree C), and then subjected to on-line HPLC/MS for deuterium analysis of each proteolytic peptide. The hydrogen exchange rate of each individual amide hydrogen was then determined independently by heteronuclear two-dimensional NMR on 15N-enriched C22A FKBP. A maximum entropy method (MEM) algorithm makes it possible to derive the distributions of hydrogen exchange rate constants from the MS-determined deuterium exchange-in curves in either the holoprotein or its proteolytic segments. The MEM-derived rate constant distributions of C22A FKBP and different segments of C22A FKBP are compared to the rate constants determined by NMR for individual amide protons. The rate constant distributions determined by both methods are consistent and complementary, thereby validating protein fragmentation/mass spectrometry as a reliable measure of hydrogen exchange in proteins. PMID:9336843

  6. Studying ion exchange in solution and at biological membranes by FCS.

    PubMed

    Widengren, Jerker

    2013-01-01

    By FCS, a wide range of processes can be studied, covering time ranges from subnanoseconds to seconds. In principle, any process at equilibrium conditions can be measured, which reflects itself by a change in the detected fluorescence intensity. In this review, it is described how FCS and variants thereof can be used to monitor ion exchange, in solution and along biological membranes. Analyzing fluorescence fluctuations of ion-sensitive fluorophores by FCS offers selective advantages over other techniques for measuring local ion concentrations, and, in particular, for studying exchange kinetics of ions on a very local scale. This opens for several areas of application. The FCS approach was used to investigate fundamental aspects of proton exchange at and along biological membranes. The protonation relaxation rate, as measured by FCS for a pH-sensitive dye, can also provide information about local accessibility/interaction of a particular labeling site and conformational states of biomolecules, in a similar fashion as in a fluorescence quenching experiment. The same FCS concept can also be applied to ion exchange studies using other ion-sensitive fluorophores, and by use of dyes sensitive to other ambient conditions the concept can be extended also beyond ion exchange studies.

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

    NASA Astrophysics Data System (ADS)

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

    2013-07-01

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

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

    SciTech Connect

    Dang, Liem X.; Annapureddy, Harsha V.

    2013-08-28

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

  9. 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

  10. 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…

  11. 75 FR 77636 - Public Information Exchange on EPA Nanomaterial Case Studies

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-12-13

    ... AGENCY Public Information Exchange on EPA Nanomaterial Case Studies AGENCY: Environmental Protection Agency (EPA). ACTION: Notice of Public Meeting to Receive Comments and Questions and To Provide Information on EPA Nanomaterial Case Studies and Their Purpose SUMMARY: EPA is announcing a public meeting...

  12. The influence of zinc(II) on thioredoxin/glutathione disulfide exchange: QM/MM studies to explore how zinc(II) accelerates exchange in higher dielectric environments.

    PubMed

    Kurian, Roby; Bruce, Mitchell R M; Bruce, Alice E; Amar, François G

    2015-08-01

    QM/MM studies were performed to explore the energetics of exchange reactions of glutathione disulfide (GSSG) and the active site of thioredoxin [Cys32-Gly33-Pro34-Cys35] with and without zinc(II), in vacuum and solvated models. The activation energy for exchange, in the absence of zinc, is 29.7 kcal mol(-1) for the solvated model. This is 3.3 kcal mol(-1) higher than the activation energy for exchange in the gas phase, due to ground state stabilization of the active site Cys-32 thiolate in a polar environment. In the presence of zinc, the activation energy for exchange is 4.9 kcal mol(-1) lower than in the absence of zinc (solvated models). The decrease in activation energy is attributed to stabilization of the charge-separated transition state, which has a 4-centered, cyclic arrangement of Zn-S-S-S with an estimated dipole moment of 4.2 D. A difference of 4.9 kcal mol(-1) in activation energy would translate to an increase in rate by a factor of about 4000 for zinc-assisted thiol-disulfide exchange. The calculations are consistent with previously reported experimental results, which indicate that metal-thiolate, disulfide exchange rates increase as a function of solvent dielectric. This trend is opposite to that observed for the influence of the dielectric environment on the rate of thiol-disulfide exchange in the absence of metal. The results suggest a dynamic role for zinc in thiol-disulfide exchange reactions, involving accessible cysteine sites on proteins, which may contribute to redox regulation and mechanistic pathways during oxidative stress.

  13. Advantages of chemical exchange-sensitive spin-lock (CESL) over chemical exchange saturation transfer (CEST) for hydroxyl- and amine-water proton exchange studies.

    PubMed

    Jin, Tao; Kim, Seong-Gi

    2014-11-01

    The chemical exchange (CE) rate of endogenous hydroxyl and amine protons with water is often comparable to the difference in their chemical shifts. These intermediate exchange processes have been imaged by the CE saturation transfer (CEST) approach with low-power and long-duration irradiation. However, the sensitivity is not optimal and, more importantly, the signal is contaminated by slow magnetization transfer processes. Here, the properties of CEST signals are compared with those of a CE-sensitive spin-lock (CESL) technique irradiating at the labile proton frequency. First, using a higher power and shorter irradiation in CE-MRI, we obtain: (i) an increased selectivity to faster CE rates via a higher sensitivity to faster CEs and a lower sensitivity to slower CEs and magnetization transfer processes; and (ii) a decreased in vivo asymmetric magnetization transfer contrast measured at ±15 ppm. The sensitivity gain of CESL over CEST is higher for a higher power and shorter irradiation. Unlike CESL, CEST signals oscillate at a very high power and short irradiation. Second, time-dependent CEST and CESL signals are well modeled by analytical solutions of CE-MRI with an asymmetric population approximation, which can be used for quantitative CE-MRI and validated by simulations of Bloch-McConnell equations and phantom experiments. Finally, the in vivo amine-water proton exchange contrast measured at 2.5 ppm with ω1 = 500 Hz is 18% higher in sensitivity for CESL than CEST at 9.4 T. Overall, CESL provides better exchange rate selectivity and sensitivity than CEST; therefore, CESL is more suitable for CE-MRI of intermediate exchange protons.

  14. 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.

  15. 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.

  16. Pulmonary gas exchange and educational level: a community study.

    PubMed

    Welle, I; Eide, G E; Gulsvik, A; Bakke, P S

    2004-04-01

    Socio-economic status (SES) is related to increased risk of airway disease in terms of forced expiratory volume in one second (FEV1) and forced vital capacity. No data are available as to what extent SES predicts alveolar function in a general population. In this cross-sectional study, 1,275 subjects aged 18-73 yrs underwent pulmonary testing, including the single-breath carbon monoxide transfer capacity of the lungs (TL,CO). Educational level was used as an index for SES. Mean +/- SD TL,CO % predicted was 97% among those with primary school education, 99% among those with secondary school education and 104% among those with a university degree. In a multiple linear regression analysis, adjusting for age, height, haemoglobin, carboxyhaemoglobin, smoking habits, occupational exposure, FEV1 and body mass index, TL,CO was significantly related to educational level in males but not in females. Occupational exposure was not significant. In this study, socio-economic status was found to be an independent determinant of TL,CO. Even in an affluent country such as Norway, socio-environmental risk factors may differ based on individuals' SES. Such risk factors may, for instance, be higher exposure to airborne pollutants, poorer housing conditions, or lower consumption of fruit and vegetables. Further exploration is called for.

  17. 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.

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

    PubMed

    Burba, Peter; Van den Bergh, Johan

    2004-03-01

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

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

    NASA Astrophysics Data System (ADS)

    Straus, Rita N.; Jockusch, Rebecca A.

    2017-02-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-03-01

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

  1. 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.

  2. 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.

  3. 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…

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

    ERIC Educational Resources Information Center

    Schuitema, Jaap; Veugelers, Wiel

    2011-01-01

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

  5. 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…

  6. 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.

  7. CFD Simulation Studies on the Performance of Rectangular Coil Heat Exchanger

    NASA Astrophysics Data System (ADS)

    Samsudeen, N.; Anantharaman, N.; Raviraj, Pol.

    2010-10-01

    The simulation studies are made to understand the concept of heat transfer by convection in a rectangular coiled type heat exchanger. The rectangular coil heat exchanger consists of inner and outer coil arrangements with several straight portions and bends so that the exterior flow is very similar to flow within tube-bundles. The present work focuses mainly on exploring the various flow pattern and temperature distribution through the pipe. Computer simulation studies were performed for four different angle of tube bundle inclination (0°, 30°, 60°, and 90°) with two set flow arrangements (inline and staggered arrangement) in the shell side of the heat exchanger. The simulation results show that the effect of the tube bundle inclination on the fluid velocity distribution and the heat transfer performance is observed maximum for the coil with tube bundle inclination angle between 30 degrees and 60 degrees with the staggered arrangement than with the inline arrangement due to proper mixing in the shell side and the outside flow over the tube bundle helps to create turbulence without increasing the velocity in the shell side of the heat exchanger.

  8. Isotopic Studies of Hydrogen and Deuterium Phase IV at Multi-Megabar Pressures

    NASA Astrophysics Data System (ADS)

    Gregoryanz, Eugene; Guillaume, Christophe; Scheler, Thomas; Howie, Ross

    2013-06-01

    The recent discovery of the mixed atomic and molecular phase IV of hydrogen (deuterium) is exemplary of how the studies of hydrogen at multi-megabar pressures is constitutive to the understanding of simple systems at extreme compressions. Through a series of high pressure Raman spectroscopic experiments we have conducted an isotopic comparison between hydrogen and deuterium in phase I. Isotopic studies not only reveal differences in phase stability, imposing constraints on the P-T phase diagram, but also provide strong evidence for structural phenomena, such as proton (deuteron) tunnelling. New data will be presented over a wide temperature range.

  9. Ion-exchange of monovalent and bivalent cations with NaA zeolite membranes : a molecular dynamics study

    NASA Astrophysics Data System (ADS)

    Murad, S.; Jia, W.; Krishnamurthy, M.

    2004-01-01

    Molecular simulations using the method of molecular dynamics have been carried out to study the dynamics and energetics of ion exchanges between monovalent and bivalent cations in supercritical and subcritical (liquid) electrolyte solutions (here Li+, and Ca++ in aqueous solutions of LiCl and CaCl2) and an ion exchange membrane (NaA zeolite) using direct simulations of up to a nanosecond or more. NaA zeolites are widely used in many commercial ion-exchange processes including detergents. Results show that with appropriate driving forces, such ion exchange processes can be clearly witnessed and investigated using molecular simulations at these timescales, especially for supercritical solutions. An attempt is made to understand the phenomenon of ion exchange at the molecular level. Results have shown that the ion-exchange process is primarily energetically driven and entropic forces do not appear to be playing a significant role in the exchanges observed. For supercritical LiCl solutions, small differences were found between the energy of the Li+ inside and outside the membrane. In contrast, for Na+ there was a considerable energetic advantage in being outside the membrane, making the overall exchange process energetically favourable. In subcritical (liquid) LiCl solutions an exchange was found to be more favourable energetically than supercritical solutions. For Ca++ similar trends were observed, except the differences in the energies were much larger (compared to the corresponding Li+ exchanges), making them more energetically efficient, as has also been observed experimentally. In addition to clarifying the molecular basis for these exchanges, simulations can also potentially be very useful to determine the behaviour (e.g. state dependence, etc.) of hydrodynamic parameters commonly used to characterize ion-exchange processes at a fundamental molecular level, and to determine if the hydrodynamic equations used for ion-exchange processes are applicable to nano

  10. 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)

  11. Gas exchange between plant canopies and the atmosphere: Case-studies for ammonia

    NASA Astrophysics Data System (ADS)

    Denmead, O. T.; Freney, J. R.; Dunin, F. X.

    We first present the elements of an inverse Lagrangian model of gas transport in plant canopies. The model allows the inference of sites of gas exchange in the canopy and their source and sink strengths from measured profiles of mean gas concentration and statistics of the canopy turbulence. The practical application of the model is demonstrated through a case study of the fate of ammonia volatilized from fertilizer applied to the floor of a sugarcane crop. Some of the lost ammonia was absorbed by the foliage of the crop; the rest was lost to the atmosphere above. While there was excellent agreement between model predictions of the net flux from the canopy and independent micrometeorological measurements of ammonia flux in the air-layer above it, verification of flux predictions within the canopy was much more difficult. Appeal was made to a process-based model of canopy gas exchange that describes gas transport to and from foliage surfaces in terms of diffusion across aerodynamic, boundary-layer and stomatal resistances in response to a difference in ammonia concentration between the air and leaf sub-stomatal cavities. There was acceptable agreement between the two models in their predictions of foliage ammonia uptake. Next, we apply the process model to a study of the recapture of volatilized ammonia by sugarcane crops with different leaf area indices (LAI). The study indicated recoveries increasing almost linearly with LAI and suggested probable recoveries in excess of 20% for canopies with LAIs of 2 or more. These and other published studies of ammonia exchange between canopy and atmosphere that employed both the inverse Lagrangian and process models suggest that their coupling provides a powerful tool for studying canopy gas exchange.

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

    SciTech Connect

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

    2004-05-01

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

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

    SciTech Connect

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

    2004-05-01

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

  14. 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)

  15. NMR and IR spectroscopic study of proton exchange between o-nitrophenol and methanol in CCl/sub 4/

    SciTech Connect

    Bureiko, S.F.; Golubev, N.S.; Lange, I.Y.

    1982-08-01

    The kinetics of proton exchange in solution between o-nitrophenol and methanol have been studied by dynamic NMR and IR spectroscopy, and a method has been developed for the simultaneous determination of the rate constants for H-H, H-D, and D-H exchange from /sup 1/H NMR spectra.

  16. A Motivation Case Study of English/Japanese Language Exchange Partners Using Computer Mediated Communication and Telecommunication.

    ERIC Educational Resources Information Center

    Long, Robert Harrison

    This case study examines the motivation of two intermediate foreign language learners engaged in a remote language exchange partnership. A learner of English in Japan and a learner of Japanese in Australia completed language exchange activities using the telephone, Internet text chat, and e-mail over 10 weeks. Quantitative and qualitative methods…

  17. Performance of replica-exchange Wang-Landau sampling for the study of spin systems

    NASA Astrophysics Data System (ADS)

    Li, Ying Wai; Eisenbach, Markus; Vogel, Thomas; Wüst, Thomas; Landau, David P.

    2014-03-01

    The recently proposed replica-exchange Wang-Landau sampling (REWL) is a novel, massively parallel Monte Carlo method which allows for the parallelization of Wang-Landau sampling based on a replica-exchange framework. The robustness of the scheme is demonstrated by its broad applicability on a variety of spin systems: from the simplest models with discrete or continuous energy domains, to complex systems captured by large-scale first principles density functional theory calculations. The accuracy of REWL is studied by comparing the thermodynamic properties with exact solutions and results obtained by the original, serial Wang-Landau sampling. The principles for the speed-up, the strong and weak scaling behavior of REWL are also investigated when different parameter settings are employed. We will show, with the aid of selected spin systems, that the method accelerates the simulations significantly with a possible improved accuracy. Phys. Rev. Lett. 110, 210603 (2013)

  18. Optical study of electron-electron exchange interaction in CdTe/ZnTe quantum dots

    NASA Astrophysics Data System (ADS)

    Kazimierczuk, T.; Smoleński, T.; Kobak, J.; Goryca, M.; Pacuski, W.; Golnik, A.; Fronc, K.; Kłopotowski, Ł.; Wojnar, P.; Kossacki, P.

    2013-05-01

    We present an experimental study of electron-electron exchange interaction in self-assembled CdTe/ZnTe quantum dots based on the photoluminescence measurements. The character and strength of this interaction are obtained by simultaneous observation of various recombination channels of a doubly negatively charged exciton X2-, including previously unrecognized emission lines related to the electron-singlet configuration in the final state. A typical value of the electron singlet-triplet splitting, which corresponds to the exchange integral of electron-electron interaction, has been determined as 20.4 meV with a spread of 1.4 meV across the wide population of quantum dots. We also evidence an unexpected decrease of energy difference between the singlet and triplet states under a magnetic field in Faraday geometry.

  19. Germany-US Nuclear Theory Exchange Program for QCD Studies of Hadrons & Nuclei 'GAUSTEQ'

    SciTech Connect

    Dudek, Jozef; Melnitchouk, Wally

    2016-03-07

    GAUSTEQ was a Germany-U.S. exchange program in nuclear theory whose purpose was to focus research efforts on QCD studies of hadrons and nuclei, centered around the current and future research programs of Jefferson Lab and the Gesellschaft fur Schwerionenforschung (GSI) in Germany. GAUSTEQ provided travel support for theoretical physicists at US institutions conducting collaborative research with physicists in Germany. GSI (with its Darmstadt and Helmholtz Institute Mainz braches) served as the German “hub” for visits of U.S. physicists, while Jefferson Lab served as the corresponding “hub” for visits of German physicists visiting U.S. institutions through the reciprocal GUSTEHP (German-US Theory Exchange in Hadron Physics) program. GAUSTEQ was funded by the Office of Nuclear Physics of the U.S. Department of Energy, under Contract No.DE-SC0006758 and officially managed through Old Dominion University in Norfolk, Virginia. The program ran between 2011 and 2015.

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

    NASA Technical Reports Server (NTRS)

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

    1993-01-01

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

  1. Heat transfer enhancement by dynamic corrugated heat exchanger wall: Numerical study

    NASA Astrophysics Data System (ADS)

    Kumar, P.; Schmidmayer, K.; Topin, F.; Miscevic, M.

    2016-09-01

    A new concept of heat exchanger at sub-millimeter scale is proposed for applications in cooling on-board electronics devices, in which the quality of the exchanges between fluid and wall is very critical. In the proposed system, the upper wall of the channel is deformed dynamically to obtain a sinusoidal wave on this surface. The lower wall is exposed to constant heat flux simulating the imprint of an electronic component. A systematic 3-D numerical study in transient regime on the different deformation parameters allowed obtaining both the pumping characteristics and the heat transfer characteristics of the system. It was observed that the dynamic deformation of the wall induces a significant pumping effect. The intensification of the heat transfer is very important even for highly degraded waveforms, although the pumping efficiency is reduced in this case.

  2. 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.

  3. Water exchange in plant tissue studied by proton NMR in the presence of paramagnetic centers.

    PubMed

    Bacić, G; Ratković, S

    1984-04-01

    The proton NMR relaxation of water in maize roots in the presence of paramagnetic centers, Mn2+, Mn- EDTA2 -, and dextran-magnetite was measured. It was shown that the NMR method of Conlon and Outhred (1972, Biochem. Biophys. Acta. 288:354-361) can be applied to a heterogenous multicellular system, and the water exchange time between cortical cells and the extracellular space can be calculated. The water exchange is presumably controlled by the intracellular unstirred layers. The Mn- EDTA2 - complex is a suitable paramagnetic compound for complex tissue, while the application of dextran-magnetite is probably restricted to studies of water exchange in cell suspensions. The water free space of the root and viscosity of the cells cytoplasm was estimated with the use of Mn- EDTA2 -. The convenience of proton NMR for studying the multiphase uptake of paramagnetic ions by plant root as well as their transport to leaves is demonstrated. A simple and rapid NMR technique (spin-echo recovery) for continuous measurement of the uptake process is presented.

  4. Study of a market model with conservative exchanges on complex networks

    NASA Astrophysics Data System (ADS)

    Braunstein, Lidia A.; Macri, Pablo A.; Iglesias, J. R.

    2013-04-01

    Many models of market dynamics make use of the idea of conservative wealth exchanges among economic agents. A few years ago an exchange model using extremal dynamics was developed and a very interesting result was obtained: a self-generated minimum wealth or poverty line. On the other hand, the wealth distribution exhibited an exponential shape as a function of the square of the wealth. These results have been obtained both considering exchanges between nearest neighbors or in a mean field scheme. In the present paper we study the effect of distributing the agents on a complex network. We have considered archetypical complex networks: Erdös-Rényi random networks and scale-free networks. The presence of a poverty line with finite wealth is preserved but spatial correlations are important, particularly between the degree of the node and the wealth. We present a detailed study of the correlations, as well as the changes in the Gini coefficient, that measures the inequality, as a function of the type and average degree of the considered networks.

  5. Microcalorimetric study of adsorption of glycomacropeptide on anion-exchange chromatography adsorbent.

    PubMed

    Lira, Rafael A; Minim, Luis A; Bonomo, Renata C F; Minim, Valéria P R; da Silva, Luis H M; da Silva, Maria C H

    2009-05-15

    The adsorption of glycomacropeptide (GMP) from cheese whey on an anion-exchange adsorbent was investigated using isothermal titration microcalorimetry to measure thermodynamic information regarding such processes. Isotherms data were measured at temperatures of 25 and 45 degrees C, pH 8.2 and various ionic strengths (0-0.08 molL(-1) NaCl). The equilibrium data were fit using the Langmuir model and the process was observed to be reversible. Temperature was observed to positively affect the interaction of the protein and adsorbent. Microcalorimetric studies indicated endothermic adsorption enthalpy in all cases, except at 45 degrees C and 0.0 molL(-1) NaCl. The adsorption process was observed to be entropically driven at all conditions studied. It was concluded that the increase in entropy, attributed to the release of hydration waters as well as bounded ions from the adsorbent and protein surface due to interactions of the protein and adsorbent, was a major driving force for the adsorption of GMP on the anion-exchange adsorbent. These results could allow for design of more effective ion-exchange separation processes for proteins.

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

    SciTech Connect

    Place, B.G.

    1990-09-01

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

  7. 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

  8. Computer fluid dynamics (CFD) study of a plate heat exchanger working with nanofluids

    NASA Astrophysics Data System (ADS)

    Stan, Liviu-Constantin; Cǎlimǎnescu, Ioan

    2016-12-01

    The industry fosters many types of heat exchangers such double pipe or plate heat exchangers (HX), but lately the plate HX are gaining the high ground in many applications. Such a plate HX is made out of serial plate modules packed together allowing the warm and cold fluids to pass through and exchange the heat. The paper is demonstrating the functioning of a medium sized plate HX functioning with 10% Al2O3 and water nanofluids flowing in both cold and warm sides of the HX. The influence of the nanofluid properties will be investigated as impact upon the outlet temperature of the fluid leaving the HX. Using the RSM methodology. The main conclusion of this study is that there is a balance between the nanofluids increased conductivity and their increased viscosity. The nanofluids are working well for those applications where the flow is not impeded by narrow fluid passages where the bigger influence of the viscosity is actually worsening the heat transfer conditions instead of increasing it, since the influence of viscosity in that kind of applications is three time bigger. A nanofluid conductivity threshold was also detected over which the nanofluids say with 15$ or 20% alumina content is useless for the overall heat transfer conditions.

