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Sample records for ligand exchange high

  1. Amphiphilic ligand exchange reaction-induced supercapacitor electrodes with high volumetric and scalable areal capacitances

    Science.gov (United States)

    Nam, Donghyeon; Heo, Yeongbeom; Cheong, Sanghyuk; Ko, Yongmin; Cho, Jinhan

    2018-05-01

    We introduce high-performance supercapacitor electrodes with ternary components prepared from consecutive amphiphilic ligand-exchange-based layer-by-layer (LbL) assembly among amine-functionalized multi-walled carbon nanotubes (NH2-MWCNTs) in alcohol, oleic acid-stabilized Fe3O4 nanoparticles (OA-Fe3O4 NPs) in toluene, and semiconducting polymers (PEDOT:PSS) in water. The periodic insertion of semiconducting polymers within the (OA-Fe3O4 NP/NH2-MWCNT)n multilayer-coated indium tin oxide (ITO) electrode enhanced the volumetric and areal capacitances up to 408 ± 4 F cm-3 and 8.79 ± 0.06 mF cm-2 at 5 mV s-1, respectively, allowing excellent cycling stability (98.8% of the initial capacitance after 5000 cycles) and good rate capability. These values were higher than those of the OA-Fe3O4 NP/NH2-MWCNT multilayered electrode without semiconducting polymer linkers (volumetric capacitance ∼241 ± 4 F cm-3 and areal capacitance ∼1.95 ± 0.03 mF cm-2) at the same scan rate. Furthermore, when the asymmetric supercapacitor cells (ASCs) were prepared using OA-Fe3O4 NP- and OA-MnO NP-based ternary component electrodes, they displayed high volumetric energy (0.36 mW h cm-3) and power densities (820 mW cm-3).

  2. Organic-inorganic hybrid perovskite quantum dots with high PLQY and enhanced carrier mobility through crystallinity control by solvent engineering and solid-state ligand exchange.

    Science.gov (United States)

    Woo Choi, Jin; Woo, Hee Chul; Huang, Xiaoguang; Jung, Wan-Gil; Kim, Bong-Joong; Jeon, Sie-Wook; Yim, Sang-Youp; Lee, Jae-Suk; Lee, Chang-Lyoul

    2018-05-22

    The photoluminescence quantum yield (PLQY) and charge carrier mobility of organic-inorganic perovskite QDs were enhanced by the optimization of crystallinity and surface passivation as well as solid-state ligand exchange. The crystallinity of perovskite QDs was determined by the Effective solvent field (Esol) of various solvents for precipitation. The solvent with high Esol could more quickly countervail the localized field generated by the polar solvent, and it causes fast crystallization of the dissolved precursor, which results in poor crystallinity. The post-ligand adding process (PLAP) and post-ligand exchange process (PLEP) increase the PLQY of perovskite QDs by reducing non-radiative recombination and the density of surface defect states through surface passivation. Particularly, the post ligand exchange process (PLEP) in the solid-state improved the charge carrier mobility of perovskite QDs in addition to the PLQY enhancement. The ligand exchange with short alkyl chain length ligands could improve the packing density of perovskite QDs in films by reducing the inter-particle distance between perovskite QDs. The maximum hole mobility of 6.2 × 10-3 cm2 V-1 s-1, one order higher than that of pristine QDs without the PLEP, is obtained at perovskite QDs with hexyl ligands. By using PLEP treatment, compared to the pristine device, a 2.5 times higher current efficiency in perovskite QD-LEDs was achieved due to the improved charge carrier mobility and PLQY.

  3. Chiral ligand exchange high-speed countercurrent chromatography: mechanism, application and comparison with conventional liquid chromatography in enantioseparation of aromatic α-hydroxyl acids

    Science.gov (United States)

    Tong, Shengqiang; Shen, Mangmang; Cheng, Dongping; Ito, Yoichiro; Yan, Jizhong

    2014-01-01

    This work concentrates on the separation mechanism and application of chiral ligand exchange high-speed countercurrent chromatography (HSCCC) in enantioseparations, and comparison with traditional chiral ligand exchange high performance liquid chromatography (HPLC). The enantioseparation of ten aromatic α-hydroxyl acids were performed by these two chromatographic methods. Results showed that five of the racemates were successfully enantioseparated by HSCCC while only three of the racemates could be enantioseparated by HPLC using a suitable chiral ligand mobile phase additive. For HSCCC, the two-phase solvent system was composed of butanol-water (1:1, v/v), to which N-n-dodecyl-L-proline was added in the organic phase as chiral ligand and cupric acetate was added in the aqueous phase as a transition metal ion. Various operation parameters in HSCCC were optimized by enantioselective liquid-liquid extraction. Based on the results of the present studies the separation mechanism for HSCCC was proposed. For HPLC, the optimized mobile phase composed of aqueous solution containing 6 mmol L−1 L-phenylalanine and 3 mmol L−1 cupric sulfate and methanol was used for enantioseparation. Among three ligands tested on a conventional reverse stationary phase column, only one was found to be effective. In the present studies HSCCC presented unique advantages due to its high versatility of two-phase solvent systems and it could be used as an alternative method for enantioseparations. PMID:25087742

  4. Ligand Exchange Kinetics of Environmentally Relevant Metals

    Energy Technology Data Exchange (ETDEWEB)

    Panasci, Adele Frances [Univ. of California, Davis, CA (United States)

    2014-07-15

    The interactions of ground water with minerals and contaminants are of broad interest for geochemists but are not well understood. Experiments on the molecular scale can determine reaction parameters (i.e. rates of ligand exchange, activation entropy, activation entropy, and activation volume) that can be used in computations to gain insight into reactions that occur in natural groundwaters. Experiments to determine the rate of isotopic ligand exchange for three environmentally relevant metals, rhodium (Rh), iron (Fe), and neptunium (Np), are described. Many environmental transformations of metals (e.g. reduction) in soil occur at trivalent centers, Fe(III) in particular. Contaminant ions absorb to mineral surfaces via ligand exchange, and the reversal of this reaction can be dangerous, releasing contaminants into the environment. Ferric iron is difficult to study spectroscopically because most of its complexes are paramagnetic and are generally reactive toward ligand exchange; therefore, Rh(III), which is diamagnetic and less reactive, was used to study substitution reactions that are analogous to those that occur on mineral oxide surfaces. Studies on both Np(V) and Np(VI) are important in their own right, as 237Np is a radioactive transuranic element with a half-life of 2 million years.

  5. The influence of ligand field effects on the magnetic exchange of high-spin Co(II)-semiquinonate complexes.

    Science.gov (United States)

    Bencini, Alessandro; Beni, Alessandra; Costantino, Ferdinando; Dei, Andrea; Gatteschi, Dante; Sorace, Lorenzo

    2006-02-07

    [Co(Me(4)cyclam)(tropolonate)](PF(6)) was synthesised and structurally characterised. Its electronic and W-band EPR spectra have been analysed by means of the angular overlap calculation of the Spin Hamiltonian parameters that provided also a satisfactory reproduction of the temperature dependence of the magnetic susceptibility. The present results can be interpreted assuming a pseudo-octahedral character for the Co(II) center. This prompted us to reconsider the model formerly used for the analysis of the magnetic coupling between hs-Co(II) and the paramagnetic o-semiquinonate ligand in the corresponding derivatives [Co(Me(4)cyclam)(PhenSQ)](PF(6)) and [Co(Me(4)cyclam)(DTBSQ)](PF(6)). These results indicate that the effect of the magnetic coupling is active only below 50 K and that a more refined model of exchange coupling between Co(II) and semiquinonato ligands is needed to quantitatively analyze the magnetic behaviour of this class of systems.

  6. Chiral ligand-exchange high-performance liquid chromatography with copper (II)-L-phenylalanine complexes for separation of 3,4-dimethoxy-α-methylphenylalanine racemes.

    Science.gov (United States)

    Jia, Dong-Xu; Ai, Zheng-Gui; Xue, Ya-Ping; Zheng, Yu-Guo

    2014-11-01

    L-3, 4-dimethoxy-α-methylphenylalanine (L-DMMD) is an important intermediate for the synthesis of 3-hydroxy-α-methyl-L-tyrosine (L-methyldopa). This paper describes an efficient, accurate, and low-priced method of high-performance liquid chromatography (HPLC) using chiral mobile phase and conventional C18 column to separate L-DMMD from its enantiomers. The effects of ligands, copper salts, organic modifiers, pHs of mobile phase, and temperatures on the retention factors (k') and selectivity (α) were evaluated to achieve optimal separation performance. Then, thermal analysis of the optimal separation conditions was investigated as well. It was confirmed that the optimal mobile phase was composed of 20 % (v/v) methanol, 8 mM L-phenylalanine (L-Phe), and 4 mM cupric sulfate in water of pH 3.2, and the column temperature was set at 20 °C. Baseline separation of two enantiomers could be obtained through the conventional C18 column with a resolution (R) of 3.18 in less than 18 min. Thermodynamic data (∆∆H and ∆∆S) obtained by Van't Hoff plots revealed the chiral separation was an enthalpy-controlled process. To the best of our knowledge, this is the first report regarding the enantioseparation of DMMD by chiral ligand-exchange HPLC.

  7. Simultaneous measurement of proline and related compounds in oak leaves by high-performance ligand-exchange chromatography and electrospray ionization mass spectrometry for environmental stress studies.

    Science.gov (United States)

    Oufir, Mouhssin; Schulz, Nadine; Sha Vallikhan, Patan Shaik; Wilhelm, Eva; Burg, Kornel; Hausman, Jean-Francois; Hoffmann, Lucien; Guignard, Cedric

    2009-02-13

    A mass spectrometer was coupled to high-performance ligand-exchange liquid chromatography (HPLEC) for simultaneous analysis of stress associated solutes such as proline, hydroxyproline, methylproline, glycine betaine and trigonelline extracted from leaves of drought stressed oaks and an internal standard namely N-acetylproline. Methanol/chloroform/water extracts were analyzed using an Aminex HPX-87C column and specifically quantified by the positive ion mode of an electrospray ionisation-mass spectrometry (ESI-MS) in single ion monitoring (SIM) mode. The recovery of N-acetyl proline added to oak leaf extracts ranged from 85.2 to 122.1% for an intra-day study. Standard calibration curves showed good linearity in the measured range from 0.3125 to 10micromolL(-1) with the lowest correlation coefficient of 0.99961 for trigonelline. The advantages of this alternative procedure, compared to previously published methods using fluorescence or amperometric detections, are the simultaneous and direct detection of osmoprotectants in a single chromatographic run, a minimal sample preparation, a good specificity and reduced limits of quantification, ranging from 0.1 to 0.6micromolL(-1). Fifty-six days of water deficit exposure resulted in increased foliar free proline levels (2.4-fold, P<0.001, 155micromolg(-1) FW) and glycine betaine contents (2.5-fold, P<0.05, 175micromolg(-1) FW) of drought stressed oak compared to control.

  8. Ligands Exchange Process on Gold Nanoparticles in Acetone Solution

    Science.gov (United States)

    Hu, C. L.; Mu, Y. Y.; Bian, Z. C.; Luo, Z. H.; Luo, K.; Huang, A. Z.

    2018-05-01

    The ligands exchange process on gold nanoparticles (GNPs) was proceeded by using hydrophobic group (PPh3) and hydrophilic group (THPO) in acetone solution. The FTIR and XPS results demonstrated that part of THPO was replaced by PPh3 which was dissolved in polar solution (acetone); the results were in accordance with the electrochemical analysis where the differential capacity decreased with increasing exchange time. After 12 h, the exchange process terminated and the final ratio of PPh3 and THPO was about 1.4: 1. This ratio remained unchanged although the PPh3 and THPO modified GNPs re-dispersed in the PPh3 acetone solution demonstrating the stable adsorption of both ligands after exchanging for 12 h. The TEM images showed that the gold nanoparticles were self-assembled from scattered to arranged morphology due to the existence of hydrophilic and hydrophobic ligands and led to Janus gold nanoparticles.

  9. Reversible Size Control of Silver Nanoclusters via Ligand-exchange

    KAUST Repository

    Bootharaju, Megalamane Siddaramappa

    2015-05-21

    The properties of atomically monodisperse noble metal nanoclusters (NCs) are intricately intertwined with their precise molecular formula. The vast majority of size-specific NC syntheses start from the reduction of the metal salt and thiol ligand mixture. Only in gold was it recently shown that ligand-exchange could induce the growth of NCs from one atomically precise species to another; a process of yet unknown reversibility. Here, we present a process for the ligand-exchange-induced growth of atomically precise silver NCs, in a biphasic liquid-liquid system, which is particularly of interest because of its complete reversibility and ability to occur at room temperature. We explore this phenomenon in-depth using Ag35(SG)18 [SG= glutathionate] and Ag44(4-FTP)30 [4-FTP= 4-fluorothiophenol] as model systems. We show that the ligand-exchange conversion of Ag35(SG)18 into Ag44(4-FTP)30 is rapid (< 5 min) and direct, while the reverse process proceeds slowly through intermediate cluster sizes. We adapt a recently developed theory of reverse Ostwald ripening to model the NCs’ interconvertibility. The model’s predictions are in good agreement with the experimental observations, and they highlight the importance of small changes in the ligand-metal binding energy in determining the final equilibrium NC size. Based on the insight provided by this model, we demonstrated experimentally that by varying the choice of ligands, ligand-exchange can be used to obtain different sized NCs. The findings in this work establish ligand-exchange as a versatile tool for tuning cluster sizes.

  10. Reversible Size Control of Silver Nanoclusters via Ligand-exchange

    KAUST Repository

    Bootharaju, Megalamane Siddaramappa; Burlakov, Victor M.; Besong, Tabot M.D.; Joshi, Chakra Prasad; AbdulHalim, L; Black, David; Whetten, Robert; Goriely, Alain; Bakr, Osman

    2015-01-01

    The properties of atomically monodisperse noble metal nanoclusters (NCs) are intricately intertwined with their precise molecular formula. The vast majority of size-specific NC syntheses start from the reduction of the metal salt and thiol ligand mixture. Only in gold was it recently shown that ligand-exchange could induce the growth of NCs from one atomically precise species to another; a process of yet unknown reversibility. Here, we present a process for the ligand-exchange-induced growth of atomically precise silver NCs, in a biphasic liquid-liquid system, which is particularly of interest because of its complete reversibility and ability to occur at room temperature. We explore this phenomenon in-depth using Ag35(SG)18 [SG= glutathionate] and Ag44(4-FTP)30 [4-FTP= 4-fluorothiophenol] as model systems. We show that the ligand-exchange conversion of Ag35(SG)18 into Ag44(4-FTP)30 is rapid (< 5 min) and direct, while the reverse process proceeds slowly through intermediate cluster sizes. We adapt a recently developed theory of reverse Ostwald ripening to model the NCs’ interconvertibility. The model’s predictions are in good agreement with the experimental observations, and they highlight the importance of small changes in the ligand-metal binding energy in determining the final equilibrium NC size. Based on the insight provided by this model, we demonstrated experimentally that by varying the choice of ligands, ligand-exchange can be used to obtain different sized NCs. The findings in this work establish ligand-exchange as a versatile tool for tuning cluster sizes.

  11. Development and Application of Ligand-Exchange Reaction Method ...

    African Journals Online (AJOL)

    Purpose: This paper presents an improved kinetic-spectrophotometric procedure for determining clonazepam (CZP) in pharmaceutical formulations and human serum. Methods: The method is based on ligand-exchange reaction. The reaction was followed spectrophotometrically by measuring the rate of change of ...

  12. Multiscale simulations of ligand adsorption and exchange on gold nanoparticles.

    Science.gov (United States)

    Gao, Hui-Min; Liu, Hong; Qian, Hu-Jun; Jiao, Gui-Sheng; Lu, Zhong-Yuan

    2018-01-17

    We have developed a multiscale model that combines first-principles methods with atomistic and mesoscopic simulations to explore the molecular structures and packing density of the ligands present on the gold nanoparticle (AuNP) surface, as well as the adsorption/exchange reaction kinetics of cetyltrimethylammonium bromide (CTAB)/PEG-SH ligands on different facets of gold, namely, Au(111), Au(100), and Au(110). Our model predicts that on clean gold surfaces, CTAB adsorption is diffusion limited. Specifically, CTAB has the preferentially higher adsorption rate and coverage density on Au(100) and Au(110) surfaces, forming a more compact layer with respect to that on the Au(111) surface, which could result in greater growth of gold nanoparticles along the (111) direction. As opposed to CTAB adsorption, the exchange reaction between PEG-SH with CTAB shows no selectivity to different crystal faces, and the reaction process follows Langmuir diffusion kinetics. Kinetic analysis reveals that, in water, the exchange reaction is zeroth order with respect to the concentration of an incoming PEG-SH, indicative of a dissociative exchange mechanism. The observed rate constant decreases exponentially with the PEG-SH chain length, consistent with a diffusion process for the free PEG-SH in water. In particular, we show that the exchange efficiency increases as the chain rigidness and size of the incoming ligand and/or steric bulk of the initial protecting ligand shell are decreased. Our objectives are to provide a model to assess the kinetics and thermodynamics of the adsorption/exchange reaction process, and we expect that these findings will have important implications for routine surface characterization of AuNPs.

  13. Nickel speciation and complexation kinetics in freshwater by ligand exchange and DPCSV

    NARCIS (Netherlands)

    Han Bin Xue,; Jansen, S.; Prasch, A.; Sigg, L.

    2001-01-01

    A technique of ligand exchange with DMG (dimethylglyoxime) and DPCSV was applied to determine Ni speciation in lake, river, and groundwater samples. The working conditions related to ligand-exchange equilibrium were optimized, and the ligand-exchange kinetics were examined. The observed

  14. Ligand exchange chromatography of free amino acids and proteins on porous microparticulate zirconium oxide

    International Nuclear Information System (INIS)

    Blackwell, J.A.; Carr, P.W.

    1992-01-01

    The Lewis acid sites present on the underlying zirconium oxide particles are responsible for the unusual elution sequence for amino acids on copper loaded, phosphated zirconium oxide supports reported in an earlier study. To more thoroughly examine the effect of these strong Lewis acid sites in this paper. The authors have studied ligand exchange chromatography on copper loaded zirconium oxide particles. It is shown here that carboxylate functional groups on amino acid solutes strongly interact with surface Lewis acid sites. Addition of competing hard Lewis bases to the eluent attenuates these specific interactions. The result is a chromatographic system with high selectivity which is also suitable for ligand exchange chromatography of proteins

  15. Ligand and proton exchange dynamics in recombinant human myoglobin mutants.

    Science.gov (United States)

    Lambright, D G; Balasubramanian, S; Boxer, S G

    1989-05-05

    Site-specific mutants of human myoglobin have been prepared in which lysine 45 is replaced by arginine (K45R) and aspartate 60 by glutamate (D60E), in order to examine the influence of these residues and their interaction on the dynamics of the protein. These proteins were studied by a variety of methods, including one and two-dimensional proton nuclear magnetic resonance spectroscopy, exchange kinetics for the distal and proximal histidine NH protons as a function of pH in the met cyano forms, flash photolysis of the CO forms, and ligand replacement kinetics. The electronic absorption and proton nuclear magnetic resonance spectra of the CO forms of these proteins are virtually identical, indicating that the structure of the heme pocket is unaltered by these mutations. There are, however, substantial changes in the dynamics of both CO binding and proton exchange for the mutant K45R, whereas the mutant D60E exhibits behavior indistinguishable from the reference human myoglobin. K45R has a faster CO bimolecular recombination rate and slower CO off-rate relative to the reference. The kinetics for CO binding are independent of pH (6.5 to 10) as well as ionic strength (0 to 1 M-NaCl). The exchange rate for the distal histidine NH is substantially lower for K45R than the reference, whereas the proximal histidine NH exchange rate is unaltered. The exchange behavior of the human proteins is similar to that reported for a comparison of the exchange rates for myoglobins having lysine at position 45 with sperm whale myoglobin, which has arginine at this position. This indicates that the differences in exchange rates reflects largely the Lys----Arg substitution. The lack of a simple correlation for the CO kinetics with this substitution means that these are sensitive to other factors as well. Specific kinetic models, whereby substitution of arginine for lysine at position 45 can affect ligand binding dynamics, are outlined. These experiments demonstrate that a relatively

  16. Neat and complete: Thiolate-ligand exchange on a silver molecular nanoparticle

    KAUST Repository

    AbdulHalim, Lina G.

    2014-11-12

    Atomically precise thiolate-protected noble metal molecular nanoparticles are a promising class of model nanomaterials for catalysis, optoelectronics, and the bottom-up assembly of true molecular crystals. However, these applications have not fully materialized due to a lack of ligand exchange strategies that add functionality, but preserve the properties of these remarkable particles. Here we present a method for the rapid (<30 s) and complete thiolate-for-thiolate exchange of the highly sought after silver molecular nanoparticle [Ag44(SR)30]-4. Only by using this method were we able to preserve the precise nature of the particles and simultaneously replace the native ligands with ligands containing a variety of functional groups. Crucially, as a result of our method we were able to process the particles into smooth thin films, paving the way for their integration into solution-processed devices.

  17. Neat and complete: Thiolate-ligand exchange on a silver molecular nanoparticle

    KAUST Repository

    AbdulHalim, Lina G.; Kothalawala, Nuwan; Sinatra, Lutfan; Dass, Amala; Bakr, Osman

    2014-01-01

    Atomically precise thiolate-protected noble metal molecular nanoparticles are a promising class of model nanomaterials for catalysis, optoelectronics, and the bottom-up assembly of true molecular crystals. However, these applications have not fully materialized due to a lack of ligand exchange strategies that add functionality, but preserve the properties of these remarkable particles. Here we present a method for the rapid (<30 s) and complete thiolate-for-thiolate exchange of the highly sought after silver molecular nanoparticle [Ag44(SR)30]-4. Only by using this method were we able to preserve the precise nature of the particles and simultaneously replace the native ligands with ligands containing a variety of functional groups. Crucially, as a result of our method we were able to process the particles into smooth thin films, paving the way for their integration into solution-processed devices.

  18. Charge-Transfer Effects in Ligand Exchange Reactions of Au25 Monolayer-Protected Clusters.

    Science.gov (United States)

    Carducci, Tessa M; Blackwell, Raymond E; Murray, Royce W

    2015-04-16

    Reported here are second-order rate constants of associative ligand exchanges of Au25L18 nanoparticles (L = phenylethanethiolate) of various charge states, measured by proton nuclear magnetic resonance at room temperature and below. Differences in second-order rate constants (M(-1) s(-1)) of ligand exchange (positive clusters ∼1.9 × 10(-5) versus negative ones ∼1.2 × 10(-4)) show that electron depletion retards ligand exchange. The ordering of rate constants between the ligands benzeneselenol > 4-bromobenzene thiol > benzenethiol reveals that exchange is accelerated by higher acidity and/or electron donation capability of the incoming ligand. Together, these observations indicate that partial charge transfer occurs between the nanoparticle and ligand during the exchange and that this is a rate-determining effect in the process.