  9. Kinetic study of the mass transfer of bovine serum albumin in anion-exchange chromatography.

    PubMed

    Miyabe, K; Guiochon, G

    2000-01-14

    A kinetic study was made on the mass transfer phenomena of bovine serum albumin (BSA) in two different anion-exchange columns (Resource-Q and TSK-GEL-DEAE-5PW). The analysis of the concentration dependence of the lumped mass transfer rate coefficient (km,L) provided the information about the kinetics of the several mass transfer processes in the columns and the anion exchangers, i.e., the axial dispersion, the fluid-to-particle mass transfer, the intraparticle diffusion, and the adsorption/desorption. In the Resource-Q column, the intraparticle diffusion had a dominant contribution to the band broadening compared with those of the other processes. The surface diffusion coefficient (Ds) of BSA showed a positive concentration dependence, by which the linear dependence of km,L on the BSA concentration seemed to be interpreted. On the other hand, in the TSK-GEL-DEAE-5PW column, the contribution of the adsorption/desorption was also important and almost same as that due to the intraparticle diffusion. There are some differences between the intrinsic properties of the mass transfer kinetics inside the two anion exchangers. It was likely that the positive concentration dependence of Ds was explained by the heterogeneous surface model.

  10. Study of heat exchange in cooling systems of heat-stressed structures

    NASA Astrophysics Data System (ADS)

    Vikulin, A. V.; Yaroslavtsev, N. L.; Zemlyanaya, V. A.

    2017-01-01

    Increasing working parameters of the cycle of gas-turbine engines, complicating design of gas-turbine plants, as well as growing aerodynamic, thermal, static, and dynamic loads, necessitate the development of promising cooling systems for heat-stressed structures. This work is devoted to an experimental study of heat exchange in ducts equipped with systems of inclined and cross walls (fins). It has been found that an increase in the Reynolds number Re from 3000 to 20000 leads to a decrease in the heat exchange, which is characterized by the relative Nusselt number overline{Nu}, by 19-30% at the angle of inclination of the walls φ = 0, 40°, 50°, and 90° if the length of the walls x w is comparable to the spacing b s and by 12-15% at φ = 30° and 90° if x w ≫ b s. If cross walls are used in cooling ducts, the length of the walls x w plays the governing role; an increase in this characteristic from 1.22 × 10-3 to 3.14 × 10-3 m leads to an increase in the intensity of heat exchange by 30-40% and to a decrease in the capacity of the entire system of the walls. It has been shown that, on surfaces with wavy fins, the intensity of heat exchange is closest to that determined in the models under study. For example, values of the Colborne criterion StPr2/3 for ducts equipped with wavy fins and for the models under study differ only slightly (by 2-20% depending on the value of the angle φ). However, the difference for surfaces with short plate fins and ducts equipped with inclined walls is high (30-40%). This is due to the design features of these surfaces and to the severe effect of the inlet portion on heat exchange, since the surfaces are characterized by a higher ratio of the duct length to the hydraulic diameter L/d h at small fin thicknesses ((0.1-0.15) × 10-3 m). The experimental results can be used in developing designs of nozzle and rotor blades of high-temperature gas turbines in gas-turbine engines and plants.

  11. 1H NMR studies of substrate hydrogen exchange reactions catalyzed by L-methionine gamma-lyase.

    PubMed

    Esaki, N; Nakayama, T; Sawada, S; Tanaka, H; Soda, K

    1985-07-16

    Hydrogen exchange reactions of various L-amino acids catalyzed by L-methionine gamma-lyase (EC 4.4.1.11) have been studied. The enzyme catalyzes the rapid exchange of the alpha- and beta-hydrogens of L-methionine and S-methyl-L-cysteine with deuterium from the solvent. The rate of alpha-hydrogen exchange was about 40 times faster than that of the enzymatic elimination reaction of the sulfur-containing amino acids. The enzyme also catalyzes the exchange reaction of alpha- and beta-hydrogens of the following straight-chain L-amino acids which are not susceptible to elimination: norleucine, norvaline, alpha-aminobutyrate, and alanine. The exchange rates of the alpha-hydrogen and the total beta-hydrogens of L-alanine and L-alpha-aminobutyrate with deuterium followed first-order kinetics. For L-norvaline, L-norleucine, S-methyl-L-cysteine, and L-methionine, the rate of alpha-hydrogen exchange followed first-order kinetics, but the rate of total beta-hydrogen exchange decreased due to a primary isotope effect at the alpha-position. One beta-hydrogen of S-methyl-L-cysteine was exchanged faster than the other, although both the beta-hydrogens were exchanged completely with deuterium ultimately. L-Phenylalanine and L-tryptophan slowly underwent alpha-hydrogen exchange. The pro-R hydrogen of glycine was deuterated stereospecifically. None of the following amino acids were susceptible to the enzymatic hydrogen exchange: D isomers of the above amino acids, branched chain L-amino acids, acidic L-amino acids, and basic L-amino acids.(ABSTRACT TRUNCATED AT 250 WORDS)

  12. Exchange frequency in replica exchange molecular dynamics

    NASA Astrophysics Data System (ADS)

    Sindhikara, Daniel; Meng, Yilin; Roitberg, Adrian E.

    2008-01-01

    The effect of the exchange-attempt frequency on sampling efficiency is studied in replica exchange molecular dynamics (REMD). We show that sampling efficiency increases with increasing exchange-attempt frequency. This conclusion is contrary to a commonly expressed view in REMD. Five peptides (1-21 residues long) are studied with a spectrum of exchange-attempt rates. Convergence rates are gauged by comparing ensemble properties between fixed length test REMD simulations and longer reference simulations. To show the fundamental correlation between exchange frequency and convergence time, a simple model is designed and studied, displaying the same basic behavior of much more complex systems.

  13. Improving community health through marketing exchanges: A participatory action research study on water, sanitation, and hygiene in three Melanesian countries.

    PubMed

    Barrington, D J; Sridharan, S; Saunders, S G; Souter, R T; Bartram, J; Shields, K F; Meo, S; Kearton, A; Hughes, R K

    2016-12-01

    Diseases related to poor water, sanitation and hygiene (WaSH) are major causes of mortality and morbidity. While pursuing marketing approaches to WaSH to improve health outcomes is often narrowly associated with monetary exchange, marketing theory recognises four broad marketing exchange archetypes: market-based, non-market-based, command-based and culturally determined. This diversity reflects the need for parameters broader than monetary exchange when improving WaSH. This study applied a participatory action research process to investigate how impoverished communities in Melanesian urban and peri-urban informal settlements attempt to meet their WaSH needs through marketing exchange. Exchanges of all four archetypes were present, often in combination. Motivations for participating in the marketing exchanges were based on social relationships alongside WaSH needs, health aspirations and financial circumstances. By leveraging these motivations and pre-existing, self-determined marketing exchanges, WaSH practitioners may be able to foster WaSH marketing exchanges consistent with local context and capabilities, in turn improving community physical, mental and social health.

  14. Ric-8A, a G protein chaperone with nucleotide exchange activity induces long-range secondary structure changes in Gα

    PubMed Central

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

    2016-01-01

    Cytosolic Ric-8A has guanine nucleotide exchange factor (GEF) activity and is a chaperone for several classes of heterotrimeric G protein α subunits in vertebrates. Using Hydrogen-Deuterium Exchange-Mass Spectrometry (HDX-MS) we show that Ric-8A disrupts the secondary structure of the Gα Ras-like domain that girds the guanine nucleotide-binding site, and destabilizes the interface between the Gαi1 Ras and helical domains, allowing domain separation and nucleotide release. These changes are largely reversed upon binding GTP and dissociation of Ric-8A. HDX-MS identifies a potential Gα interaction site in Ric-8A. Alanine scanning reveals residues crucial for GEF activity within that sequence. HDX confirms that, like G protein-coupled receptors (GPCRs), Ric-8A binds the C-terminus of Gα. In contrast to GPCRs, Ric-8A interacts with Switches I and II of Gα and possibly at the Gα domain interface. These extensive interactions provide both allosteric and direct catalysis of GDP unbinding and release and GTP binding. DOI: http://dx.doi.org/10.7554/eLife.19238.001 PMID:28008853

  15. Ric-8A, a G protein chaperone with nucleotide exchange activity induces long-range secondary structure changes in Gα.

    PubMed

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

    2016-12-23

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

  16. A two-process model describes the hydrogen exchange behavior of cytochrome c in the molten globule state with various extents of acetylation.

    PubMed

    Szewczuk, Z; Konishi, Y; Goto, Y

    2001-08-14

    Acetylation of Lys residues of horse cytochrome c steadily stabilizes the molten globule state in 18 mM HCl as more Lys residues are acetylated [Goto and Nishikiori (1991) J. Mol. Biol. 222, 679-686]. The dynamic features of the molten globule state were characterized by hydrogen/deuterium exchange of amide protons, monitored by mass spectrometry as each deuteration increased the protein mass by 1 Da. Electrospray mass spectrometry enabled us to monitor simultaneously the exchange kinetics of more than seven species with a different number of acetyl groups. One to four Lys residue-acetylated cytochrome c showed almost no protection of the amide protons from rapid exchange. The transition from the unprotected to the protected state occurred between five and eight Lys residue-acetylated species. For species with more than nine acetylated Lys residues, the exchange kinetics were independent of the extent of acetylation, and 26 amide protons were protected at 60 min of exchange, indicating the formation of a rigid hydrophobic core with hydrogen-bonded secondary structures. The apparent transition to the protected state required a higher degree of acetylation than the conformational transition measured by circular dichroism, which had a midpoint at about four acetylated residues. This difference in the transitions suggested a two-process model in which the exchange occurs either from the protected folded state or from the unprotected unfolded state through global unfolding. On the basis of a two-process model and with the reported values of the exchange and stability parameters, we simulated the exchange kinetics of a series of acetylated cytochrome c species. The simulated kinetics reproduced the observed kinetics well, indicating validity of this model for hydrogen exchange of the molten globule state.

  17. Study of Double Pomeron Exchange with the SFM detector at the CERN ISR

    NASA Astrophysics Data System (ADS)

    Fischer, H. G.; Geist, W.; Makariev, M.

    2014-11-01

    Selected results from the study of Double Pomeron Exchange with the Split Field Magnet detector at the CERN Intersecting Storage Rings are presented. This concerns various general features of central pionic systems as well as the spectroscopy in the π+π- channel, emphasizing the production properties of the f2(1270) meson. This summary refers to a series of publications over a time span of 17 years based on the work of the CCHK1,2 and ABCDHW3-7 collaborations at the CERN ISR.

  18. Experimental study of the Kirchhoff-Law-Johnson-Noise secure key exchange

    NASA Astrophysics Data System (ADS)

    Mingesz, Robert

    2014-09-01

    The Kirchhoff-Law-Johnson-Noise (KLJN) secure key distribution system provides a way of exchanging secure keys by using classical physics (electricity and thermodynamics). Several theoretical studies have addressed the performance and applicability of the communication protocol, and they have indicated that it is protected against all known types of attacks. However, until now, there have been very few real physical implementations and experimental tests of the protocol. With our work, we continue filling this gap. Details of implementing a KLJN based system are presented using a dedicated hardware and an off-the-shelf solution as well. Furthermore, the results of experimental tests and analysis of the performance will be presented.

  19. First-principles study of exchange interactions of yttrium iron garnet

    NASA Astrophysics Data System (ADS)

    Xie, Li-Shan; Jin, Guang-Xi; He, Lixin; Bauer, Gerrit E. W.; Barker, Joseph; Xia, Ke

    2017-01-01

    Yttrium iron garnet is the ubiquitous magnetic insulator used for studying pure spin currents. The exchange constants reported in the literature vary considerably between different experiments and fitting procedures. Here we calculate them from first principles. The local Coulomb correction (U -J ) of density-functional theory is chosen such that the parametrized spin model reproduces the experimental Curie temperature and a large electronic band gap, ensuring an insulating phase. The magnon spectrum calculated with our parameters agrees reasonably well with that measured by neutron scattering. A residual disagreement about the frequencies of optical modes indicates the limits of the present methodology.

  20. Anion-exchange method for determination of phytate in foods: collaborative study.

    PubMed

    Harland, B F; Oberleas, D

    1986-01-01

    Phytate, a naturally occurring organic compound found in plant seeds, roots, and tubers, was determined in a collaborative study using a modified anion-exchange method. Seven samples (peanut flour, oats, rice, isolated soybean protein, a vegetarian diet composite, wheat bran, and whole wheat bread), supplied as blind duplicate samples, were analyzed in triplicate by 7 collaborators. Phytate concentrations in the samples ranged from 2.38 to 46.70 mg/g. Relative standard deviations (RSD = CV) for repeatability ranged from 2.5 to 10.1%, and for reproducibility, from 4.5 to 11.0%. The method has been adopted official first action.

  1. Use of micrometeorological techniques to study the isotopic exchange in ecosystems

    NASA Astrophysics Data System (ADS)

    Santos, E.; Wagner-Riddle, C.; Brown, S. E.; Stropes, K.

    2015-12-01

    The combination of micrometeorological techniques with high frequency concentration measurements of stable isotopes are a powerful tool to study the temporal dynamics of isotope signatures at the ecosystem level. The objective of this study was to study the isotopic composition of the net CO2 exchange (NEE) above and with corn and tall grass canopies. Profiles of stable isotopes of CO2 (12C-CO2, 13C-CO2 and 18O-CO2) were measured using tunable diode laser trace gas analyzers and multiport sampling systems in corn (12C-CO2 and 13C-CO2, only) and tall grass canopies. These measurements were combined with the flux gradient method and Lagrangian dispersion analysis to estimate the isotopic signatures of the net CO2 flux. The use of a gradient of a concentration threshold to screen half hourly period improved the estimates of flux signatures by the isotope flux ratio approach. The Langrangian dispersion analysis and the isotope flux ratio method estimates showed good agreement above the corn canopy, indicating that the former method can be a viable alternative to study the isotopic exchange within plant canopies. The 13CO2 composition of NEE showed a downward trend near the end of the growing season, which may be related to a reduction of autotrophic respiration in the soil.

  2. Photoluminescence Studies of Silver-Exchanged Cadmium Selenide Crystals. Modification of a Chemical Sensor for Aniline Derivatives by Heterojunction Formation

    DTIC Science & Technology

    1991-05-20

    Photoluminescence Studies of Silver-Exchanged Cadmium Selenide Crystals. Modification of a Chemical Sensor for Aniline Derivatives by Heterojunction...I__I 413r005 1 7TT..E (include Security Classification,) Photoluminescence Studies of Silver-Exchanged Cadmium Selenide Crystals. Moifification of a...Physical Chemistry 7 CO)SA7! CODES !8 S8.BECT TERMS Continue on reverse it. necessary and identity oy block nu’noer) Z.ELD CROUP SuB-GROUP cadmium

  3. Study of a class of Landau-Lifshitz equations of ferromagnetism without exchange energy

    NASA Astrophysics Data System (ADS)

    Deng, Wei

    Landau-Lifshitz equations of ferromagnetism, which are based on several competing energy contributions, are important mathematical models for the evolution of magnetization field m of a ferromagnetic material. Many problems, such as existence, stability, regularity, asymptotic behavior, thin-film limit and numerical computation, have been well studied for the Landau-Lifshitz equations that include the so-called exchange energy. However, these problems turn out to be quite challenging for equations without the exchange energy. The main reason is that when the exchange energy is included, one automatically has the magnetization vector m ∈ L ∞((0,∞); H1(Ω)) from energy estimates, which gives some compactness and stability that are needed for using the standard methods; however, in the cases without the exchange energy, one only has m ∈ L∞ ((0, ∞); L∞(Ω)), which is too rough to get the needed compactness and stability. In this thesis, we investigate some problems for models of reduced Landau-Lifshitz equations with no-exchange energy. In Chapter 1, we introduce the Landau-Lifshitz theory of ferromagnetism and summarize the main results of the thesis. The readers can check out the main results quickly in this chapter and then go to the corresponding chapters for details of proof, more discussions and further references. In Chapter 2, we study the quasi-stationary limit of a simple Landau-Lifshitz-Maxwell system with the permittivity parameter ɛ approaching zero and, using this quasi-stationary limit, establish the existence of global weak solutions to the reduced Landau-Lifshitz equations with initial value m0∈ L∞(Ω). In Chapter 3, we establish a local L2-stability theorem for the global weak solutions in finite time. The key in the proof of stability theorem is that we split the nonlocal term H m into two parts: one is bounded in L ∞(Ω) and the other bounded in L 2(Ω). Using this stability theorem, we also provide another proof for the

  4. Study of cation-exchange capacity of soil near fluorspar mining with special reference to Kadipani mine (Gujarat, India).

    PubMed

    Pradhan, Alka; Deshmukh, Jitendra P

    2011-10-01

    One of the important functions of soil is exchange of cations, whereby essential trace metals are made available to plants as nutrients. Both minerals and organics fractions of soil exchange the cations. Clay minerals exchange cation because of the presence of negatively charged sites on the mineral while organic materials exchange cations by means of their carboxylate groups and other basic functional groups. Cation exchange in soil provides trace metal nutrients to plant. The metal ions are taken up by the roots while H+ is exchanged for the metal ions. Therefore, the measurement of Cation Exchange Capacity (CEC) of soil is important and this becomes more significant when the mining activity is carried out in the surrounding environment as mining activity may adversely impact the soil texture and organic matter content and sometimes changes the pH which is the main regulator of CEC in soil. The studies related to the assessment of CEC of soil were carried out. 14 soil samples, including one sample of mine site, were collected during summer season from different villages within 10 km radius from the mine site. These samples were then analyzed. The efforts were made to establish the CEC of soil quality of Kadipani, Distt. Vadodara, Gujarat, India. This study is useful for making the decisions regarding the environmental measures required for mining activity.

  5. 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.

    2016-12-01

    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.

  6. 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.

  7. Gas exchange in fruits related to skin condition and fruit ripening studied with diode laser spectroscopy

    NASA Astrophysics Data System (ADS)

    Huang, Jing; Zhang, Hao; Lin, Huiying; Li, Tianqi; Mei, Liang; Svanberg, Katarina; Svanberg, Sune

    2016-12-01

    The concentration of the biologically active molecular oxygen gas is of crucial importance for fruits in the metabolic respiration, maturation, and ripening processes. In our study, oxygen content and oxygen transport in fruits, exemplified by apples and guavas, were studied noninvasively by gas in scattering media absorption spectroscopy. The technique is based on the fact that free gases typically have 10,000 times narrower absorption features than the bulk material. The technique was demonstrated in studies of the influence of the fruit skin in regulating the internal oxygen balance, by observing the signal response of the internal oxygen gas to a transient change in the ambient gas concentration on peeled and unpeeled fruits. In addition, the gas exchange rate at different ripening stages was also studied in intact guavas.

  8. Integration of computational modeling with membrane transport studies reveals new insights into amino acid exchange transport mechanisms.

    PubMed

    Widdows, Kate L; Panitchob, Nuttanont; Crocker, Ian P; Please, Colin P; Hanson, Mark A; Sibley, Colin P; Johnstone, Edward D; Sengers, Bram G; Lewis, Rohan M; Glazier, Jocelyn D

    2015-06-01

    Uptake of system L amino acid substrates into isolated placental plasma membrane vesicles in the absence of opposing side amino acid (zero-trans uptake) is incompatible with the concept of obligatory exchange, where influx of amino acid is coupled to efflux. We therefore hypothesized that system L amino acid exchange transporters are not fully obligatory and/or that amino acids are initially present inside the vesicles. To address this, we combined computational modeling with vesicle transport assays and transporter localization studies to investigate the mechanisms mediating [(14)C]L-serine (a system L substrate) transport into human placental microvillous plasma membrane (MVM) vesicles. The carrier model provided a quantitative framework to test the 2 hypotheses that l-serine transport occurs by either obligate exchange or nonobligate exchange coupled with facilitated transport (mixed transport model). The computational model could only account for experimental [(14)C]L-serine uptake data when the transporter was not exclusively in exchange mode, best described by the mixed transport model. MVM vesicle isolates contained endogenous amino acids allowing for potential contribution to zero-trans uptake. Both L-type amino acid transporter (LAT)1 and LAT2 subtypes of system L were distributed to MVM, with L-serine transport attributed to LAT2. These findings suggest that exchange transporters do not function exclusively as obligate exchangers.

  9. Quantum Chemical Study of the Water Exchange Mechanism of the Americyl(VI) Aqua Ion.

    PubMed

    Fabrizio, Alberto; Rotzinger, François P

    2016-11-07

    The water exchange reaction of the americyl(VI) aqua ion was investigated with quantum chemical methods, density functional theory (DFT), and wave function theory (WFT). Associative and dissociative substitution mechanisms were studied, whereby DFT produced inaccurate results for the associative mechanism in contrast to WFT. The Gibbs activation energies (ΔG(‡)) for the dissociative (D) and the associative interchange (Ia) mechanisms, computed with WFT taking into account static and dynamic electron correlation, near-degeneracy, and spin-orbit coupling, are equal within the error limits of the calculations. ΔG(‡) for the water exchange of americyl(VI) via the dissociative mechanism is considerably lower than those for uranyl(VI) and plutonyl(VI) (for which the Ia mechanism is preferred) due to ligand-field effects. On the basis of the present computations, it is not possible to distinguish the Ia from the D mechanism for americyl(VI). In contrast to two other theoretical studies, the dissociative mechanism cannot be ruled out.

  10. 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.

  11. The results of therapeutic plasma exchange in patients with severe hyperthyroidism: a retrospective multicenter study.

    PubMed

    Keklik, Muzaffer; Kaynar, Leylagul; Yilmaz, Mehmet; Sivgin, Serdar; Solmaz, Musa; Pala, Cigdem; Aribas, Sulbiye; Akyol, Gulsah; Unluhizarci, Kursat; Cetin, Mustafa; Eser, Bulent; Unal, Ali

    2013-06-01

    Hyperthyroidism characterized by elevated serum levels of circulating thyroid hormones. The aim of hyperthyroidism treatment is to achieve a euthyroid state as soon as possible and to maintain euthyroid status. However, drug withdrawal and utilization of alternative therapies are needed in cases in which leucopenia or impairment in liver functions is observed during medical therapy. In the present study, we aimed to present our cases which underwent therapeutic plasma exchange (TPE) due to severe hyperthyroidism. The results of 22 patients who underwent therapeutic plasma exchange due to hyperthyroidism in Apheresis Units of Erciyes University and Gaziantep University, between 2006 and 2012, were retrospectively reviewed. These cases had severe thyrotoxic values despite anti-thyroid drug use. After TPE, we observed a significant decrease in free thyroxin (FT4) (p<0.001) and free triiodotyhronin (FT3) (p<0.004) levels. There was statistically significant increase in the mean values of TSH levels after TPE (p<0.001). Clinical improvement was achieved in hyperthyroidism by TPE in 20 cases (91%). Both FT3 and FT4 levels remained above the normal limits in two of 22 patients. TPE should be considered as an effective and safe therapeutic option to achieve euthyroid state before surgery or radioactive iodine treatment. TPE is a useful option in cases with severe hyperthyroidism unresponsive to anti-thyroid agents and in those with clinical manifestations of cardiac failure and in patients with severe adverse events during anti-thyroid therapy.

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. Defect-tuning exchange bias of ferromagnet/antiferromagnet core/shell nanoparticles by numerical study.

    PubMed

    Mao, Zhongquan; Zhan, Xiaozhi; Chen, Xi

    2012-07-11

    The influence of non-magnetic defects on the exchange bias (EB) of ferromagnet (FM)/antiferromagnet (AFM) core/shell nanoparticles is studied by Monte Carlo simulations. It is found that the EB can be tuned by defects in different positions. Defects at both the AFM and FM interfaces reduce the EB field while they enhance the coercive field by decreasing the effective interface coupling. However, the EB field and the coercive field show respectively a non-monotonic and a monotonic dependence on the defect concentration when the defects are located inside the AFM shell, indicating a similar microscopic mechanism to that proposed in the domain state model. These results suggest a way to optimize the EB effect for applications.

  20. Folding analysis of hormonal polypeptide calcitonins and the oxidized calcitonins using electrospray ionization mass spectrometry combined with H/D exchange.

    PubMed

    Nabuchi, Yoshiaki; Asoh, Yoshinori; Takayama, Mitsuo

    2004-11-01

    Conformational change of calcitonins has been examined by measuring the rate of hydrogen/deuterium (H/D) exchange in amino acids. Time dependent m/z shift caused by H/D exchange was monitored by electrospray ionization quadrupole ion trap mass spectrometry (ESI-QIT MS). The rate constants of H/D exchange were calculated from apparent first-order kinetics. The time course of H/D exchange exhibited two phases of faster and slower exchange. The smaller rate constant (k2) estimated from the slower H/D exchange was correlated with an alpha-helix content that reflected the folding state. The order of k2 values obtained for human calcitonin (hCT), porcine calcitonin (pCT), salmon calcitonin (sCT), and elcatonin (ECT) was hCT > pCT approximately sCT > ECT. Although the amino acid sequence of sCT is similar to that of ECT, their k2 values were considerably different. The results suggest that ECT is relatively rigid on the N-terminal side cyclic structure in the folded state. Further, the effect of methionine oxidation on k2 has been examined. In the oxidized pCT that possesses similar biological activity with the intact pCT, the k2 values obtained were nearly equal. The k2 of hCT increased via methionine oxidation, and the biological activity was weakened by oxidation. This suggested that methionine oxidation of hCT produced unfolding in the secondary structure and that oxidative unfolding of hCT led to the loss of biological activity. The results indicate that the H/D exchange rate constant may be used as an informative parameter to elucidate the relationship between the folded state and biological activity of polypeptides like calcitonins with secondary structure.

  1. 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.

  2. Studies on the batch adsorption of plasmid DNA onto anion-exchange chromatographic supports.

    PubMed

    Ferreira, G N; Cabral, J M; Prazeres, D M

    2000-01-01

    The adsorption of a supercoiled 4.8 kbp plasmid onto quaternary ammonium anion-exchangers was studied in a finite bath. Equilibrium experiments were performed with pure plasmid, at 25 degrees C, using commercial Q-Sepharose matrices differing in particle diameter (High Performance, 34 microm; Fast Flow, 90 microm; and Big Beads, 200 microm) and a recently commercialized ion-exchanger, Streamline QXL (d(p) = 200 microm) at different salt concentrations (0.5, 0.7, and 1 M NaCl). Plasmid adsorption was found to follow second-order kinetics (Langmuir isotherm) with average association constants K(A) = 0.32+/-0.12 mL microg(-)(1) and K(A) = 0.25+/-0.15 mL microg(-1) at 0.5 and 0.7 M Nacl, respectively. The maximum binding capacities were not dependent on the ionic strength in the range 0.5-0.7 M but decreased with increasing particle diameter, suggesting that adsorption mainly occurs at the surface of the particles. No adsorption was found at 1 M NaCl. A nonporous model was applied to describe the uptake rate of plasmid onto Streamline QXL at 0.5 M NaCl. The overall process rate was controlled by mass transfer in the regions of low relative amounts of adsorbent (initial stages) and kinetically controlled in the later stages of the process for high relative amounts of adsorbent. The forward reaction rate constant (k(1) = 0.09+/-0.01 mL mg(-1) s(-1)) and film mass transfer coefficient (K(f) = (6 +/- 2) x 10(-4) cm s(-1)) were calculated. Simulations were performed to study the effect of the relative amount of adsorbent on the overall process rate, yield, and media capacity utilization.

  3. Kafirin adsorption on ion-exchange resins: isotherm and kinetic studies.

    PubMed

    Kumar, Prashant; Lau, Pei Wen; Kale, Sandeep; Johnson, Stuart; Pareek, Vishnu; Utikar, Ranjeet; Lali, Arvind

    2014-08-22

    Kafirin is a natural, hydrophobic and celiac safe prolamin protein obtained from sorghum seeds. Today kafirin is found to be useful in designing delayed delivery systems and coatings of pharmaceuticals and nutraceuticals where its purity is important and this can be obtained by adsorptive chromatography. This study is the first scientific insight into the isotherm and kinetic studies of kafirin adsorption on anion- and cation-exchange resins for practical applications in preparative scale chromatography. Adsorption isotherms of kafirin were determined for five anion- and two cation-exchange resins in batch systems. Isotherm parameters such as maximum binding capacity and dissociation constant were determined from Langmuir isotherm, and adsorptive capacity and affinity constant from Freundlich isotherm. Langmuir isotherm was found to fit the adsorption equilibrium data well. Batch uptake kinetics for kafirin adsorption on these resins was also carried out and critical parameters including the diffusion coefficient, film mass transfer coefficient, and Biot number for film-pore diffusion model were calculated. Both the isotherm and the kinetic parameters were considered for selection of appropriate resin for kafirin purification. UNOsphere Q (78.26 mg/ml) and Toyopearl SP-650M (57.4 mg/ml) were found to offer better kafirin binding capacities and interaction strength with excellent uptake kinetics under moderate operating conditions. With these adsorbents, film diffusion resistance was found to be major governing factor for adsorption (Bi<10 and δ<1). Based on designer objective function, UNOsphere Q was found be best adsorbent for binding of kafirin. The data presented is valuable for designing large scale preparative adsorptive chromatographic kafirin purification systems.

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

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

    It is generally believed that the presence of a fluid phase enhances the reactivity of minerals and promotes exchange reactions between minerals that are physically separated from each other. Two end-member mechanisms can be considered for the bulk equilibration of the mineral with the fluid: volume diffusion and dissolution-precipitation. A key parameter, which may control the overall kinetic behavior, is the solubility of the relevant elements within the fluid (e.g., [1]). We investigated the reaction mechanism of a model system to identify the role of the various parameters, in particular those controlling the solubility. Two polished spinel crystals (hercynite with xFe=0.6 and synthetic Mg-spinel) react in the presence of H2O at 750 °C and 0.2 GPa in a welded-shut Au-capsule for 1-24 hrs. The crystals are physically separated by a tube of noble metal dividing the capsule into two connected chambers. The surface of the reacted crystals is analyzed using optical methods and SEM and the near surface chemistry is studied via RBS. From the latter we are able to extract Fe-concentration depth profiles. First results show an increasing surface concentration of Fe in Mg-spinel with time. The depth profiles for experiments up to 8 hours reveal a decrease of Fe-concentration within the first 100 nm from the surface towards the center of the Mg-spinel. The Fe depth profiles can be simulated with a simplified diffusion model, assuming a fixed surface concentration and their shapes indicate that the inter-diffusion coefficient in spinel is concentration dependent. Our derived Fe-Mg diffusion coefficient [D(Fe-Mg) ≈ 1x10-19 m2/s for pure MgAl2O4) and its compositional dependence is consistent with an independent experimental study using thin film diffusion couples that were annealed at dry conditions at 1 atm [2]. The observed kinetic behavior of the experimental system was simulated using the model of [1]. The model geometry is identical to the present experimental setup

  5. Study of plasma off-gas treatment from spent ion exchange resin pyrolysis.

    PubMed

    Castro, Hernán Ariel; Luca, Vittorio; Banchi, Hugo Luis

    2017-03-23

    Polystyrene divinylbenzene-based ion exchange resins are employed extensively within nuclear power plants (NPPs) and research reactors for purification and chemical control of the cooling water system. To maintain the highest possible water quality, the resins are regularly replaced as they become contaminated with a range of isotopes derived from compromised fuel elements as well as corrosion and activation products including (14)C, (60)Co, (90)Sr, (129)I, and (137)Cs. Such spent resins constitute a major proportion (in volume terms) of the solid radioactive waste generated by the nuclear industry. Several treatment and conditioning techniques have been developed with a view toward reducing the spent resin volume and generating a stable waste product suitable for long-term storage and disposal. Between them, pyrolysis emerges as an attractive option. Previous work of our group suggests that the pyrolysis treatment of the resins at low temperatures between 300 and 350 °C resulted in a stable waste product with a significant volume reduction (>50%) and characteristics suitable for long-term storage and/or disposal. However, another important issue to take into account is the complexity of the off-gas generated during the process and the different technical alternatives for its conditioning. Ongoing work addresses the characterization of the ion exchange resin treatment's off-gas. Additionally, the application of plasma technology for the treatment of the off-gas current was studied as an alternative to more conventional processes utilizing oil- or gas-fired post-combustion chambers operating at temperatures in excess of 1000 °C. A laboratory-scale flow reactor, using inductively coupled plasma, operating under sub-atmospheric conditions was developed. Fundamental experiments using model compounds have been performed, demonstrating a high destruction and removal ratio (>99.99%) for different reaction media, at low reactor temperatures and moderate power

  6. 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…

  7. 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…

  8. Coarse-Grained Conformational Sampling of Protein Structure Improves the Fit to Experimental Hydrogen-Exchange Data

    PubMed Central

    Devaurs, Didier; Antunes, Dinler A.; Papanastasiou, Malvina; Moll, Mark; Ricklin, Daniel; Lambris, John D.; Kavraki, Lydia E.

    2017-01-01

    Monitoring hydrogen/deuterium exchange (HDX) undergone by a protein in solution produces experimental data that translates into valuable information about the protein's structure. Data produced by HDX experiments is often interpreted using a crystal structure of the protein, when available. However, it has been shown that the correspondence between experimental HDX data and crystal structures is often not satisfactory. This creates difficulties when trying to perform a structural analysis of the HDX data. In this paper, we evaluate several strategies to obtain a conformation providing a good fit to the experimental HDX data, which is a premise of an accurate structural analysis. We show that performing molecular dynamics simulations can be inadequate to obtain such conformations, and we propose a novel methodology involving a coarse-grained conformational sampling approach instead. By extensively exploring the intrinsic flexibility of a protein with this approach, we produce a conformational ensemble from which we extract a single conformation providing a good fit to the experimental HDX data. We successfully demonstrate the applicability of our method to four small and medium-sized proteins. PMID:28344973

  9. 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.

  10. 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.

  11. Process Model for Studying Regional 13C Stable Isotope Exchange between Vegetation and Atmosphere

    NASA Astrophysics Data System (ADS)

    Chen, J. M.; Chen, B.; Huang, L.; Tans, P.; Worthy, D.; Ishizawa, M.; Chan, D.

    2007-12-01

    The variation of the stable isotope 13CO2 in the air in exchange with land ecosystems results from fractionation processes in both plants and soil during photosynthesis and respiration. Its diurnal and seasonal variations therefore contain information on the carbon cycle. We developed a model (BEPS-iso) to simulate its exchange between vegetation and the atmosphere. To be useful for regional carbon cycle studies, the model has the following characteristics: (i) it considers the turbulent mixing in the vertical profile from the soil surface to the top of the planetary boundary layer (PBL); (ii) it scales individual leaf photosynthetic discrimination to the whole canopy through the separation of sunlit and shaded leaf groups; (iii) through simulating leaf-level photosynthetic processes, it has the capacity to mechanistically examine isotope discrimination resulting from meteorological forcings, such as radiation, precipitation and humidity; and (iv) through complete modeling of radiation, energy and water fluxes, it also simulates soil moisture and temperature needed for estimating ecosystem respiration and the 13C signal from the soil. After validation using flask data acquired at 20 m level on a tower near Fraserdale, Ontario, Canada, during intensive campaigns (1998-2000), the model has been used for several purposes: (i) to investigate the diurnal and seasonal variations in the disequilibrium in 13C fractionation between ecosystem respiration and photosynthesis, which is an important step in using 13C measurements to separate these carbon cycle components; (ii) to quantify the 13C rectification in the PBL, which differs significantly from CO2 rectification because of the diurnal and seasonal disequilibriums; and (iii) to model the 13C spatial and temporal variations over the global land surface for the purpose of CO2 inversion using 13C as an additional constraint.

  12. Experimental study on cross-flow induced vibrations in heat exchanger tube bundle

    NASA Astrophysics Data System (ADS)

    Khushnood, Shahab; Nizam, Luqman Ahmad

    2017-03-01

    Vibration in heat exchangers is one of the main problems that the industry has faced over last few decades. Vibration phenomenon in heat exchangers is of major concern for designers and process engineers since it can lead to the tube damage, tube leakage, baffle damage, tube collision damage, fatigue, creep etc. In the present study, vibration response is analyzed on single tube located in the centre of the tube bundle having parallel triangular arrangement (60°) with P/ D ratio of 1.44. The experiment is performed for two different flow conditions. This kind of experiment has not been reported in the literature. Under the first condition, the tube vibration response is analyzed when there is no internal flow in the tube and under the second condition, the response is analyzed when the internal tube flow is maintained at a constant value of 0.1 m/s. The free stream shell side velocity ranges from 0.8 m/s to 1.3 m/s, the reduced gap velocity varies from 1.80 to 2.66 and the Reynolds number varies from 44500 to 66000. It is observed that the internal tube flow results in larger vibration amplitudes for the tube than that without internal tube flow. It is also established that over the current range of shell side flow velocity, the turbulence is the dominant excitation mechanism for producing vibration in the tube since the amplitude varies directly with the increase in the shell side velocity. Damping has no significant effect on the vibration behavior of the tube for the current velocity range.

  13. Study of multi-electron ionization and charge exchange in HIBF

    NASA Astrophysics Data System (ADS)

    Wu, Linchun

    Beam ion stripping on background gases or plasma in a Heavy Ion Beam Fusion (HIBF) chamber increases the charge state of the beam and the diameter of the focus, complicating the final focusing on the focusing target. To model beam transport in the chamber, it is necessary to know the beam charge-state evolution, including both ionization and charge exchange dynamics. The main objective of this research is to explore theoretical approaches including scaling law. Improved models are developed to calculate multi-electron loss, especially ion stripping and charge exchange cross sections, for both near-term experiments and future power plant scale HIBF research. First, a new space-charge neutralization approach that uses electron injection is proposed for the ion beam transport in HIBF chamber. An analytical study was performed to illustrate the plasma dynamics and final neutralization effects with this technique. The results examine the effect of different injected electron profiles. Next, to improve the accuracy of such simulations, methods to improve cross sections of ionization and charge exchange are studied. Both classical and quantum mechanical approaches are examined. Attention is focused on the interaction by low-charge-state heavy ions. Multi-electron processes for dressed ions, including screening and anti-screening effects, internuclear forces, are given special attention, This analysis is complex and requires a combining several different theoretical approaches. Finally, a Classic Trajectory Monte Carlo (CTMC) model based on an improvement of Olson's n-body CTMC method is presented. This model solves the n-body ion-atom ionization problem in a regime of intent to HIBF. In the paper, a new and complete computational module for these interactions has been developed. The cross section data for Xe, Cs, and Bi ions colliding with various background gases (Xe, N2, Ar and Flibe) is presented. After the calculation of the cross section data, the predicted energy

  14. 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.

  15. Interface effects on the magnetic properties of exchange coupled Co/Fe multilayers studied by Brillouin light scattering

    NASA Astrophysics Data System (ADS)

    D'Orazio, F.; Lucari, F.; Carlotti, G.; Gubbiotti, G.; Carbucicchio, M.; Ruggiero, G.

    2001-05-01

    Exchange-coupled 5[Co ( x) /Fe (3 x) ]/Co ( x) with x=5, 10, 15 nm multilayers were grown by UHV electron-beam evaporation. The influence of the interface magnetic anisotropy and interlayer exchange interaction on the magnetic properties was studied by means of Brillouin light scattering from thermally excited spin waves. Both the Damon-Eshbach surface mode of the total multilayer and bulk standing modes are present in the BLS spectra. A careful study of spin waves frequency dependence on the applied magnetic field allowed the determination of the magnetic parameters of the Co/Fe multilayers.

  16. 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.

  17. Diffusion, relaxation, and chemical exchange in casein gels: a nuclear magnetic resonance study.

    PubMed

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

    2005-01-15

    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.

  18. Fouling of an anion exchange chromatography operation in a monoclonal antibody process: Visualization and kinetic studies

    PubMed Central

    Close, Edward J; Salm, Jeffrey R; Iskra, Timothy; Sørensen, Eva; Bracewell, Daniel G

    2013-01-01

    Fouling of chromatographic resins over their operational lifetimes can be a significant problem for commercial bioseparations. In this article, scanning electron microscopy (SEM), batch uptake experiments, confocal laser scanning microscopy (CLSM) and small-scale column studies were applied to characterize a case study where fouling had been observed during process development. The fouling was found to occur on an anion exchange (AEX) polishing step following a protein A affinity capture step in a process for the purification of a monoclonal antibody. Fouled resin samples analyzed by SEM and batch uptake experiments indicated that after successive batch cycles, significant blockage of the pores at the resin surface occurred, thereby decreasing the protein uptake rate. Further studies were performed using CLSM to allow temporal and spatial measurements of protein adsorption within the resin, for clean, partially fouled and extensively fouled resin samples. These samples were packed within a miniaturized flowcell and challenged with fluorescently labeled albumin that enabled in situ measurements. The results indicated that the foulant has a significant impact on the kinetics of adsorption, severely decreasing the protein uptake rate, but only results in a minimal decrease in saturation capacity. The impact of the foulant on the kinetics of adsorption was further investigated by loading BSA onto fouled resin over an extended range of flow rates. By decreasing the flow rate during BSA loading, the capacity of the resin was recovered. These data support the hypothesis that the foulant is located on the particle surface, only penetrating the particle to a limited degree. The increased understanding into the nature of the fouling can help in the continued process development of this industrial example. Scanning electron microscopy (SEM), batch uptake experiments, confocal laser scanning microscopy (CLSM) and small-scale column experiments were applied to characterize a

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

    NASA Technical Reports Server (NTRS)

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

    2009-01-01

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

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

    NASA Technical Reports Server (NTRS)

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

    2008-01-01

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

  1. Design and study of the mask exchange system based on Delta parallel mechanism

    NASA Astrophysics Data System (ADS)

    Zhang, Feifan; Wang, Jianping; Zhou, Hongfei; Zhou, Zengxiang; Chu, Jiaru

    2016-07-01

    Mask exchange system is the main part of Multi-Object Broadband Imaging Echellette (MOBIE) on the Thirty Meter Telescope (TMT). The robot is one of the key parts in the mask exchange process. In view of the facts that the scheme the on-board robot is hard to meet the requirements of TMT and the traditional industrial robot is difficult to use in the Mask Exchange System (MEX). The delta parallel mechanism has much advantages such as good dynamic performance, high speed and could integrate a vision recognition system to identify the masks. The design for MEX based on off-board Delta parallel mechanism was proposed in the paper.

  2. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-01-01

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

  4. 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

  5. Numerical studies on sizing/ rating of plate fin heat exchangers for a modified Claude cycle based helium liquefier/ refrigerator

    NASA Astrophysics Data System (ADS)

    Goyal, M.; Chakravarty, A.; Atrey, M. D.

    2017-02-01

    Performance of modern helium refrigeration/ liquefaction systems depends significantly on the effectiveness of heat exchangers. Generally, compact plate fin heat exchangers (PFHE) having very high effectiveness (>0.95) are used in such systems. Apart from basic fluid film resistances, various secondary parameters influence the sizing/ rating of these heat exchangers. In the present paper, sizing calculations are performed, using in-house developed numerical models/ codes, for a set of high effectiveness PFHE for a modified Claude cycle based helium liquefier/ refrigerator operating in the refrigeration mode without liquid nitrogen (LN2) pre-cooling. The combined effects of secondary parameters like axial heat conduction through the heat exchanger metal matrix, parasitic heat in-leak from surroundings and variation in the fluid/ metal properties are taken care of in the sizing calculation. Numerical studies are carried out to predict the off-design performance of the PFHEs in the refrigeration mode with LN2 pre-cooling. Iterative process cycle calculations are also carried out to obtain the inlet/ exit state points of the heat exchangers.