  19. Identification of individual protein-ligand NOEs in the limit of intermediate exchange

    International Nuclear Information System (INIS)

    Reibarkh, Mikhail; Malia, Thomas J.; Hopkins, Brian T.; Wagner, Gerhard

    2006-01-01

    Interactions of proteins with small molecules or other macromolecules play key roles in many biological processes and in drug action, and NMR is an excellent tool for their structural characterization. Frequently, however, line broadening due to intermediate exchange completely eliminates the signals needed for measuring specific intermolecular NOEs. This limits the use of NMR for detailed structural studies in such kinetic situations. Here we show that an optimally chosen excess of ligand over protein can reduce the extent of line broadening for both the ligand and the protein. This makes observation of ligand resonances possible but reduces the size of the measurable NOEs due to the residual line broadening and the non-stoichiometric concentrations. Because the solubility of small molecule drug leads are often limited to high micromolar concentrations, protein concentrations are restricted to even lower values in the low micromolar range. At these non-stoichiometric concentrations and in the presence of significant residual line broadening, conventional NOESY experiments very often are not sensitive enough to observe intermolecular NOEs since the signals inverted by the NOESY preparation pulse sequence relax prior to significant NOE build up. Thus, we employ methods related to driven NOE spectroscopy to investigate protein-ligand interactions in the intermediate exchange regime. In this approach, individual protein resonances are selectively irradiated for up to five seconds to build up measurable NOEs at the ligand resonances. To enable saturation of individual protein resonances we prepare deuterated protein samples selectively protonated at a few sites so that the 1D 1 H spectrum of the protein is resolved well enough to permit irradiation of individual protein signals, which do not overlap with the ligand spectrum. This approach is suitable for measuring a sufficiently large number of protein-ligand NOEs that allow calculation of initial complex structures

  20. Isotopic studies on ligand exchange between complex and simple cyanides in water medium and in liquid hydrogen cyanide. Part 2. Radiocyanide ligand exchange study between hydrogen cyanide and octacyanotungstate(4) in water solutions of mineral acids

    International Nuclear Information System (INIS)

    Zielinski, M.

    1979-01-01

    Radiocyanide ligand exchange between potassium octacyanotungstate(4) and hydrogen cyanide in aqueous solutions of sulfuric acid and between octacyanotungstic(4) acid and hydrogen cyanide in aqueous solutions have been investigated experimentally. The observed enhancement of the rate of ligand exchange in acidic medium has been rationalized in terms of the proposed new general reaction scheme taking into account the reversible decomposition of complex cyanide at low pH, and irreversible one at high pH. The discussion on the results obtained has been carried out within the framework of derived formal kinetic equations. (author)

  1. A robust ligand exchange approach for preparing hydrophilic, biocompatible photoluminescent quantum dots

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Sujuan; Zhou, Changhua [Key Laboratory for Special Functional Materials of the Ministry of Education, Henan University, Kaifeng 475004 (China); Yuan, Hang [Life Science Division, Graduate School at Shenzhen, Tsinghua University, Shenzhen 518055 (China); Shen, Huaibin [Key Laboratory for Special Functional Materials of the Ministry of Education, Henan University, Kaifeng 475004 (China); Zhao, Wenxiu [Life Science Division, Graduate School at Shenzhen, Tsinghua University, Shenzhen 518055 (China); Ma, Lan, E-mail: malan@sz.tsinghua.edu.cn [Life Science Division, Graduate School at Shenzhen, Tsinghua University, Shenzhen 518055 (China); Li, Lin Song, E-mail: lsli@henu.edu.cn [Key Laboratory for Special Functional Materials of the Ministry of Education, Henan University, Kaifeng 475004 (China)

    2013-08-01

    Graphical abstract: - Highlights: • Aqueous CdSe/ZnS QDs were prepared using polymaleic anhydrides as capping ligand. • Effect of reaction temperature and time were systematically studied in the synthesis process. • Water-soluble QDs exhibited a good stability in physiological relevant environment. • The aqueous QDs were applied as biological probe to detect human embryonic stem cell. - Abstract: This paper describes a robust ligand exchange approach for preparing biocompatible CdSe/ZnS quantum dots (QDs) to make bioprobe for effective cell imaging. In this method, polymaleic anhydride (PMA) ligand are first used to replace original hydrophobic ligand (oleic acid) and form a protection shell with multiple hydrophilic groups to coat and protect CdSe/ZnS QDs. The as-prepared aqueous QDs exhibit small particle size, good colloidal stability in aqueous solutions with a wide range of pH, salt concentrations and under thermal treatment, which are necessary for biological applications. The use of this new class of aqueous QDs for effective cell imaging shows strong fluorescence signal to human embryonic stem cell, which demonstrate that PMA coated QDs are fully satisfied with the requirements of preparing high quality biological probe.

  2. Characterization of Colloidal Quantum Dot Ligand Exchange by X-ray Photoelectron Spectroscopy

    Science.gov (United States)

    Atewologun, Ayomide; Ge, Wangyao; Stiff-Roberts, Adrienne D.

    2013-05-01

    Colloidal quantum dots (CQDs) are chemically synthesized semiconductor nanoparticles with size-dependent wavelength tunability. Chemical synthesis of CQDs involves the attachment of long organic surface ligands to prevent aggregation; however, these ligands also impede charge transport. Therefore, it is beneficial to exchange longer surface ligands for shorter ones for optoelectronic devices. Typical characterization techniques used to analyze surface ligand exchange include Fourier-transform infrared spectroscopy, x-ray diffraction, transmission electron microscopy, and nuclear magnetic resonance spectroscopy, yet these techniques do not provide a simultaneously direct, quantitative, and sensitive method for evaluating surface ligands on CQDs. In contrast, x-ray photoelectron spectroscopy (XPS) can provide nanoscale sensitivity for quantitative analysis of CQD surface ligand exchange. A unique aspect of this work is that a fingerprint is identified for shorter surface ligands by resolving the regional XPS spectrum corresponding to different types of carbon bonds. In addition, a deposition technique known as resonant infrared matrix-assisted pulsed laser evaporation is used to improve the CQD film uniformity such that stronger XPS signals are obtained, enabling more accurate analysis of the ligand exchange process.

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

    Science.gov (United States)

    Zheng, Yao-Rong; Stang, Peter J

    2009-03-18

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

  4. Group IV nanocrystals with ion-exchangeable surface ligands and methods of making the same

    Science.gov (United States)

    Wheeler, Lance M.; Nichols, Asa W.; Chernomordik, Boris D.; Anderson, Nicholas C.; Beard, Matthew C.; Neale, Nathan R.

    2018-01-09

    Methods are described that include reacting a starting nanocrystal that includes a starting nanocrystal core and a covalently bound surface species to create an ion-exchangeable (IE) nanocrystal that includes a surface charge and a first ion-exchangeable (IE) surface ligand ionically bound to the surface charge, where the starting nanocrystal core includes a group IV element.

  5. Kinetic study on ligand exchange reaction between EC and 99mTc-GH

    International Nuclear Information System (INIS)

    Wu Chunying; Luo Shineng; Fang Ping; Huang Heyun; Xie Minhao; Meng Hong

    1995-01-01

    The ligand exchange reaction between EC and 99m Tc-GH and its influence factors such as concentrations of EC and pH were described. The concentration of EC has no influence on the exchange reaction rate constant, while pH is the most important influence factor. The rate constants of ligand exchange reaction at different pH values were determined. The results showed that in order to make the labelling yield of 99m Tc-EC higher than 90%, pH of the reaction must be higher than 8

  6. Functionalization of Cadmium Selenide Quantum Dots with Poly(ethylene glycol): Ligand Exchange, Surface Coverage, and Dispersion Stability.

    Science.gov (United States)

    Wenger, Whitney Nowak; Bates, Frank S; Aydil, Eray S

    2017-08-22

    Semiconductor quantum dots synthesized using rapid mixing of precursors by injection into a hot solution of solvents and surfactants have surface ligands that sterically stabilize the dispersions in nonpolar solvents. Often, these ligands are exchanged to disperse the quantum dots in polar solvents, but quantitative studies of quantum dot surfaces before and after ligand exchange are scarce. We studied exchanging trioctylphosphine (TOP) and trioctylphosphine oxide (TOPO) ligands on as-synthesized CdSe quantum dots dispersed in hexane with a 2000 g/mol thiolated poly(ethylene glycol) (PEG) polymer. Using infrared spectroscopy we quantify the absolute surface concentration of TOP/TOPO and PEG ligands per unit area before and after ligand exchange. While 50-85% of the TOP/TOPO ligands are removed upon ligand exchange, only a few are replaced with PEG. Surprisingly, the remaining TOP/TOPO ligands outnumber the PEG ligands, but these few PEG ligands are sufficient to disperse the quantum dots in polar solvents such as chloroform, tetrahydrofuran, and water. Moreover, as-synthesized quantum dots once easily dispersed in hexane are no longer dispersible in nonpolar solvents after ligand exchange. A subtle coverage-dependent balance between attractive PEG-solvent interactions and repulsive TOP/TOPO-solvent interactions determines the dispersion stability.

  7. Characterization of poly(allylamine) as a polymeric ligand for ion-exchange protein chromatography.

    Science.gov (United States)

    Li, Ming; Li, Yanying; Yu, Linling; Sun, Yan

    2017-02-24

    This work reports poly(allylamine) (PAA), as a polymeric ion-exchange ligand for protein chromatography. Sepharose FF was modified with PAA, and six anion exchangers with ionic capacities (ICs) from 165 to 618mmol/L were prepared. Inverse size exclusion chromatography, adsorption equilibrium, uptake kinetics and column elution were performed. It was found that both the adsorption capacity and effective diffusivity maintained low values in the IC range of 165-373mmol/L, but they started to increase beyond 373mmol/L, and increased by 80% and 23 times, respectively, when the IC reached 618mmol/L. Interestingly, a drastic decrease of pore size was observed around the IC of 373mmol/L. The results suggest that the PAA chains played an important role in protein adsorption by altering the inner pore structure of the gels. It is considered that, PAA chains turn from inextensible states with multipoint-grafting on the pore surface at low coupling densities (IC373mmol/L). These characters of the grafted chains at higher IC values benefit in protein adsorption by three-dimensional binding and encouraged the happening of "chain delivery" of bound proteins on the chains. Besides, the ion exchangers showed favorable adsorption and uptake properties in a wide ionic strength range, 0-500mmol/L NaCl, indicating much better salt tolerance feature than the so-far reported ion exchangers. Moreover, a mild condition of pH 5.0 offered effective recovery of bound proteins in elution chromatography. The results indicate that the PAA-based anion exchanger of a high IC value is promising for high-capacity protein chromatography dealing with feedstock of a wide range of ionic strengths. Copyright © 2016 Elsevier B.V. All rights reserved.

  8. Effect of Ligand Exchange on the Photoluminescence Properties of Cu-Doped Zn-In-Se Quantum Dots

    Science.gov (United States)

    Dong, Xiaofei; Xu, Jianping; Yang, Hui; Zhang, Xiaosong; Mo, Zhaojun; Shi, Shaobo; Li, Lan; Yin, Shougen

    2018-04-01

    The surface-bound ligands of a semiconductor nanocrystal can affect its electron transition behavior. We investigate the photoluminescence (PL) properties of Cu-doped Zn-In-Se quantum dots (QDs) through the exchange of oleylamine with 6-mercaptohexanol (MCH). Fourier transform infrared and 1H nuclear magnetic resonance spectroscopies, and mass spectrometry reveal that the short-chain MCH molecules are bound to the QD surface. The emission peaks remain unchanged after ligand exchange, and the PL quantum yield is reduced from 49% to 38%. The effects of particle size and defect type on the change in PL behavior upon ligand substitution are excluded through high-resolution transmission electron microscopy, UV-Vis absorption, and PL spectroscopies. The origin of the decreased PL intensity is associated with increased ligand density and the stronger ligand electron-donating abilities of MCH-capped QDs that induce an increase in the nonradiative transition probability. A lower PL quenching transition temperature is observed for MCH-capped QDs and is associated with increasing electron-acoustic phonon coupling due to the lower melting temperature of MCH.

  9. Inorganic-ligand exchanging time effect in PbS quantum dot solar cell

    International Nuclear Information System (INIS)

    Kim, Byung-Sung; Hong, John; Hou, Bo; Cho, Yuljae; Sohn, Jung Inn; Cha, SeungNam; Kim, Jong Min

    2016-01-01

    We investigate time-dependent inorganic ligand exchanging effect and photovoltaic performance of lead sulfide (PbS) nanocrystal films. With optimal processing time, volume shrinkage induced by residual oleic acid of the PbS colloidal quantum dot (CQD) was minimized and a crack-free film was obtained with improved flatness. Furthermore, sufficient surface passivation significantly increased the packing density by replacing from long oleic acid to a short iodide molecule. It thus facilities exciton dissociation via enhanced charge carrier transport in PbS CQD films, resulting in the improved power conversion efficiency from 3.39% to 6.62%. We also found that excess iodine ions on the PbS surface rather hinder high photovoltaic performance of the CQD solar cell.

  10. Inorganic-ligand exchanging time effect in PbS quantum dot solar cell

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Byung-Sung; Hong, John; Hou, Bo; Cho, Yuljae; Sohn, Jung Inn, E-mail: junginn.sohn@eng.ox.ac.uk, E-mail: seungnam.cha@eng.ox.ac.uk; Cha, SeungNam, E-mail: junginn.sohn@eng.ox.ac.uk, E-mail: seungnam.cha@eng.ox.ac.uk [Department of Engineering Science, University of Oxford, Parks Road, Oxford OX1 3PJ (United Kingdom); Kim, Jong Min [Department of Engineering, University of Cambridge, 9 JJ Thomson Avenue, Cambridge CB3 0FA (United Kingdom)

    2016-08-08

    We investigate time-dependent inorganic ligand exchanging effect and photovoltaic performance of lead sulfide (PbS) nanocrystal films. With optimal processing time, volume shrinkage induced by residual oleic acid of the PbS colloidal quantum dot (CQD) was minimized and a crack-free film was obtained with improved flatness. Furthermore, sufficient surface passivation significantly increased the packing density by replacing from long oleic acid to a short iodide molecule. It thus facilities exciton dissociation via enhanced charge carrier transport in PbS CQD films, resulting in the improved power conversion efficiency from 3.39% to 6.62%. We also found that excess iodine ions on the PbS surface rather hinder high photovoltaic performance of the CQD solar cell.

  11. Kinetics and mechanism of ligand-exchange reactions of Cd(II) chelates

    Energy Technology Data Exchange (ETDEWEB)

    Nivorozhkin, L.E.; Kalabin, G.A.; Nivorozhkin, A.L.; Valeev, R.B.; Minkin, V.I.

    1987-03-01

    Tetrahedral Cd(II) bis(5-thio(or seleno)pyrazole-4-carboxaldiminates) of types II and III have been synthesized for the first time. The kinetics of the degenerate ligand exchange and enantiomerization of the complexes obtained have been studied by dynamic /sup 111/Cd, /sup 77/Se, and /sup 1/H (s = 1/2) NMR. The rate of intramolecular enantiomerization (k = 1/tau) is more than an order of magnitude greater than the corresponding values for processes of degenerate ligand exchange (a second-order reaction) determined from the dynamics of the averaging of the /sup 111/Cd-/sup 77/Se and /sup 111/Cd-N=CH spin-spin coupling constants. The cleavage and formation processes of the Cd-Se and Cd-N bonds are isoenergetic (..delta.. G/sub 298//sup not equal to/ = 14.4 kcal/mole for chelate II with X = Se and R = CH/sub 2/C/sub 6/H/sub 5/). The free energies of activation of degenerate ligand exchange determined form the dynamics of the averaging of the /sup 111/Cd N=CH spin-spin coupling constant increase from 12.7 to 17.9 kcal/mole along the following series for R: C/sub 2/H/sub 5/ < Ar < CH/sub 2/C/sub 6/H/sub 5/ < t-C/sub 4/H/sub 9/ < cyclo-C/sub 6/H/sub 11/. Replacement of the sulfur atom in the chelate ring by selenium results in increases in the rates of ligand exchange. A mechanism of degenerate ligand exchange has been proposed.

  12. In situ spectroscopy of ligand exchange reactions at the surface of colloidal gold and silver nanoparticles

    International Nuclear Information System (INIS)

    Dinkel, Rebecca; Peukert, Wolfgang; Braunschweig, Björn

    2017-01-01

    Gold and silver nanoparticles with their tunable optical and electronic properties are of great interest for a wide range of applications. Often the ligands at the surface of the nanoparticles have to be exchanged in a second step after particle formation in order to obtain a desired surface functionalization. For many techniques, this process is not accessible in situ . In this review, we present second-harmonic scattering (SHS) as an inherently surface sensitive and label-free optical technique to probe the ligand exchange at the surface of colloidal gold and silver nanoparticles in situ and in real time. First, a brief introduction to SHS and basic features of the SHS of nanoparticles are given. After that, we demonstrate how the SHS intensity decrease can be correlated to the thiol coverage which allows for the determination of the Gibbs free energy of adsorption and the surface coverage. (topical review)

  13. Ligand isotopic exchange of tris(acetylacetonato)germanium(IV) perchlorate in organic solvents

    International Nuclear Information System (INIS)

    Nagasawa, Akira; Saito, Kazuo

    1978-01-01

    The ligand isotopic exchange between tris(acetylacetonato)germanium(IV) perchlorate and acetylacetone[ 14 C] has been studied in 1,1,2,2-tetrachloroethane (TCE), nitromethane (NM), and acetonitrile (AN), at 100 - 120 0 C. In these solvents, the rate formula was R = k[H 2 O][complex]; the concentrations of the complex, free ligand, and water in solution were in the ranges from 0.01 to 0.1 mol dm -3 . The activation enthalpies and entropies for the k's are 105, 98, and 90 kJ mol -1 ; and -25, -53, and -69 JK -1 mol -1 , in TCE, NM, and AN, respectively. Influence of acid and base concentrations, and deuterium isotope effect on the rate in AN suggest that the rate controlling step of the exchange is governed by the ease of the proton transfer between the leaving and the incoming acac - in an intermediate. (auth.)

  14. Dynamics of ligand exchange and association processes in solutions of transition 3d-metal fluorides

    International Nuclear Information System (INIS)

    Nazmutdinova, G.A.; Shtyrlin, V.G.; Zakharov, A.V.; Sal'nikov, Yu.I.

    1993-01-01

    By 19 NMR in combination with ESR spectroscopy rate constants and activation parameters of fluoride-ion exchange reactions in solutions of VOF 5 3- and FeF 6 3- complexes were determined. Associative character of the studied reactions of ligand exchange is shown. Dependence of fluoride complex reactivity on the charge, electron structure of the central ion and formation of hydrogen bonds of coordinated F - ions with solvent molecules was demonstrated. Stability constants, rates of formation and dissociation of intercomplex associates in fluoride solutions were ascertained

  15. Fine-tuning the Wall Thickness of Ordered Mesoporous Graphene by Exploiting Ligand Exchange of Colloidal Nanocrystals

    Science.gov (United States)

    Han, Dandan; Yan, Yancui; Wei, Jishi; Wang, Biwei; Li, Tongtao; Guo, Guannan; Yang, Dong; Xie, Songhai; Dong, Angang

    2017-12-01

    Because of their unique physical properties, three-dimensional (3D) graphene has attracted enormous attention over the past years. However, it is still a challenge to precisely control the layer thickness of 3D graphene. Here, we report a novel strategy to rationally adjust the wall thickness of ordered mesoporous graphene (OMG). By taking advantage of ligand exchange capability of colloidal Fe3O4 nanocrystals, we are able to fine-tune the wall thickness of OMG from 2 to 6 layers of graphene by tailoring the hydrocarbon ligands attached to the nanocrystal surface. When evaluated as electrocatalyst for oxygen reduction reaction upon S and N doping, the 4-layer OMG is found to show better catalytic performance compared with its 2- and 6-layer counterparts, which we attribute to the enhanced exposure of active sites resulting from its ultrathin wall thickness and high surface area.

  16. Ultrafiltration technique in conjunction with competing ligand exchange method for Ni–humics speciation in aquatic environment

    Digital Repository Service at National Institute of Oceanography (India)

    Chakraborty, P.; Boissel, M.; Reuillon, A.; Babu, P.V.R.; Parthiban, G.

    The combination of ultrafiltration technique with competing ligand exchange method provides a better understanding of interactions between Ni and different molecular weight fractions of humic acid (HA) at varying pH in aquatic environment...

  17. Ligand exchange reactions of the heme group in hemoglobin and myoglobin as studied by pulse radiolysis

    International Nuclear Information System (INIS)

    Raap, I.A.

    1978-01-01

    In this thesis, the kinetic aspects of the ligand exchange reactions of hemoglobin are studied using the pulse radiolysis technique, in particular, the reactions of hydrated electrons with methemoglobin. A hitherto unobserved transient state of the heme group is observed which appears immediately after the rapid reduction process. The absorption spectrum of this new species has the characteristics of a ferrous low-spin state and can therefore be ascribed to the formation of a hemochrome non-equilibrium state. The subsequent relaxation of this intermediate structure into a deoxy-conformation is dependent on the amount of proton activity in the solution and on the presence of organic and inorganic phosphate anions. The final absorption spectrum of the heme group is shown to correspond to a ferrous high-spin state in the relaxed quaternary conformation. This is in agreement with the kinetics observen the binding of carbon monoxide and oxygen to partially reduced methemoglobin. At reduction degrees of methemoglobin as well as of valncy 8ybrids where there is an important contribution from species with two reduced subunits, the binding of carbon monoxide to hemoglobin occurs with on-rate constants characteristic for the tensed quaternary conformation. It is argued that this conformational change of hemoglobin (the R-to-T transition) takes place very rapidly, which suggests the participation of an activated relaxed conformation. In addition, it is found that there is a distinct heterogeneity in the binding of oxygen to partially reduced methemoglobin even at low degrees of reduction

  18. Rapid and Efficient Collection of Platinum from Karstedt's Catalyst Solution via Ligands-Exchange-Induced Assembly.

    Science.gov (United States)

    Yang, Gonghua; Wei, Yanlong; Huang, Zhenzhu; Hu, Jiwen; Liu, Guojun; Ou, Ming; Lin, Shudong; Tu, Yuanyuan

    2018-02-21

    Reported herein is a novel strategy for the rapid and efficient collection of platinum from Karstedt's catalyst solution. By taking advantage of a ligand-exchange reaction between alkynols and the 1,3-divinyltetramethyldisiloxane ligand (M Vi M Vi ) that coordinated with platinum (Pt(0)), the Karstedt's catalyst particles with a size of approximately 2.5 ± 0.7 nm could be reconstructed and assembled into larger particles with a size of 150 ± 35 nm due to the hydrogen bonding between the hydroxyl groups of the alkynol. In addition, because the silicone-soluble M Vi M Vi ligand of the Karstedt's catalyst was replaced by water-soluble alkynol ligands, the resultant large particles were readily dispersed in water, resulting in rapid, efficient, and complete collection of platinum from the Karstedt's catalyst solutions with platinum concentrations in the range from ∼20 000 to 0.05 ppm. Our current strategy not only was used for the rapid and efficient collection of platinum from the Karstedt's catalyst solutions, but it also enabled the precise evaluation of the platinum content in the Karstedt's catalysts, even if this platinum content was extremely low (i.e., 0.05 ppm). Moreover, these platinum specimens that were efficiently collected from the Karstedt's catalyst solutions could be directly used for the evaluation of platinum without the need for pretreatment processes, such as calcination and digestion with hydrofluoric acid, that were traditionally used prior to testing via inductively coupled plasma mass spectrometry in conventional methods.