  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. Heat exchangers for cardioplegia systems: in vitro study of four different concepts.

    PubMed

    Drummond, Mário; Novello, Waldyr Parorali; de Arruda, Antonio Celso Fonseca; Braile, Domingo Marcolino

    2003-05-01

    The aim of this work is the evaluation of four different heat exchangers used for myocardium during cardioplegic system in cardiac surgeries. Four types of shell and tube heat exchangers made of different exchange elements were constructed, as follows: stainless steel tubes, aluminium tubes, polypropylene hollow fiber, and bellows type. The evaluation was performed by in vitro tests of parameters such as heat transfer, pressure drop, and hemolysis tendency. The result has shown that all four systems tested were able to achieve the heat performance, and to offer low resistance to flow, and safety, as well as have low tendency to hemolysis. However, we can emphasize that the bellows type heat exchanger has a significant difference with regard to the other three types.

  8. 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

  9. 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.

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

    PubMed Central

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

    2013-01-01

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

  11. 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.

  12. 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.

  13. Biochemical, Biophysical and Cellular Techniques to Study the Guanine Nucleotide Exchange Factor, GIV/Girdin.

    PubMed

    Ghosh, Pradipta; Aznar, Nicolas; Swanson, Lee; Lo, I-Chung; Lopez-Sanchez, Inmaculada; Ear, Jason; Rohena, Cristina; Kalogriopoulos, Nicholas; Joosen, Linda; Dunkel, Ying; Sun, Nina; Nguyen, Peter; Bhandari, Deepali

    2016-12-07

    Canonical signal transduction via heterotrimeric G proteins is spatiotemporally restricted, i.e., triggered exclusively at the plasma membrane, only by agonist activation of G protein-coupled receptors via a finite process that is terminated within a few hundred milliseconds. Recently, a rapidly emerging paradigm has revealed a noncanonical pathway for activation of heterotrimeric G proteins via the nonreceptor guanidine-nucleotide exchange factor, GIV/Girdin. Biochemical, biophysical, and functional studies evaluating this pathway have unraveled its unique properties and distinctive spatiotemporal features. As in the case of any new pathway/paradigm, these studies first required an in-depth optimization of tools/techniques and protocols, governed by rationale and fundamentals unique to the pathway, and more specifically to the large multimodular GIV protein. Here we provide the most up-to-date overview of protocols that have generated most of what we know today about noncanonical G protein activation by GIV and its relevance in health and disease. © 2016 by John Wiley & Sons, Inc.

  14. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2010-04-01

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

  16. NMR study of the exchange coupling in the trinuclear cluster of the multicopper oxidase Fet3p

    PubMed Central

    Zaballa, María-Eugenia; Ziegler, Lynn; Kosman, Daniel J.; Vila, Alejandro J.

    2010-01-01

    Fet3p from Saccharomyces cerevisiae is a multicopper oxidase (MCO) which oxidizes Fe2+ to Fe3+. The electronic structure of the different copper centers in this family of enzymes has been extensively studied and discussed for years with a particular focus on the exchange coupling regime in the trinuclear cluster (TNC). Using NMR spectroscopy we have quantified the exchange coupling constant in the type 3 center in a fully metallated oxidase; this value in Fet3p is significantly higher than that reported for proteins containing isolated type 3 centers as in tyrosinase. We also provide evidence of exchange coupling between the type 2 and the type 3 Cu2+ ions, which supports the crystallographic evidence of dioxygen binding to the TNC. This work provides the foundation for the application of NMR to these complex systems. PMID:20698686

  17. 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

  18. 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…

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

    NASA Astrophysics Data System (ADS)

    Conover, Timothy Allan

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

  20. 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

  1. The radon cycle and its daughters - an application to the study of troposphere-stratosphere exchanges

    NASA Astrophysics Data System (ADS)

    Lambert, G.; Polian, G.; Jegou, A.; Sanak, J.; Ardouin, B.; Buisson, A.; Le Roulley, J. C.

    1982-12-01

    The global activities of the natural radioactive nuclides Rn-222, Pb-210, Bi-210, and Po-210 in the whole atmosphere are studied. A two-box model which assumes the existence of a steady state for the whole atmosphere is employed since the residence times of the aerosols and air masses are different in the troposphere and in the stratosphere. In each reservoir, the production of a nuclide by radioactive decay of its precursor is balanced simultaneously by its own radioactivity, by the flux of atoms transferred to or from the other reservoir, and in the case of the troposphere, by scavenging. The model is used to consider an unknown emanation of Rn-222 from the soil of the continents and also the existence of possible volcanic sources for each nuclide. Among other results, it is found that the Rn-222 emanation rate from the surface of the continents is 0.72 atom/sq cm-sec, and about 2 percent of this flux is able to reach the stratosphere. The scavenging constant of the submicronic aerosols in the troposphere is determined to be 0.00011/min, which corresponds to a mean residence time of 6.5 days in the global troposphere. The flux of air exchanged across the tropopause is determined to be between 4.2-9 x 10 to the 12th kg/min, which corresponds to a mean residence time in the stratosphere between 0.23-0.50 year.

  2. Replica exchange molecular dynamics study of the truncated amyloid beta (11-40) trimer in solution.

    PubMed

    Ngo, Son Tung; Hung, Huynh Minh; Truong, Duc Toan; Nguyen, Minh Tho

    2017-01-18

    Amyloid beta (Aβ) oligomers are neurotoxic compounds that destroy the brain of Alzheimer's disease patients. Recent studies indicated that the trimer is one of the most cytotoxic forms of low molecular weight Aβ oligomers. As there was limited information about the structure of the Aβ trimer, either by experiment or by computation, we determined in this work the structure of the 3Aβ11-40 oligomer for the first time using the temperature replica exchange molecular dynamics simulations in the presence of an explicit solvent. More than 20.0 μs of MD simulations were performed. The probability of the β-content and random coil structure of the solvated trimer amounts to 42 ± 6 and 49 ± 7% which is in good agreement with experiments. Intermolecular interactions in central hydrophobic cores play a key role in stabilizing the oligomer. Intermolecular polar contacts between D23 and residues 24-29 replace the salt bridge D23-K28 to secure the loop region. The hydrophilic region of the N-terminus is maintained by the intermolecular polar crossing contacts H13A-Q15B and H13B-Q15C. The difference in the free energy of binding between the constituting monomers and the others amounts to -36 ± 8 kcal mol(-1). The collision cross section of the representative structures of the trimer was computed to be 1330 ± 47 Å(2), which is in good agreement with previous experiments.

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

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

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

  4. 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

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

    PubMed Central

    Ahmadi, Maryam; Ghazisaeidi, Marjan; Bashiri, Azadeh

    2015-01-01

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

  6. The study of RMB exchange rate complex networks based on fluctuation mode

    NASA Astrophysics Data System (ADS)

    Yao, Can-Zhong; Lin, Ji-Nan; Zheng, Xu-Zhou; Liu, Xiao-Feng

    2015-10-01

    In the paper, we research on the characteristics of RMB exchange rate time series fluctuation with methods of symbolization and coarse gaining. First, based on fluctuation features of RMB exchange rate, we define the first type of fluctuation mode as one specific foreign currency against RMB in four days' fluctuating situations, and the second type as four different foreign currencies against RMB in one day's fluctuating situation. With the transforming method, we construct the unique-currency and multi-currency complex networks. Further, through analyzing the topological features including out-degree, betweenness centrality and clustering coefficient of fluctuation-mode complex networks, we find that the out-degree distribution of both types of fluctuation mode basically follows power-law distributions with exponents between 1 and 2. The further analysis reveals that the out-degree and the clustering coefficient generally obey the approximated negative correlation. With this result, we confirm previous observations showing that the RMB exchange rate exhibits a characteristic of long-range memory. Finally, we analyze the most probable transmission route of fluctuation modes, and provide probability prediction matrix. The transmission route for RMB exchange rate fluctuation modes exhibits the characteristics of partially closed loop, repeat and reversibility, which lays a solid foundation for predicting RMB exchange rate fluctuation patterns with large volume of data.

  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. Plasma-exchange treatment for severe carbamazepine intoxication: a case study.

    PubMed

    Kozanoglu, Ilknur; Kahveci, Suat; Asma, Suheyl; Yeral, Mahmut; Noyan, Aytul; Boga, Can; Ozdogu, Hakan

    2014-06-01

    Acute poisoning is an important cause of morbidity and mortality during childhood. This manuscript reports the positive outcome of a pediatric case with a history of accidental carbamazepine intake treated using plasma exchange. A 3-year-old male presented with severe carbamazepine intoxication. He was comatose and had generalized tonic clonic seizure, ventricular tachycardia, and hypotension. Although he did not respond to classical therapies, we performed two sessions of plasma exchange. The patient recovered rapidly and was discharged from the hospital six days from the time of carbamazepine ingestion with no complication or neurologic impairment. Plasma exchange can be performed safely in very small children, and it might be the first line treatment, particularly for intoxication with drugs that have high plasma-protein-binding properties.

  9. Parametric performance studies on fluidized-bed heat exchangers. Task 1: Fouling characteristics

    NASA Astrophysics Data System (ADS)

    Stoeffler, R. C.

    1982-09-01

    Analyses and experiments are being performed to investigate the heat transfer performance of single and multistage shallow fluidized beds for application to the recovery of heat from sources such as waste heat, and coal combustion or coal gasification. Tests were conducted to investigate the effects of liquid condensate fouling on fluidized bed heat exchanger performance. Liquid condensates used in these tests were water and glycerol (which is more viscous than water). The tests showed that fluidized bed heat exchanger performance is degraded by condensation within the bed and the degradation is caused by bed particles adhering to the heat exchanger surface, not by particle agglomeration. Liquid condensate did not continuously build up within the bed. After a period of dry out, heat transfer equal to that obtained prior to condensation was again obtained.

  10. Studies on the solid-state ion exchange of nickel ions into zeolites using DRS technique

    NASA Astrophysics Data System (ADS)

    Zanjanchi, M. A.; Ebrahimian, A.

    2004-05-01

    The coordination of Ni 2+ ions in the dehydrated nickel-exchanged zeolites was investigated from the analysis of diffuse reflectance spectra. Solid-state ion exchange method was used to prepare nickel-containing mordenite, Y, L and mazzite zeolites. In the dehydrated mordenite and zeolite Y, nickel cations are presented in both forms of tetrahedral and distorted tetrahedral symmetries. The relative amount of tetrahedral and distorted tetrahedral nickel species are related to the heating temperature and heating time used for calcinations. In the dehydrated zeolite L and mazzite, Ni 2+ ions are mainly in the distorted octahedral symmetries.

  11. Atmosphere-ocean ozone exchange: A global modeling study of biogeochemical, atmospheric, and waterside turbulence dependencies

    NASA Astrophysics Data System (ADS)

    Ganzeveld, L.; Helmig, D.; Fairall, C. W.; Hare, J.; Pozzer, A.

    2009-12-01

    The significance of the removal of tropospheric ozone by the oceans, covering ˜2/3 of the Earth's surface, has only been addressed in a few studies involving water tank, aircraft, and tower flux measurements. On the basis of results from these few observations of the ozone dry deposition velocity (VdO3), atmospheric chemistry models generally apply an empirical, constant ocean uptake rate of 0.05 cm s-1. This value is substantially smaller than the atmospheric turbulent transport velocity for ozone. On the other hand, the uptake is higher than expected from the solubility of ozone in clean water alone, suggesting that there is an enhancement in oceanic ozone uptake, e.g., through a chemical destruction mechanism. We present an evaluation of a global-scale analysis with a new mechanistic representation of atmosphere-ocean ozone exchange. The applied atmosphere chemistry-climate model includes not only atmospheric but also waterside turbulence and the role of waterside chemical loss processes as a function of oceanic biogeochemistry. The simulations suggest a larger role of biogeochemistry in tropical and subtropical ozone oceanic uptake with a relative small temporal variability, whereas in midlatitude and high-latitude regions, highly variable ozone uptake rates are expected because of the stronger influence of waterside turbulence. Despite a relatively large range in the explicitly calculated ocean uptake rate, there is a surprisingly small sensitivity of simulated Marine Boundary Layer ozone concentrations compared to the sensitivity for the commonly applied constant ocean uptake approach. This small sensitivity points at compensating effects through inclusion of the process-based ocean uptake mechanisms to consider variability in oceanic O3 deposition consistent with that in atmospheric and oceanic physical, chemical, and biological processes.

  12. (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.

  13. A comparative study of ion exchange kinetics in zinc/lead-modified zeolite-clinoptilolite systems.

    PubMed

    Trgo, M; Perić, J; Medvidović, N Vukojević

    2006-08-25

    The kinetics of zinc and lead ions removal by modified zeolite-clinoptilolite has been investigated. The rate of the ion exchange process for lead ions is faster than for zinc ions, as well as the time needed to reach the equilibrium. The ion exchange capacity of zeolite of lead ions is doubly higher than that of zinc ions. Diffusion models according to the Vermeulen's approximation, the parabolic diffusion model and the homogeneous diffusion model have been tested with the experimental data of ion exchange for zinc and lead. For both systems examined, the best fit of the models proposed with the experimental data was shown by the Vermeulen's approximation and the homogeneous diffusion model with t-->t(infinity). The diffusion coefficients are calculated from kinetic models of lead ions they are of the order of 10(-6)cm(2)/min, constant for all examined initial concentrations and not dependent on time. The diffusion coefficients in the system of zinc ions is of the order of 10(-8)cm(2)/min, also independent of initial concentrations, but decreasing with time from the beginning of ion exchange to the equilibrium.

  14. 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…

  15. Study and development of a cryogenic heat exchanger for life support systems

    NASA Technical Reports Server (NTRS)

    Soliman, M. M.

    1973-01-01

    A prototype cryogenic heat exchanger for removal of waste heat from a spacecraft environmental control life support system was developed. The heat exchanger uses the heat sink capabilities of the cryogenic propellants and, hence, can operate over all mission phases from prelaunch to orbit, to post landing, with quiescent periods during orbit. A survey of candidate warm fluids resulted in the selection of E-2, a fluorocarbon compound, because of its low freezing point and high boiling point. The final design and testing of the heat exchanger was carried out, however, using Freon-21, which is similar to E-2 except for its low boiling point. This change was motivated by the desire for cost effectiveness of the experimental program. The transient performance of the heat exchanger was demonstrated by an analog simulation of the heat sink system. Under the realistic transient heat load conditions (20 sec ramp from minimum to maximum Freon-21 inlet temperature), the control system was able to maintain the warm fluid outlet temperature within + or - 3 F. For a 20-sec ramp from 0 F to -400 F in the hydrogen inlet temperature, at maximum heat load, the warm fluid outlet temperature was maintained within + or - 7 F.

  16. 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…

  17. Creating Sustainable Cities through Knowledge Exchange: A Case Study of Knowledge Transfer partnerships

    ERIC Educational Resources Information Center

    Hope, Alex

    2016-01-01

    Purpose: The purpose of this paper is to examine the use of knowledge transfer partnership (KTP)as a means for universities to generate and exchange knowledge to foster sustainable cities and societies. Design/methodology/approach: This paper reports on a series of separate yet interrelated KTPs between a university and the local authority in the…

  18. "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…

  19. 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.

  20. Ferromagnetic resonance studies of exchange coupled ultrathin Py/Cr/Py trilayers

    NASA Astrophysics Data System (ADS)

    Topkaya, R.; Erkovan, M.; Öztürk, A.; Öztürk, O.; Aktaş, B.; Özdemir, M.

    2010-07-01

    Magnetic properties of ultrathin Py/Cr/Py trilayers have been investigated as a function of Cr spacer layer thickness by using ferromagnetic resonance (FMR) and vibrating sample magnetometer (VSM) techniques. The Cr spacer layer thickness was increased from 4 to 40 Å with 1 Å steps to determine the dependence of interlayer exchange coupling between ferromagnetic layers on the spacer layer thickness. Two strong and well resolved peaks were observed which correspond to a strong (acoustic) and weak (optic) modes of magnetization precession in the effective dc field due to the exciting external microwave field as the external dc field orientation comes close to the film normal. The separation of the two modes in the field axis depends on the thickness of Cr spacer layer. An interchange in the relative positions of the acoustic and optic modes has been observed for a particular thickness of Cr spacer layer as well. A computer program for magnetically exchange coupled N magnetic layers was written to simulate the experimental FMR spectra and to obtain the magnetic parameters of ultrathin Py/Cr/Py trilayers. FMR data have been analyzed from every aspect by using this program and interlayer exchange coupling constant was calculated for the prepared structures. It was found that the relative position of the peaks depends on the nature (sign) of the interlayer exchange coupling between ferromagnetic layers through Cr spacer layer. In Py/Cr/Py trilayers, strength of the interlayer exchange coupling constant oscillates and changes its sign with Cr spacer layer thickness with a period of about 11 Å.

  1. Swinger RNAs with sharp switches between regular transcription and transcription systematically exchanging ribonucleotides: Case studies.

    PubMed

    Seligmann, Hervé

    2015-09-01

    During RNA transcription, DNA nucleotides A,C,G, T are usually matched by ribonucleotides A, C, G and U. However occasionally, this rule does not apply: transcript-DNA homologies are detectable only assuming systematic exchanges between ribonucleotides. Nine symmetric (X ↔ Y, e.g. A ↔ C) and fourteen asymmetric (X ↔ Y ↔ Z, e.g. A ↔ C ↔ G) exchanges exist, called swinger transcriptions. Putatively, polymerases occasionally stabilize in unspecified swinger conformations, possibly similar to transient conformations causing punctual misinsertions. This predicts chimeric transcripts, part regular, part swinger-transformed, reflecting polymerases switching to swinger polymerization conformation(s). Four chimeric Genbank transcripts (three from human mitochondrion and one murine cytosolic) are described here: (a) the 5' and 3' extremities reflect regular polymerization, the intervening sequence exchanges systematically between ribonucleotides (swinger rule G ↔ U, transcript (1), with sharp switches between regular and swinger sequences; (b) the 5' half is 'normal', the 3' half systematically exchanges ribonucleotides (swinger rule C ↔ G, transcript (2), with an intercalated sequence lacking homology; (c) the 3' extremity fits A ↔ G exchanges (10% of transcript length), the 5' half follows regular transcription; the intervening region seems a mix of regular and A ↔ G transcriptions (transcript 3); (d) murine cytosolic transcript 4 switches to A ↔ U + C ↔ G, and is fused with A ↔ U + C ↔ G swinger transformed precursor rRNA. In (c), each concomitant transcript 5' and 3' extremities match opposite genome strands. Transcripts 3 and 4 combine transcript fusions with partial swinger transcriptions. Occasional (usually sharp) switches between regular and swinger transcriptions reveal greater coding potential than detected until now, suggest stable polymerase swinger conformations.

  2. 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

    2015-04-03

    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

  3. New studies of optical pumping, spin resonances, and spin exchange in mixtures of inert gases and alkali-metal vapors

    NASA Astrophysics Data System (ADS)

    Jau, Yuan-Yu

    In this thesis, we present new studies of alkali-hyperfine resonances, new optical pumping of alkali-metal atoms, and the new measurements of binary spin-exchange cross-section between alkali-metal atoms and xenon atoms. We report a large light narrowing effect of the hyperfine end-resonance signals, which was predicted from our theory and observed in our experiments. By increasing the intensity of the circularly polarized pumping beam, alkali-metal atoms are optically pumped into a state of static polarization, and trapped into the hyperfine end-state. Spin exchange between alkali-metal atoms has minimal effect on the end-resonance of the highly spin-polarized atoms. This new result will possibly benefit the design of atomic clocks and magnetometer. We also studied the pressure dependence of the atomic-clock resonance linewidth and pointed out that the linewidth was overestimated by people in the community of atomic clock. Next, we present a series study of coherent population trapping (CPT), which is a promising technique with the same or better performance compared to the traditional microwave spectroscopy. For miniature atomic clocks, CPT method is thought to be particularly advantages. From our studies, we invented a new optical-pumping method, push-pull optical pumping, which can pump atoms into nearly pure 0-0 superposition state, the superposition state of the two ground-state hyperfine sublevels with azimuthal quantum number m = 0. We believe this new invention will bring a big advantage to CPT frequency standards, the quantum state preparation for cold atoms or hot vapor, etc. We also investigated the pressure dependence of CPT excitation and the line shape of the CPT resonance theoretically and experimentally. These two properties are important for CPT applications. A theoretical study of "photon cost" of optical pumping is also presented. Finally, we switch our attention to the problem of spin exchange between alkali-metal atoms and xenon gas. This

  4. 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.

  5. A new approach to measuring protein backbone protection with high spatial resolution using H/D exchange and electron capture dissociation

    PubMed Central

    Abzalimov, Rinat R.; Bobst, Cedric E.; Kaltashov, Igor A.

    2013-01-01

    Inadequate spatial resolution remains one of the most serious limitations of hydrogen/deuterium exchange mass spectrometry (HDX MS), especially when applied to larger proteins (over 30 kDa). Supplementing proteolytic fragmentation of the protein in solution with ion dissociation in the gas phase has been used successfully by several groups to obtain near-residue level resolution. However, the restrictions imposed by the LC/MS/MS mode of operation on the data acquisition time frame makes it difficult in many cases to obtain signal-to-noise ratio adequate for reliable assignment of the backbone amide protection levels at individual residues. This restriction is lifted in the present work by eliminating the LC separation step from the workflow and taking advantage of the high resolving power and dynamic range of a Fourier transform ion cyclotron resonance mass spectrometer (FT ICR MS). A residue-level resolution is demonstrated for a peptic fragment of a 37 kDa recombinant protein (N-lobe of human serum transferrin) using electron-capture dissociation as an ion fragmentation tool. The absence of hydrogen scrambling in the gas phase prior to ion dissociation is verified using redundant HDX MS data generated by FT ICR MS. The backbone protection pattern generated by direct HDX MS/MS is in excellent agreement with the known crystal structure of the protein, but also provides information on conformational dynamics, which is not available from the static X-ray structure. PMID:23978257

  6. Structure and thermodynamics of amylin dimer studied by Hamiltonian-temperature replica exchange molecular dynamics simulations.