  19. Studies on ligand exchange reaction of functionalized mercaptothiadiazole compounds onto citrate capped gold nanoparticles

    International Nuclear Information System (INIS)

    Kalimuthu, Palraj; John, S. Abraham

    2010-01-01

    Mercaptothiadiazole ligands functionalized with thiol (2,5-dimercapto-1,3,4-thiadiazole (DMT)) and methyl (5-methyl-2-mercapto-1,3,4-thiadiazole (MMT)) groups capped onto citrate capped gold nanoparticles (C-AuNPs) by ligand exchange reaction was investigated by UV-vis spectroscopy, FT-IR spectroscopy and transmission electron microscopy (TEM) techniques. The surface plasmon resonance band at 522 nm for C-AuNPs was shifted to 530 nm after capping with DMT whereas an additional band was observed at 630 nm due to aggregation in addition to a shift in the band at 522 nm after capping of MMT onto C-AuNPs. Thus, capping of DMT onto C-AuNPs leads to the formation of stable AuNPs while capping of MMT leads to the formation of unstable AuNPs. FT-IR studies show that the citrate ions were completely replaced by both DMT and MMT ligands from the AuNPs. TEM images indicate that the size and shape of the AuNPs remain same after capping of these ligands.

  20. Novel peptide ligand with high binding capacity for antibody purification

    DEFF Research Database (Denmark)

    Lund, L. N.; Gustavsson, P. E.; Michael, R.

    2012-01-01

    Small synthetic ligands for protein purification have become increasingly interesting with the growing need for cheap chromatographic materials for protein purification and especially for the purification of monoclonal antibodies (mAbs). Today, Protein A-based chromatographic resins are the most...... commonly used capture step in mAb down stream processing; however, the use of Protein A chromatography is less attractive due to toxic ligand leakage as well as high cost. Whether used as an alternative to the Protein A chromatographic media or as a subsequent polishing step, small synthetic peptide...... ligands have an advantage over biological ligands; they are cheaper to produce, ligand leakage by enzymatic degradation is either eliminated or significantly reduced, and they can in general better withstand cleaning in place (CIP) conditions such as 0.1 M NaOH. Here, we present a novel synthetic peptide...

  1. Ligand exchange chromatography for analysis and preparative separation of tritium-labelled amino acids

    International Nuclear Information System (INIS)

    Zolotarev, Yu.A.; Zaitsev, D.A.; Penkina, V.I.; Dostavalov, I.N.; Myasoedov, N.F.

    1988-01-01

    Racemic tritium-labelled amino acids were separated into optical isomers by chromatography on a chiral polyacrylamide sorbent filled with copper ions. The polyacrylamide sorbent is synthesized by Mannich's reaction through the action of formaldehyde and L-phenylalanine upon polyacrylamide Biogel P-4 in an alkali phosphate buffer. Tritium-labelled amino acids are eluted by a weak alkali solution of ammonium carbonate. Data are presented on the ligand exchange chromatography of amino acids depending on the degree to which the sorbent is filled with copper ions and on the eluent concentration. Amino acids are isolated from the eluent on short columns filled with sulfonated cation exchanger in the H + form. HPLC on modified silica gel sorbents is also used for the analysis of tritium-labelled optically active amino acids. Amino acids are eluted by a weakly acidic water-methanol solution containing ammonium acetate. UV and scintillation flow type detectors are used. (author) 7 refs.; 8 figs

  2. New Ru(II) complexes for dual photoreactivity: ligand exchange and (1)O2 generation.

    Science.gov (United States)

    Knoll, Jessica D; Albani, Bryan A; Turro, Claudia

    2015-08-18

    Uncovering the factors that govern the electronic structure of Ru(II)-polypyridyl complexes is critical in designing new compounds for desired photochemical reactions, and strategies to tune excited states for ligand dissociation and (1)O2 production are discussed herein. The generally accepted mechanism for photoinduced ligand dissociation proposes that population of the dissociative triplet ligand field ((3)LF) state proceeds through thermal population from the vibrationally cooled triplet metal-to-ligand charge transfer ((3)MLCT) state; however, temperature-dependent emission spectroscopy provides varied activation energies using the emission and ligand exchange quantum yields for [Ru(bpy)2(L)2](2+) (bpy = 2,2'-bipyridine; L = CH3CN or py). This suggests that population of the (3)LF state proceeds from the vibrationally excited (3)MLCT state. Because the quantum yield of ligand dissociation for nitriles is much more efficient than that for py, steric bulk was introduced into the ligand set to distort the pseudo-octahedral geometry and lower the energy of the (3)LF state. The py dissociation quantum yield with 500 nm irradiation in a series of [Ru(tpy)(NN)(py)](2+) complexes (tpy = 2,2':6',2″-terpyridine; NN = bpy, 6,6'-dimethyl-2,2'-bipyridine (Me2bpy), 2,2'-biquinoline (biq)) increases by 2-3 orders of magnitude with the sterically bulky Me2bpy and biq ligands relative to bpy. Ultrafast transient absorption spectroscopy reveals population of the (3)LF state within 3-7 ps when NN is bulky, and density functional theory calculations support stabilized (3)LF states. Dual activity via ligand dissociation and (1)O2 production can be achieved by careful selection of the ligand set to tune the excited-state dynamics. Incorporation of an extended π system in Ru(II) complexes such as [Ru(bpy)(dppn)(CH3CN)2](2+) (dppn = benzo[i]dipyrido[3,2-a:2',3'-c]phenazine) and [Ru(tpy)(Me2dppn)(py)](2+) (Me2dppn = 3,6-dimethylbenzo[i]dipyrido[3,2-a:2',3'-c]phenazine) introduces

  3. New Ru(II) Complexes for Dual Photoreactivity: Ligand Exchange and 1O2 Generation

    Science.gov (United States)

    Knoll, Jessica D.; Albani, Bryan A.; Turro, Claudia

    2016-01-01

    CONSPECTUS Uncovering the factors that govern the electronic structure of Ru(II)–polypyridyl complexes is critical in designing new compounds for desired photochemical reactions, and strategies to tune excited states for ligand dissociation and 1O2 production are discussed herein. The generally accepted mechanism for photoinduced ligand dissociation proposes that population of the dissociative triplet ligand field (3LF) state proceeds through thermal population from the vibrationally cooled triplet metal-to-ligand charge transfer (3MLCT) state; however, temperature-dependent emission spectroscopy provides varied activation energies using the emission and ligand exchange quantum yields for [Ru(bpy)2(L)2]2+ (bpy = 2,2′-bipyridine; L = CH3CN or py). This suggests that population of the 3LF state proceeds from the vibrationally excited 3MLCT state. Because the quantum yield of ligand dissociation for nitriles is much more efficient than that for py, steric bulk was introduced into the ligand set to distort the pseudo-octahedral geometry and lower the energy of the 3LF state. The py dissociation quantum yield with 500 nm irradiation in a series of [Ru(tpy)(NN)(py)]2+ complexes (tpy = 2,2′:6′,2″-terpyridine; NN = bpy, 6,6′-dimethyl-2,2′-bipyridine (Me2bpy), 2,2′-biquinoline (biq)) increases by 2–3 orders of magnitude with the sterically bulky Me2bpy and biq ligands relative to bpy. Ultrafast transient absorption spectroscopy reveals population of the 3LF state within 3–7 ps when NN is bulky, and density functional theory calculations support stabilized 3LF states. Dual activity via ligand dissociation and 1O2 production can be achieved by careful selection of the ligand set to tune the excited-state dynamics. Incorporation of an extended π system in Ru(II) complexes such as [Ru(bpy)(dppn)(CH3CN)2]2+ (dppn = benzo[i]dipyrido[3,2-a:2′,3′-c]phenazine) and [Ru(tpy)(Me2dppn)(py)]2+ (Me2dppn = 3,6-dimethylbenzo[i]dipyrido[3,2-a:2′,3

  4. Fine-Tuning the Wall Thickness of Ordered Mesoporous Graphene by Exploiting Ligand Exchange of Colloidal Nanocrystals

    Directory of Open Access Journals (Sweden)

    Dandan Han

    2017-12-01

    Full Text Available Because of their unique physical properties, three-dimensional (3D graphene has attracted enormous attention over the past years. However, it is still a challenge to precisely control the layer thickness of 3D graphene. Here, we report a novel strategy to rationally adjust the wall thickness of ordered mesoporous graphene (OMG. By taking advantage of ligand exchange capability of colloidal Fe3O4 nanocrystals, we are able to fine-tune the wall thickness of OMG from 2 to 6 layers of graphene. When evaluated as electrocatalyst for oxygen reduction reaction upon S and N doping, the 4-layer OMG is found to show better catalytic performance compared with their 2- and 6-layer counterparts, which we attribute to the enhanced exposure of active sites arising from the thin wall thickness and high surface area.

  5. N-Decyl-S-trityl-(R)-cysteine, a new chiral selector for "green" ligand-exchange chromatography applications.

    Science.gov (United States)

    Carotti, Andrea; Ianni, Federica; Camaioni, Emidio; Pucciarini, Lucia; Marinozzi, Maura; Sardella, Roccaldo; Natalini, Benedetto

    2017-09-10

    In search for new enantioselectivity profiles, the N-decyl-S-trityl-(R)-cysteine [C 10 -(R)-STC] was synthesized through a one-step procedure and then hydrophobically adsorbed onto an octadecylsilica surface to generate a stable chiral stationary phase for ligand-exchange chromatography (CLEC-CSP) applications. The CLEC analysis was carried out on underivatized amino acids, by using a Cu(II) sulphate (1.0mM) containing aqueous eluent system. Most of the analysed compounds (34 out of 45) were enantiodiscriminated by the C 10 -(R)-STC-based CSP, with resolution factor (R S ) values up to 8.86. Conformationally rigid and hydrophobic ligands often experienced the largest enantioselectivity effects. A high loadability emerged from the analysis of rac-NorVal (selected as prototype test compound): up to 20mg/mL were efficiently enantioseparated with the CLEC-CSP. Two in-line hand-made cartridges filled with a strong cation-exchange resin allowed the effective catching of Cu(II) ions after the semi-preparative enantioseparation. The quantitative recovery of the rac-NorVal enantiomers was made possible by flowing through the cartridge a 5% (v) ammonia solution. The CLEC phase proved successful in the enantioselective analysis of a commercially available (S)-Leu containing tablet. Furthermore, in order to understand the molecular basis for a successful use of the C 10 -(R)-STC-based CLEC system, a descriptive structure-separation relationship study was performed. As a result, all compounds with a MEAN-QPlogS (a hydrophilicity descriptor) value lower than 0.373 can be most likely enantioseparated with the CLEC system under investigation. In the work, the numerous aspects complying with the principles of green chromatography are highlighted and discussed. Copyright © 2017 Elsevier B.V. All rights reserved.

  6. Speciation of Co(II) and Ni(II) in anaerobic bioreactors measured by competitive ligand exchange - adsorptive stripping voltammetry

    NARCIS (Netherlands)

    Jansen, S.; Steffen, F.; Threels, W.F.; Leeuwen, van H.P.

    2005-01-01

    Competitive ligand exchange-adsorptive stripping voltammetry is applied to speciation analysis of dissolved Ni(II) and Co(II) in an anaerobic bioreactor and similar batch media. Co and Ni speciation in these media can be measured down to concentration levels of ca. 1 nM. Sulfide interference is

  7. Phonon Raman spectra of colloidal CdTe nanocrystals: effect of size, non-stoichiometry and ligand exchange

    Directory of Open Access Journals (Sweden)

    Lokteva Irina

    2011-01-01

    Full Text Available Abstract Resonant Raman study reveals the noticeable effect of the ligand exchange on the nanocrystal (NC surface onto the phonon spectra of colloidal CdTe NC of different size and composition. The oleic acid ligand exchange for pyridine ones was found to change noticeably the position and width of the longitudinal optical (LO phonon mode, as well as its intensity ratio to overtones. The broad shoulder above the LO peak frequency was enhanced and sharpened after pyridine treatment, as well as with decreasing NC size. The low-frequency mode around 100 cm-1 which is commonly related with the disorder-activated acoustical phonons appears in smaller NCs but is not enhanced after pyridine treatment. Surprisingly, the feature at low-frequency shoulder of the LO peak, commonly assigned to the surface optical phonon mode, was not sensitive to ligand exchange and concomitant close packing of the NCs. An increased structural disorder on the NC surface, strain and modified electron-phonon coupling is discussed as the possible reason of the observed changes in the phonon spectrum of ligand-exchanged CdTe NCs. PACS: 63.20.-e, 78.30.-j, 78.67.-n, 78.67.Bf

  8. Time-dependent photoluminescence spectroscopy as a tool to measure the ligand exchange kinetics on a quantum dot surface

    NARCIS (Netherlands)

    Koole, R.; Schapotschnikow, P.Z.; de Mello Donega, C.; Vlugt, T.J.H.; Meijerink, A.

    2008-01-01

    The exchange kinetics of native ligands that passivate CdSe quantum dots (hexadecylamine (HDA), trioctylphosphine oxide (TOPO), and trioctylphosphine (TOP)) by thiols is followed in situ. This is realized by measuring, in real-time, the decrease in emission intensity of the QDs upon addition of

  9. Uniform thin film electrode made of low-temperature-sinterable silver nanoparticles: optimized extent of ligand exchange from oleylamine to acrylic acid

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Yung Jong; Kim, Na Rae; Lee, Changsoo; Lee, Hyuck Mo, E-mail: hmlee@kaist.ac.kr [Department of Materials Science and Engineering (Korea, Republic of)

    2017-02-15

    Lowering the sintering temperature of nanoparticles in the electrode deposition process holds both academic and industrial interest because of the potential applications of such electrodes in polymer devices and flexible electronics. In addition, achieving uniform electrode formation after ligand exchange is equally important as lowering the sintering temperature. Here, we report a simple chemical treatment by the addition of ligand-exchanging interfaces to lower the sintering temperature; we also determine the optimum extent of ligand exchange for crack-free electrode formation. First, we investigated the structural change of Ag thin films with respect to the concentration of acrylic acid (AA) solutions. Second, we used thermal analysis to evaluate the effects of changes in the sintering temperature. We observed that the resulting conductivity of the Ag patterns was only one order of magnitude lower than that of bulk Ag when the patterns were sintered at 150 °C. The simple chemical treatment developed in this work for solution-processed Ag electrode formation can be adopted for flexible electronics, which would eliminate the need for vacuum and high-temperature processes.

  10. Oxygen Atom Exchange between H2O and Non-Heme Oxoiron(IV) Complexes: Ligand Dependence and Mechanism.

    Science.gov (United States)

    Puri, Mayank; Company, Anna; Sabenya, Gerard; Costas, Miquel; Que, Lawrence

    2016-06-20

    Detailed studies of oxygen atom exchange (OAE) between H2(18)O and synthetic non-heme oxoiron(IV) complexes supported by tetradentate and pentadentate ligands provide evidence that they proceed by a common mechanism but within two different kinetic regimes, with OAE rates that span 2 orders of magnitude. The first kinetic regime involves initial reversible water association to the Fe(IV) complex, which is evidenced by OAE rates that are linearly dependent on [H2(18)O] and H2O/D2O KIEs of 1.6, while the second kinetic regime involves a subsequent rate determining proton-transfer step between the bound aqua and oxo ligands that is associated with saturation behavior with [H2(18)O] and much larger H2O/D2O KIEs of 5-6. [Fe(IV)(O)(TMC)(MeCN)](2+) (1) and [Fe(IV)(O)(MePy2TACN)](2+) (9) are examples of complexes that exhibit kinetic behavior in the first regime, while [Fe(IV)(O)(N4Py)](2+) (3), [Fe(IV)(O)(BnTPEN)](2+) (4), [Fe(IV)(O)(1Py-BnTPEN)](2+) (5), [Fe(IV)(O)(3Py-BnTPEN)](2+) (6), and [Fe(IV)(O)(Me2Py2TACN)](2+) (8) represent complexes that fall in the second kinetic regime. Interestingly, [Fe(IV)(O)(PyTACN)(MeCN)](2+) (7) exhibits a linear [H2(18)O] dependence below 0.6 M and saturation above 0.6 M. Analysis of the temperature dependence of the OAE rates shows that most of these complexes exhibit large and negative activation entropies, consistent with the proposed mechanism. One exception is complex 9, which has a near-zero activation entropy and is proposed to undergo ligand-arm dissociation during the RDS to accommodate H2(18)O binding. These results show that the observed OAE kinetic behavior is highly dependent on the nature of the supporting ligand and are of relevance to studies of non-heme oxoiron(IV) complexes in water or acetonitrile/water mixtures for applications in photocatalysis and water oxidation chemistry.

  11. Analysis of ligand-protein exchange by Clustering of Ligand Diffusion Coefficient Pairs (CoLD-CoP)

    Science.gov (United States)

    Snyder, David A.; Chantova, Mihaela; Chaudhry, Saadia

    2015-06-01

    NMR spectroscopy is a powerful tool in describing protein structures and protein activity for pharmaceutical and biochemical development. This study describes a method to determine weak binding ligands in biological systems by using hierarchic diffusion coefficient clustering of multidimensional data obtained with a 400 MHz Bruker NMR. Comparison of DOSY spectrums of ligands of the chemical library in the presence and absence of target proteins show translational diffusion rates for small molecules upon interaction with macromolecules. For weak binders such as compounds found in fragment libraries, changes in diffusion rates upon macromolecular binding are on the order of the precision of DOSY diffusion measurements, and identifying such subtle shifts in diffusion requires careful statistical analysis. The "CoLD-CoP" (Clustering of Ligand Diffusion Coefficient Pairs) method presented here uses SAHN clustering to identify protein-binders in a chemical library or even a not fully characterized metabolite mixture. We will show how DOSY NMR and the "CoLD-CoP" method complement each other in identifying the most suitable candidates for lysozyme and wheat germ acid phosphatase.

  12. High temperature alloys and ceramic heat exchanger

    International Nuclear Information System (INIS)

    Okamoto, Masaharu

    1984-04-01

    From the standpoint of energy saving, the future operating temperatures of process heat and gas turbine plants will become higher. For this purpose, ceramics is the most promissing candidate material in strength for application to high-temperature heat exchangers. This report deals with a servey of characteristics of several high-temperature metallic materials and ceramics as temperature-resistant materials; including a servey of the state-of-the-art of ceramic heat exchanger technologies developed outside of Japan, and a study of their application to the intermediate heat exchanger of VHTR (a very-high-temperature gas-cooled reactor). (author)

  13. Complete relaxation and conformational exchange matrix (CORCEMA) analysis of intermolecular saturation transfer effects in reversibly forming ligand-receptor complexes.

    Science.gov (United States)

    Jayalakshmi, V; Krishna, N Rama

    2002-03-01

    A couple of recent applications of intermolecular NOE (INOE) experiments as applied to biomolecular systems involve the (i) saturation transfer difference NMR (STD-NMR) method and (ii) the intermolecular cross-saturation NMR (ICS-NMR) experiment. STD-NMR is a promising tool for rapid screening of a large library of compounds to identify bioactive ligands binding to a target protein. Additionally, it is also useful in mapping the binding epitopes presented by a bioactive ligand to its target protein. In this latter application, the STD-NMR technique is essentially similar to the ICS-NMR experiment, which is used to map protein-protein or protein-nucleic acid contact surfaces in complexes. In this work, we present a complete relaxation and conformational exchange matrix (CORCEMA) theory (H. N. B. Moseley et al., J. Magn. Reson. B 108, 243-261 (1995)) applicable for these two closely related experiments. As in our previous work, we show that when exchange is fast on the relaxation rate scale, a simplified CORCEMA theory can be formulated using a generalized average relaxation rate matrix. Its range of validity is established by comparing its predictions with those of the exact CORCEMA theory which is valid for all exchange rates. Using some ideal model systems we have analyzed the factors that influence the ligand proton intensity changes when the resonances from some protons on the receptor protein are saturated. The results show that the intensity changes in the ligand signals in an intermolecular NOE experiment are very much dependent upon: (1) the saturation time, (2) the location of the saturated receptor protons with respect to the ligand protons, (3) the conformation of the ligand-receptor interface, (4) the rotational correlation times for the molecular species, (5) the kinetics of the reversibly forming complex, and (6) the ligand/receptor ratio. As an example of a typical application of the STD-NMR experiment we have also simulated the STD effects for a

  14. Microsoft Exchange Server 2013 high availability

    CERN Document Server

    Mota, Nuno

    2014-01-01

    This book is a hands-on practical guide that provides the reader with a number of clear scenarios and examples, making it easier to understand and apply the new concepts. Each chapter can be used as a reference, or it can be read from beginning to end, allowing consultants/administrators to build a solid and highly available Exchange 2013 environment. If you are a messaging professional who wants to learn to design a highly available Exchange 2013 environment, this book is for you. Although not a definite requirement, practical experience with Exchange 2010 is expected, without being a subject

  15. Anion exchange chromatography of 99mTc(Sn)-EHDP complexes: determination of the charge of the components and influence of pH and ligand concentration

    International Nuclear Information System (INIS)

    Huigen, Y.M.; Diender, M.; Gelsema, W.J.; De Ligny, C.L.