    PubMed

    Laghaei, Rozita; Mousseau, Normand; Wei, Guanghong

    2011-03-31

    The loss of the insulin-producing β-cells in the pancreatic islets of Langerhans, responsible for type-II diabetes, is associated with islet amyloid deposits. The main component of these deposits is the amyloid fibrils formed by the 37-residue human islet amyloid polypeptide (hIAPP also known as amylin). Although the fibrils are well characterized by cross β structure, the structure of the transient oligomers formed in the early stage of aggregation remains elusive. In this study, we apply the Hamiltonian-temperature replica exchange molecular dynamics to characterize the structure and thermodynamics of a full-length hIAPP dimer in both the presence and the absence of the Cys2-Cys7 disulfide bond. We compare these results with those obtained on the monomeric and dimeric forms of rat IAPP (rIAPP) with a disulfide bridge which differ from the hIAPP by 6 amino acids in the C-terminal region, but it is unable to form fibrils. Using a coarse-grained protein force field (OPEP-the Optimized Potential for Efficient peptide structure Prediction) running for a total of 10-28 μs per system studied, we show that sequences sample α-helical structure in the N-terminal region but that the length of this secondary element is shorter and less stable for the chains without the disulfide bridge (residues 5-16 for hIAPP with the bridge vs 10-16 for hIAPP without the bridge). This α-helix is known to be an important transient stage in the formation of oligomers. In the C-terminal, the amyloidogenic region of hIAPP, β-strands are seen for residues 17-26 and 30-35. On the contrary, no significant β-sheet content in the C-terminal is observed for either the monomeric or the dimeric rIAPP. These numerical results are fully consistent with recent experimental findings that the N-terminal residues are not part of the fibril by forming α-helical structure but rather play a significant role in stabilizing the amyloidogenic region available for the fibrillation.

  7. Real Space Renormalization Group Study of the S=1/2 XXZ Chains with Fibonacci Exchange Modulation

    NASA Astrophysics Data System (ADS)

    Hida, Kazuo

    2004-08-01

    Ground state properties of the S=1/2 antiferromagnetic XXZ chain with Fibonacci exchange modulation are studied using the real space renormalization group method for strong modulation. The quantum dynamical critical behavior with a new universality class is predicted in the isotropic case. Combining our results with the weak coupling renormalization group results by Vidal et al., the ground state phase diagram is obtained.

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

    PubMed Central

    2015-01-01

    An efficient laboratory experiment has been developed for undergraduate students to conduct 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 1H NMR. Students also visualize a significant kinetic isotope effect (kH/kD ≈ 3 to 4) by adding iodine tincture to solutions of unlabeled resorcinol and the 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

  9. 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

  10. Magneto-optical indicator film study of the hybrid exchange spring formation and evolution processes

    NASA Astrophysics Data System (ADS)

    Nikitenko, V. I.; Gornakov, V. S.; Kabanov, Yu. P.; Shapiro, A. J.; Shull, R. D.; Chien, C. L.; Jiang, J. S.; Bader, S. D.

    2003-03-01

    The elementary events of the remagnetization processes in nanocomposite magnetic bilayers were investigated using iron-garnet indicator films with in-plane anisotropy. We have observed hybrid domain walls consisting of both ferromagnetic and antiferromagnetic sections perpendicular to the interface. The external magnetic field shifts only the ferromagnetic part of the domain walls. This leads to the formation of a hybrid exchange spin spring parallel to the interface. The processes of spring nucleation and untwisting occur at different locations. With the field oriented antiparallel to the macroscopic unidirectional anisotropy, remagnetization of the soft ferromagnet layer in the hard/soft nanocomposite starts by the formation of an exchange spring consisting of micrometer-scale sub-domains with opposite direction spin twisting. A rotating magnetic field (smaller than some critical value) creates firstly a single-chiral spin spiral; this spiral then loses stability, incoherently untwists and gradually inverts its chirality with increasing field rotation. Untwisting of the hybrid exchange spring at higher fields leads to the creation of unusual hybrid non-180° domain walls. The initial (ground) state of the bilayer with such noncollinear magnetized domains is not restored after stopping the field rotation and returning it to zero. The revealed phenomena are attributed to the influence of the dispersion in the unidirectional anisotropy induced by magnetization frustration in the interface and bilayer crystal lattice defects.

  11. The current situation of the study on twisted tape inserts in pipe exchangers

    NASA Astrophysics Data System (ADS)

    Man, Changzhong; Wang, Chong; Yao, Jinyu

    2014-12-01

    Heat transfer enhancement is used in many applications including heat exchangers, air conditioning, and refrigeration systems; hence many researchers have conducted experimental and numerical researches on heat transfer enhancement and have developed various techniques and methods. As a passive heat transfer technique, twisted tapes are widely used in various industries for their cost savings, lower maintenance requirements and the fact that they are easily set up. This paper introduces the principle of heat transfer enhancement of twisted tapes and reviews some of the experimental works done by researchers on this technique in recent years. The variously modified twisted tape inserts are widely researched and used to enhance heat transfer efficiency for heat exchangers. Twisted tapes perform better in low Re conditions and in square tubes. However, they could also cause higher pressure drops. Twisted tapes have great potential and profound implications if they can be used in traditional heat exchangers. Besides this, some correlations between the Nusselt number and friction factors are presented in this paper.

  12. 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.

  13. 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.

  14. 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…

  15. Prospects for HERMES-spin structure studies at HERA

    SciTech Connect

    Jackson, H.E.

    1994-12-31

    HERMES (HERA Measurement of Spin), is a second generation experiment to study the spin structure of the nucleon by using polarized internal gas targets in the HERA 35-GeV electron storage ring. Scattered electrons and coincident hadrons will be detected in an open geometry spectrometer which will include particle identification. Measurements are planned for each of the inclusive structure functions, g{sub 1},(x), g{sub 2}(x), b{sub 1}(x) and A(x), as well as the study of semi-inclusive pion and kaon asymmetries. Targets of hydrogen, deuterium and {sup 3}He will be studied. The accuracy of data for the inclusive structure functions will equal or exceed that of current experiments. The semi-inclusive asymmetries will provide a unique and sensitive probe of the flavor dependence of quark helicity distributions and properties of the quark sea. Monte Carlo simulations of HERMES data for experiment asymmetries and polarized structure functions are discussed.

  16. 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…

  17. 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…

  18. 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…

  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…

  1. A comparative study of linear and non-linear regression analysis for ammonium exchange by clinoptilolite zeolite.

    PubMed

    Karadag, Dogan; Koc, Yunus; Turan, Mustafa; Ozturk, Mustafa

    2007-06-01

    Ammonium ion exchange from aqueous solution using clinoptilolite zeolite was investigated at laboratory scale. Batch experimental studies were conducted to evaluate the effect of various parameters such as pH, zeolite dosage, contact time, initial ammonium concentration and temperature. Freundlich and Langmuir isotherm models and pseudo-second-order model were fitted to experimental data. Linear and non-linear regression methods were compared to determine the best fitting of isotherm and kinetic model to experimental data. The rate limiting mechanism of ammonium uptake by zeolite was determined as chemical exchange. Non-linear regression has better performance for analyzing experimental data and Freundlich model was better than Langmuir to represent equilibrium data.

  2. Interaction of strontium and europium with an aquatic fulvic acid studied by ultrafiltration and ion exchange techniques

    NASA Astrophysics Data System (ADS)

    Nordén, Maria; Ephraim, James; Allard, Bert

    The complexation of an aquatic fulvic acid, FA, with Sr2+ and Eu3+ was studied using an ultrafiltration technique and an ion exchange distribution method. The total amount of bound metal (Sr2+ and Eu3+) was measured as a function of pH at low metal concentrations (trace levels) and constant FA concentration. In the Sr-FA system the bound metal fraction increased slightly with pH, and the values obtained from the two experimental techniques were comparable. For Eu-FA, according to the ultrafiltration data, the fraction of bound metal ion was relatively insensitive to pH changes, whereas values from the ion exchange measurements showed a strong and positive dependence on pH. The results are discussed in the light of possible intrinsic problems of the two methods.

  3. The Benefits of Past and Current Regional Hydroclimate Projects to the Third Pole Environment (TPE) Water and Energy Exchanges Studies

    NASA Astrophysics Data System (ADS)

    Benedict, Sam; van Oevelen, Peter

    2014-05-01

    To improve understanding of the various processes at work on spatial and temporal scales from regional to global the Regional Hydroclimate Projects (RHP's) are established as part of the Global Energy and Water Exchanges (GEWEX)Project to link the regional observations and process understanding to the global scale. This is done through exchange of observations, data, modeling, transferability studies etc. In this presentation the series of RHP's that were underway over North and South America, Europe and Asia continuously from the early 1990's up to the present will be examined, the reasons they were established, how they evolved and how they are evolving or are likely to evolve in the future, with an emphasis on where they can and should benefit similar work proposed for the TPE. The results will be presented in the context of the World Climate Research Programme (WCRP) Grand Challenge related to the development of a water strategy that addresses the issue of past and future changes in Water, in general, and the GEWEX science question on global water resource systems, in particular. This material will address issues associated with how changes in land surface and hydrology influence past and future changes in water availability and security, how new observations lead to improvements in water management and how models become better in global and regional climate predictions and projections of precipitation and how these outcomes relate to the TPE Water and Energy Exchanges Studies.

  4. 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.

  5. Lead exchange into zeolite and clay minerals: A [sup 29]Si, [sub 27]Al, [sup 23]Na solid-state NMR study

    SciTech Connect

    Liang, J.J.; Sherriff, B.L. )

    1993-08-01

    Chabazite, vermiculite, montmorillonite, hectorite, and kaolinite were used to remove Pb, through ion exchange, from 0.01 M aqueous Pb(NO[sub 3])[sub 2] solutions. These minerals contained 27 (Na-chabazite), 16, 9, 9, and 0.5 wt % of Pb, respectively, after equilibration with the solutions. Ion exchange reached equilibrium within 24 h for Na-chabazite and vermiculite, but in less than 5 min for montmorillonite and hectorite. Na-chabazite took up more Pb than natural (Ca, Na)-chabazite (7 wt % Pb), whereas no such difference was observed in different cation forms of the clay minerals. Calcite impurities, associated with the clay minerals, effectively removed Pb from the aqueous solutions by the precipitation of cerussite (PbCO[sub 3]). [sup 29]Si, [sup 27]Al, and [sup 23]Na magic angle spinning (MAS) nuclear magnetic resonance (NMR), [sup 23]Na double rotation (DOR) NMR, and [sup 23]Na variable-temperature MAS NMR were used to study the ion exchange mechanisms. In Na-chabazite, cations in all three possible sites take part in the fast chemical exchange. The chemical exchange passes from the fast exchange regime to the slow regime at [minus]80 to [minus]100[degrees]C. One site contains a relatively low population of exchangeable cations. The other two more shielded sites contain most of the exchangeable cation. The exchangeable cations in chabazite and vermiculite were found to be close to the SiO[sub 4] and AlO[sub 4] tetrahedra, while those in the other clay minerals were more distant. Two sites (or groups of sites) for exchangeable cations were observed in hectorite. Lead tended to occupy the one which corresponds to the [minus]8 ppM peak on the [sup 23]Na MAS NMR spectrum. The behavior of the exchangeable cations in the interlayer sites was similar in all the clay minerals studied. 27 refs., 7 figs., 4 tabs.

  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. Micromagnetic finite element study for magnetic properties of nanocomposite exchange coupled Nd2Fe14B/α-Fe multilayer systems

    NASA Astrophysics Data System (ADS)

    Ryo, Hyok-Su; Hu, Lian-Xi; Kim, Jin-Guk; Yang, Yu-Lin

    2017-03-01

    In this study, magnetic properties of exchange coupled nanocomposite multilayer thin films constructed alternately with magnetic hard Nd2Fe14B layers and soft α-Fe layers have been studied by micromagnetic finite element method (FEM). According to the results, effects of the thicknesses of layers and the magneto-crystalline anisotropy on the magnetic properties of the Nd2Fe14B/α-Fe multilayer systems have been estimated. On the other hand, the results have been analyzed by means of efficiency of interphase exchange coupling, which can be estimated by volume ratios of exchange coupled areas between magnetically hard Nd2Fe14B and soft α-Fe phase layers. The results show that the magnetic properties of exchange coupled Nd2Fe14B/α-Fe multilayer systems can be enhanced by efficient interphase exchange coupling between magnetically hard Nd2Fe14B layers and soft α-Fe layers.

  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 author…

  9. 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.

  10. 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).

  11. Formulation Study on Immobilization of Spent Ion Exchange Resins in Polymer Cements

    SciTech Connect

    Lili Xia; Meiqiong Lin; Bao Liangjin

    2006-07-01

    Applying normal design and correlative computer software, a new matrix material and an excellent waste formulation were developed. Based on the theory calculations and normal design in this paper, using polymer complex cement as immobilization matrix that mixed with simulating spent ion exchange resin a new waste formulation was carried out. The characterization of solidified waste had been done after 28 days curing. The results conformed to the treatment of the waste about the requests of the national standard [GB14569-93-1]. Leach index of the solidified waste was excellent. An optimized formulation was recommended. (authors)

  12. Studies on gas transport through dry cellulose acetate membranes prepared by solvent exchange technique

    SciTech Connect

    Lui, A.; Talbot, F.D.F.; Sourirajan, S.; Fouda, A.; Matsuura, T.

    1988-10-01

    The mechanism of gas transport through pores on the surface of dry cellulose acetate membranes under pressure was identified for membranes prepared by the solvent exchange technique using pure gas permeation rate data. The pure gases were helium, methane and carbon dioxide. The variables involved in the membrane preparation variables involved in the membrane preparation are the shrinkage temperature, the first solvent, the second solvent and the combinations thereof. Different conditions of membrane preparation produce different pore sizes. Depending on this pore size, one of the following mechanisms becomes dominant: Knudsen, surface and size exclusion.

  13. Evidence for the presence of three different anion exchangers in a red cell. Functional expression studies in Xenopus oocytes.

    PubMed

    Guizouarn, H; Musch, M W; Goldstein, L

    2003-05-15

    Anion exchangers (AE) are transmembrane proteins catalyzing electroneutral exchange of Cl(-) for HCO3-. To date, three different genes coding for this protein, AE1, AE2 and AE3, have been identified in many species. AE1 is considered to be the unique anion exchanger expressed in erythrocytes. In this paper we propose the presence of three different AEs in skate erythrocytes, a skAE1, a skAE2 and a skAE3, cloned by RT-PCR (reverse-transcriptase polymerase chain reaction). These three skAE have a similar predicted secondary structure. All three skAE are divided in two main domains: a hydrophilic cytoplasmic N-terminal domain and a C-terminal domain crossing the lipid bilayer at least 12 times. The greatest similarity is found in the membrane-spanning domain of the three skAE. The size as well as the amino-acid sequence of the cytoplasmic domain differ significantly among three anion exchangers. Functional expression studies in Xenopus oocytes led to the conclusion that skAE-1 and -2 share some functional features (Cl-dependence and DIDS sensitivity). The skAE3 could not be expressed in Xenopus oocytes. These data are in agreement with expression data obtained with AEs of different species utilizing the oocyte system. It is highly probable that these three new AE sequences come from three different genes, thus suggesting for the first time the presence of the three AE genes in Chondrichthyes.

  14. Dynamics of metal-humate complexation equilibria as revealed by isotope exchange studies - a matter of concentration and time

    NASA Astrophysics Data System (ADS)

    Lippold, Holger; Eidner, Sascha; Kumke, Michael U.; Lippmann-Pipke, Johanna

    2017-01-01

    Complexation with dissolved humic matter can be crucial in controlling the mobility of toxic or radioactive contaminant metals. For speciation and transport modelling, a dynamic equilibrium process is commonly assumed, where association and dissociation run permanently. This is, however, questionable in view of reported observations of a growing resistance to dissociation over time. In this study, the isotope exchange principle was employed to gain direct insight into the dynamics of the complexation equilibrium, including kinetic inertisation phenomena. Terbium(III), an analogue of trivalent actinides, was used as a representative of higher-valent metals. Isotherms of binding to (flocculated) humic acid, determined by means of 160Tb as a radiotracer, were found to be identical regardless of whether the radioisotope was introduced together with the bulk of stable 159Tb or subsequently after pre-equilibration for up to 3 months. Consequently, there is a permanent exchange of free and humic-bound Tb since all available binding sites are occupied in the plateau region of the isotherm. The existence of a dynamic equilibrium was thus evidenced. There was no indication of an inertisation under these experimental conditions. If the small amount of 160Tb was introduced prior to saturation with 159Tb, the expected partial desorption of 160Tb occurred at much lower rates than observed for the equilibration process in the reverse procedure. In addition, the rates decreased with time of pre-equilibration. Inertisation phenomena are thus confined to the stronger sites of humic molecules (occupied at low metal concentrations). Analysing the time-dependent course of isotope exchange according to first-order kinetics indicated that up to 3 years are needed to attain equilibrium. Since, however, metal-humic interaction remains reversible, exchange of metals between humic carriers and mineral surfaces cannot be neglected on the long time scale to be considered in predictive

  15. Tank 241-AZ-102 SuperLig 639 Technetium Ion Exchange Eluate Evaporation Study

    SciTech Connect

    King, W.D.

    2001-02-15

    As part of the Hanford River Protection Project (RPP), the Savannah River Technology Center (SRTC) has conducted tests on the pretreatment and vitrification of a radioactive waste sample from Hanford Tank 241-AZ-102. The original, AZ-102 sample which was received at SRTC was characterized and filtered to remove entrained solids.1 The sample was then passed sequentially through ion exchange columns containing SuperLig{reg_sign} 644 and 639 resins for the removal of cesium and technetium ions (Tc removed as pertechnetate, TcO{sub 4}{sup {minus}}), respectively.2 The cesium and technetium absorbed to the resins was then eluted to give separate eluate solutions containing relatively high concentrations of Cs{sup +} and TcO{sub 4}{sup {minus}}. According to the current plant design, the decontaminated Tank 241-AZ-102 sample and the eluate solutions will be subjected to separate evaporation and vitrification processes to give low- and high-activity waste glasses, respectively. This report describes evaporation testing of the Tc eluate solution derived from ion exchange processing of the Tank 241-AZ-102 sample with SuperLig 639 resin.

  16. Electron paramagnetic resonance studies of copper ion-exchanged ZSM-5

    SciTech Connect

    Larsen, S.C.; Aylor, A.; Bell, A.T.; Reimer, J.A. )

    1994-11-03

    Electron paramagnetic resonance (EPR) spectroscopy was utilized to probe the oxidation state and coordination environment of copper in ion-exchanged CuZSM-5. EPR spectra of hydrated samples were consistent with octahedral coordination. Square pyramidal and square-planar sites were identified in pretreated CuZSM-5 samples, and the relative concentration of square-pyramidal sites in these samples was linearly correlated with the copper-exchange level. The extent of autoreduction was monitored by EPR and it was determined that a substantial fraction (approximately 40-60%) of the copper was reduced and the reduction process was reversible in the presence of water. A mechanism for the autoreduction of copper is proposed that is consistent with the EPR results. Further, the reactivity of the proposed copper species was probed in reducing and oxidizing environments and in the presence of nitric oxide. The increase in EPR signal intensity that was observed after room-temperature NO exposure of pretreated and oxidized CuZSM-5 is attributed to the formation of copper nitrite and nitrate species. High-temperature in situ EPR experiments revealed that on the time scale of the EPR experiment, the paramagnetic copper environment did not change at elevated temperatures in the presence of nitric oxide. 39 refs., 13 figs., 3 tabs.

  17. Large scale micromagnetic simulations to study the exchange interaction between a ferromagnet and an antiferromagnet

    NASA Astrophysics Data System (ADS)

    Saha, Jyotirmoy Balaram

    In recent years, the topic of exchange bias has generated a strong research interest both in the scientific and technological community owing at least partly to its use in Giant Magnetoresistive Heads and potential use in other spin-valve devices. Although a large amount of effort has already been invested in this field, there are still deficiencies in the standard model. Such a model's capability should go beyond just predicting basic loop characteristics and additionally, should predict most experimental observations like temperature, grain-size and antiferromagnetic thickness dependence of exchange bias. It should also link the loop shape asymmetry and training effect to the symmetry of the antiferromagnet and the mechanism/s responsible for magnetization reversal. This research work was geared towards building such a model wherein the input parameters would be accurately estimated from material characteristics. This effort has produced a reasonable numerical match with experimental outcomes that goes far beyond similar endeavors and additionally has reproduced many experimentally observed trends. Almost a quarter million magnetic elements were simulated to enable the observation of domain nucleation during magnetization reversal. This significant scientific breakthrough is a novel feature of the project and has not been achieved in previous theoretical work.

  18. Kinetics and thermodynamics studies of copper exchange on Na-montmorillonite clay mineral.

    PubMed

    El-Batouti, Mervette; Sadek, Olfat M; Assaad, Fayez F

    2003-03-15

    The kinetics of Cu ion exchange on Na-montmorillonite clay has been investigated at 20, 30, and 40 degrees C in water, methanol, and ethanol. The reaction is endothermic in nature. Solvent effects on the reaction rate have been discussed. The thermodynamic activation parameters were calculated and discussed in terms of solvation effects. A multiple reaction rate order equation was used to describe the adsorption process. Lower rates and higher activation energies (Ea) were observed in aqueous solution than in either of the alcohols. The Ea values ranged from 20.88 kJmol(-1) in water to 9.20 kJmol(-1) in ethanol, while at 20 degrees C the rate constant (k) varied from 0.111 ppm(-1)s(-1) in water to 0.205 ppm(-1)s(-1) in ethanol. The main factor influencing the rate of the adsorption process is the mobility of the adsorbed Cu cations, which is apparently larger in alcohols than in water, due to the difference in the molar activation energy of the solvent. The determined isokinetic temperature indicates that the reaction is enthalpy-controlled, where the interaction between solvent and clay surface plays an important role. A reaction mechanism that describes the solvent effect on the rate of Cu ion exchange is proposed.