    1991-01-01

    The components of a 99m Tc(Sn)-EHDP complex mixture were separated by means of normal pressure and high-pressure anion exchange chromatography. Precautions were taken to prevent the dissociation of the complexes during chromatography. The charges of the components were determined according to the methods of Wilson and Pinkerton (1985) and Russell and Bischoff (1985). The values of the charges obtained with the two methods are not in agreement. Russell and Bischoff's method, in which a reference ion is used, must be preferred. However, even with this method the accuracy of the data obtained is probably limited, due to the difficulty of making corrections for activity coefficients of highly-charge ions at the rather high electrolyte concentrations that must be used in the ion exchange method. So, we think that it is only warranted to conclude that the mean charge of the components of 99m Tc(Sn)-EHDP is about -6 at pH 7, and that the charges of the individual components are in the range of -4 to -9. The influence of pH and ligand concentration in the reaction mixture was determined with high pressure anion exchange chromatography. It was found that a decrease in the pH of the reaction mixture favours the production of complexes with a long retention time, which leads to a slightly higher mean charge. The ligand concentration of the reaction mixture scarcely influenced the relative concentrations of the components. (author)

  16. Enhanced Open-Circuit Voltage in Colloidal Quantum Dot Photovoltaics via Reactivity-Controlled Solution-Phase Ligand Exchange

    KAUST Repository

    Jo, Jea Woong; Kim, Younghoon; Choi, Jongmin; de Arquer, F. Pelayo Garcí a; Walters, Grant; Sun, Bin; Ouellette, Olivier; Kim, Junghwan; Proppe, Andrew H.; Quintero-Bermudez, Rafael; Fan, James; Xu, Jixian; Tan, Chih Shan; Voznyy, Oleksandr; Sargent, Edward H.

    2017-01-01

    The energy disorder that arises from colloidal quantum dot (CQD) polydispersity limits the open-circuit voltage (VOC) and efficiency of CQD photovoltaics. This energy broadening is significantly deteriorated today during CQD ligand exchange and film assembly. Here, a new solution-phase ligand exchange that, via judicious incorporation of reactivity-engineered additives, provides improved monodispersity in final CQD films is reported. It has been found that increasing the concentration of the less reactive species prevents CQD fusion and etching. As a result, CQD solar cells with a VOC of 0.7 V (vs 0.61 V for the control) for CQD films with exciton peak at 1.28 eV and a power conversion efficiency of 10.9% (vs 10.1% for the control) is achieved.

  17. Enhanced Open-Circuit Voltage in Colloidal Quantum Dot Photovoltaics via Reactivity-Controlled Solution-Phase Ligand Exchange

    KAUST Repository

    Jo, Jea Woong

    2017-10-09

    The energy disorder that arises from colloidal quantum dot (CQD) polydispersity limits the open-circuit voltage (VOC) and efficiency of CQD photovoltaics. This energy broadening is significantly deteriorated today during CQD ligand exchange and film assembly. Here, a new solution-phase ligand exchange that, via judicious incorporation of reactivity-engineered additives, provides improved monodispersity in final CQD films is reported. It has been found that increasing the concentration of the less reactive species prevents CQD fusion and etching. As a result, CQD solar cells with a VOC of 0.7 V (vs 0.61 V for the control) for CQD films with exciton peak at 1.28 eV and a power conversion efficiency of 10.9% (vs 10.1% for the control) is achieved.

  18. Transforming single domain magnetic CoFe_2O_4 nanoparticles from hydrophobic to hydrophilic by novel mechanochemical ligand exchange

    International Nuclear Information System (INIS)

    Munjal, Sandeep; Khare, Neeraj

    2017-01-01

    Single-phase uniform-sized (~9 nm) cobalt ferrite (CFO) nanoparticles have been synthesized by hydrothermal synthesis using oleic acid as a surfactant. The as-synthesized oleic acid-coated CFO (OA-CFO) nanoparticles were well dispersible in nonpolar solvents but not dispersible in water. The OA-CFO nanoparticles have been successfully transformed to highly water-dispersible citric acid-coated CFO (CA-CFO) nanoparticles using a novel single-step ligand exchange process by mechanochemical milling, in which small chain citric acid molecules replace the original large chain oleic acid molecules available on CFO nanoparticles. The OA-CFO nanoparticle’s hexane solution and CA-CFO nanoparticle’s water solution remain stable even after 6 months and show no agglomeration and their dispersion stability was confirmed by zeta-potential measurements. The contact angle measurement shows that OA-CFO nanoparticles are hydrophobic whereas CA-CFO nanoparticles are superhydrophilic in nature. The potentiality of as-synthesized OA-CFO and mechanochemically transformed CA-CFO nanoparticles for the demulsification of highly stabilized water-in-oil and oil-in-water emulsions has been demonstrated.

  19. Synthesis and Optical Properties of Thiol Functionalized CdSe/ZnS (Core/Shell Quantum Dots by Ligand Exchange

    Directory of Open Access Journals (Sweden)

    Huaping Zhu

    2014-01-01

    Full Text Available The colloidal photoluminescent quantum dots (QDs of CdSe (core and CdSe/ZnS (core/shell were synthesized at different temperatures with different growth periods. Optical properties (i.e., UV/Vis spectra and photoluminescent emission spectra of the resulting QDs were investigated. The shell-protected CdSe/ZnS QDs exhibited higher photoluminescent (PL efficiency and stability than their corresponding CdSe core QDs. Ligand exchange with various thiol molecules was performed to replace the initial surface passivation ligands, that is, trioctylphosphine oxide (TOPO and trioctylphosphine (TOP, and the optical properties of the surface-modified QDs were studied. The thiol ligand molecules in this study included 1,4-benzenedimethanethiol, 1,16-hexadecanedithiol, 1,11-undecanedithiol, biphenyl-4,4′-dithiol, 11-mercapto-1-undecanol, and 1,8-octanedithiol. After the thiol functionalization, the CdSe/ZnS QDs exhibited significantly enhanced PL efficiency and storage stability. Besides surface passivation effect, such enhanced performance of thiol-functionalized QDs could be due to cross-linked assembly formation of dimer/trimer clusters, in which QDs are linked by dithiol molecules. Furthermore, effects of ligand concentration, type of ligand, and heating on the thiol stabilization of QDs were also discussed.

  20. Probing Ligand Exchange in the P450 Enzyme CYP121 from Mycobacterium tuberculosis: Dynamic Equilibrium of the Distal Heme Ligand as a Function of pH and Temperature.

    Science.gov (United States)

    Fielding, Andrew J; Dornevil, Kednerlin; Ma, Li; Davis, Ian; Liu, Aimin

    2017-12-06

    CYP121 is a cytochrome P450 enzyme from Mycobacterium tuberculosis that catalyzes the formation of a C-C bond between the aromatic groups of its cyclodityrosine substrate (cYY). The crystal structure of CYP121 in complex with cYY reveals that the solvent-derived ligand remains bound to the ferric ion in the enzyme-substrate complex. Whereas in the generally accepted P450 mechanism, binding of the primary substrate in the active-site triggers the release of the solvent-derived ligand, priming the metal center for reduction and subsequent O 2 binding. Here we employed sodium cyanide to probe the metal-ligand exchange of the enzyme and the enzyme-substrate complex. The cyano adducts were characterized by UV-vis, EPR, and ENDOR spectroscopies and X-ray crystallography. A 100-fold increase in the affinity of cyanide binding to the enzyme-substrate complex over the ligand-free enzyme was observed. The crystal structure of the [CYP121(cYY)CN] ternary complex showed a rearrangement of the substrate in the active-site, when compared to the structure of the binary [CYP121(cYY)] complex. Transient kinetic studies showed that cYY binding resulted in a lower second-order rate constant (k on (CN) ) but a much more stable cyanide adduct with 3 orders of magnitude slower k off (CN) rate. A dynamic equilibrium between multiple high- and low-spin species for both the enzyme and enzyme-substrate complex was also observed, which is sensitive to changes in both pH and temperature. Our data reveal the chemical and physical properties of the solvent-derived ligand of the enzyme, which will help to understand the initial steps of the catalytic mechanism.

  1. New Ru(II) Complexes for Dual Photoreactivity: Ligand Exchange and 1O2 Generation

    OpenAIRE

    Knoll, Jessica D.; Albani, Bryan A.; Turro, Claudia

    2015-01-01

    Uncovering the factors that govern the electronic structure of Ru(II)–polypyridyl complexes is critical in designing new compounds for desired photochemical reactions, and strategies to tune excited states for ligand dissociation and 1O2 production are discussed herein. The generally accepted mechanism for photoinduced ligand dissociation proposes that population of the dissociative triplet ligand field (3LF) state proceeds through thermal population from the vibrationally cooled triplet meta...

  2. Surface polyPEGylation of Eu{sup 3+} doped luminescent hydroxyapatite nanorods through the combination of ligand exchange and metal free surface initiated atom transfer radical polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Zeng, Guangjian; Liu, Meiying [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Heng, Chunning [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Shaanxi Key Laboratory of Degradable Biomedical Materials, Shaanxi R& D Center of Biomaterials and Fermentation Engineering, School of Chemical and Engineering, Northwest University, Xi’an 710069 (China); Huang, Qiang; Mao, Liucheng; Huang, Hongye [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Hui, Junfeng [Shaanxi Key Laboratory of Degradable Biomedical Materials, Shaanxi R& D Center of Biomaterials and Fermentation Engineering, School of Chemical and Engineering, Northwest University, Xi’an 710069 (China); Deng, Fengjie, E-mail: fengjiedeng@aliyun.com [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Zhang, Xiaoyong, E-mail: xiaoyongzhang1980@gmail.com [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Wei, Yen, E-mail: weiyen@tsinghua.edu.cn [Department of Chemistry and The Tsinghua Center for Frontier Polymer Research, Tsinghua University, Beijing 100084 (China)

    2017-03-31

    Highlights: • Surface modification of HAp nanorods through the combination of ligand exchange reaction and metal free SI-ATRP. • HAp-polyPEGMA displayed high water dispersibility, good biocompatibility and biological imaging capability. • Metal free ATRP can overcome the toxic and fluorescence quenching effects of metal catalysts of conventional ATRP. - Abstract: The Eu{sup 3+} doped luminescent hydroxyapatite (HAp) nanorods with uniform size and morphology can be synthesized by hydrothermal route. However, these HAp nanorods are coated by hydrophobic oleylamine, which makes them difficult to be dispersed in aqueous solution and impede their biomedical applications. In this work, Eu{sup 3+} doped luminescent polymers functionalized HAp nanorods were prepared through the combination of ligand exchange reaction and metal free surface initiated atom transfer radical polymerization (ATRP) method. In this procedure, the amino group functionalized HAp nanorods were first prepared by ligand exchange reaction using adenosine monophosphate (AMP) as ligand. Then the Br-containing initiators (HAp-Br) were introduced onto the surface of HAp-AMP nanorods through the amidation reaction. Finally, polymers functionalized HAp nanorods were prepared by metal free ATRP method using poly(ethylene glycol) methacrylate (PEGMA) as monomer and 10-phenylphenothiazine (PTH) as organic photocatalyst. The properties of these obtained HAp nanocomposites (HAP-polyPEGMA nanorods) were characterized by means of transmission electron microscopy, Fourier transformed infrared spectroscopy, X-ray photoelectron spectroscopy and thermogravimetric analysis in detail. The cell imaging of these HAP-polyPEGMA nanorods was examined using laser scanning confocal microscope to evaluate their biomedical applications. We demonstrated for the first time that hydrophobic luminescent HAp nanorods can be functionalized with polyPEGMA through the combination of ligand exchange reaction and metal free surface

  3. Surface polyPEGylation of Eu"3"+ doped luminescent hydroxyapatite nanorods through the combination of ligand exchange and metal free surface initiated atom transfer radical polymerization

    International Nuclear Information System (INIS)

    Zeng, Guangjian; Liu, Meiying; Heng, Chunning; Huang, Qiang; Mao, Liucheng; Huang, Hongye; Hui, Junfeng; Deng, Fengjie; Zhang, Xiaoyong; Wei, Yen

    2017-01-01

    Highlights: • Surface modification of HAp nanorods through the combination of ligand exchange reaction and metal free SI-ATRP. • HAp-polyPEGMA displayed high water dispersibility, good biocompatibility and biological imaging capability. • Metal free ATRP can overcome the toxic and fluorescence quenching effects of metal catalysts of conventional ATRP. - Abstract: The Eu"3"+ doped luminescent hydroxyapatite (HAp) nanorods with uniform size and morphology can be synthesized by hydrothermal route. However, these HAp nanorods are coated by hydrophobic oleylamine, which makes them difficult to be dispersed in aqueous solution and impede their biomedical applications. In this work, Eu"3"+ doped luminescent polymers functionalized HAp nanorods were prepared through the combination of ligand exchange reaction and metal free surface initiated atom transfer radical polymerization (ATRP) method. In this procedure, the amino group functionalized HAp nanorods were first prepared by ligand exchange reaction using adenosine monophosphate (AMP) as ligand. Then the Br-containing initiators (HAp-Br) were introduced onto the surface of HAp-AMP nanorods through the amidation reaction. Finally, polymers functionalized HAp nanorods were prepared by metal free ATRP method using poly(ethylene glycol) methacrylate (PEGMA) as monomer and 10-phenylphenothiazine (PTH) as organic photocatalyst. The properties of these obtained HAp nanocomposites (HAP-polyPEGMA nanorods) were characterized by means of transmission electron microscopy, Fourier transformed infrared spectroscopy, X-ray photoelectron spectroscopy and thermogravimetric analysis in detail. The cell imaging of these HAP-polyPEGMA nanorods was examined using laser scanning confocal microscope to evaluate their biomedical applications. We demonstrated for the first time that hydrophobic luminescent HAp nanorods can be functionalized with polyPEGMA through the combination of ligand exchange reaction and metal free surface initiated

  4. Synthesis of freestanding water-soluble indium oxide nanocrystals capped by alanine nitric acid via ligand exchange for thin film transistors and effects of ligands on the electrical properties

    International Nuclear Information System (INIS)

    Choi, Jin-Kyu; Koh, Ye-Seul; Jeong, Hyun-Dam

    2015-01-01

    We demonstrate synthesis of freestanding water-soluble indium oxide nanocrystals (In 2 O 3 NCs) by ligand exchange to β-alanine nitric acid (Ala·HNO 3 ) and its application for active channel layer in thin film transistors (TFTs), with investigation of the effect of curing temperatures on the TFT properties in terms of thermal behaviour of the ligand molecules at 150, 300, and 350 °C. After ligand exchange from long alkyl ligand (myristic acid, MA) to short Ala·HNO 3 , the mobility of NC TFTs cured at 150 °C increased by over 1 order of magnitude, from 1.3 × 10 −4 cm 2 V -1 s −1 to 4.5 × 10 −3 cm 2 V -1 s −1 , due to enhanced tunnelling rate (Γ) between adjective NCs. Higher curing temperatures such as 300 and 350 °C, inducing thermal decomposition of the organic ligands, led to further enhancement of the mobility, particularly up to 2.2 cm 2 V -1 s −1 for the In 2 O 3 NC-Ala·HNO 3 TFT cured at 350 °C. It is also found that the ligand exchange of In 2 O 3 NC in acidic condition (e.g. HNO 3 ) would be simple and effective to reduce the surface defects by surface etching, which may lead to better device performances. - Graphical abstract: Display Omitted - Highlights: • Freestanding water-soluble In 2 O 3 nanocrystals (NCs) were synthesized by ligand exchange. • Thin film transistors (TFTs) of colloidal NCs were fabricated by spin-coating method. • Water-soluble In 2 O 3 NC TFTs showed higher mobilities due to shorter ligand length. • Surface defects of NCs were notably reduced by surface etching during ligand exchange

  5. High throughput screening of ligand binding to macromolecules using high resolution powder diffraction

    Science.gov (United States)

    Von Dreele, Robert B.; D'Amico, Kevin

    2006-10-31

    A process is provided for the high throughput screening of binding of ligands to macromolecules using high resolution powder diffraction data including producing a first sample slurry of a selected polycrystalline macromolecule material and a solvent, producing a second sample slurry of a selected polycrystalline macromolecule material, one or more ligands and the solvent, obtaining a high resolution powder diffraction pattern on each of said first sample slurry and the second sample slurry, and, comparing the high resolution powder diffraction pattern of the first sample slurry and the high resolution powder diffraction pattern of the second sample slurry whereby a difference in the high resolution powder diffraction patterns of the first sample slurry and the second sample slurry provides a positive indication for the formation of a complex between the selected polycrystalline macromolecule material and at least one of the one or more ligands.

  6. Quaternary Cu2ZnSnS4 quantum dot-sensitized solar cells: Synthesis, passivation and ligand exchange

    Science.gov (United States)

    Bai, Bing; Kou, Dongxing; Zhou, Wenhui; Zhou, Zhengji; Tian, Qingwen; Meng, Yuena; Wu, Sixin

    2016-06-01

    The quaternary Cu2ZnSnS4 (CZTS) QDs had been successfully introduced into quantum dot-sensitized solar cells (QDSC) via hydrolysis approach in our previous work [Green Chem. 2015, vol. 17, p. 4377], but the obtained cell efficiency was still limited by low open-circuit voltage and fill factor. Herein, we use 1-dodecanethiol (DDT) as capping ligand for fairly small-sized CZTS QDs synthesis to improve their intrinsic properties. Since this strong bonded capping ligand can not be replaced by 3-mercaptopropionic acid (MPA) directly, the nature cation (Cu, Zn or Sn)-DDT units of QDs are first exchanged by the preconjugated Cd-oleate via successive ionic layer adsorption and reaction (SILAR) procedure accompanied with the formation of a core/shell structure. The weak bonded oleic acid (OA) can be finally replaced by MPA and the constructed water soluble CZTS/CdSe QDSC achieves an impressive conversion efficiency of 4.70%. The electron transport and recombination dynamic processes are confirmed by intensity-modulated photocurrent spectroscopy (IMPS)/intensity-modulated photovoltage spectroscopy (IMVS) measurements. It is found that the removal of long alkyl chain is conducive to improve the electron transport process and the type-II core/shell structure is beneficial to accelerate electron transport and retard charge recombination. This effective ligand removal strategy is proved to be more convenient for the applying of quaternary QDs in QDSC and would boost a more powerful efficiency in the future work.

  7. Roles of Bridging Ligand Topology and Conformation in Controlling Exchange Interactions between Paramagnetic Molybdenum Fragments in Dinuclear and Trinuclear Complexes.

    Science.gov (United States)

    Ung VÂ, V&acaron;n Ân; Cargill Thompson, Alexander M. W.; Bardwell, David A.; Gatteschi, Dante; Jeffery, John C.; McCleverty, Jon A.; Totti, Federico; Ward, Michael D.

    1997-07-30

    The magnetic properties of two series of dinuclear complexes, and one trinuclear complex, have been examined as a function of the bridging pathway between the metal centers. The first series of dinuclear complexes is [{Mo(V)(O)(Tp)Cl}(2)(&mgr;-OO)], where "OO" is [1,4-O(C(6)H(4))(n)O](2)(-) (n = 1, 1; n = 2, 3), [4,4'-O(C(6)H(3)-2-Me)(2)O](2)(-) (4), or [1,3-OC(6)H(4)O](2)(-) (2) [Tp = tris(3,5-dimethylpyrazolyl)hydroborate]. The second series of dinuclear complexes is [{Mo(I)(NO)(Tp)Cl}(2)(&mgr;-NN)], where "NN" is 4,4'-bipyridyl (5), 3,3'-dimethyl-4,4'-bipyridine (6), 3,8-phenanthroline (7), or 2,7-diazapyrene (8). The trinuclear complex is [{Mo(V)(O)(Tp)Cl}(3)(1,3,5-C(6)H(3)O(3))] (9), whose crystal structure was determined [9.5CH(2)Cl(2): C(56)H(81)B(3)Cl(13)Mo(3)N(18)O(6); monoclinic, P2(1)/n; a = 13.443, b = 41.46(2), c = 14.314(6) Å; beta = 93.21(3) degrees; V = 7995(5) Å(3); Z = 4; R(1) = 0.106]. In these complexes, the sign and magnitude of the exchange coupling constant J is clearly related to both the topology and the conformation of the bridging ligand [where J is derived from H = -JS(1)().S(2)() for 1-8 and H = -J(S(1)().S(2)() + S(2)().S(3)() + S(1)().S(3)()) for 9]. The values are as follows: 1, -80 cm(-)(1); 2, +9.8 cm(-)(1); 3, -13.2 cm(-)(1); 4, -2.8 cm(-)(1); 5, -33 cm(-)(1); 6, -3.5 cm(-)(1); 7, -35.6 cm(-)(1); 8, -35.0 cm(-)(1); 9, +14.4 cm(-)(1). In particular the following holds: (1) J is negative (antiferromagnetic exchange) across the para-substituted bridges ligands of 1 and 3-8 but positive (ferromagnetic exchange) across the meta-substituted bridging ligands of 2 and 9. (2) J decreases in magnitude dramatically as the bridging ligand conformation changes from planar to twisted (compare 3 and 4, or 6 and 8). These observations are consistent with a spin-polarization mechanism for the exchange interaction, propagated across the pi-system of the bridging ligand by via overlap of bridging ligand p(pi) orbitals with the d(pi) magnetic

  8. Selective high-affinity polydentate ligands and methods of making such

    Energy Technology Data Exchange (ETDEWEB)

    Denardo, Sally J.; Denardo, Gerald L.; Balhorn, Rodney L.

    2018-02-06

    This invention provides novel polydentate selective high affinity ligands (SHALs) that can be used in a variety of applications in a manner analogous to the use of antibodies. SHALs typically comprise a multiplicity of ligands that each bind different region son the target molecule. The ligands are joined directly or through a linker thereby forming a polydentate moiety that typically binds the target molecule with high selectivity and avidity.

  9. Synthesis of freestanding water-soluble indium oxide nanocrystals capped by alanine nitric acid via ligand exchange for thin film transistors and effects of ligands on the electrical properties

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Jin-Kyu; Koh, Ye-Seul; Jeong, Hyun-Dam, E-mail: hdjeong@chonnam.ac.kr

    2015-07-15

    We demonstrate synthesis of freestanding water-soluble indium oxide nanocrystals (In{sub 2}O{sub 3} NCs) by ligand exchange to β-alanine nitric acid (Ala·HNO{sub 3}) and its application for active channel layer in thin film transistors (TFTs), with investigation of the effect of curing temperatures on the TFT properties in terms of thermal behaviour of the ligand molecules at 150, 300, and 350 °C. After ligand exchange from long alkyl ligand (myristic acid, MA) to short Ala·HNO{sub 3}, the mobility of NC TFTs cured at 150 °C increased by over 1 order of magnitude, from 1.3 × 10{sup −4} cm{sup 2}V{sup -1}s{sup −1} to 4.5 × 10{sup −3} cm{sup 2}V{sup -1}s{sup −1}, due to enhanced tunnelling rate (Γ) between adjective NCs. Higher curing temperatures such as 300 and 350 °C, inducing thermal decomposition of the organic ligands, led to further enhancement of the mobility, particularly up to 2.2 cm{sup 2}V{sup -1}s{sup −1} for the In{sub 2}O{sub 3} NC-Ala·HNO{sub 3} TFT cured at 350 °C. It is also found that the ligand exchange of In{sub 2}O{sub 3} NC in acidic condition (e.g. HNO{sub 3}) would be simple and effective to reduce the surface defects by surface etching, which may lead to better device performances. - Graphical abstract: Display Omitted - Highlights: • Freestanding water-soluble In{sub 2}O{sub 3} nanocrystals (NCs) were synthesized by ligand exchange. • Thin film transistors (TFTs) of colloidal NCs were fabricated by spin-coating method. • Water-soluble In{sub 2}O{sub 3} NC TFTs showed higher mobilities due to shorter ligand length. • Surface defects of NCs were notably reduced by surface etching during ligand exchange.

  10. Field-effect measurements of mobility and carrier concentration of Cu2S colloidal quantum dot thin films after ligand exchange

    International Nuclear Information System (INIS)

    Brewer, Adam S.; Arnold, Michael S.

    2014-01-01

    Colloidal quantum dots (CQDs) of copper sulfide (Cu 2 S), an earth-abundant semiconductor, have a number of intriguing applications that require knowledge of their electrical properties. Depending on stoichiometry, mobility, and surface treatment, applications include photoabsorbers for solar cells, tunable plasmonics, and counter-electrodes for polysulfate electrolytes. However, there have not been any direct measurements of electrical properties in Cu 2 S CQD thin films. Here, we exchange as synthesized dodecanethiol ligands with short ethanedithiol or ethylenediamine ligands to form thin films of coupled Cu 2 S CQDs. The mobility and carrier concentration were found to vary by ligand treatment from 10 −5 cm 2 /Vs and 10 19 holes/cm 3 for ethanedithiol ligands to 10 −3 cm 2 /Vs and 10 20 holes/cm 3 for ethylenediamine. These results are consistent with the carrier concentrations inferred from sub-bandgap surface-plasmon-resonances measured by infrared spectroscopy. These results will be useful when designing Cu 2 S materials for future applications. - Highlights: • Colloidal Cu2S quantum dots were synthesized and characterized. • Ligand exchange was performed to alter the Cu2S nanocrystal properties. • Ligand exchange was studied using photoluminescence and infrared spectroscopy. • Field effect mobility and carrier concentration were directly measured. • Carrier concentration was compared to estimates from surface plasmon resonances

  11. High energy multi-gluon exchange amplitudes

    International Nuclear Information System (INIS)

    Jaroszewicz, T.

    1980-11-01

    We examine perturbative high energy n-gluon exchange amplitudes calculated in the Coulomb gauge. If n exceeds the minimum required by the t-channel quantum numbers, such amplitudes are non-leading in lns. We derive a closed system of coupled integral equations for the corresponding two-particle n-gluon vertices, obtained by summing the leading powers of ln(N μ psup(μ)), where psup(μ) is the incident momentum and Nsup(μ) the gauge-defining vector. Our equations are infra-red finite, provided the external particles are colour singlets. (author)

  12. Kinetic study on ligand exchange reaction between ethylenedicysteine and 99mTc- glucoheptonate (99mTc-GH)

    International Nuclear Information System (INIS)

    Wu, C.Y.; Ji, S.R.; Lu, C.X.; Ding, S.Y.; Chen, Z.P.; Lin, X.T.

    2002-01-01

    Aim: 99m Tc-L,L-ethylenedicysteine( 99m Tc-EC)is a new type of renal imaging agent. It can be labeled very easily and efficiently at room temperature through direct labeling at pH 12. The need for direct labeling at pH 12 does not compromise the simplicity and ease of preparation of 99m Tc-EC and its practical usefulness in daily routine. On the basis of the labeling experiments, we developed a ligand exchange labeling method, in which the labeling EC with 99m Tc can be performed at pH 8. In order to provide a theoretic basis, a detailed kinetic study of ligand exchange reaction between 99m Tc- glucoheptonate( 99m Tc-GH) and EC was carried out. Materials and Methods: 99m Tc-EC is prepared as follows: 99m Tc-GH + EC → 99m Tc-EC + GH, labeling can be easily performed by adding 99m TcO 4 - (2∼6ml generator elute) to glucoheptonate solution containing SnCl 2 .2H 2 O solution to form 99m Tc-GH, then freshly prepared 99m Tc-GH is transferred to the aqueous solution of different concentrations of EC at different pH value, after being shaken, 99m Tc-EC was formed. Radiolabeling yield(RLY) and radiochemical purity(RCP) of 99m Tc-GH and 99m Tc-EC were measured by Xinhua No.1 paper with developing system of Me 2 CO/H 2 O/con.NH 3 .H 2 O=9/3/1(V/V). 99m Tc-GH(RCP must be over 98%, 80ul, 3.6∼7.4MBq) was added to 1ml of 0.5mol/L phosphate buffer(pH 12) containing different amount of EC(150, 75, 50 and 15ug), the sample was taken out at different time intervals and RCP was determined. The solution of EC(30ul, 5g/L) was added to 1ml of 0.5mol/L phosphate buffer at different pH value(pH11, 10, 9, 8, 7), after completely vortexed, 99m Tc-GH(RCP must be over 98%, 80ul, 3.6∼7.4MBq) was then added, the sample was taken out and RCP was determined as above. The rate constant(k) of ligand exchange reaction at different concentrations of EC and different reaction pH values were calculated out by integrating. Plot ln[1/(1-RLY)] vs t(time) showed a liner relationship, and the rate

  13. Exchange interactions in a dinuclear manganese (II) complex with cyanopyridine-N-oxide bridging ligands

    Energy Technology Data Exchange (ETDEWEB)

    Markosyan, A.S. [Faculty of Physics, M.V. Lomonosov Moscow State University, 119992 Moscow (Russian Federation); Department of Applied Physics, Stanford University (United States); Gaidukova, I.Yu.; Ruchkin, A.V. [Faculty of Physics, M.V. Lomonosov Moscow State University, 119992 Moscow (Russian Federation); Anokhin, A.O. [Institute of Metal Physics, Ural Division of the Russian, Ekaterinburg (Russian Federation); Irkhin, V.Yu., E-mail: valentin.irkhin@imp.uran.ru [Institute of Metal Physics, Ural Division of the Russian, Ekaterinburg (Russian Federation); Ryazanov, M.V.; Kuz’mina, N.P. [Faculty of Chemistry, M.V. Lomonosov Moscow State University, 119992 Moscow (Russian Federation); Nikiforov, V.N. [Faculty of Physics, M.V. Lomonosov Moscow State University, 119992 Moscow (Russian Federation)

    2014-01-01

    The magnetic properties of dinuclear manganese(II) complex [Mn(hfa){sub 2}cpo]{sub 2} (where hfa is hexafluoroacetylacetonate anion and cpo is 4-cyanopyridine-N-oxide) are presented. The non-monotonous dependence of magnetic susceptibility is explained in terms of the hierarchy of exchange parameters by using exact diagonalization. The thermodynamic behavior of pure cpo and [Mn(hfa){sub 2}(cpo)]{sub 2} is simulated numerically by an extrapolation to spin S=5/2. The Mn–Mn exchange integral is evaluated.

  14. Stability Investigation of Ligand-Exchanged CdSe/ZnS-Y (Y = 3-Mercaptopropionic Acid or Mercaptosuccinic Acid through Zeta Potential Measurements

    Directory of Open Access Journals (Sweden)

    Ngoc Thuy Vo

    2016-01-01

    Full Text Available Quantum dots have been considered to be promising candidates for bioapplications because of their high sensitivity, rapid response, and reliability. The synthesis of high-quality quantum dots that can be dissolved in water and other biological media is a crucial step toward their further application in biology. Starting with a one-pot reaction and the successive ionic layer adsorption and reaction (SILAR method, we produced the CdSe/ZnS core/shell structure. Through a ligand-exchange mechanism, we coated the as-made CdSe/ZnS structure with 3-mercaptopropionic acid (MPA or mercaptosuccinic acid (MSA. Various techniques, including photoluminescence (PL, ultraviolet-visible (UV-Vis spectroscopy, transmission electron microscopy (TEM, X-ray diffraction (XRD, and Fourier transform infrared (FTIR spectroscopy, were utilized to characterize the ligand-coated CdSe/ZnS structure. The results show enhanced luminescence intensity, CdSe surface passivation by ZnS, and successful coating with MPA and MSA. The stability of quantum dots in solutions with different pH values was investigated by performing zeta potential measurements. The results revealed that the quantum dots shifted from displaying hydrophobic to hydrophilic behavior and could be connected with bioagents.

  15. Dendrimer ligands-capped CH3NH3PbBr3 perovskite nanocrystals with delayed halide exchange and record stability against both moisture and water

    Science.gov (United States)

    Xu, Yiren; Xu, Shuhong; Shao, Haibao; Jiang, Han; Cui, Yiping; Wang, Chunlei

    2018-06-01

    CH3NH3PbBr3 perovskite nanocrystals (NCs) suffer from poor stability because of their high sensitivity to environmental moisture and water. To solve this problem, previous works mainly focus on embedding perovskite NCs into water-resistant matrix to form large composites (size of microns or larger). As an alternative solution without serious changing of NC size, enhancing the stability of perovskite NCs themselves by ligand engineering is rarely reported. In this work, we used hyperbranched polyamidoamine (PAMAM) dendrimers with two different generations (G0 and G4) to synthesize CH3NH3PbBr3 perovskite NCs with high photoluminescence (PL) quantum yields (QY) above 70% and a new record stability. A novel dendrimers generation-dependent stability of perovskite NCs was observed. The water-resistance time is 18 h (27 h) for perovskite NCs capped by G0 (G4) generation of PAMAM, which is 7 times (11 times) longer than that of traditional oleic acid-capped NCs. Similar PAMAM generation-related stability is also observed in moisture-resistance tests. The stability time against moisture is 500 h (800 h) for G0 (G4) generation of PAMAM-capped perovskite NCs, which is a new record stability time against moisture for CH3NH3PbBr3 perovskite NCs. In addition, our results also indicate that PAMAM ligands outside perovskite NCs can dramatically slow down the speed of halide exchange. Even for the mixture of perovskite NCs with two different halide composition, the original luminescence properties of PAMAM-capped perovskite NCs can retain after mixing. In view of slow halide exchange speed, excellent water and moisture stability, PAMAM dendrimers-capped perovskite NCs and their mixture are available as color conversion single layer in fabrication of light-emitting diodes (LED).

  16. Dendrimer ligands-capped CH3NH3PbBr3 perovskite nanocrystals with delayed halide exchange and record stability against both moisture and water.

    Science.gov (United States)

    Xu, Yiren; Xu, Shuhong; Shao, Haibao; Jiang, Han; Cui, Yiping; Wang, Chunlei

    2018-06-08

    CH 3 NH 3 PbBr 3 perovskite nanocrystals (NCs) suffer from poor stability because of their high sensitivity to environmental moisture and water. To solve this problem, previous works mainly focus on embedding perovskite NCs into water-resistant matrix to form large composites (size of microns or larger). As an alternative solution without serious changing of NC size, enhancing the stability of perovskite NCs themselves by ligand engineering is rarely reported. In this work, we used hyperbranched polyamidoamine (PAMAM) dendrimers with two different generations (G0 and G4) to synthesize CH 3 NH 3 PbBr 3 perovskite NCs with high photoluminescence (PL) quantum yields (QY) above 70% and a new record stability. A novel dendrimers generation-dependent stability of perovskite NCs was observed. The water-resistance time is 18 h (27 h) for perovskite NCs capped by G0 (G4) generation of PAMAM, which is 7 times (11 times) longer than that of traditional oleic acid-capped NCs. Similar PAMAM generation-related stability is also observed in moisture-resistance tests. The stability time against moisture is 500 h (800 h) for G0 (G4) generation of PAMAM-capped perovskite NCs, which is a new record stability time against moisture for CH 3 NH 3 PbBr 3 perovskite NCs. In addition, our results also indicate that PAMAM ligands outside perovskite NCs can dramatically slow down the speed of halide exchange. Even for the mixture of perovskite NCs with two different halide composition, the original luminescence properties of PAMAM-capped perovskite NCs can retain after mixing. In view of slow halide exchange speed, excellent water and moisture stability, PAMAM dendrimers-capped perovskite NCs and their mixture are available as color conversion single layer in fabrication of light-emitting diodes (LED).

  17. Reversible, high molecular weight palladium and platinum coordination polymers based on phosphorus ligands

    NARCIS (Netherlands)

    Paulusse, J.M.J.; Huijbers, J.P.J.; Sijbesma, R.P.

    2005-01-01

    A general strategy for the preparation and characterization of high molecular weight coordination polymers based on bifunctional phosphorus ligands and palladium or platinum dichloride is described. Metal-to-ligand stoichiometry is of key importance for the formation of linear coordination polymers

  18. Reversible, High Molecular Weight Palladium and Platinum Coordination Polymers Based on Phosphorus Ligands

    NARCIS (Netherlands)

    Paulusse, Jos Marie Johannes; Huijbers, Jeroen P.J.; Sijbesma, Rint P.

    2005-01-01

    A general strategy for the preparation and characterization of high molecular weight coordination polymers based on bifunctional phosphorus ligands and palladium or platinum dichloride is described. Metal-to-ligand stoichiometry is of key importance for the formation of linear coordination polymers

  19. Conformational change of adenosine deaminase during ligand-exchange in a crystal.

    Science.gov (United States)

    Kinoshita, Takayoshi; Tada, Toshiji; Nakanishi, Isao

    2008-08-15

    Adenosine deaminase (ADA) perpetuates chronic inflammation by degrading extracellular adenosine which is toxic for lymphocytes. ADA has two distinct conformations: open form and closed form. From the crystal structures with various ligands, the non-nucleoside type inhibitors bind to the active site occupying the critical water-binding-position and sustain the open form of apo-ADA. In contrast, substrate mimics do not occupy the critical position, and induce the large conformational change to the closed form. However, it is difficult to predict the binding of (+)-erythro-9-(2-hydroxy-3-nonyl)adenine (EHNA), as it possesses characteristic parts of both the substrate and the non-nucleoside inhibitors. The crystal structure shows that EHNA binds to the open form through a novel recognition of the adenine base accompanying conformational change from the closed form of the PR-ADA complex in crystalline state.

  20. Removal of phosphate using copper-loaded polymeric ligand exchanger prepared by radiation grafting of polypropylene/polyethylene (PP/PE) nonwoven fabric

    Science.gov (United States)

    Barsbay, Murat; Kavaklı, Pınar Akkaş; Güven, Olgun

    2010-03-01

    A novel polymeric ligand exchanger (PLE) was prepared for the removal of phosphate ions from water. 2,2'-dipyridylamine (DPA), a bidentate ligand forming compound with high coordination capacity with a variety of metal ions was bound to glycidyl methacrylate (GMA) grafted polypropylene/polyethylene (PP/PE) nonwoven fabric synthesized by radiation-induced grafting technique. DPA attachment on epoxy ring of GMA units was tested in different solvents, i.e. methanol, ethanol, dioxane and dimethylsulfoxide (DMSO). The highest amount of modification was achieved in dioxane. In order to prepare the corresponding PLE for the removal of phosphate, DPA-immobilized fabric was loaded with Cu(II) ions. Phosphate adsorption experiments were performed in batch mode at different pH (5-9) and phosphate concentrations. The fabric was found to be effective for the removal of phosphate ions. At every stage of preparation and use, the nonwoven fabric was characterized by thermal (i.e. DSC and TGA) and spectroscopic (FTIR) methods. Competitive adsorption experiments were also carried out using two solutions with different concentration levels at pH 7 to see the effect of competing ions. Phosphate adsorption was found to be effective and selective from solutions having trace amounts of competitive anions. It is expected that the novel PLE synthesized can be used for the removal of phosphate ions in low concentrations over a large range of pH.

  1. Bromine–lithium exchange: An efficient tool in the modular construction of biaryl ligands

    Directory of Open Access Journals (Sweden)

    Laurence Bonnafoux

    2011-09-01

    Full Text Available Regioselective bromine–lithium exchange reactions on polybrominated biaryls enable the modular synthesis of various polysubstituted biphenyls such as bis(dialkylphosphino-, bis(diarylphosphino- and dialkyl(diarylphosphinobiphenyls. All permutations of substituents at the ortho positions of the biphenyls are possible. In a similar manner, one can gain access to monophosphine analogues. So far, such a process, based on the effective discrimination between bromine atoms as a function of their chemical environment, has been observed only sporadically.

  2. Design of Ion-Exchange Resins Through EDTA and DTPA Modified Ligands

    Directory of Open Access Journals (Sweden)

    2014-07-01

    Catechol, resorcinol, and their admixtures with EDTA and DTPA moieties were converted into polymeric resins by alkaline polycondensation with formaldehyde. The resins were characterized by FTIR spectroscopy, elemental analysis, ion-exchange capacity, and distribution coefficient (D for heavy metal and radionuclide such as Cs and Sr. 137Cs and 90Sr constitutes a major source of heat in nuclear waste streams and in regards to recent nuclear event their remediation in complex solution – sea water - represent an important issue.

  3. Inhibition of ligand exchange kinetics via active-site trapping with an antibody fragment.

    Science.gov (United States)

    Oyen, David; Steyaert, Jan; Barlow, John N

    2014-04-01

    We describe the first example of an inhibitory antibody fragment (nanobody ca1697) that binds simultaneously to an enzyme (the enzyme dihydrofolate reductase from Escherichia coli) and its bound substrate (folate). Binding of the antibody to the substrate causes a 20-fold reduction in the rate of folate exchange kinetics. This work opens up the prospect of designing new types of antibody-based inhibitors of enzymes and receptors through suitable design of immunogens.

  4. On-column ligand exchange for structure-based drug design: a case study with human 11β-hydroxysteroid dehydrogenase type 1

    International Nuclear Information System (INIS)

    Qin, Wenying; Judge, Russell A.; Longenecker, Kenton L.; Solomon, Larry R.; Harlan, John E.

    2012-01-01

    An on-column ligand- and detergent-exchange method was developed to obtain ligand–protein complexes for an adamantane series of compounds with 11β-HSD1 after a variety of other complexation methods had failed. An interesting byproduct of the method was the observation of artificial trimers in the crystal structures. Successfully forming ligand–protein complexes with specific compounds can be a significant challenge in supporting structure-based drug design for a given protein target. In this respect, an on-column ligand- and detergent-exchange method was developed to obtain ligand–protein complexes of an adamantane series of compounds with 11β-hydroxysteroid dehydrogenase type 1 (11β-HSD1) after a variety of other complexation methods had failed. This report describes the on-column exchange method and an unexpected byproduct of the method in which artificial trimers were observed in the structures

  5. Amino propynyl benzoic acid building block in rigid spacers of divalent ligands binding to the Syk SH2 domains with equally high affinity as the natural ligand

    NARCIS (Netherlands)

    Dekker, Frank J; de Mol, Nico J; Fischer, Marcel J E; Liskamp, Rob M J; Dekker, Frank

    2003-01-01

    The construction of rigid spacers composed of amino propynyl benzoic acid building blocks is described. These spacers were used to link two phosphopeptide ligand sites towards obtaining divalent ligands with a high affinity for Syk tandem SH2 domains, which are important in signal transduction. The

  6. Ligand modeling and design

    Energy Technology Data Exchange (ETDEWEB)

    Hay, B.P. [Pacific Northwest National Lab., Richland, WA (United States)

    1997-10-01

    The purpose of this work is to develop and implement a molecular design basis for selecting organic ligands that would be used in the cost-effective removal of specific radionuclides from nuclear waste streams. Organic ligands with metal ion specificity are critical components in the development of solvent extraction and ion exchange processes that are highly selective for targeted radionuclides. The traditional approach to the development of such ligands involves lengthy programs of organic synthesis and testing, which in the absence of reliable methods for screening compounds before synthesis, results in wasted research effort. The author`s approach breaks down and simplifies this costly process with the aid of computer-based molecular modeling techniques. Commercial software for organic molecular modeling is being configured to examine the interactions between organic ligands and metal ions, yielding an inexpensive, commercially or readily available computational tool that can be used to predict the structures and energies of ligand-metal complexes. Users will be able to correlate the large body of existing experimental data on structure, solution binding affinity, and metal ion selectivity to develop structural design criteria. These criteria will provide a basis for selecting ligands that can be implemented in separations technologies through collaboration with other DOE national laboratories and private industry. The initial focus will be to select ether-based ligands that can be applied to the recovery and concentration of the alkali and alkaline earth metal ions including cesium, strontium, and radium.

  7. One-step ligand exchange reaction as an efficient way for functionalization of magnetic nanoparticles

    International Nuclear Information System (INIS)

    Mrówczyński, Radosław; Rednic, Lidia; Turcu, Rodica; Liebscher, Jürgen

    2012-01-01

    Novel magnetic Fe 3 O 4 nanoparticles (NPs) covered by one layer of functionalized fatty acids, bearing entities (Hayashi catalyst, biotin, quinine, proline, and galactose) of high interest for practical application in nanomedicine or organocatalysis, were synthesized. The functionalized fatty acids were obtained by Cu(I)-catalyzed azide–alkyne cycloaddition (CuAAC) of azido fatty acids with alkynes. All the magnetic NPs show superparamagnetic behavior with high values of magnetization and high colloidal stability in DCM solution.

  8. Beneficial phosphate recovery from reverse osmosis (RO) concentrate of an integrated membrane system using polymeric ligand exchanger (PLE).

    Science.gov (United States)

    Kumar, Manish; Badruzzaman, Mohammad; Adham, Samer; Oppenheimer, Joan

    2007-05-01

    Phosphorus (P) discharge to surface water is a major environmental problem. Wastewater treatment is targeted towards removal of this nutrient to prevent degradation of surface water. Integrated membrane systems (IMS) are increasingly being considered for wastewater reclamation, and provide excellent removal of P compounds. However, reverse osmosis (RO), which forms an integral part of these IMSs, concentrates most dissolved substances including P-species such as phosphates in the RO waste stream. In this study, removal of phosphate from this stream using polymeric ligand exchange (PLE) resins was investigated. Further, the possibility of phosphate recovery through struvite (MgNH(4)PO(4).6H(2)O) precipitation was tested. Struvite has been promoted as a slow release fertilizer in recent years. This study demonstrates that PLEs can be successfully used to remove phosphate from RO-concentrate, and to recover more than 85% of the adsorbed phosphorus from the exhausted media and precipitated as a beneficial product (struvite). The approach, presented in this study, suggests advantages of providing economic benefit from a waste product (RO) while avoiding phosphorus discharge to the environment.

  9. Effect of competing ions and causticization on the ammonia adsorption by a novel poly ligand exchanger (PLE) ammonia adsorption reagent.