  19. A Computational Study of a Recreated G Protein-GEF Reaction Intermediate Competent for Nucleotide Exchange: Fate of the Mg Ion

    PubMed Central

    Ben Hamida-Rebaï, Mériam; Robert, Charles H.

    2010-01-01

    Small G-proteins of the superfamily Ras function as molecular switches, interacting with different cellular partners according to their activation state. G-protein activation involves the dissociation of bound GDP and its replacement by GTP, in an exchange reaction that is accelerated and regulated in the cell by guanine-nucleotide exchange factors (GEFs). Large conformational changes accompany the exchange reaction, and our understanding of the mechanism is correspondingly incomplete. However, much knowledge has been derived from structural studies of blocked or inactive mutant GEFs, which presumably closely represent intermediates in the exchange reaction and yet which are by design incompetent for carrying out the nucleotide exchange reaction. In this study we have used comparative modelling to recreate an exchange-competent form of a late, pre-GDP-ejection intermediate species in Arf1, a well-characterized small G-protein. We extensively characterized three distinct models of this intermediate using molecular dynamics simulations, allowing us to address ambiguities related to the mutant structural studies. We observed in particular the unfavorable nature of Mg associated forms of the complex and the establishment of closer Arf1-GEF contacts in its absence. The results of this study shed light on GEF-mediated activation of this small G protein and on predicting the fate of the Mg ion at a critical point in the exchange reaction. The structural models themselves furnish additional targets for interfacial inhibitor design, a promising direction for exploring potentially druggable targets with high biological specificity. PMID:20174625

  20. Salt, phosphate and the Bohr effect at the hemoglobin beta chain C terminus studied by hydrogen exchange.

    PubMed

    Louie, G; Englander, J J; Englander, S W

    1988-06-20

    Hydrogen exchange experiments using functional labeling and fragment separation methods were performed to study interactions at the C terminus of the hemoglobin beta subunit that contribute to the phosphate effect and the Bohr effect. The results show that the H-exchange behavior of several peptide NH at the beta chain C terminus is determined by a transient, concerted unfolding reaction involving five or more residues, from the C-terminal His146 beta through at least Ala142 beta, and that H-exchange rate can be used to measure the stabilization free energy of interactions, both individually and collectively, at this locus. In deoxy hemoglobin at pH 7.4 and 0 degrees C, the removal of 2,3-diphosphoglycerate (DPG) or pyrophosphate (loss of a salt to His143 beta) speeds the exchange of the beta chain C-terminal peptide NH protons by 2.5-fold (at high salt), indicating a destabilization of the C-terminal segment by 0.5 kcal of free energy. Loss of the His146 beta 1 to Asp94 beta 1 salt link speeds all these protons by 6.3-fold, indicating a bond stabilization free energy of 1.0 kcal. When both these salt links are removed together, the effect is found to be strictly additive; all the protons exchange faster by 16-fold indicating a loss of 1.5 kcal in stabilization free energy. Added salt is slightly destabilizing when DPG is present but provides some increased stability, in the 0.2 kcal range, when DPG is absent. The total allosteric stabilization energy at each beta chain C terminus in deoxy hemoglobin under these conditions is measured to be 3.8 kcal (pH 7.4, 0 degrees C, with DPG). In oxy hemoglobin at pH 7.4 and 0 degrees C, stability at the beta chain C terminus is essentially independent of salt concentration, and the NES modification, which in deoxy hemoglobin blocks the His146 beta to Asp94 beta salt link, has no destabilizing effect, either at high or low salt. These results appear to show that the His146 beta salt link, which participates importantly in the

  1. Exchange between the upper tropical troposphere and the lower stratosphere studied with aircraft observations

    NASA Astrophysics Data System (ADS)

    Tuck, A. F.; Hovde, S. J.; Kelly, K. K.; Mahoney, M. J.; Proffitt, M. H.; Richard, E. C.; Thompson, T. L.

    2003-12-01

    Exchange between the upper tropical troposphere and the lower stratosphere is considered by examining WB57F and ER-2 aircraft observations of water, ozone, wind, and temperature in the potential temperature range 360 < θ < 420 K. These processes are examined in part by using the technique of unified scale invariance on the airborne data, as has been done previously for the lower stratospheric polar vortex. Scale invariance is found, on scales from a few hundred meters to the maximum flown, 2700 km (25 great circle degrees). The results apply both to vertical exchange at the tropical tropopause and to isentropic exchange at the subtropical jet stream. All scales participate in the maintenance of the mean state, with substantial contributions from relatively infrequent but intense events in the long tails of the probability distributions. Past data are examined and found to fit this general framework. A unique mapping of tropical tropopause temperature to the total hydrogen content of the middleworld and overworld should not be expected; the head of the "tape recorder" is at 50-60 hPa rather than 90-100 hPa. The tropical tropopause is observed at potential temperatures θT greater than the maximum moist static surface values θW, such that θT - θW varies between 10 K in fall and up to 40 K in spring. The meridional gradient of θT is directed from the subtropical jet stream to the inner tropics, with θT declining by approximately 10 K from near 30°N to near 10°N in the vicinity of 95°W. The maintenance of these θT values is discussed. Total water (measured as the sum of vapor and vaporized ice) and ozone, major absorbers of solar radiation and emitters/absorbers of terrestrial infrared radiation, show scale invariance in the upper tropical troposphere. The implications of this result for the notion of a conservative cascade of energy via fluid dynamics from the largest to the smallest scales are discussed. The scaling exponents Hz for total water and ozone in

  2. Exchange Network

    EPA Pesticide Factsheets

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

  3. Gas exchange

    MedlinePlus Videos and Cool Tools

    ... during exhalation. Gas exchange is the delivery of oxygen from the lungs to the bloodstream, and the ... share a membrane with the capillaries in which oxygen and carbon dioxide move freely between the respiratory ...

  4. 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)

  5. Experimental Background Studies in the Two Photon Exchange (TPE) Experiment at Jefferson Lab

    SciTech Connect

    Cristian Peña, W. K. Brooks, Hayk Hakobyan

    2010-08-01

    This work is based on the improvement of an existing simulation for the two photon exchange (TPE) experiment at Jefferson Lab developed within the GEANT4 framework. This experiment will determine the ratio of the positron-proton elastic scattering cross section and the electron-proton elastic scattering cross section with high precision. To accomplish this measurement requires the use of a variety of devices and complex arrangements, creating background particles that manage to reach the detector system (CLAS). A number of test runs have identified the sources of background in the detector guided by previous simulations. Even so, the remaining background can be reduced considerably by the microscopic identification and locating of the background sources performed by our new simulation.

  6. Experimental Background Studies in the Two Photon Exchange (TPE) Experiment at Jefferson Lab

    SciTech Connect

    Pena, Cristian; Brooks, W. K.; Hakobyan, Hayk

    2010-08-04

    This work is based on the improvement of an existing simulation for the two photon exchange (TPE) experiment at Jefferson Lab developed within the GEANT4 framework. This experiment will determine the ratio of the positron-proton elastic scattering cross section and the electron-proton elastic scattering cross section with high precision. To accomplish this measurement requires the use of a variety of devices and complex arrangements, creating background particles that manage to reach the detector system (CLAS). A number of test runs have identified the sources of background in the detector guided by previous simulations. Even so, the remaining background can be reduced considerably by the microscopic identification and locating of the background sources performed by our new simulation.

  7. 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.

  8. 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.

  9. A three-dimensional, quantum mechanical study of exchange and charge transfer processes in the (Ar+H2) + system

    NASA Astrophysics Data System (ADS)

    Baer, Michael; Nakamura, Hiroki

    1987-10-01

    A three-dimensional quantum mechanical study of the (Ar+H2)+ system was carried out within the reactive infinite order sudden approximation. All three arrangement channels for exchange and charge transfer were treated simultaneously. Steric factors, opacity functions, angular distributions, and integral cross sections were calculated. Whenever possible, these were compared with both experimental and trajectory surface hopping (TSH) results. Whereas the fit with the TSH results was reasonable, the fit obtained with the experiment was less satisfactory. The reason for that can be attributed at least partially to the semiempirical DIM potential employed in the calculation.

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

    NASA Astrophysics Data System (ADS)

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

    2015-11-01

    Using a millifluidics and macroscale setup, we study quantitatively the impact of gas exchange on bacterial growth. In millifluidic environments, the permeability of the incubator materials allows an unlimited oxygen supply by diffusion. Moreover, the efficiency of diffusion at small scales makes the supply instantaneous in comparison with the cell division time. In hermetic closed vials, the amount of available oxygen is low. The growth curve has the same trend but is quantitatively different from the millifluidic situation. The analysis of all the data allows us to write a quantitative modeling enabling us to capture the entire growth process.

  11. 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.

  12. 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.

  13. Thermal and Mechanical Non-Equilibrium Effects on Turbulent Flows: Fundamental Studies of Energy Exchanges Through Direct Numerical Simulations, Molecular Simulations and Experiments

    DTIC Science & Technology

    2016-02-26

    AFRL-AFOSR-VA-TR-2016-0104 Thermal and mechanical non-equilibrium effects on turbulent flows:fundamental studies of energy exchanges through direct ...flows: fundamental studies of energy exchanges through direct numerical simulations, molecular simulations and experiments 5a.  CONTRACT NUMBER 5b...control of basic fluid dynamic processes is of direct relevance to AFOSR scientific objectives especially for turbulence flows. The very limited

  14. 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.

  15. A flash-photolysis electron spin resonance study of radicals formed from carboxylic acids; exchange effects in spin-polarized radicals

    NASA Astrophysics Data System (ADS)

    McLauchlan, K. A.; Ritchie, A. J. D.

    The time-integration spectroscopy (TIS) technique has been applied to the study of transient radicals created by flash photolysis of solutions of benzene-1,2,4,5-tetracarboxylic acid (pyromellitic acid), benzene-1,2,-dicarboxylic acid (phthalic acid) and benzene-1,4-dicarboxylic acid (terephthalic acid). In these systems electron transfer, proton transfer and rotational isomerism all affect the spin-polarized spectra observed. The exchange processes are analysed theoretically, in the case of proton exchange for the first time in the polarized situation, and it is shown that the two different exchange processes can be simply differentiated in the time-dependent TIS spectra.

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

    SciTech Connect

    Kara, Mahmut; Zacharias, Martin W.

    2013-03-05

    Chemical modification or radiation can cause DNA damage, which plays a crucial role for mutagenesis of DNA, carcinogenesis, and aging. DNA damage can also alter the fine structure of DNA that may serve as a recognition signal for DNA repair enzymes. A new, advanced sampling replica-exchange method has been developed to specifically enhance the sampling of conformational substates in duplex DNA during molecular dynamics (MD) simulations. The approach employs specific biasing potentials acting on pairs of pseudodihedral angles of the nucleic acid backbone that are added in the replica simulations to promote transitions of the most common substates of the DNA backbone. The sampled states can exchange with a reference simulation under the control of the original force field. The application to 7,8-dihydro-8oxo-guanosine, one of the most common oxidative damage in DNA indicated better convergence of sampled states during 10 ns simulations compared to 20 times longer standard MD simulations. It is well suited to study systematically the fine structure and dynamics of large nucleic acids under realistic conditions, including explicit solvent and ions. The biasing potential-replica exchange MD simulations indicated significant differences in the population of nucleic acid backbone substates in the case of 7,8-dihydro-8oxo-guanosine compared to a regular guanosine in the same sequence context. This concerns both the ratio of the B-DNA substates BI and BII associated with the backbone dihedral angles ε and z but also coupled changes in the backbone dihedral angles a and g. Such differences may play a crucial role in the initial recognition of damaged DNA by repair enzymes.

  17. Estuary/ocean exchange and tidal mixing in a Gulf of Maine Estuary: A Lagrangian modeling study

    NASA Astrophysics Data System (ADS)

    Bilgili, Ata; Proehl, Jeffrey A.; Lynch, Daniel R.; Smith, Keston W.; Swift, M. Robinson

    2005-12-01

    A Lagrangian particle method embedded within a 2-D finite element code, is used to study the transport and ocean-estuary exchange processes in the well-mixed Great Bay Estuarine System in New Hampshire, USA. The 2-D finite element model, driven by residual, semi-diurnal and diurnal tidal constituents, includes the effects of wetting and drying of estuarine mud flats through the use of a porous medium transport module. The particle method includes tidal advection, plus a random walk model in the horizontal that simulates sub-grid scale turbulent transport processes. Our approach involves instantaneous, massive [O(500,000)] particle releases that enable the quantification of ocean-estuary and inter-bay exchanges in a Markovian framework. The effects of the release time, spring-neap cycle, riverine discharge and diffusion strength on the intra-estuary and estuary-ocean exchange are also investigated. The results show a rather dynamic interaction between the ocean and the estuary with a fraction of the exiting particles being caught up in the Gulf of Maine Coastal Current and swept away. Three somewhat different estimates of estuarine residence time are calculated to provide complementary views of estuary flushing. Maps of residence time versus release location uncover a strong spatial dependency of residence time within the estuary that has very important ramifications for local water quality. Simulations with and without the turbulent random walk show that the combined effect of advective shear and turbulent diffusion is very effective at spreading particles throughout the estuary relatively quickly, even at low (1 m 2/s) diffusivity. The results presented here show that a first-order Markov Chain approach has applicability and a high potential for improving our understanding of the mixing processes in estuaries.

  18. 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.

  19. Stimulated Raman scattering of picosecond light pulses in hydrogen, deuterium, and methane

    SciTech Connect

    Hanna, D.C.; Pointer, D.J.; Pratt, D.J.

    1986-02-01

    Experimental results are presented on stimulated Raman scattering of short pulses of approximately 100 ps duration in H/sub 2/, D/sub 2/, and CH/sub 4/, both in capillary waveguides and in a tight focusing geometry. Experimentally determined thresholds are in good agreement with calculation. Low thresholds (<20 ..mu..J) are observed in CH/sub 4/ and preliminary results using a mode-locked dye laser as pump indicate a useful source of tunable short pulse radiation in the near infrared.

  20. Chiral glycine formation on cold interstellar grains by quantum tunneling hydrogen-deuterium substitution reactions

    NASA Astrophysics Data System (ADS)

    Oba, Yasuhiro; Watanabe, Naoki; Osamura, Yoshihiro; Kouchi, Akira

    2015-08-01

    We report experimental evidence that chiral glycine (NH2CHDCOOH) is formed by the surface reaction of normal glycine (NH2CH2COOH) solid with deuterium (D) atom at 12 K under the simulative conditions of interstellar molecular clouds. Chiral glycine formation is most likely initiated by the tunneling abstraction reaction of H atom by D atom followed by the addition of D atom to the glycine radical (NH2CHCOOH). Given that chiral glycine can form in such a primordial low-temperature environment, it might source molecular chirality as molecular clouds evolve into planetary systems.

  1. Absorption and desorption of hydrogen, deuterium, and tritium for Zr--V--Fe getter

    SciTech Connect

    Ichimura, K.; Inoue, N.; Watanabe, K.; Takeuchi, T.

    1984-07-01

    Nonevaporable getters have wide applicability for developing the tritium handling techniques for thermonuclear fusion devices. From this viewpoint, mechanisms of the absorption and desorption of hydrogen isotopes and the isotope effects were investigated for a Zr--V--Fe alloy (St-707) by means of the mass analyzed thermal desorption spectroscopy. It was observed that the absorption rate was proportional to the first power of the pressure, indicating that the rate limiting step is the dissociative adsorption of hydrogen isotopes on the surface. The activation energy was very small, in the order of magnitude of a few tens of calories per mole in a temperature range from -196 to 200 /sup 0/C. The desorption rate was proportional to the square of the amount of absorption, indicating that the rate limiting step is the associative desorption reaction of hydrogen atoms or ions diffused to the surface from the bulk. The rate constants for hydrogen and deuterium were determined as k/sub d/(H/sub 2/) = (5.3/sup +2.6//sub -1.7/)exp(-(28.0 +- 0.7) x 10/sup 3//RT) and k/sub d/(D/sub 2/) = (5.0/sup +2.7//sub -1.7/)exp(-(28.6 +- 0.8) x 10/sup 3//RT) in (1/Pa 1 s), respectively, where R is in (cal/mol deg). With regard to tritium, the rate constant was evaluated as k/sub d/(T/sub 2/) = (5.0/sup +20//sub -4.0/)exp(-(29.3 +- 3) x 10/sup 3//RT), however, the frequency factor will have to be corrected by knowing the relative sensitivity factor of the mass spectrometer for tritium (T/sub 2/).

  2. Temperature-dependent adsorption of hydrogen, deuterium, and neon on porous Vycor glass

    NASA Astrophysics Data System (ADS)

    Huber, T. E.; Scardino, D.; Tsou, H. L.

    1995-10-01

    Adsorption isotherms of H2, D2, and Ne have been measured in the temperature range from 15 K to the corresponding critical points in samples of porous Vycor glass. From the Brunauer-Emmett-Teller theory the surface layer coverages are determined. These are found to be temperature dependent. A model-independent approach allows us to fit the data for coverages ranging from submonolayer to thin film, below capillary condensation, for each adsorbate at all temperatures with a temperature-independent curve. This characteristic curve represents the distribution of adsorption sites versus the adsorption potential. In the intermediate coverage range, the isotherms exhibit the modified Frenkel-Halsey-Hill (FHH) behavior. The adsorption saturates for low-adsorption potentials. The characteristic curve is a useful universal curve since it is roughly the same for the three species investigated. We examine the relative strengths of the surface potentials and densities of the two isotopic modifications of hydrogen and of the more classical Ne adsorbed on porous Vycor glass. The characteristic adsorption curve is compared with results from two models for the adsorbate: Dubinin's isotherm for microporous solids and its extension to rough surfaces which places importance on the porosity of the surface, and Halsey's model, which is an extension of the FHH isotherm that takes into account the long-range variations of substrate adsorption potential.

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

    PubMed

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

    1970-01-30

    The water content of the breccia is 150 to 455 ppm, with a deltaD from-580 to -870 per mil. Hydrogen gas content is 40 to 53 ppm with a deltaD of -830 to -970 per mil. The CO(2) is 290 to 418 ppm with delta (13)C = + 2.3 to + 5.1 per mil and delta(18)O = 14.2 to 19.1 per mil. Non-CO(2) carbon is 22 to 100 ppm, delta(13)C = -6.4 to -23.2 per mil. Lunar dust is 810 ppm H(2)O (D = 80 ppm) and 188 ppm total carbon(delta(13)C = -17.6 per mil). The (18)O analyses of whole rocks range from 5.8 to 6.2 per mil. The temperature of crystallization of type B rocks is 1100 degrees to 1300 degrees C, based on the oxygen isotope fractionation between coexisting plagioclase and ilmenite.

  4. 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.

  5. Isotopic effect of parametric instabilities during lower hybrid waves injection into hydrogen/deuterium plasmas

    NASA Astrophysics Data System (ADS)

    Zhao, Aihui; Gao, Zhe

    2017-01-01

    Based on the local dispersion relation, the parametric instability (PI) was numerically investigated for the injection of lower hybrid waves (LHWs) into hydrogen and deuterium plasmas separately. Numerical calculations under typical scrape-off layer parameters in tokamak plasmas show that both the unstable regions of the PI and the values of growth rates are close for two cases, in spite of the decaying channel of the ion sound quasimode or ion cyclotron quasimode (ICQM). These numerical results could be understood by the analyses based on the fluid model. Parameter dependences are also similar for hydrogen and deuterium plasmas. For example, the ICQM growth rate increases with an increasing density, a decreasing temperature, and a decreasing magnetic field in deuterium plasmas as it does in hydrogen plasmas. The isotopic effect of the PI during the LHW injection is weak. As a result, the lower hybrid current drive efficiency at a high density in deuterium plasmas cannot be much improved over hydrogen plasmas if the PI process dominates the behavior of LHWs at the plasma edge.

  6. Native-state hydrogen-exchange studies of a fragment complex can provide structural information about the isolated fragments

    PubMed Central

    Chakshusmathi, G.; Ratnaparkhi, Girish S.; Madhu, P. K.; Varadarajan, R.

    1999-01-01

    Ordered protein complexes are often formed from partially ordered fragments that are difficult to structurally characterize by conventional NMR and crystallographic techniques. We show that concentration-dependent hydrogen exchange studies of a fragment complex can provide structural information about the solution structures of the isolated fragments. This general methodology can be applied to any bimolecular or multimeric system. The experimental system used here consists of Ribonuclease S, a complex of two fragments of Ribonuclease A. Ribonuclease S and Ribonuclease A have identical three-dimensional structures but exhibit significant differences in their dynamics and stability. We show that the apparent large dynamic differences between Ribonuclease A and Ribonuclease S are caused by small amounts of free fragments in equilibrium with the folded complex, and that amide exchange rates in Ribonuclease S can be used to determine corresponding rates in the isolated fragments. The studies suggest that folded RNase A and the RNase S complex exhibit very similar dynamic behavior. Thus cleavage of a protein chain at a single site need not be accompanied by a large increase in flexibility of the complex relative to that of the uncleaved protein. PMID:10393919

  7. 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

  8. Enhancing studies of the connectome in autism using the autism brain imaging data exchange II.

    PubMed

    Di Martino, Adriana; O'Connor, David; Chen, Bosi; Alaerts, Kaat; Anderson, Jeffrey S; Assaf, Michal; Balsters, Joshua H; Baxter, Leslie; Beggiato, Anita; Bernaerts, Sylvie; Blanken, Laura M E; Bookheimer, Susan Y; Braden, B Blair; Byrge, Lisa; Castellanos, F Xavier; Dapretto, Mirella; Delorme, Richard; Fair, Damien A; Fishman, Inna; Fitzgerald, Jacqueline; Gallagher, Louise; Keehn, R Joanne Jao; Kennedy, Daniel P; Lainhart, Janet E; Luna, Beatriz; Mostofsky, Stewart H; Müller, Ralph-Axel; Nebel, Mary Beth; Nigg, Joel T; O'Hearn, Kirsten; Solomon, Marjorie; Toro, Roberto; Vaidya, Chandan J; Wenderoth, Nicole; White, Tonya; Craddock, R Cameron; Lord, Catherine; Leventhal, Bennett; Milham, Michael P

    2017-03-14

    The second iteration of the Autism Brain Imaging Data Exchange (ABIDE II) aims to enhance the scope of brain connectomics research in Autism Spectrum Disorder (ASD). Consistent with the initial ABIDE effort (ABIDE I), that released 1112 datasets in 2012, this new multisite open-data resource is an aggregate of resting state functional magnetic resonance imaging (MRI) and corresponding structural MRI and phenotypic datasets. ABIDE II includes datasets from an additional 487 individuals with ASD and 557 controls previously collected across 16 international institutions. The combination of ABIDE I and ABIDE II provides investigators with 2156 unique cross-sectional datasets allowing selection of samples for discovery and/or replication. This sample size can also facilitate the identification of neurobiological subgroups, as well as preliminary examinations of sex differences in ASD. Additionally, ABIDE II includes a range of psychiatric variables to inform our understanding of the neural correlates of co-occurring psychopathology; 284 diffusion imaging datasets are also included. It is anticipated that these enhancements will contribute to unraveling key sources of ASD heterogeneity.