    Science.gov (United States)

    Chen, Quanzhou; Zhou, Kanggen; Hu, Yuanjuan; Liu, Fang; Wang, Aihe

    2017-03-01

    In this paper, a poly ligand exchanger, Cu(II)-loaded chelating resin named ammonia adsorption reagent (AMAR), bearing the functional group of weak iminodiacetate acid, was prepared to efficiently remove ammonia from solutions. Batch adsorption equilibrium experiments were conducted under a range of conditions. The effects of pH on the removal of ammonia by AMAR were investigated at 25 °C. The copper loaded on the resin forms a complex with NH 3 in solution under alkaline condition. The effect of alkaline dosage (AD) on the ammonia adsorption was investigated. The maximum breakthrough bed volumes were obtained when the AD was set as 0.75 mmol OH - /mL. The higher AD did not guarantee the better ammonia removal efficiency due to the forming of Cu(OH) 2 precipitate between OH - in solutions and Cu(II) on the resin. The effect of competing ions on the adsorption breakthrough curve of virgin AMAR and causticized AMAR was also investigated. The results demonstrated that the existence of competing ions had a negative impact on the adsorption capacity for both virgin AMAR and causticized AMAR. After causticization, the AMAR was more resistant to the competing ions comparing with virgin AMAR. The bivalent Ca 2+ affects the ammonia adsorption more than does the monovalent Na + .

  10. High-affinity multivalent wheat germ agglutinin ligands by one-pot click reaction

    Directory of Open Access Journals (Sweden)

    Henning S. G. Beckmann

    2012-06-01

    Full Text Available A series of six mono-, di-, and trivalent N,N’-diacetylchitobiose derivatives was conveniently prepared by employing a one-pot procedure for Cu(II-catalyzed diazo transfer and Cu(I-catalyzed azide–alkyne cycloaddition (CuAAC starting from commercially available amines. These glycoclusters were probed for their binding potencies to the plant lectin wheat germ agglutinin (WGA from Triticum vulgaris by an enzyme-linked lectin assay (ELLA employing covalently immobilized N-acetylglucosamine (GlcNAc as a reference ligand. IC50 values were in the low micromolar/high nanomolar range, depending on the linker between the two disaccharides. Binding enhancements β up to 1000 for the divalent ligands and 2800 for a trivalent WGA ligand, compared to N,N’-diacetylchitobiose as the corresponding monovalent ligand, were observed. Molecular modeling studies, in which the chitobiose moieties were fitted into crystallographically determined binding sites of WGA, correlate the binding enhancements of the multivalent ligands with their ability to bind to the protein in a chelating mode. The best WGA ligand is a trivalent cluster with an IC50 value of 220 nM. Calculated per mol of contained chitobiose, this is the best WGA ligand known so far.

  11. One-step ligand exchange reaction as an efficient way for functionalization of magnetic nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Mrowczynski, Radoslaw [Humboldt-University Berlin, Department of Chemistry (Germany); Rednic, Lidia; Turcu, Rodica [National Institute of Research and Development for Isotopic and Molecular Technologies (Romania); Liebscher, Juergen, E-mail: liebscher@chemie.hu-berlin.de [Humboldt-University Berlin, Department of Chemistry (Germany)

    2012-07-15

    Novel magnetic Fe{sub 3}O{sub 4} nanoparticles (NPs) covered by one layer of functionalized fatty acids, bearing entities (Hayashi catalyst, biotin, quinine, proline, and galactose) of high interest for practical application in nanomedicine or organocatalysis, were synthesized. The functionalized fatty acids were obtained by Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC) of azido fatty acids with alkynes. All the magnetic NPs show superparamagnetic behavior with high values of magnetization and high colloidal stability in DCM solution.

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

    Science.gov (United States)

    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.

  13. Ion exchange resins as high-dose radiation dosimeters

    International Nuclear Information System (INIS)

    Alian, A.; Dessouki, A.; El-Assay, N.B.

    1984-01-01

    This paper reports on the possibility of using various types of ion exchange resins as high-dose radiation dosimeters, by analysis of the decrease in exchange capacity with absorbed dose. The resins studied are Sojuzchim-export-Moscow Cation Exchanger KU-2 and Anion Exchanger AV-17 and Merck Cation Exchanger I, and Merck Anion Exchangers II and III. Over the dose range 1 to 100 kGy, the systems show linearity between log absorbed dose and decrease in resin ion exchange capacity. The slope of this response function differs for the different resins, depending on their ionic form and degree of cross-linking. The radiation sensitivity increases in the order KU-2; Exchanger I; AV-17; Exchanger II; Exchanger III. Merck resins with moisture content of 21% showed considerably higher radiation sensitivity than those with 2 to 3% moisture content. The mechanism of radiation-induced denaturing of the ion exchanger resins involves cleavage and decomposition of functional substituents, with crosslinking playing a stabilizing role, with water and its radiolytic products serving to inhibit radical recombination and interfering with the protection cage effect of crosslinking. (author)

  14. High temperature heat exchange: nuclear process heat applications

    International Nuclear Information System (INIS)

    Vrable, D.L.

    1980-09-01

    The unique element of the HTGR system is the high-temperature operation and the need for heat exchanger equipment to transfer nuclear heat from the reactor to the process application. This paper discusses the potential applications of the HTGR in both synthetic fuel production and nuclear steel making and presents the design considerations for the high-temperature heat exchanger equipment

  15. Plan charge exchange scattering at high energies

    International Nuclear Information System (INIS)

    Saleem, M.; Bhatti, S.; Fazal-e-Aleem; Rafique, M.

    1980-01-01

    By a phenomenological choice of the residue functions, a very good fit with experiment for the pion-nucleon charge exchange reaction at Fermilab energies is obtained on a simple Regge-pole model using a quadratic rho trajectory and energy-independent parameters

  16. Nanoparticle Photoresists: Ligand Exchange as a New, Sensitive EUV Patterning Mechanism

    KAUST Repository

    Kryask, Marie

    2013-01-01

    Hybrid nanoparticle photoresists and their patterning using DUV, EUV, 193 nm lithography and e-beam lithography has been investigated and reported earlier. The nanoparticles have demonstrated very high EUV sensitivity and significant etch resistance compared to other standard photoresists. The current study aims at investigating and establishing the underlying mechanism for dual tone patterning of these nanoparticle photoresist systems. Infrared spectroscopy and UV absorbance studies supported by mass loss and dissolution studies support the current model. © 2013SPST.

  17. Quantifying high-affinity binding of hydrophobic ligands by isothermal titration calorimetry.

    Science.gov (United States)

    Krainer, Georg; Broecker, Jana; Vargas, Carolyn; Fanghänel, Jörg; Keller, Sandro

    2012-12-18

    A fast and reliable quantification of the binding thermodynamics of hydrophobic high-affinity ligands employing a new calorimetric competition experiment is described. Although isothermal titration calorimetry is the method of choice for a quantitative characterization of intermolecular interactions in solution, a reliable determination of a dissociation constant (K(D)) is typically limited to the range 100 μM > K(D) > 1 nM. Interactions displaying higher or lower K(D) values can be assessed indirectly, provided that a suitable competing ligand is available whose K(D) falls within the directly accessible affinity window. This established displacement assay, however, requires the high-affinity ligand to be soluble at high concentrations in aqueous buffer and, consequently, poses serious problems in the study of protein binding involving small-molecule ligands dissolved in organic solvents--a familiar case in many drug-discovery projects relying on compound libraries. The calorimetric competition assay introduced here overcomes this limitation, thus allowing for a detailed thermodynamic description of high-affinity receptor-ligand interactions involving poorly water-soluble compounds. Based on a single titration of receptor into a dilute mixture of the two competing ligands, this competition assay provides accurate and precise values for the dissociation constants and binding enthalpies of both high- and moderate-affinity ligands. We discuss the theoretical background underlying the approach, demonstrate its practical application to metal ion chelation and high-affinity protein-inhibitor interactions, and explore its potential and limitations with the aid of simulations and statistical analyses.

  18. Preparation of Human Serum Albumin Macroaggregated (MAA) labelled with 99mTc via Ligand Exchange

    International Nuclear Information System (INIS)

    El-Mohty, A.A.; El-Ghany, E.A.; Amin, A.A.; El-Koaly, M.T.; Raieh, M.

    2000-01-01

    An alternative method for the preparation of human serum albumin macroaggregated (MAA) labelled with 99m Tc for lung scanning is described. The method is based on the use of stannous methylene diphosphonate (Sn-MDP) as a reducing agent. The may be also increase the number of binding sites in the MAA. The different parameters affecting the labelling yield and in-vitro stability of 99m Tc-MAA have been studied in order to determine the optimum conditions for labelling macroaggregated with 99m Tc. A high labelling yield (98.9%) was achieved and more than 98% of 99m Tc-MAA coated with Sn-MDP. The determined lung uptake in mice was found to be ≥ 90% which better than the reported data. A particular procedure compared to the existing reported procedures, which is recommended for the preparation of Sn-MDP coated MAA labelled with 99m Tc for lung perfusion imaging

  19. Transforming single domain magnetic CoFe{sub 2}O{sub 4} nanoparticles from hydrophobic to hydrophilic by novel mechanochemical ligand exchange

    Energy Technology Data Exchange (ETDEWEB)

    Munjal, Sandeep; Khare, Neeraj, E-mail: nkhare@physics.iitd.ernet.in [Indian Institute of Technology Delhi, Department of Physics (India)

    2017-01-15

    Single-phase uniform-sized (~9 nm) cobalt ferrite (CFO) nanoparticles have been synthesized by hydrothermal synthesis using oleic acid as a surfactant. The as-synthesized oleic acid-coated CFO (OA-CFO) nanoparticles were well dispersible in nonpolar solvents but not dispersible in water. The OA-CFO nanoparticles have been successfully transformed to highly water-dispersible citric acid-coated CFO (CA-CFO) nanoparticles using a novel single-step ligand exchange process by mechanochemical milling, in which small chain citric acid molecules replace the original large chain oleic acid molecules available on CFO nanoparticles. The OA-CFO nanoparticle’s hexane solution and CA-CFO nanoparticle’s water solution remain stable even after 6 months and show no agglomeration and their dispersion stability was confirmed by zeta-potential measurements. The contact angle measurement shows that OA-CFO nanoparticles are hydrophobic whereas CA-CFO nanoparticles are superhydrophilic in nature. The potentiality of as-synthesized OA-CFO and mechanochemically transformed CA-CFO nanoparticles for the demulsification of highly stabilized water-in-oil and oil-in-water emulsions has been demonstrated.

  20. Ligand-Free Nanocrystals of Highly Emissive Cs4PbBr6 Perovskite

    KAUST Repository

    Zhang, Yuhai

    2018-02-23

    Although ligands of long carbon chains are very crucial to form stable colloidal perovskite nanocrystals (NCs), they create a severe barrier for efficient charge injection or extraction in quantum-dot-based optoelectronics, such as light emitting diode or solar cell. Here, we report a new approach to preparing ligand-free perovskite NCs of CsPbBr, which retained high photoluminescence quantum yield (44%). Such an approach involves a polar solvent (acetonitrile) and two small molecules (ammonium acetate and cesium chloride), which replace the organic ligand and still protect the nanocrystals from dissolution. The successful removal of hydrophobic long ligands was evidenced by Fourier transform infrared spectroscopy, ζ potential analysis, and thermogravimetric analysis. Unlike conventional perovskite NCs that are extremely susceptible to polar solvents, the ligand-free CsPbBr NCs show robust resistance to polar solvents. Our ligand-free procedure opens many possibilities not only from a material hybridization perspective but also in optimizing charge injection and extraction in semiconductor quantum-dot-based optoelectronics applications.

  1. Samarium ion exchanged montmorillonite for high temperature cumene cracking reaction

    International Nuclear Information System (INIS)

    Binitha, N.N.

    2009-01-01

    Full text: Nano material Montmorillonite clay is cation exchanged with samarium and its catalytic influence in cumene cracking reaction is investigated. Effect of exchange with sodium ions on further exchange with samarium ions is also noted. Acidity measurements are done using TPD of ammonia. The retention of basic structure is proved from FTIR spectra and XRD patterns. Elemental analysis result shows that samarium exchange has occurred, which is responsible for the higher catalytic activity. Surface area and pore volume remains more or less unaffected upon exchange. Thermogravimetric analysis indicates the enhanced thermal stability on exchanging. Cumene cracking reaction is carried out at atmospheric pressure in a fixed bed glass reactor at 673 K. The predominance of Bronsted acidity is confirmed from high selectivity to benzene. (author)

  2. Equilibrium dialysis-ligand exchange: adaptation of the method for determination of conditional stability constants of radionuclide-fulvic acid complexes

    International Nuclear Information System (INIS)

    Glaus, M.A.; Hummel, W.; Van Loon, L.R.

    1995-01-01

    The equilibrium dialysis-ligand exchange technique (EDLE) is used to determine conditional stability constants for the complexation of metal ions with humic acid, particularly in high pH solutions. Here, this technique has been adapted to measure conditional stability constants with fulvic acid. Fulvic acid permeates across all membranes during the experiment. The quantities involved therefore have to be determined analytically and taken into account when calculating the conditional stability constants. Co(II) and Laurentian Soil fulvic (LFA) acid were selected as a test system in order to investigate the time scale required to establish chemical and diffusion equilibria. After an incubation time of approximately two days, the conditional stability constants measured for the formation of Co-LFA-complexes are not time dependent, although across the whole time period investigated, LFA was still diffusing in increasing amounts across the dialysis membrane. This work demonstrates that the modified EDLE technique can be used in the determination of conditional metal stability constants of fulvic acid. (authors)

  3. Effect of the competition of Cu(II) and Ni(II) on the kinetic and thermodynamic stabilities of Cr(III)-organic ligand complexes using competitive ligand exchange (EDTA).

    Science.gov (United States)

    Cunha, Graziele da Costa; Goveia, Danielle; Romão, Luciane Pimenta Cruz; de Oliveira, Luciana Camargo

    2015-05-01

    The effect of competition of Cu(II) and Ni(II) on the kinetic stability of Cr(III) complexed with natural organic matter (NOM) was characterized using EDTA exchange with single-stage tangential-flow ultrafiltration. For a water sample from Serra de Itabaiana, 3% of spiked Cr(III) was exchanged, while for a sample from the Itapanhaú River, 7, 10, 10, and 21% was exchanged in experiments using Cr(III) alone and in combination with Cu(II), Ni(II), or Cu(II) + Ni(II), respectively. Times required to reach exchange equilibrium with EDTA were less than 360 min. The influence of competition from Ni(II) and Cu(II) on the availability of complexed Cr(III) was low, demonstrating preference of the ligand sites for Cr(III). This was correlated with sample humification, as confirmed by EPR and (13)C NMR analyses. Exchange efficiency was in the order Cu > Ni > Cr, and the process could be readily described by first order kinetics, with average rate constants of 0.35-0.37 h(-1). Copyright © 2015 Elsevier Ltd. All rights reserved.

  4. Surface polyPEGylation of Eu3+ doped luminescent hydroxyapatite nanorods through the combination of ligand exchange and metal free surface initiated atom transfer radical polymerization

    Science.gov (United States)

    Zeng, Guangjian; Liu, Meiying; Heng, Chunning; Huang, Qiang; Mao, Liucheng; Huang, Hongye; Hui, Junfeng; Deng, Fengjie; Zhang, Xiaoyong; Wei, Yen

    2017-03-01

    The Eu3+ doped luminescent hydroxyapatite (HAp) nanorods with uniform size and morphology can be synthesized by hydrothermal route. However, these HAp nanorods are coated by hydrophobic oleylamine, which makes them difficult to be dispersed in aqueous solution and impede their biomedical applications. In this work, Eu3+ doped luminescent polymers functionalized HAp nanorods were prepared through the combination of ligand exchange reaction and metal free surface initiated atom transfer radical polymerization (ATRP) method. In this procedure, the amino group functionalized HAp nanorods were first prepared by ligand exchange reaction using adenosine monophosphate (AMP) as ligand. Then the Br-containing initiators (HAp-Br) were introduced onto the surface of HAp-AMP nanorods through the amidation reaction. Finally, polymers functionalized HAp nanorods were prepared by metal free ATRP method using poly(ethylene glycol) methacrylate (PEGMA) as monomer and 10-phenylphenothiazine (PTH) as organic photocatalyst. The properties of these obtained HAp nanocomposites (HAP-polyPEGMA nanorods) were characterized by means of transmission electron microscopy, Fourier transformed infrared spectroscopy, X-ray photoelectron spectroscopy and thermogravimetric analysis in detail. The cell imaging of these HAP-polyPEGMA nanorods was examined using laser scanning confocal microscope to evaluate their biomedical applications. We demonstrated for the first time that hydrophobic luminescent HAp nanorods can be functionalized with polyPEGMA through the combination of ligand exchange reaction and metal free surface initiated ATRP. As compared with the traditional ATRP, the metal free ATRP can overcome the toxic and fluorescence quenching effects of metal catalysts such as copper ions. More importantly, the strategy described in this work should also be utilized for fabrications of many other luminescent polymer nanocomposites due to its good monomer adoptability.

  5. High Effectiveness Heat Exchanger for Cryogenic Refrigerators, Phase I

    Data.gov (United States)

    National Aeronautics and Space Administration — We propose an innovative high performance cryogenic heat exchanger manufactured of titanium by photo-etching and diffusion bonding. This is a parallel plate design...

  6. Heat exchangers and recuperators for high temperature waste gases

    Science.gov (United States)

    Meunier, H.

    General considerations on high temperature waste heat recovery are presented. Internal heat recovery through combustion air preheating and external heat recovery are addressed. Heat transfer and pressure drop in heat exchanger design are discussed.

  7. Influence of ligand-bridged substitution on the exchange coupling constant of chromium-wheels host complexes: a density functional theory study

    Science.gov (United States)

    Sadeghi Googheri, Motahare; Abolhassani, Mohammad Reza; Mirzaei, Mahmoud

    2018-05-01

    Designing and introducing novel wheel-shaped supramolecular as host complexes with new magnetic properties is the theme of the day. So in this study, new eight binuclear chromium (III) complexes, as models of real chromium-wheel host complexes, were designed based on changing of bridged-ligands and exchange coupling constants (J) of them were calculated using the broken symmetry density functional theory approach. Substitution of fluorine ligand in fluoro-bridged model [Cr2F(tBuCO2)2(H2O)2(OH)4]-1 by halogen anions (Cl-, Br- and I- ) decreased the antiferromagnetic exchange coupling between Cr(III) centres such that by going from F- to I- the J values became more positive. In the case of hydroxo-bridged model [Cr2OH(tBuCO2)2(H2O)2(OH)4]-1, replacement of hydroxyl by methoxy anion (OMe-) strengthened the antiferromagnetic property of the complex but substitution by sulfanide (SH-) and amide (NH2-) anions weakened it and changed the nature of complexes to ferromagnetic. Because of their different magnetic properties, these new investigated complexes can be suggested as interesting synthetic targets. Also, the J value changes due to ligand substitution were evaluated and it was found that the Cr-X bond strength and partial charges of involved atoms were the most effective factors on it.

  8. A highly sensitive quantitative cytosensor technique for the identification of receptor ligands in tissue extracts.

    Science.gov (United States)

    Lenkei, Z; Beaudet, A; Chartrel, N; De Mota, N; Irinopoulou, T; Braun, B; Vaudry, H; Llorens-Cortes, C

    2000-11-01

    Because G-protein-coupled receptors (GPCRs) constitute excellent putative therapeutic targets, functional characterization of orphan GPCRs through identification of their endogenous ligands has great potential for drug discovery. We propose here a novel single cell-based assay for identification of these ligands. This assay involves (a) fluorescent tagging of the GPCR, (b) expression of the tagged receptor in a heterologous expression system, (c) incubation of the transfected cells with fractions purified from tissue extracts, and (d) imaging of ligand-induced receptor internalization by confocal microscopy coupled to digital image quantification. We tested this approach in CHO cells stably expressing the NT1 neurotensin receptor fused to EGFP (enhanced green fluorescent protein), in which neurotensin promoted internalization of the NT1-EGFP receptor in a dose-dependent fashion (EC(50) = 0.98 nM). Similarly, four of 120 consecutive reversed-phase HPLC fractions of frog brain extracts promoted internalization of the NT1-EGFP receptor. The same four fractions selectively contained neurotensin, an endogenous ligand of the NT1 receptor, as detected by radioimmunoassay and inositol phosphate production. The present internalization assay provides a highly specific quantitative cytosensor technique with sensitivity in the nanomolar range that should prove useful for the identification of putative natural and synthetic ligands for GPCRs.

  9. Highly photoluminescent europium tetraphenylimidodiphosphinate ternary complexes with heteroaromatic co-ligands. Solution and solid state studies

    Energy Technology Data Exchange (ETDEWEB)

    Pietraszkiewicz, Marek, E-mail: mpietraszkiewicz@ichf.edu.pl [Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw (Poland); Pietraszkiewicz, Oksana; Karpiuk, Jerzy; Majka, Alina [Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw (Poland); Dutkiewicz, Grzegorz; Borowiak, Teresa [Adam Mickiewicz University, Faculty of Chemistry, Department of Crystallography, Grunwaldzka 6, 60-780 Poznań (Poland); Kaczmarek, Anna M. [L3–Luminescent Lanthanide Lab, f-element coordination chemistry, Ghent University, Department of Inorganic and Physical Chemistry, Krijgslaan 281, Building S3, 9000 Gent (Belgium); Van Deun, Rik, E-mail: rik.vandeun@ugent.be [L3–Luminescent Lanthanide Lab, f-element coordination chemistry, Ghent University, Department of Inorganic and Physical Chemistry, Krijgslaan 281, Building S3, 9000 Gent (Belgium)

    2016-02-15

    Tetraphenylimidodiphosphinate (tpip) forms neutral 3:1 complexes with lanthanide ions. These complexes can accommodate one ancillary planar heterocyclic ligand to complement their coordination sphere of Eu{sup 3+} to coordination number 8. Several co-ligands were tested to form new complexes: 1,10-phenanthroline, bathophenanthroline, 2,4,6-tris(2-pyridyl)-1,3,5-triazine, dipyrido[3,2-f:2′,3′-h]quinoxaline and 2,2′:6′,2′′-terpyridine. The addition of heterocyclic N,N-bidentate co-ligands to the coordination sphere results in a dramatic (by a factor of 45–50) luminescence enhancement of the parent Eu(tpip){sub 3}. The solid-state measurements confirmed that the ancillary ligands strongly increased the photoluminescence quantum yield (PLQY) of the investigated complexes. - Highlights: • We have disovered highly photoluminescent ternary Eu(III) complexes. • They consist of Eu(III) tetraphenylimidodiphosphinate, and planar heterocyclic ligands. • The increase in photoluminescence quantum yields in solution is enhanced up to 50 times in solution. • The solid-state photoluminescence exceeds 80% at room temperature.

  10. Highly photoluminescent europium tetraphenylimidodiphosphinate ternary complexes with heteroaromatic co-ligands. Solution and solid state studies

    International Nuclear Information System (INIS)

    Pietraszkiewicz, Marek; Pietraszkiewicz, Oksana; Karpiuk, Jerzy; Majka, Alina; Dutkiewicz, Grzegorz; Borowiak, Teresa; Kaczmarek, Anna M.; Van Deun, Rik

    2016-01-01

    Tetraphenylimidodiphosphinate (tpip) forms neutral 3:1 complexes with lanthanide ions. These complexes can accommodate one ancillary planar heterocyclic ligand to complement their coordination sphere of Eu 3+ to coordination number 8. Several co-ligands were tested to form new complexes: 1,10-phenanthroline, bathophenanthroline, 2,4,6-tris(2-pyridyl)-1,3,5-triazine, dipyrido[3,2-f:2′,3′-h]quinoxaline and 2,2′:6′,2′′-terpyridine. The addition of heterocyclic N,N-bidentate co-ligands to the coordination sphere results in a dramatic (by a factor of 45–50) luminescence enhancement of the parent Eu(tpip) 3 . The solid-state measurements confirmed that the ancillary ligands strongly increased the photoluminescence quantum yield (PLQY) of the investigated complexes. - Highlights: • We have disovered highly photoluminescent ternary Eu(III) complexes. • They consist of Eu(III) tetraphenylimidodiphosphinate, and planar heterocyclic ligands. • The increase in photoluminescence quantum yields in solution is enhanced up to 50 times in solution. • The solid-state photoluminescence exceeds 80% at room temperature.

  11. Ligand-Free Nanocrystals of Highly Emissive Cs4PbBr6 Perovskite

    KAUST Repository

    Zhang, Yuhai; Sinatra, Lutfan; Alarousu, Erkki; Yin, Jun; El-Zohry, Ahmed M.; Bakr, Osman; Mohammed, Omar F.

    2018-01-01

    diode or solar cell. Here, we report a new approach to preparing ligand-free perovskite NCs of CsPbBr, which retained high photoluminescence quantum yield (44%). Such an approach involves a polar solvent (acetonitrile) and two small molecules (ammonium

  12. High Efficiency Heat Exchanger for High Temperature and High Pressure Applications

    Energy Technology Data Exchange (ETDEWEB)

    Sienicki, James J. [Argonne National Lab. (ANL), Argonne, IL (United States). Nuclear Engineering Division; Lv, Qiuping [Argonne National Lab. (ANL), Argonne, IL (United States). Nuclear Engineering Division; Moisseytsev, Anton [Argonne National Lab. (ANL), Argonne, IL (United States). Nuclear Engineering Division

    2017-09-29

    CompRex, LLC (CompRex) specializes in the design and manufacture of compact heat exchangers and heat exchange reactors for high temperature and high pressure applications. CompRex’s proprietary compact technology not only increases heat exchange efficiency by at least 25 % but also reduces footprint by at least a factor of ten compared to traditional shell-and-tube solutions of the same capacity and by 15 to 20 % compared to other currently available Printed Circuit Heat Exchanger (PCHE) solutions. As a result, CompRex’s solution is especially suitable for Brayton cycle supercritical carbon dioxide (sCO2) systems given its high efficiency and significantly lower capital and operating expenses. CompRex has already successfully demonstrated its technology and ability to deliver with a pilot-scale compact heat exchanger that was under contract by the Naval Nuclear Laboratory for sCO2 power cycle development. The performance tested unit met or exceeded the thermal and hydraulic specifications with measured heat transfer between 95 to 98 % of maximum heat transfer and temperature and pressure drop values all consistent with the modeled values. CompRex’s vision is to commercialize its compact technology and become the leading provider for compact heat exchangers and heat exchange reactors for various applications including Brayton cycle sCO2 systems. One of the limitations of the sCO2 Brayton power cycle is the design and manufacturing of efficient heat exchangers at extreme operating conditions. Current diffusion-bonded heat exchangers have limitations on the channel size through which the fluid travels, resulting in excessive solid material per heat exchanger volume. CompRex’s design allows for more open area and shorter fluid proximity for increased heat transfer efficiency while sustaining the structural integrity needed for the application. CompRex is developing a novel improvement to its current heat exchanger design where fluids are directed to alternating

  13. SKF 525-A and cytochrome P-450 ligands inhibit with high affinity the binding of [3H]dextromethorphan and σligands to guinea pig brain

    International Nuclear Information System (INIS)

    Klein, M.; Canoll, P.D.; Musacchio, J.M.

    1991-01-01

    The DM 1 /σ 1 site binds dextromethorphan (DM) and σ receptor ligands. The broad binding specificity of this site and its peculiar subcellular distribution prompted us to explore the possibility that this site is a member of the cytochrome P-450 superfamily of enzymes. We tested the effects of the liver microsomal monooxygenase inhibitor SKF 525-A (Proadifen), and other P-450 substrates on the binding of [ 3 H]dextromethorphan, [ 3 H]3-(3-Hydroxyphenyl)-N-(1-propyl)piperidine and (+)-[ 3 H]1,3-Di-o-tolyl-guanidine ([ 3 H]DTG) to the guinea pig brain. SKF 525-A, l-lobeline and GBR-12909 inhibited the binding of the three labeled ligands with nM affinity. Each drug has identical nM K i values for the high-affinity site labeled by the three ligands. This indicated that they displaced the labeled ligands from the common DM 1 σ 1 site. Debrisoquine and sparteine, prototypical substrates for liver debrisoquine 4-hydroxylase, displayed K i values of 9-13 and 3-4 μM respectively against the three labeled ligands. These results, the broad specificity of the DM 1 /σ 1 binding site, and its peculiar subcellular distribution, raises the possibility that this binding site is a member of the cytochrome P-450 superfamily of isozymes, rather than a neurotransmitter receptor

  14. Chiral speciation and determination of selenomethionine enantiomers in selenized yeast by ligand-exchange micellar electrokinetic capillary chromatography after solid phase extraction.

    Science.gov (United States)

    Duan, Jiankun; He, Man; Hu, Bin

    2012-12-14

    A new phenylalanine derivative (L-N-(2-hydroxy-propyl)-phenylalanine, L-HP-Phe) was synthesized and its chelate with Cu(II) (Cu(II)-(L-HP-Phe)(2)) was used as the chiral selector for the ligand-exchange (LE) chiral separation of D,L-selenomethionine (SeMet) in selenized yeast samples by micelle electrokinetic capillary chromatography (MEKC). In order to improve the sensitivity of MEKC-UV, two-step preconcentration strategy was employed, off-line solid phase extraction (SPE) and on-line large volume sample stacking (LVSS). D,L-SeMet was first retained on the Cu(II) loaded mesoporous TiO(2), then eluted by 0.1 mL of 5 mol L(-1) ammonia, and finally introduced for MEKC-UV analysis by LVSS injection after evaporation of NH(3). With the enrichment factors of 1400 and 1378, the LODs of 0.44 and 0.60 ng mL(-1) for L-SeMet and D-SeMet was obtained, respectively. The developed method was applied to the analysis of D,L-SeMet in a certified reference material of SELM-1 and a commercial nutrition yeast, and the results showed that most of SeMet in the SELM-1 selenized yeast was l isomer and the recovery for L and D isomers in the spiked commercial nutrition yeast was 96.3% and 103%, respectively. This method is featured with low running cost, high sensitivity and selectivity, and exhibits application potential in chiral analysis of seleno amino acids in real world samples. Copyright © 2012 Elsevier B.V. All rights reserved.

  15. Stability constant determinations for technetium (IV) complexation with selected amino carboxylate ligands in high nitrate solutions

    Energy Technology Data Exchange (ETDEWEB)

    Omoto, Trevor; Wall, Nathalie A. [Washington State Univ., Pullman, WA (United States). Dept. of Chemistry

    2017-10-01

    The stability constants for Tc(IV) complexation with the ligands IDA, NTA, HEDTA, and DTPA were determined in varied nitrate concentrations using liquid-liquid extraction methods. The determined log β{sub 101} stability constants at 0.5 M NaNO{sub 3} were found to be 9.2±0.3, 10.3±0.3, and 15.3±0.3 for IDA, NTA, and HEDTA, respectively. The log β{sub 111} stability constant for DTPA was determined to be 22.0±0.6. These determined stability constants show a slight decrease in magnitude as a function of increasing NaNO{sub 3} concentration. These stability constants were used to model the total dissolution of Tc(IV) in acidic aqueous solutions in the presence of each ligand. The results of these predictive models indicate that amino carboxylic ligands have a high potential for increasing the aqueous dissolution of Tc(IV); at pH 2.3, 0.01 M ligand yield dissolved Tc(IV) concentrations of 1.42.10{sup -5} M, 1.33.10{sup -5} M, 6.07.10{sup -6} M, 9.65.10{sup -7} M, for DTPA, HEDTA, NTA, and IDA, respectively.

  16. Carboxylate ligands drastically enhance the rates of oxo exchange and hydrogen peroxide disproportionation by oxo manganese compounds of potential biological significance.

    Science.gov (United States)

    Dubois, Lionel; Pécaut, Jacques; Charlot, Marie-France; Baffert, Carole; Collomb, Marie-Noëlle; Deronzier, Alain; Latour, Jean-Marc

    2008-01-01

    To mimic the carboxylate-rich active site of the manganese catalases more closely we introduced carboxylate groups into dimanganese complexes in place of nitrogen ligands. The series of dimanganese(III,IV) complexes of tripodal ligands [Mn(2)(L)(2)(O)(2)](3+/+/-/3-) was extended from those of tpa (1) and H(bpg) (2) to those of H(2)(pda) (3) and H(3)(nta) (4) (tpa=tris-picolylamine, H(bpg)=bis-picolylglycylamine, H(2)(pda)=picolyldiglycylamine, H(3)(nta)=nitrilotriacetic acid). While 3 [Mn(2)(pda)(2)(O)(2)][Na(H(2)O)(3)] could be synthesized at -20 degrees C and characterized in the solid state, 4 [Mn(2)(nta)(2)(O)(2)](3-) could be obtained and studied only in solution at -60 degrees C. A new synthetic procedure for the dimanganese(III,III) complexes was devised, using stoichiometric reduction of the dimanganese(III,IV) precursor by the benzil radical with EPR monitoring. This enabled the preparation of the parent dimanganese(III,III) complex 5 [Mn(2)(tpa)(2)(O)(2)](ClO(4))(2), which was structurally characterized. The UV/visible, IR, EPR, magnetic, and electrochemical properties of complexes 1-3 and 5 were analyzed to assess the electronic changes brought about by the carboxylate replacement of pyridine ligands. The kinetics of the oxo ligand exchanges with labeled water was examined in acetonitrile solution. A dramatic effect of the number of carboxylates was evidenced. Interestingly, the influence of the second carboxylate substitution differs from that of the first one probably because this substitution occurs on an out-of-plane coordination while the former occurs in the plane of the [Mn(2)O(2)] core. Indeed, on going from 1 to 3 the exchange rate was increased by a factor of 50. Addition of triethylamine caused a rate increase for 1, but not for 3. The abilities of 1-3 to disproportionate H(2)O(2) were assessed volumetrically. The disproportionation exhibited a sensitivity corresponding to the carboxylate substitution. These observations strongly suggest that

  17. Heat Transfer in Metal Foam Heat Exchangers at High Temperature

    Science.gov (United States)

    Hafeez, Pakeeza

    Heat transfer though open-cell metal foam is experimentally studied for heat exchanger and heat shield applications at high temperatures (˜750°C). Nickel foam sheets with pore densities of 10 and 40 pores per linear inch (PPI), have been used to make the heat exchangers and heat shields by using thermal spray coating to deposit an Inconel skin on a foam core. Heat transfer measurements were performed on a test rig capable of generating hot gas up to 1000°C. The heat exchangers were tested by exposing their outer surface to combustion gases at a temperature of 550°C and 750°C while being cooled by air flowing through them at room temperature at velocities up to 5 m/s. The temperature rise of the air, the surface temperature of the heat exchangers and the air temperature inside the heat exchanger were measured. The volumetric heat transfer coefficient and Nusselt number were calculated for different velocities. The heat transfer performance of the 40PPI sample brazed with the foil is found to be the most efficient. Pressure drop measurements were also performed for 10 and 40PPI metal foam. Thermographic measurements were done on 40PPI foam heat exchangers using a high temperature infrared camera. A high power electric heater was used to produce hot air at 300°C that passed over the foam heat exchanger while the cooling air was blown through it. Heat shields were made by depositing porous skins on metal foam and it was observed that a small amount of coolant leaking through the pores notably reduces the heat transfer from the hot gases. An analytical model was developed based assuming local thermal non-equilibrium that accounts for the temperature difference between solid and fluid phase. The experimental results are found to be in good agreement with the predicted values of the model.

  18. Isotopic studies on ligand exchange between complex and simple cyanides in aqueous medium and in liquid hydrogen cyanide. Part 1. Rate law and temperature dependence study of the radiocyanide exchange between hydrogen cyanide and octacyanotungstate(4) in aque us medium

    International Nuclear Information System (INIS)

    Zielinski, M.

    1978-01-01

    Dark radiocyanide ligand exchange in the closed system consisting of K 4 W(CN) 8 , hydrogen cyanide and water have been investigated. It has been found that the reaction is first order in respect to the complex cyanide and zero order in respect to the free hydrogen cyanide. Arrhenius activation energy within the temperature interval of 20-100 0 C equals to 32.373 kcal/mole. Enthalpy and entropy of activation are correspondingly ΔH not equal to Λ31.716kcal/mole and ΔS not equal to =5.45 e.u. A preliminary discussion of the above findings is presented. (author)

  19. Application of high resolution NMR, ESR, and gamma-ray scintillation spectroscopy to the study of ligand binding in proteins

    International Nuclear Information System (INIS)

    Lancione, G.V.

    1982-01-01

    Electron spin resonance spectroscopy has been employed to study the nature of the ligand binding site of alpha-1-antitrypsin. Spectra of spin-labeled alpha-1-antitrypsin were recorded at pH's ranging from 2.4 to 12.5. This data demonstrates the tight binding of the spin-label to the protease, and the sensitivity of the bound spin-label to informational changes in the protease inhibitor. A molecular dipstick approach has also been applied to this system and has yielded information on the geometry of the cleft accommodating the spin-label. 160 Terbium(III) exchange experiments have been performed on the acetylcholine receptor protein isolated from Torpedo californica, employing a specially designed flow dialysis apparatus constructed in the laboratory. The apparatus is designed to allow continuous monitoring of 160 Tb(III) gamma-ray emission from the protein compartment of the flow dialysis cell. Nicotinic ligand-induced displacement of 160 Tb(III) from the nicotinic binding site of the receptor was monitored as a funtion of (1) the concentration of nicotinic ligand in the washout buffer, and (2) the nature of the nicotinic ligand in the buffer. Measured 160 Tb(III) exchange half-lives indicate (1) a direct relationship between 160 Tb(III) displacement and nicotinic ligand concentration in the wash-out buffer, and (2) an enhanced 160 Tb(III) displacement for nicotinic agents possessing quaternary ammonium functions

  20. NMR study of ligand exchange and electron self-exchange between oxo-centered trinuclear clusters [Fe3(μ3-O)(μ-O2CR)6(4-R'py)3](+/0).

    Science.gov (United States)

    Novitchi, Ghenadie; Helm, Lothar; Anson, Christopher; Powell, Annie K; Merbach, André E

    2011-10-17

    The syntheses, single crystal X-ray structures, and magnetic properties of the homometallic μ₃-oxo trinuclear clusters [Fe₃(μ₃-O)(μ-O₂CCH₃)₆(4-Phpy)₃](ClO₄) (1) and [Fe₃(μ₃-O)(μ-O₂CAd)₆(4-Mepy)₃](NO₃) (2) are reported (Ad = adamantane). The persistence of the trinuclear structure within 1 and 2 in CD₂Cl₂ and C₂D₂Cl₄ solutions in the temperature range 190-390 K is demonstrated by ¹H NMR. An equilibrium between the mixed pyridine clusters [Fe₃(μ₃-O)(μ-O₂CAd)₆(4-Mepy)(3-x)(4-Phpy)(x)](NO₃) (x = 0, 1, 2, 3) with a close to statistical distribution of these species is observed in CD₂Cl₂ solutions. Variable-temperature NMR line-broadening made it possible to quantify the coordinated/free 4-Rpy exchanges at the iron centers of 1 and 2: k(ex)²⁹⁸ = 6.5 ± 1.3 × 10⁻¹ s⁻¹, ΔH(‡) = 89.47 ± 2 kJ mol⁻¹, and ΔS(‡) = +51.8 ± 6 J K⁻¹ mol⁻¹ for 1 and k(ex)²⁹⁸ = 3.4 ± 0.5 × 10⁻¹ s⁻¹, ΔH(‡) = 91.13 ± 2 kJ mol⁻¹, and ΔS(‡) = +51.9 ± 5 J K⁻¹ mol⁻¹ for 2. A limiting D mechanism is assigned for these ligand exchange reactions on the basis of first-order rate laws and positive and large entropies of activation. The exchange rates are 4 orders of magnitude slower than those observed for the ligand exchange on the reduced heterovalent cluster [Fe(III)₂Fe(II)(μ₃-O)(μ-O₂CCH₃)₆(4-Phpy)₃] (3). In 3, the intramolecular Fe(III)/Fe(II) electron exchange is too fast to be observed. At low temperatures, the 1/3 intermolecular second-order electron self-exchange reaction is faster than the 4-Phpy ligand exchange reactions on these two clusters, suggesting an outer-sphere mechanism: k₂²⁹⁸ = 72.4 ± 1.0 × 103 M⁻¹ s⁻¹, ΔH(‡) = 18.18 ± 0.3 kJ mol⁻¹, and ΔS(‡) = -90.88 ± 1.0 J K⁻¹ mol⁻¹. The [Fe₃(μ₃-O)(μ-O₂CCH₃)₆(4-Phpy)₃](+/0) electron self-exchange reaction is compared with the more than 3 orders of magnitude faster [Ru

  1. Statistical removal of background signals from high-throughput 1H NMR line-broadening ligand-affinity screens

    International Nuclear Information System (INIS)

    Worley, Bradley; Sisco, Nicholas J.; Powers, Robert

    2015-01-01

    NMR ligand-affinity screens are vital to drug discovery, are routinely used to screen fragment-based libraries, and used to verify chemical leads from high-throughput assays and virtual screens. NMR ligand-affinity screens are also a highly informative first step towards identifying functional epitopes of unknown proteins, as well as elucidating the biochemical functions of protein–ligand interaction at their binding interfaces. While simple one-dimensional 1 H NMR experiments are capable of indicating binding through a change in ligand line shape, they are plagued by broad, ill-defined background signals from protein 1 H resonances. We present an uncomplicated method for subtraction of protein background in high-throughput ligand-based affinity screens, and show that its performance is maximized when phase-scatter correction is applied prior to subtraction

  2. Multiple exchange and high-energy fixed-angle scattering

    CERN Document Server

    Halliday, I G; Orzalesi, C A; Tau, M

    1975-01-01

    The application of the eikonal ansatz to fermion fermion elastic scattering with Abelian vector gluon exchanges is discussed. The behaviours of the elastic scattering amplitude and the elastic form factor are considered and an important mechanism for fixed angle high energy elastic scattering is identified. (6 refs).

  3. Heat exchangers for high-temperature thermodynamic cycles

    International Nuclear Information System (INIS)

    Fraas, A.P.

    1975-01-01

    The special requirements of heat exchangers for high temperature thermodynamic cycles are outlined and discussed with particular emphasis on cost and thermal stress problems. Typical approaches that have been taken to a comprehensive solution intended to meet all of the many boundary conditions are then considered by examining seven typical designs including liquid-to-liquid heat exchangers for nuclear plants, a heater for a closed cycle gas turbine coupled to a fluidized bed coal combustion chamber, steam generators for nuclear plants, a fossil fuel-fired potassium boiler, and a potassium condenser-steam generator. (auth)

  4. Mixed-ligand Al complex—a new approach for more high efficient OLEDs

    International Nuclear Information System (INIS)

    Petrova, Petia K.; Tomova, Reni L.; Stoycheva-Topalova, Rumiana T.; Kaloyanova, Stefka S.; Deligeorgiev, Todor G.

    2012-01-01

    The mixed-ligand Aluminum bis(8-hydroxyquinoline) acetylacetonate (Alq 2 Acac) complex was presented and its performance as electroluminescent and electron transporting layer for OLED was studied. The photophysical properties of the novel complex were investigated and compared with the properties of the parent Alq 3 . Highly efficient OLED based on the mixed-ligand Al complex was developed with two times higher luminescence and efficiency compared to the identical OLED based on the conventional Alq 3 The better performance of the devices make the novel Al complex a very promising material for OLEDs. - Highlights: ► A novel electroluminescent Alq 2 Acac complex is presented as material for OLED. ► Electroluminescent emission of Alq 2 Acac is very similar to that of commercial Alq 3 . ► Devices with Alq 2 Acac show better characteristics compared to those with Alq 3 .

  5. Systematic study of ligand structures of metal oxide EUV nanoparticle photoresists

    KAUST Repository

    Jiang, Jing

    2015-03-19

    Ligand stabilized metal oxide nanoparticle resists are promising candidates for EUV lithography due to their high sensitivity for high-resolution patterning and high etching resistance. As ligand exchange is responsible for the patterning mechanism, we systematically studied the influence of ligand structures of metal oxide EUV nanoparticles on their sensitivity and dissolution behavior. ZrO2 nanoparticles were protected with various aromatic ligands with electron withdrawing and electron donating groups. These nanoparticles have lower sensitivity compared to those with aliphatic ligands suggesting the structures of these ligands is more important than their pka on resist sensitivity. The influence of ligand structure was further studied by comparing the nanoparticles’ solubility for a single type ligand to mixtures of ligands. The mixture of nanoparticles showed improved pattern quality. © (2015) COPYRIGHT Society of Photo-Optical Instrumentation Engineers (SPIE). Downloading of the abstract is permitted for personal use only.

  6. Resonance charge exchange mechanism at high and moderate energies

    International Nuclear Information System (INIS)

    Bogdanov, A.V.; Gevorkyan, A.S.

    1984-01-01

    Charge exchange mechanisms at high and medium energies are investigated, ta king the resonance charge exchange of a proton by an hydrogen atom as an example . It is established that there are two classical charge exchange mechanisms rel ated to direct proton knockout from the bound state and one quantum-mechanical mechanism corresponding to the electron tunnelling from one bound state to anoth er. The classical cross-section diverges for two of these mechanisms, and the quasiclassical scattering amplitude must be calculated on the base of a complex classical trajectory. Physical grounds for the choice of such trajectories are discussed and calculations of the Van Vleck determinant for these mechanisms a re presented. Contributions from different mechanisms to the total charge excha nge cross-section are analyzed. A comparison with experimental data and results of other authors is made

  7. Dynamics of ligand exchange mechanism at Cu(II) in water: An ab initio quantum mechanical charge field molecular dynamics study with extended quantum mechanical region

    International Nuclear Information System (INIS)

    Moin, Syed Tarique; Hofer, Thomas S.; Weiss, Alexander K. H.; Rode, Bernd M.