  9. Pulsed EPR studies of the exchangeable proton at the molybdenum center of dimethyl sulfoxide reductase.

    PubMed

    Raitsimring, Arnold M; Astashkin, Andrei V; Feng, Changjian; Enemark, John H; Nelson, Kimberly Johnson; Rajagopalan, K V

    2003-01-01

    Electron spin echo envelope modulation (ESEEM) spectroscopy has been used to determine the hyperfine ( hfi) and quadrupole ( nqi) interactions of the exchangeable deuteron (proton) at the Mo(V) site of DMSO reductase. The data obtained have been translated into structure-related parameters. It was found that isotropic hfi constant of the proton is not unique, but is distributed within a range of 26-36 MHz. From this hfi distribution, a 30 degrees -wide distribution of the OH bond orientations due to a rotation around the Mo-O bond was estimated. The angle between the axes of the nqi and anisotropic hfi tensors was found to be anomalously small in comparison with that expected from the Mo-O-D bond geometry. This peculiarity was attributed to the effect of spin density on the hydroxyl oxygen atom. The orientation of the Mo-OH fragment with respect to the g-frame was determined from the experimental orientations of the nqi and hfi tensor axes and a theoretical evaluation of the anisotropic hfi axis direction.

  10. 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.

  11. A Field Study of How Hydraulic Conductivity Heterogeneity Influences Hyporheic Exchange

    NASA Astrophysics Data System (ADS)

    Ryan, R. J.; Boufadel, M. C.

    2006-05-01

    A conservative solute tracer experiment was conducted in Indian Creek, a small urban stream located in Philadelphia, Pennsylvania to investigate the role of bed sediment hydraulic conductivity on hyporheic (surface- subsurface) exchange. Sodium Bromide (NaBr) was used as a conservative tracer, and it was monitored in the surface water at two stations and in the upper bed sediments (shallow hyporheic zone extending from 7.5 cm to 10 cm below the streambed). The hydraulic conductivity (K) of the upper bed sediments and the lower bed sediments (10 cm to 12.5 cm below the streambed) was measured in situ. High tracer concentrations were observed in the upper layer at locations where the hydraulic conductivity of the upper layer was larger than that of the lower layer. Low concentrations in the upper layer were observed in the converse case. A statistically significant relationship between the mass retained in the upper layer and the difference of K values between layers was observed.

  12. Morphological and transport characteristics of swollen chitosan-based proton exchange membranes studied by molecular modeling.

    PubMed

    Bahlakeh, Ghasem; Mahdi Hasani-Sadrabadi, Mohammad; Jacob, Karl I

    2017-01-01

    Chitosan biopolymer has been extensively applied in direct methanol fuel cells (DMFCs) as a potential replacement to conventional Nafion membrane for its considerably reduced methanol crossover. Here, we computationally explored the influences of methanol concentration, temperature, and pH parameters upon the nanostructure and dynamics, particularly the methanol crossover, in chitosan proton-exchange membrane (PEM) through molecular dynamics simulations. Theoretical results demonstrated the increased swelling and radius of gyration of chitosan chains at higher concentrations. Structural examinations further revealed that an increase in methanol loading weakened the water interactions with chitosan functionalities (amineNH2 , hydroxylOH, and methoxyCH2 OH) whereas improved the methanol affinities toward chitosan, reflecting higher methanol sorption capability of chitosan at enhanced concentrations. Additionally, it was found that interactions between solvents and chitosan strengthened under acidic pH conditions on account of amine protonation. The water diffusivity inside the swollen chitosan diminished by increasing CH3 OH uptake, and in contrast diffusivity of methanol was noted to enhance. Furthermore, it was observed that an enhancement in temperature or a decrease in pH intensified solvent mobility. These insights imply that supplying methanol-concentrated and/or acidic feed solutions into DMFCs based on chitosan PEMs could lower membrane performance due to the significant methanol transport dynamics.

  13. Enhancing studies of the connectome in autism using the autism brain imaging data exchange II

    PubMed Central

    Di Martino, Adriana; O’Connor, David; Chen, Bosi; Alaerts, Kaat; Anderson, Jeffrey S.; Assaf, Michal; Balsters, Joshua H.; Baxter, Leslie; Beggiato, Anita; Bernaerts, Sylvie; Blanken, Laura M. E.; Bookheimer, Susan Y.; Braden, B. Blair; Byrge, Lisa; Castellanos, F. Xavier; Dapretto, Mirella; Delorme, Richard; Fair, Damien A.; Fishman, Inna; Fitzgerald, Jacqueline; Gallagher, Louise; Keehn, R. Joanne Jao; Kennedy, Daniel P.; Lainhart, Janet E.; Luna, Beatriz; Mostofsky, Stewart H.; Müller, Ralph-Axel; Nebel, Mary Beth; Nigg, Joel T.; O’Hearn, Kirsten; Solomon, Marjorie; Toro, Roberto; Vaidya, Chandan J.; Wenderoth, Nicole; White, Tonya; Craddock, R. Cameron; Lord, Catherine; Leventhal, Bennett; Milham, Michael P.

    2017-01-01

    The second iteration of the Autism Brain Imaging Data Exchange (ABIDE II) aims to enhance the scope of brain connectomics research in Autism Spectrum Disorder (ASD). Consistent with the initial ABIDE effort (ABIDE I), that released 1112 datasets in 2012, this new multisite open-data resource is an aggregate of resting state functional magnetic resonance imaging (MRI) and corresponding structural MRI and phenotypic datasets. ABIDE II includes datasets from an additional 487 individuals with ASD and 557 controls previously collected across 16 international institutions. The combination of ABIDE I and ABIDE II provides investigators with 2156 unique cross-sectional datasets allowing selection of samples for discovery and/or replication. This sample size can also facilitate the identification of neurobiological subgroups, as well as preliminary examinations of sex differences in ASD. Additionally, ABIDE II includes a range of psychiatric variables to inform our understanding of the neural correlates of co-occurring psychopathology; 284 diffusion imaging datasets are also included. It is anticipated that these enhancements will contribute to unraveling key sources of ASD heterogeneity. PMID:28291247

  14. 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

  15. Exchange rate rebounds after foreign exchange market interventions

    NASA Astrophysics Data System (ADS)

    Hoshikawa, Takeshi

    2017-03-01

    This study examined the rebounds in the exchange rate after foreign exchange intervention. When intervention is strongly effective, the exchange rate rebounds at next day. The effect of intervention is reduced slightly by the rebound after the intervention. The exchange rate might have been 67.12-77.47 yen to a US dollar without yen-selling/dollar-purchasing intervention of 74,691,100 million yen implemented by the Japanese government since 1991, in comparison to the actual exchange rate was 103.19 yen to the US dollar at the end of March 2014.

  16. 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.

  17. 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.

  18. 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.

  19. Comparative study on performance of a zigzag printed circuit heat exchanger with various channel shapes and configurations

    NASA Astrophysics Data System (ADS)

    Lee, Sang-Moon; Kim, Kwang-Yong

    2013-07-01

    Comparative study has been performed with various channel cross-sectional shapes and channel configurations of a zigzag printed circuit heat exchanger (PCHE), which has been considered as a heat exchanging device for the gas turbine based generation systems. Three-dimensional Reynolds-averaged Navier-Stokes equations and heat transfer equations are solved to analyze conjugate heat transfer in the zigzag channels. The shear stress transport model with a low Reynolds number wall treatment is used as a turbulence closure. The global Nusselt number, Colburn j-factor, effectiveness, and friction factor are used to estimate the thermal-hydraulic performance of the PCHE. Four different shapes of channel cross section (semicircular, rectangular, trapezoidal, and circular) and four different channel configurations are tested to determine their effects on thermal-hydraulic performance. The rectangular channel shows the best thermal performance but the worst hydraulic performance, while the circular channel shows the worst thermal performance. The Colburn j-factor and friction factor are found to be inversely proportional to the Reynolds number in cold channels, while the effectiveness and global Nusselt number are proportional to the Reynolds number.

  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. The study of mercury exchange rate between air and soil surface in Hongfeng reservoir region, Guizhou, PR China

    NASA Astrophysics Data System (ADS)

    Wang, S.; Feng, X.; Qiu, G.

    2003-05-01

    In summer of 2002, we measured the exchange flux of mercury between air and soil surface using the method of Dynamic Flux Chamber (DFC) in Hongfeng lake region. At the same time, we recorded meteorological parameters such as air temperature, soil temperature, wind speed and solar radiation using a multi-function mini-weather station (global water III). Soil, moss and fertilizer samples in study area were also collected. The Hg fluxes of air/soil surface rangeed from -11.0ng m^{-2} h^{-1} to 219.0ng m^{-2}h^{-1}, averaged at 29.2 ng m^{-2} h^{-1} (n = 508). The data show that the exchange of mercury is bi-direction between air and soit surface: namely both emission and deposition of mercury occurs, but Hg emission is much more frequent than deposition process (n_{deposition} =3,n_{emission}= 505). The average mercury content in soil, moss, fertilizer sample are 249.9± 24.1ng/g (n=3), 450.4 ± 64.6ng/g (n=2), 53.4ng/g (n= 1) respectively.

  2. Feasibility and kinetics study on the direct bio-regeneration of perchlorate laden anion-exchange resin.

    PubMed

    Wang, Chao; Lippincott, Lee; Meng, Xiaoguang

    2008-11-01

    Anion exchange is one of the most promising treatment technologies for the removal of low levels of perchlorate. The spent anion-exchange resins, however, need to be disposed of or regenerated because they contain high contents of perchlorate. This study investigated the feasibility and kinetics of a direct bio-regeneration method. The method accomplished resin regeneration and biological perchlorate destruction concurrently, by directly contacting the spent resin with the perchlorate-reducing bacteria (PRB). The results indicated that the method was effective in regeneration of perchlorate and nitrate loaded resin and the resin could be repeatedly regenerated with the method. The regenerated resin was effective, stable, and durable in the filtration treatment of perchlorate in well water from the Saddle River area, NJ. Moreover, the method was also effective in regeneration of the spent A-530E resin, which had high perchlorate affinity and was yet very difficult for regeneration with the conventional brine desorption technique. Besides, the results further suggested that the perchlorate and nitrate desorption from the loaded resin coupling with their subsequent biological reduction could be the direct bio-regeneration mechanism. No biofilm was formed on the regenerated resin surface according to a scanning electron microscopy (SEM) analysis.

  3. Arsenic(V) removal using an amine-doped acrylic ion exchange fiber: Kinetic, equilibrium, and regeneration studies.

    PubMed

    Lee, Chang-Gu; Alvarez, Pedro J J; Nam, Aram; Park, Seong-Jik; Do, Taegu; Choi, Ung-Su; Lee, Sang-Hyup

    2017-03-05

    This study investigates As(V) removal from aqueous solutions using a novel amine-doped acrylic ion exchange fiber. The amine doping reaction was confirmed using FT-IR, and the surface of the fiber was characterized using FEG-SEM. The synthesis process was completed within 60min using an AlCl3·6H2O catalyst at 100°C, and the resulting in a fiber with an ion exchange capacity of 7.5meq/g. The removal efficiency of the A-60 fiber was affected by the solution pH, and the efficiency was optimum at pH 3.04. As(V) adsorption on the fiber was rapid in the first 20min and reached equilibrium in 60min. As(V) removal followed pseudo-first-order kinetics, and the Redlich-Peterson adsorption isotherm model provided the best fit of the equilibrium data. The fiber has an As(V) adsorption capacity (qe) of 205.32±3.57mg/g, which is considerably higher than literature values and commercial adsorbents. The removal efficiency of the fiber was above 83% of the initial value after nine regeneration cycles.

  4. 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

  5. Isotope tracer study of hydrogen spillover on carbon-based adsorbents for hydrogen storage.

    PubMed

    Lachawiec, Anthony J; Yang, Ralph T

    2008-06-17

    A composite material comprising platinum nanoparticles supported on molecular sieve templated carbon was synthesized and found to adsorb 1.35 wt % hydrogen at 298 K and 100 atm. The isosteric heat of adsorption for the material at low coverage was approximately 14 kJ/mol, and it approached a value of 10.6 kJ/mol as coverage increased for pressures at and above 1 atm. The increase in capacity is attributed to spillover, which is observed with the use of isotopic tracer TPD. IRMOF-8 bridged to Pt/C, a material known to exhibit hydrogen spillover at room temperature, was also studied with the hydrogen-deuterium scrambling reaction for comparison. The isotherms were reversible. For desorption, sequential doses of H2 and D2 at room temperature and subsequent TPD yield product distributions that are strong indicators of the surface diffusion controlled reverse spillover process.

  6. Effect of Taiwan mutation (D7H) on structures of amyloid-β peptides: replica exchange molecular dynamics study.

    PubMed

    Truong, Phan Minh; Viet, Man Hoang; Nguyen, Phuong H; Hu, Chin-Kun; Li, Mai Suan

    2014-07-31

    Recent experiments have shown that the Taiwan mutation (D7H) slows the fibril formation of amyloid peptides Aβ40 and Aβ42. Motivated by this finding, we have studied the influence of D7H mutation on structures of Aβ peptide monomers using the replica exchange molecular dynamics simulations with OPLS force field and implicit water model. Our study reveals that the mechanism behind modulation of aggregation rates is associated with decrease of β-content and dynamics of the salt bridge D23-K28. Estimating the bending free energy of this salt bridge, we have found that, in agreement with the experiments, the fibril formation rate of both peptides Aβ40 and Aβ42 is reduced about two times by mutation.

  7. Magnetic properties of exchange biased and of unbiased oxide/permalloy thin layers: a ferromagnetic resonance and Brillouin scattering study.

    PubMed

    Zighem, F; Roussigné, Y; Chérif, S-M; Moch, P; Ben Youssef, J; Paumier, F

    2010-10-13

    Microstrip ferromagnetic resonance and Brillouin scattering are used to provide a comparative determination of the magnetic parameters of thin permalloy layers interfaced with a non-magnetic (Al(2)O(3)) or with an antiferromagnetic oxide (NiO). It results from our microstructural study that no preferential texture is favoured in the observed polycrystalline sublayers. It is shown that the perpendicular anisotropy can be monitored using an interfacial surface energy term which is practically independent of the nature of the interface. In the interval of thicknesses investigated (5-25 nm) the saturation magnetization does not significantly differ from the reported one in bulk permalloy. In-plane uniaxial anisotropy and exchange bias anisotropy are also derived from the study of the dynamic magnetic excitations and compared with our independent evaluations using conventional magnetometry.

  8. Direct observations of Biogenic Volatile Organic Compound (BVOC) Air-Sea Exchange in the remote North Atlantic from the High-Wind Gas-Exchange Study (HiWinGS)

    NASA Astrophysics Data System (ADS)

    Kim, M.; Yang, M. X.; Blomquist, B.; Huebert, B. J.; Bertram, T. H.

    2014-12-01

    Biogenic Volatile Organic Compounds (BVOCs) are reactive trace gases that impact both chemistry and climate by regulating oxidant loadings, determining secondary organic aerosol production rates as well as altering particle hygroscopicity. While continental BVOC exchange rates are well studied, global marine flux estimates are poorly constrained. In Fall 2013, a chemical-ionization time-of-flight mass spectrometer (CI-ToF-MS) utilizing benzene cations was deployed as part of the High Wind Gas Exchange Study (HiWinGs) to quantify monoterpenes, isoprene and dimethylsulfide fluxes in the remote North Atlantic. Dimethylsulfide measurements are in strong agreement with those determined by the University of Hawaii's atmospheric pressure ionization mass-spectrometer. In the remote marine boundary layer, positive monoterpene fluxes (i.e. emissions) were observed while isoprene levels rarely exceeded the detection limit.

  9. 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.

  10. Off-resonance R1rho relaxation outside of the fast exchange limit: an experimental study of a cavity mutant of T4 lysozyme.

    PubMed

    Korzhnev, Dmitry M; Orekhov, Vladislav Yu; Dahlquist, Frederick W; Kay, Lewis E

    2003-05-01

    An (15)N off-resonance R(1rho) spin relaxation study of an L99A point mutant of T4 lysozyme is presented. Previous CPMG-based relaxation dispersion studies of exchange in this protein have established that the molecule interconverts between a populated ground state and an excited state (3.4%) with an exchange rate constant of 1450 s(-1) at 25 degrees C. It is shown that for the majority of residues in this protein the offset dependence of the R(1rho) relaxation rates cannot be well fit using models which are only valid in the fast exchange regime. In contrast, a recently derived expression by Trott and Palmer (J. Magn. Reson., 154, 157-160, 2002) which is valid over a wider window of exchange than other relations, is shown to fit the data well. Values of (signed) chemical shift differences between exchanging sites have been extracted and are in reasonable agreement with shift differences measured using CPMG methods. A set of simulations is presented which help establish the exchange regimes that are best suited to analysis by off-resonance R(1rho) techniques.

  11. 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.

  12. Study of catalysts with high stability for proton exchange membrane fuel cells

    NASA Astrophysics Data System (ADS)

    Yang, Fan

    The innovation and investigation of catalysts in proton exchange membrane fuel cells are included in this thesis. In the first part of this work, stability of the catalyst support of PEMFC catalyst is investigated. Nanoscale platinum particles were loaded on two different kinds of carbon supports, nano graphene sheets and functionalized carbon black/graphene hybrid were developed by the liquid phase reaction. The crystal structure of two kinds of catalysts was characterized by X-ray diffractometer (XRD). The morphology and particle size were characterized by scanning electron microscope (SEM) and transmission electron microscope (TEM). Pt loading was measured by thermal gravimetric analysis (TGA). The Brunauer, Emmett and Teller (BET) method was applied to test the surface area of the catalysts. The electrochemical surface area (ECSA) and mass activity during oxygen reduction reaction (ORR) process for two kinds of catalyst were tested by cyclic voltammetry method under different conditions. The stability of the catalysts were tested by accelerated durability test (ADT). The results show that although the mass activity of Pt/graphene is much lower, the stability of it is much better than that of the commercial catalyst. After adding functionalized carbon black (FCB) as spacer, the stability of the catalyst is preserved and at the meantime, the mass activity becomes higher than 20% Pt/XC72 catalyst. The lower mass activity of both catalysts are due to the limitation of the electrolyte diffusion into the carbon support because of the aggregation nature of graphene nano-sheets. After introducing functional carbon black as spacer, the mass activity and ECSA increased dramatically which proved that FCB can be applied to prevent the restacking of graphene and hence solved the diffusion problem. In the meantime, the durability was still keeping the same as Pt/graphene catalyst. In the second part of the work, the restacking problem was solved by introducing FCB as spacers

  13. 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

  14. 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.

  15. Studies of transient behavior of proton exchange membrane fuel cells (PEMFC)

    NASA Astrophysics Data System (ADS)

    Kim, Sunhoe

    The Proton Exchange Membrane Fuel Cell (PEMFC) is a technology with growing interest. The PEMFC is the most fascinating among other kinds of fuel cells for its high power density and zero emission pure water products. The use of PEMFCs will expose it to transient conditions. For instance, acceleration or deceleration in vehicle applications and turning on or off dishwashers in stationary applications may cause transient conditions of operation of PEMFCs. This dissertation presents experimental data that may be used to understand PEMFC behavior during these transients and these data may be used to verify the numerical simulations and models of PEMFC designs. The electrical load was changed with fixed inlet flowrates for the anode and cathode, and this caused hydrogen and air, stoichiometries to change. The transient experiments showed conditions and stoichiometric changes that gave the overshoot and undershoot behaviors. Data are presented to show the effects of voltage changes on the current response with four different cases of stoichiometry changes: from excess to normal, from normal to excess, from normal to starved, and from starved to normal. An overshoot behavior was observed when the cell stoichiometry changed from normal to starved condition. With a triple path flow field this overshoot was followed by an undershoot and this second order behavior is a result of, in this case, the air flowing back into the cell at the end of anode side to balance pressure. We named these phenomena as "vacuum effects" when the current density shows "undershoot" after "overshoot" behavior. For other conditions an undershoot behavior was observed when the voltage changed to cause a change from starved to normal conditions. In contrast, only exponential first order behavior was observed for voltage changes between excess and normal conditions. Various cell voltage ranges and change rates are presented to compare the overshoot and undershoot behaviors. Experiments were performed

  16. Magnetic phase transition in coupled spin-lattice systems: A replica-exchange Wang-Landau study.

    PubMed

    Perera, Dilina; Vogel, Thomas; Landau, David P

    2016-10-01

    Coupled, dynamical spin-lattice models provide a unique test ground for simulations investigating the finite-temperature magnetic properties of materials under the direct influence of the lattice vibrations. These models are constructed by combining a coordinate-dependent interatomic potential with a Heisenberg-like spin Hamiltonian, facilitating the treatment of both the atomic coordinates and the spins as explicit phase variables. Using a model parameterized for bcc iron, we study the magnetic phase transition in these complex systems via the recently introduced, massively parallel replica-exchange Wang-Landau Monte Carlo method. Comparison with the results obtained from rigid lattice (spin-only) simulations shows that the transition temperature as well as the amplitude of the peak in the specific heat curve is marginally affected by the lattice vibrations. Moreover, the results were found to be sensitive to the particular choice of interatomic potential.

  17. Magnetic phase transition in coupled spin-lattice systems: A replica-exchange Wang-Landau study

    NASA Astrophysics Data System (ADS)

    Perera, Dilina; Vogel, Thomas; Landau, David P.

    2016-10-01

    Coupled, dynamical spin-lattice models provide a unique test ground for simulations investigating the finite-temperature magnetic properties of materials under the direct influence of the lattice vibrations. These models are constructed by combining a coordinate-dependent interatomic potential with a Heisenberg-like spin Hamiltonian, facilitating the treatment of both the atomic coordinates and the spins as explicit phase variables. Using a model parameterized for bcc iron, we study the magnetic phase transition in these complex systems via the recently introduced, massively parallel replica-exchange Wang-Landau Monte Carlo method. Comparison with the results obtained from rigid lattice (spin-only) simulations shows that the transition temperature as well as the amplitude of the peak in the specific heat curve is marginally affected by the lattice vibrations. Moreover, the results were found to be sensitive to the particular choice of interatomic potential.

  18. First-principles study of mechanical, exchange interactions and the robustness in Co2MnSi full Heusler compounds

    NASA Astrophysics Data System (ADS)

    Akriche, A.; Bouafia, H.; Hiadsi, S.; Abidri, B.; Sahli, B.; Elchikh, M.; Timaoui, M. A.; Djebour, B.

    2017-01-01

    In this work we report the results of ab-initio studies of structural, mechanical, electronic and magnetic properties of Co based Co2MnSi Heusler compound in stoichiometric composition. All of which are accurately calculated by the full-potential (FP-LMTO) program combined with the spin polarized generalized gradient approximation in the density functional formalism (DFT). The total energy calculations clearly favor the ferromagnetic ground state. The lattice parameter, elastic constants and their related parameters were also evaluated and compared to experimental and theoretical values whenever possible. In this paper, the electronic properties are treated with GGA+U approach. The magnetic exchange constants temperature has been calculated using a mean field-approximation (MFA). The half-metal to metal transition was observed around 40 GPa. Increasing pressure has no impact on the total magnetic moment or the overall shape of the band structure that indicates the robustness of the electronic structure of this system.

  19. 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…

  20. 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.

  1. Experimental study of a constrained vapor bubble fin heat exchanger in the absence of external natural convection.

    PubMed

    Basu, Sumita; Plawsky, Joel L; Wayner, Peter C

    2004-11-01

    In preparation for a microgravity flight experiment on the International Space Station, a constrained vapor bubble fin heat exchanger (CVB) was operated both in a vacuum chamber and in air on Earth to evaluate the effect of the absence of external natural convection. The long-term objective is a general study of a high heat flux, low capillary pressure system with small viscous effects due to the relatively large 3 x 3 x 40 mm dimensions. The current CVB can be viewed as a large-scale version of a micro heat pipe with a large Bond number in the Earth environment but a small Bond number in microgravity. The walls of the CVB are quartz, to allow for image analysis of naturally occurring interference fringes that give the pressure field for liquid flow. The research is synergistic in that the study requires a microgravity environment to obtain a low Bond number and the space program needs thermal control systems, like the CVB, with a large characteristic dimension. In the absence of natural convection, operation of the CVB may be dominated by external radiative losses from its quartz surface. Therefore, an understanding of radiation from the quartz cell is required. All radiative exchange with the surroundings occurs from the outer surface of the CVB when the temperature range renders the quartz walls of the CVB optically thick (lambda > 4 microns). However, for electromagnetic radiation where lambda < 2 microns, the walls are transparent. Experimental results obtained for a cell charged with pentane are compared with those obtained for a dry cell. A numerical model was developed that successfully simulated the behavior and performance of the device observed experimentally.

  2. Pupil Exchange in the European Community Venice Colloquium (October 24-28, 1977). Collection Studies. Education Series No. 5.

    ERIC Educational Resources Information Center

    Commission des Communautes Europeennes (Luxembourg).

    This publication contains the papers of the Venice Colloquium held in October, 1977 by educators from European countries to discuss the topic of visits and exchanges for pupils. There are seven chapters. Chapter one discusses the context and objectives of the colloquium. Chapter two describes pupil visits and exchanges in the European community.…

  3. International Study Tours: A Key to 21st Century Academic and Industry Exchanges

    ERIC Educational Resources Information Center

    Hol, Ana; Simiana, Danielle; Lieu, Gilbert; Ong, Ivan; Feder, Josh; Dawre, Nimat; Almazi, Wakil

    2016-01-01

    This paper is based on the retrospective reviews of the Information Systems study group who went on the international study tour to India to learn, network and collaborate with academics, students and industry professionals overseas. The paper addresses concerns of local Australian Science, Technology, Engineering and Mathematics recruiters and…

  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

    ... pressing challenges that industry faces with regard to study data management? Please address each of the... regulatory requirements make the study data management process more efficient? 3. What does industry need to make clinical trials data management more effective and efficient? Please describe the...

  5. 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…

  6. Raman spectroscopic study of the aging and nitration of actinide processing anion-exchange resins in concentrated nitric acid

    SciTech Connect

    Buscher, C. T.; Donohoe, R. J.; Mecklenburg, S. L.; Berg, J. M.; Tait, C. D.; Morris, D. E. [Chemical Science and Technology Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545

    1999-08-01

    Degradation of two types of anion exchange resins, Dowex 11 and Reillex HPQ, from the action of concentrated nitric acid (4 to 12 M) and radiolysis [from depleted uranium as UO{sub 2}{sup 2+} nitrate species and {sup 239}Pu as Pu(IV) nitrate species] was followed as a function of time with Raman vibrational spectroscopy. Elevated temperatures ({approx}50 degree sign C) were used in the absence of actinide metal loading to simulate longer exposures of the resin to a HNO{sub 3} process stream and waste storage conditions. In the absence of actinide loading, only minor changes in the Dowex resin at acid concentrations {<=}10 M were observed, while at 12 M acid concentration, the emergence of a Raman peak at 1345 cm-1 indicates the addition of nitro functional groups to the resin. Similar studies with the Reillex resin show it to be more resistant to nitric acid attack at all acid concentrations. Incorporation of weakly radioactive depleted uranium as the UO{sub 2}{sup 2+} nitrate species to the ion-exchange sites of Dowex 11 under differing nitric acid concentrations (6 to 12 M) at room temperature showed no Raman evidence of resin degradation or nitration, even after several hundred days of contact. In contrast, Raman spectra for Dowex 11 in the presence of {sup 239}Pu as Pu(IV) nitrate species reveal numerous changes indicating resin alterations, including a new mode at 1345 cm-1 consistent with a Pu(IV)-nitrate catalyzed addition of nitro groups to the resin backbone. (c) 2000 Society for Applied Spectroscopy.

  7. 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.

  8. 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…

  9. 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...

  10. 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.

  11. A new metal exchanged zeolite for a present environmental problem. An in-situ XAS study

    NASA Astrophysics Data System (ADS)

    Alonso-Escobar, C.; Franch-Martí, C.; Palomares, A. E.; Rey, F.; Guilera, G.

    2013-04-01

    The medium pore zeolite, TNU-9, is prepared and studied for the selective catalytic reduction (SCR) of NO using C3H8 as the reducing agent. The catalytic activity of TNU-9 zeolites for the SCR is comparable to other known highly active zeolites but with the advantage of TNU-9 of having almost the same catalytic performance in the presence of H2O during reaction. The nature and behaviour of Cu and Co active sites contained in the TNU-9 catalysts have been studied under operation conditions using X-ray Absorption Spectroscopy (XAS) to understand the key parameters controlling the performance of this reaction.1 It was found that the well dispersed Cu and Co centres need to be in a mixed valence state to obtain good catalytic results for the SCR and that the catalytic performance is related to the topology of the TNU-9 itself.

  12. [The study of the relationship between rates of carnitine exchange and fat mass in young swimmers].

    PubMed

    Ryloval, N v; Biktimiroval, A a; Sereda, A p; SamOylOv, A s

    2016-01-01

    The study of the state of carnitine metabolism is an actual problem for the specialists who are interested in the investigating of children's health, involved in sport. Indicators of carnitine metabolism reflect mitochondrial capacity and the state of energy of the cell, which in it's turn effect on the level of physical performance of athletes and their health status. The aim of our study was to identify the characteristics of carnitine metabolism in young athletes, as well as the establishment of correlation between carnitine metabolism and body fat mass. The study included 46 young athletes 12-17 years old involved in swimming. The average age of the athletes was 15.9 ± 0.2 years. Carnitine metabolism has been studied by gas chromatography-tandem mass spectrometry, the content of body fat mass has been established by bioimpedance. The free carnitine didn't significantly differ in males (36.3 ± 1.1 mmol/l) and females (36.3 ± 1.3 mmol/l). Content of related carnitine was higher in boys--17.4 ± 0.8 mmol/l (vs 14.0 ± 0.9 mmol/l in girls, p < 0.05). Value of related carnitine/free carnitine (AC/C0) was significantly 22.5% higher in boys (0.49 ± 0.03), because of higher content of related carnitine. The content of body fat mass in boys was 9.6 ± 0.87%, and in girls--22.24 ± 1.0%. There was found a significant correlation between indicators of carnitine metabolism and fat body mass. The findings may suggest a higher mitochondrial potential of girls engaged in swimming.

  13. Heat exchanger

    DOEpatents

    Brackenbury, Phillip J.

    1986-04-01

    A heat exchanger comparising a shell attached at its open end to one side of a tube sheet and a detachable head connected to the other side of said tube sheet. The head is divided into a first and second chamber in fluid communication with a nozzle inlet and nozzle outlet, respectively, formed in said tube sheet. A tube bundle is mounted within said shell and is provided with inlets and outlets formed in said tube sheet in communication with said first and second chambers, respectively.

  14. Effective core potential study of transition metal and lanthanide catalyzed hydrogen exchange

    NASA Astrophysics Data System (ADS)

    Cundari, Thomas R.; Stevens, Walter J.; Sommerer, Shaun O.

    1993-12-01

    An effective core potential study of H2 activation by the sigma-bond metathesis mechanism is reported for a range of simple Cl2MH catalyst models: M=Sc, Y, La, Lu, Zr+, B, and Al. Several points of interest are noted. Effective core potentials methods allow the study of metals from the transition, lanthanide and main group series with near equal facility. A single-determinant wavefunction is found to be sufficient for a qualitatively correct description of the ground and transition states in these reactions; changes in optimized geometries are minimal upon inclusion of correlation at the multiconfiguration self-consistent field (MCSCF) level. Calculated barriers are the highest using restricted Hartree-Fock (RHF) and multiconfiguration self-consistent field wavefunctions and lowest using Møller-Plesset second-order perturbation theory and second-order configuration interaction (SOCI) methods. Trends as a function of metal species on H2 activation barriers are consistent for all wavefunctions employed. As MP2 and RHF wavefunctions are most amenable to larger, more experimentally relevant systems, the use of RHF wavefunctions to determine stationary point geometries followed by MP2 calculations to assess their relative energies seems to be an attractive theoretical approach for computational investigations of hydrogenation and important related reactions.

  15. The ESA SMOS+SOS Project: Oceanography using SMOS for innovative air-sea exchange studies

    NASA Astrophysics Data System (ADS)

    Banks, Chris; Gommenginger, Christine; Boutin, Jacqueline; Reul, Nicolas; Martin, Matthew; Ash, Ellis; Reverdin, Gilles; Donlon, Craig

    2013-04-01

    We report on the work plan of the SMOS+Surface Ocean Salinity and Synergy (SMOS+SOS) project. SMOS+SOS is funded through the Support to Science Element (STSE) component of the European Space Agency's (ESA) Earth Observation Envelope Programme. The SMOS+SOS consortium consists of four organisations namely the National Oceanography Centre (UK), the LOCEAN/IFREMER/CATDS research team (France), the Met Office (UK) and Satellite Oceanographic Consultants Ltd (UK). The end of the SMOS+SOS project will be marked by a final open workshop most likely hosted by the UK Met Office in September/October 2014. The project is concerned with demonstrating the performance and scientific value of SMOS Sea Surface Salinity (SSS) products through a number of well-defined case studies. The case studies include: Amazon/Orinoco plumes (freshwater outflow); Agulhas and Gulf Stream (strong water mass boundary); Tropical Pacific/Atlantic (strong precipitation regime); sub-tropical North Atlantic (ie SPURS; strong evaporative regime); and Equatorial Pacific (equatorial upwelling). With SMOS measuring the SSS in the top cm of the ocean, validating SMOS against in situ salinity data taken typically at a few meters depth introduces assumptions about the vertical structure of salinity in the upper ocean. To address these issues, the project will examine and quantify discrepancies between SMOS and in situ surface salinity data at various depths in different regions characterised by strong precipitation or evaporation regimes. Equally, data editing and spatio-temporal averaging play a central role in determining the quality, errors and correlations in SMOS SSS data. The project will explore various processing and spatio-temporal averaging choices to define the SMOS SSS products that best address the needs of the oceanographic and data assimilation user community. One key aspect of this project is to determine how one can achieve useful accuracy/uncertainty in SSS without jeopardising SMOS's ability

  16. 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.

  17. 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.

  18. Fast exhaust channel optical absorption method and apparatus to study the gas exchange in large diesel engines

    NASA Astrophysics Data System (ADS)

    Vattulainen, J.; Hernberg, R.; Hattar, C.; Gros, S.

    1998-01-01

    An optical absorption spectroscopic method and apparatus with shorter than 1 ms response time have been used to study the gas exchange processes in realistic conditions for a single cylinder of a large diesel engine. The method is based on measuring the differential line-of-sight optical uv absorption of the exhaust-gas-contained SO2 as a function of time in the exhaust port area just after the exhaust valves. The optical absorption by SO2 is determined from light transmission measurements at 280 and 340 nm performed through optical probes installed into the exhaust channel wall. The method has been applied to a continuously fired, large, medium speed production-line-type diesel engine with 990 kW rated power. The test engine was operated with standard light fuel oil (MDO Termoshell) and with light fuel oil treated with a sulfur additive {Di-Tert-Butyldisulfid [(CH3)3C]2S2}. The latter was to improve the optical absorption signals without increasing the fouling of the exhaust channel optical probes as in the case of heavier fuel oil qualities. In the reported case of a four-stroke diesel engine measurement results show that the method can provide time-resolved information of the SO2 density in the exhaust channel and thus give information on the single-cylinder gas exchange. During the inlet and exhaust valve overlap period the moment of fresh air entering into the measurement volume can be detected. If independent exhaust gas temperature and pressure data are available, the absorption measurements can readily be used for determining the burnt gas fraction in the exhaust channel. In this work the possibility of using the optical absorption measurement to determine the instaneous exhaust gas temperature was studied. Based on known fuel properties and conventional averaged SO2 measurements from the exhaust channel a known concentration of SO2 was assumed in the exhaust gas after the exhaust valves opening and before the inlet and exhaust valves overlap period

  19. A Comprehensive Study of the Solubility, Thermochemistry, Ion Exchange and Precipitation Kinetics of NO3 Cancrinite and No3 Sodalite

    SciTech Connect

    Jove-Colon, Carlos; Navrotsky, Alexandra

    2004-12-31

    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. This report focuses on the portion of the work performed at UC Davis by Professor Navrotsky's group.

  20. 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.

  1. 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.

  2. 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.

  3. Study of Mesoscale Eddies in the Gulf of Lion and their role in the coastal-offshore exchanges.

    NASA Astrophysics Data System (ADS)

    Hu, Z. Y.; Doglioli, A. M.; Petrenko, A. A.; Compbell, R.; Diaz, F.; Dekeyser, I.

    2010-05-01

    The main objective of LAgrangian Transport EXperiment (LATEX) project (2008-2011) is to study the influence of mesoscale structures on shelf-offshore exchanges in the Gulf of Lion (GoL). The LATEX strategy combines use of data from Lagrangian drifters, satellite images and hull-mounted ADCP data with numerical modeling. In this work, we simulate the mesoscale structures, occurring at the interface between the continental slope and the coastal margin in the GoL, by using a realistic numerical model. Numerical studies show a clear influence of mesoscale eddies on matter and energies transfers between the coastal zone and open sea. The features of the eddies such as their size, position and behaviour issued from the numerical modeling help us set up the sampling strategy of the cruises. The in situ measurements allow us to validate the numerical results and furthermore, combined with the modeling results, to well understand the eddies's dynamics. A numerical Lagrangian diagnostic tool is applied to analyze the model outputs. Qualitative and quantitative simulations are made in order to evaluate the eddies' potential impact on the coastal-offshore transfer of matter and energy.

  4. Experimental study on the optimal purge duration of a proton exchange membrane fuel cell with a dead-ended anode

    NASA Astrophysics Data System (ADS)

    Lin, Yu-Fen; Chen, Yong-Song

    2017-02-01

    When a proton exchange membrane fuel cell (PEMFC) is operated with a dead-ended anode, impurities gradually accumulate within the anode, resulting in a performance drop. An anode purge is thereby ultimately required to remove impurities within the anode. A purge strategy comprises purge interval (valve closed) and purge duration (valve is open). A short purge interval causes frequent and unnecessary activation of the valve, whereas a long purge interval leads to excessive impurity accumulation. A short purge duration causes an incomplete performance recovery, whereas a long purge duration results in low hydrogen utilization. In this study, a series of experimental trials was conducted to simultaneously measure the hydrogen supply rate and power generation of a PEMFC at a frequency of 50 Hz for various operating current density levels and purge durations. The effect of purge duration on the cell's energy efficiency was subsequently analyzed and discussed. The results showed that the optimal purge duration for the PEMFC was approximately 0.2 s. Based on the results of this study, a methodical process for determining optimal purge durations was ultimately proposed for widespread application. Purging approximately one-fourth of anode gas can obtain optimal energy efficiency for a PEMFC with a dead-ended anode.

  5. 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.

  6. MRS studies of neuroenergetics and glutamate/glutamine exchange in rats: Extensions to hyperammonemic models.

    PubMed

    Lanz, Bernard; Rackayova, Veronika; Braissant, Olivier; Cudalbu, Cristina

    2016-12-23

    In vivo Magnetic Resonance Spectroscopy is a useful tool to characterize brain biochemistry as well as its alteration in a large number of major central nervous system diseases. The present review will focus on the study of the glutamate-glutamine cycle, an important biochemical pathway in excitatory neurotransmission, analyzed using in vivo MRS of different accessible nuclei: (1)H, (13)C, (15)N and (31)P. The different methodological aspects of data acquisition, processing and absolute quantification of the MRS data for each nucleus will be presented, as well as the description of the mathematical modeling approach to interpret the MRS measurements in terms of biochemical kinetics. The unique advantages of MRS, especially its non-invasive nature enabling longitudinal monitoring of brain disease progression and/or effect of treatment is illustrated in the particular context of hyperammonemic disorders with a specific focus on animal models. We review the current possibilities given by in vivo MRS to investigate some of the molecular mechanisms involved in hyperammonemic disorders and to give a better understanding of the process of development of hepatic encephalopathy, a severe neuropsychiatric disorder that frequently accompanies liver disease.

  7. Na-Ca exchange and the trigger for sarcoplasmic reticulum Ca release: studies in adult rabbit ventricular myocytes.

    PubMed Central

    Litwin, S E; Li, J; Bridge, J H

    1998-01-01

    The importance of Na-Ca exchange as a trigger for sarcoplasmic reticulum (SR) Ca release remains controversial. Therefore, we measured whole-cell Ca currents (ICa), Na-Ca exchange currents (INaCa), cellular contractions, and intracellular Ca transients in adult rabbit cardiac myocytes. We found that changing pipette Na concentration markedly affected the relationship between cell shortening (or Ca transients) and voltage, but did not affect the Ca current-voltage relationship. We then inhibited Na-Ca exchange and varied SR content (by changing the number of conditioning pulses before each test pulse). Regardless of SR Ca content, the relationship between contraction and voltage was bell-shaped in the absence of Na-Ca exchange. Next, we rapidly and completely blocked ICa by applying nifedipine to cells. Cellular shortening was variably reduced in the presence of nifedipine. The component of shortening blocked by nifedipine had a bell-shaped relationship with voltage, whereas the "nifedipine-insensitive" component of contraction increased with voltage. With the SR disabled (ryanodine and thapsigargin pretreatment), ICa could initiate late-peaking contractions that were approximately 70% of control amplitude. In contrast, nifedipine-insensitive contractions could not be elicited in the presence of ryanodine and thapsigargin. Finally, we recorded reverse Na-Ca exchange currents that were activated by membrane depolarization. The estimated sarcolemmal Ca flux occurring by Na-Ca exchange (during voltage clamp steps to +30 mV) was approximately 10-fold less than that occurring by ICa. Therefore, Na-Ca exchange alone is unlikely to raise cytosolic Ca concentration enough to directly activate the myofilaments. We conclude that reverse Na-Ca exchange can trigger SR Ca release. Because of the sigmoidal relationship between the open probability of the SR Ca release channel and pCa, the effects of ICa and INaCa may not sum in a linear fashion. Rather, the two triggers may act

  8. 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.

  9. 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).

  10. 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

  11. 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.

  12. CLOSED-LOOP TREATMENT OF ELECTROLYTIC AND ELECTROLESS NICKEL RINSE WATER BY POINT-OF-USE ION EXCHANGE: A CASE STUDY.

    EPA Science Inventory

    Closed-Loop Treatment of Electrolytic and Electroless Nickel Rinse Water by Point-Of-Use Ion Exchange: A Case Study.

    Dave Szlag1, Joe Leonhardt2, Albert Foster1, Mike Goss1 and Paul Bolger1.
    1 U.S. EPA, N