    2013-01-01

    Ab initio quantum mechanical charge field molecular dynamics (QMCF-MD) were successfully applied to Cu(II) embedded in water to elucidate structure and to understand dynamics of ligand exchange mechanism. From the simulation studies, it was found that using an extended large quantum mechanical region including two shells of hydration is required for a better description of the dynamics of exchanging water molecules. The structural features characterized by radial distribution function, angular distribution function and other analytical parameters were consistent with experimental data. The major outcome of this study was the dynamics of exchange mechanism and reactions in the first hydration shell that could not be studied so far. The dynamical data such as mean residence time of the first shell water molecules and other relevant data from the simulations are close to the results determined experimentally. Another major characteristic of hydrated Cu(II) is the Jahn-Teller distortion which was also successfully reproduced, leading to the final conclusion that the dominating aqua complex is a 6-coordinated species. The ab initio QMCF-MD formalism proved again its capabilities of unraveling even ambiguous properties of hydrated species that are far difficult to explore by any conventional quantum mechanics/molecular mechanics (QM/MM) approach or experiment

  8. Dynamics of ligand exchange mechanism at Cu(II) in water: an ab initio quantum mechanical charge field molecular dynamics study with extended quantum mechanical region.

    Science.gov (United States)

    Moin, Syed Tarique; Hofer, Thomas S; Weiss, Alexander K H; Rode, Bernd M

    2013-07-07

    Ab initio quantum mechanical charge field molecular dynamics (QMCF-MD) were successfully applied to Cu(II) embedded in water to elucidate structure and to understand dynamics of ligand exchange mechanism. From the simulation studies, it was found that using an extended large quantum mechanical region including two shells of hydration is required for a better description of the dynamics of exchanging water molecules. The structural features characterized by radial distribution function, angular distribution function and other analytical parameters were consistent with experimental data. The major outcome of this study was the dynamics of exchange mechanism and reactions in the first hydration shell that could not be studied so far. The dynamical data such as mean residence time of the first shell water molecules and other relevant data from the simulations are close to the results determined experimentally. Another major characteristic of hydrated Cu(II) is the Jahn-Teller distortion which was also successfully reproduced, leading to the final conclusion that the dominating aqua complex is a 6-coordinated species. The ab initio QMCF-MD formalism proved again its capabilities of unraveling even ambiguous properties of hydrated species that are far difficult to explore by any conventional quantum mechanics/molecular mechanics (QM/MM) approach or experiment.

  9. Predicting High Frequency Exchange Rates using Machine Learning

    OpenAIRE

    Palikuca, Aleksandar; Seidl,, Timo

    2016-01-01

    This thesis applies a committee of Artificial Neural Networks and Support Vector Machines on high-dimensional, high-frequency EUR/USD exchange rate data in an effort to predict directional market movements on up to a 60 second prediction horizon. The study shows that combining multiple classifiers into a committee produces improved precision relative to the best individual committee members and outperforms previously reported results. A trading simulation implementing the committee classifier...

  10. Fc-Binding Ligands of Immunoglobulin G: An Overview of High Affinity Proteins and Peptides

    Directory of Open Access Journals (Sweden)

    Weonu Choe

    2016-12-01

    Full Text Available The rapidly increasing application of antibodies has inspired the development of several novel methods to isolate and target antibodies using smart biomaterials that mimic the binding of Fc-receptors to antibodies. The Fc-binding domain of antibodies is the primary binding site for e.g., effector proteins and secondary antibodies, whereas antigens bind to the Fab region. Protein A, G, and L, surface proteins expressed by pathogenic bacteria, are well known to bind immunoglobulin and have been widely exploited in antibody purification strategies. Several difficulties are encountered when bacterial proteins are used in antibody research and application. One of the major obstacles hampering the use of bacterial proteins is sample contamination with trace amounts of these proteins, which can invoke an immune response in the host. Many research groups actively develop synthetic ligands that are able to selectively and strongly bind to antibodies. Among the reported ligands, peptides that bind to the Fc-domain of antibodies are attractive tools in antibody research. Besides their use as high affinity ligands in antibody purification chromatography, Fc-binding peptides are applied e.g., to localize antibodies on nanomaterials and to increase the half-life of proteins in serum. In this review, recent developments of Fc-binding peptides are presented and their binding characteristics and diverse applications are discussed.

  11. Highly Fluorescent Group 13 Metal Complexes with Cyclic, Aromatic Hydroxamic Acid Ligands

    Energy Technology Data Exchange (ETDEWEB)

    Seitz, Michael; Moore, Evan G.; Raymond, Kenneth N.

    2008-02-11

    The neutral complexes of two ligands based on the 1-oxo-2-hydroxy-isoquinoline (1,2-HOIQO) motif with group 13 metals (Al, Ga, In) show bright blue-violet luminescence in organic solvents. The corresponding transition can be attributed to ligand-centered singlet emission, characterized by a small Stokes shifts of only a few nm combined with lifetimes in the range between 1-3 ns. The fluorescence efficiency is high, with quantum yields of up to 37% in benzene solution. The crystal structure of one of the indium(III) complexes (trigonal space group R-3, a = b = 13.0384(15) {angstrom}, c = 32.870(8) {angstrom}, ? = {beta} = 90{sup o}, {gamma} = 120{sup o}, V = 4839.3(14) {angstrom}{sup 3}, Z = 6) shows a six-coordinate geometry around the indium center which is close to trigonal-prismatic, with a twist angle between the two trigonal faces of 20.7{sup o}. Time-dependent density functional theory (TD-DFT) calculations (Al and Ga: B3LYP/6-31G(d)); In: B3LYP/LANL2DZ of the fac and mer isomers with one of the two ligands indicate that there is no clear preference for either one of the isomeric forms of the metal complexes. In addition, the metal centers do not have a significant influence on the electronic structure, and as a consequence, on the predominant intraligand optical transitions.

  12. Highly efficient bioinspired molecular Ru water oxidation catalysts with negatively charged backbone ligands.

    Science.gov (United States)

    Duan, Lele; Wang, Lei; Li, Fusheng; Li, Fei; Sun, Licheng

    2015-07-21

    The oxygen evolving complex (OEC) of the natural photosynthesis system II (PSII) oxidizes water to produce oxygen and reducing equivalents (protons and electrons). The oxygen released from PSII provides the oxygen source of our atmosphere; the reducing equivalents are used to reduce carbon dioxide to organic products, which support almost all organisms on the Earth planet. The first photosynthetic organisms able to split water were proposed to be cyanobacteria-like ones appearing ca. 2.5 billion years ago. Since then, nature has chosen a sustainable way by using solar energy to develop itself. Inspired by nature, human beings started to mimic the functions of the natural photosynthesis system and proposed the concept of artificial photosynthesis (AP) with the view to creating energy-sustainable societies and reducing the impact on the Earth environments. Water oxidation is a highly energy demanding reaction and essential to produce reducing equivalents for fuel production, and thereby effective water oxidation catalysts (WOCs) are required to catalyze water oxidation and reduce the energy loss. X-ray crystallographic studies on PSII have revealed that the OEC consists of a Mn4CaO5 cluster surrounded by oxygen rich ligands, such as oxyl, oxo, and carboxylate ligands. These negatively charged, oxygen rich ligands strongly stabilize the high valent states of the Mn cluster and play vital roles in effective water oxidation catalysis with low overpotential. This Account describes our endeavors to design effective Ru WOCs with low overpotential, large turnover number, and high turnover frequency by introducing negatively charged ligands, such as carboxylate. Negatively charged ligands stabilized the high valent states of Ru catalysts, as evidenced by the low oxidation potentials. Meanwhile, the oxygen production rates of our Ru catalysts were improved dramatically as well. Thanks to the strong electron donation ability of carboxylate containing ligands, a seven

  13. Enantioseparation of dansyl amino acids and dipeptides by chiral ligand exchange capillary electrophoresis based on Zn(II)-L-hydroxyproline complexes coordinating with γ-cyclodextrins.

    Science.gov (United States)

    Mu, Xiaoyu; Qi, Li; Qiao, Juan; Yang, Xinzheng; Ma, Huimin

    2014-10-10

    A chiral ligand exchange capillary electrophoresis (CLE-CE) method using Zn(II) as the central ion and L-4-hydroxyproline as the chiral ligand coordinating with γ-cyclodextrin (γ-CD) was developed for the enantioseparation of amino acids (AAs) and dipeptides. The effects of various separation parameters, including the pH of the running buffer, the ratio of Zn(II) to L-4-hydroxyproline, the concentration of complexes and cyclodextrins (CDs) were systematically investigated. After optimization, it has been found that eight pairs of labeled AAs and six pairs of labeled dipeptides could be baseline-separated with a running electrolyte of 100.0mM boric acid, 5.0mM ammonium acetate, 3.0mM Zn(II), 6.0mM L-hydroxyproline and 4.0mM γ-CD at pH 8.2. The quantitation of AAs and dipeptides was conducted and good linearity (r(2)≥0.997) and favorable repeatability (RSD≤3.6%) were obtained. Furthermore, the proposed method was applied in determining the enantiomeric purity of AAs and dipeptides. Meanwhile, the possible enantiorecognition mechanism based on the synergistic effect of chiral metal complexes and γ-CD was explored and discussed briefly. Copyright © 2014 Elsevier B.V. All rights reserved.

  14. Efficient Route to Highly Water-Soluble Aromatic Cyclic Hydroxamic Acid Ligands

    Energy Technology Data Exchange (ETDEWEB)

    Seitz, Michael; Raymond, Kenneth N.

    2008-02-06

    2-Hydroxyisoquinolin-1-one (1,2-HOIQO) is a new member of the important class of aromatic cyclic hydroxamic acid ligands which are widely used in metal sequestering applications and metal chelating therapy. The first general approach for the introduction of substituents at the aromatic ring of the chelating moiety is presented. As a useful derivative, the highly water-soluble sulfonic acid has been synthesized by an efficient route that allows general access to 1,2-HOQIO 3-carboxlic acid amides, which are the most relevant for applications.

  15. Novel and high affinity fluorescent ligands for the serotonin transporter based on (s)-citalopram

    DEFF Research Database (Denmark)

    Kumar, Vivek; Rahbek-Clemmensen, Troels; Billesbølle, Christian B

    2014-01-01

    Novel rhodamine-labeled ligands, based on (S)-citalopram, were synthesized and evaluated for uptake inhibition at the human serotonin, dopamine, and norepinephrine transporters (hSERT, hDAT, and hNET, respectively) and for binding at SERT, in transiently transfected COS7 cells. Compound 14 demons...... demonstrated high affinity binding and selectivity for SERT (K i = 3 nM). Visualization of SERT, using confocal laser scanning microscopy, validated compound 14 as a novel tool for studying SERT expression and distribution in living cells....

  16. In Silico Generation of Peptides by Replica Exchange Monte Carlo: Docking-Based Optimization of Maltose-Binding-Protein Ligands.

    Directory of Open Access Journals (Sweden)

    Anna Russo

    Full Text Available Short peptides can be designed in silico and synthesized through automated techniques, making them advantageous and versatile protein binders. A number of docking-based algorithms allow for a computational screening of peptides as binders. Here we developed ex-novo peptides targeting the maltose site of the Maltose Binding Protein, the prototypical system for the study of protein ligand recognition. We used a Monte Carlo based protocol, to computationally evolve a set of octapeptides starting from a polialanine sequence. We screened in silico the candidate peptides and characterized their binding abilities by surface plasmon resonance, fluorescence and electrospray ionization mass spectrometry assays. These experiments showed the designed binders to recognize their target with micromolar affinity. We finally discuss the obtained results in the light of further improvement in the ex-novo optimization of peptide based binders.

  17. Direct versus ligand-exchange synthesis of [PtAg28(BDT)12(TPP)4]4− nanoclusters: effect of a single-atom dopant on the optoelectronic and chemical properties

    KAUST Repository

    Bootharaju, Megalamane Siddaramappa; Kozlov, Sergey M.; Cao, Zhen; Harb, Moussab; Parida, Manas R.; Hedhili, Mohamed N.; Mohammed, Omar F.; Bakr, Osman; Cavallo, Luigi; Basset, Jean-Marie

    2017-01-01

    to offer monodisperse doped NCs. For instance, the direct synthesis of PtAg28 NCs produces a mixture of [Ag29(BDT)12(TPP)4]3- and [PtAg28(BDT)12(TPP)4]4- NCs (TPP: triphenylphosphine; BDT: 1,3-benzenedithiolate). Here, we designed a ligand-exchange (LE

  18. Heterometallic and homometallic complexes containing bifunctional ligands and their application in high-temperature oxide superconductor materials

    Science.gov (United States)

    Breeze, Steven R.

    We have been interested in the development of soluble precursors for the production of YBasb2Cusb3Osb{7-delta} and Bisb2(Ca,Sr)sbn+1CusbnOsb(2n + 4) + delta, superconductor materials. Several heterometallic and homometallic complexes containing the constituent metals of these superconductors and bifunctional ligands such as aminoalcohols, acetates and thioethers have been isolated and structurally characterized. The thermal decomposition properties and magnetic properties of some of these compounds have been investigated. The first ligand system investigated involved 1,3-bis(dimethylamino)-2-propanol (bdmapH). By varying the ratio of bdmapH, Cu(OCHsb3)sb2, and M(Osb2CCFsb3)sb2 (M = Ca, Sr) several heterometallic complexes have been obtained, including Srsb2Cusb2(bdmap)sb4(Osb2CCFsb3)sb4, CaCu(bdmap)sb2(Osb2CCFsb3)sb3(Hsb2O), Srsb2Cusb4(bdmap)sb6-(Osb2CCFsb3)sb4(musb 3-OH)sb2(THF)sb2 and SrCusb2(bdmap)sb3(Osb2CCFsb3)sb3(THF). With the exception of Srsb2Cusb4(bdmap)sb6(Osb2CCFsb3)sb4(musb 3-OH)sb2(THF)sb2, these compounds thermally decompose to form mixtures of fluorides and oxides. An analogous acetate compound SrCusb2(bdmap)sb3(Osb2CCHsb3)sb3(THF) has been produced, which forms the corresponding oxide at high temperature. A bismuth dimer, Bisb2(bdmap)sb2(Osb2CCHsb3)sb4(Hsb2O), has also been obtained. Superconducting powder of the Bisb2Srsb2CaCusb2Osb{8 + delta} and epitaxial superconducting films of the YBasb2Cusb3Osb{7-delta} superconductor have been produced using the bdmap and acetate ligands as cross-linking reagents. The second ligand system investigated involved di-2-pyridylmethanediol. Only homonuclear complexes have been obtained by using this ligand, including the mononuclear compound Cu ((2-py)sb2CO(OH)) sb2(HOsb2CCH sb3)sb2*CHsb2Clsb2, the tetranuclear compound Cusb4 ((2-py)sb2CO(OH)) sb2(Osb2CCHsb 3)sb6(Hsb2O)sb2*CHsb2Clsb2, and the bismuth dimer Bisb2 ((2-py)sb2CO(OH)) sb2(Osb 2CCFsb3)sb4*(THF)sb2. The tetranuclear Cusb4 compound was found to be

  19. Synthesis and spectroscopic behavior of highly luminescent trinuclear europium complexes with tris-β-diketone ligand

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Dunjia, E-mail: dunjiawang@163.com; Pi, Yan; Liu, Hua; Wei, Xianhong; Hu, Yanjun; Zheng, Jing

    2014-11-15

    Highlights: • Synthesis of the tris-β-diketone ligand and its trinuclear europium complexes. • Photoluminescence behavior of trinuclear europium complexes. • Analysis of the Judd–Ofelt intensity parameters (Ω{sub t}), lifetime (τ) and quantum yield (η). - Abstract: A new tris-β-diketone ligand, 2-[4,6-bis-(1-benzoyl-2-oxo-2-phenyl-ethyl)-[1,3,5]triazin-2-yl] -1,3-diphenyl-propane-1,3-dione (H{sub 3}L), and its trinuclear europium complexes, Eu{sub 3}(DBM){sub 6}L (C1), Eu{sub 3}(DBM){sub 6}(Bipy){sub 3}L (C2) and Eu{sub 3}(DBM){sub 6}(Phen){sub 3}L (C3) were synthesized and their spectroscopic behaviors were studied by FT-IR, {sup 1}H NMR, UV–vis and photoluminescence spectroscopic techniques. These europium complexes exhibited the characteristic emission bands that arise from the {sup 5}D{sub 0} → {sup 7}F{sub J} (J = 0–4) transitions of the europium ion in solid state. The Ω{sub 2} and Ω{sub 4} intensity parameters, lifetime (τ) and luminescence quantum yield (η) were calculated according to the emission spectra and luminescence decay curves in solid state. The results indicated that these trinuclear europium complexes displayed a longer lifetime (τ) and higher luminescence quantum efficiency (η), especially complexes C2 (τ = 0.820 ms, η = 46.5%) and C3 (τ = 0.804 ms, η = 47.4%), which due to the effect of two additional europium ion lumophors and the introduction of the third ligands, Bipy or Phen in trinuclear complexes. Their Ω{sub 2} values demonstrated that the europium ion in these complexes is in a highly polarizable chemical environment.

  20. High density and ligand affinity confer ultrasensitive signal detection by a guanylyl cyclase chemoreceptor

    Science.gov (United States)

    Pichlo, Magdalena; Bungert-Plümke, Stefanie; Weyand, Ingo; Seifert, Reinhard; Bönigk, Wolfgang; Strünker, Timo; Kashikar, Nachiket Dilip; Goodwin, Normann; Müller, Astrid; Körschen, Heinz G.; Collienne, Ursel; Pelzer, Patric; Van, Qui; Enderlein, Jörg; Klemm, Clementine; Krause, Eberhard; Trötschel, Christian; Poetsch, Ansgar; Kremmer, Elisabeth

    2014-01-01

    Guanylyl cyclases (GCs), which synthesize the messenger cyclic guanosine 3′,5′-monophosphate, control several sensory functions, such as phototransduction, chemosensation, and thermosensation, in many species from worms to mammals. The GC chemoreceptor in sea urchin sperm can decode chemoattractant concentrations with single-molecule sensitivity. The molecular and cellular underpinnings of such ultrasensitivity are not known for any eukaryotic chemoreceptor. In this paper, we show that an exquisitely high density of 3 × 105 GC chemoreceptors and subnanomolar ligand affinity provide a high ligand-capture efficacy and render sperm perfect absorbers. The GC activity is terminated within 150 ms by dephosphorylation steps of the receptor, which provides a means for precise control of the GC lifetime and which reduces “molecule noise.” Compared with other ultrasensitive sensory systems, the 10-fold signal amplification by the GC receptor is surprisingly low. The hallmarks of this signaling mechanism provide a blueprint for chemical sensing in small compartments, such as olfactory cilia, insect antennae, or even synaptic boutons. PMID:25135936

  1. Promising materials for HTGR high temperature heat exchangers

    International Nuclear Information System (INIS)

    Kuznetsov, E.V.; Tokareva, T.B.; Ryabchenkov, A.V.; Novichkova, O.V.; Starostin, Yu.D.

    1989-01-01

    The service conditions for high-temperature heat-exchangers with helium coolant of HTGRs and requirements imposed on materials for their production are discussed. The choice of nickel-base alloys with solid-solution hardening for long-term service at high temperatures is grounded. Results of study on properties and structure of types Ni-25Cr-5W-5Mo and Ni-20Cr-20W alloy in the temperature range of 900 deg. - 1,000 deg. C are given. The ageing of Ni-25Cr-5W-5Mo alloy at 900 deg. - 950 deg. C results in decreased corrosion-mechanical properties and is caused by the change of structural metal stability. Alloy with 20% tungsten retains a high stability of both structure and properties after prolonged exposure in helium at above temperatures. The alloy has also increased resistance to delayed fracture and low-cycle fatigue at high temperatures. The developed alloy of type Ni-20Cr-20W with microalloying is recommended for production of tubes for HTGR high-temperature heat-exchangers with helium coolant. (author). 3 refs, 8 figs

  2. Mixed-ligand Al complex-a new approach for more high efficient OLEDs

    Energy Technology Data Exchange (ETDEWEB)

    Petrova, Petia K., E-mail: petia@clf.bas.bg [Institute of Optical Materials and Technologies ' Acad. J. Malinowski' , Bulgarian Academy of Sciences, Acad. G Bonchev st., bl. 109, 1113 Sofia (Bulgaria); Tomova, Reni L.; Stoycheva-Topalova, Rumiana T. [Institute of Optical Materials and Technologies ' Acad. J. Malinowski' , Bulgarian Academy of Sciences, Acad. G Bonchev st., bl. 109, 1113 Sofia (Bulgaria); Kaloyanova, Stefka S.; Deligeorgiev, Todor G. [Applied Organic Chemistry, Faculty of Chemistry, University of Sofia, Sofia 1164 (Bulgaria)

    2012-02-15

    The mixed-ligand Aluminum bis(8-hydroxyquinoline) acetylacetonate (Alq{sub 2}Acac) complex was presented and its performance as electroluminescent and electron transporting layer for OLED was studied. The photophysical properties of the novel complex were investigated and compared with the properties of the parent Alq{sub 3}. Highly efficient OLED based on the mixed-ligand Al complex was developed with two times higher luminescence and efficiency compared to the identical OLED based on the conventional Alq{sub 3} The better performance of the devices make the novel Al complex a very promising material for OLEDs. - Highlights: Black-Right-Pointing-Pointer A novel electroluminescent Alq{sub 2}Acac complex is presented as material for OLED. Black-Right-Pointing-Pointer Electroluminescent emission of Alq{sub 2}Acac is very similar to that of commercial Alq{sub 3}. Black-Right-Pointing-Pointer Devices with Alq{sub 2}Acac show better characteristics compared to those with Alq{sub 3}.

  3. Role of protein-glutathione contacts in defining glutaredoxin-3 [2Fe-2S] cluster chirality, ligand exchange and transfer chemistry.

    Science.gov (United States)

    Sen, Sambuddha; Cowan, J A

    2017-10-01

    Monothiol glutaredoxins (Grx) serve as intermediate cluster carriers in iron-sulfur cluster trafficking. The [2Fe-2S]-bound holo forms of Grx proteins display cysteinyl coordination from exogenous glutathione (GSH), in addition to contact from protein-derived Cys. Herein, we report mechanistic studies that investigate the role of exogenous glutathione in defining cluster chirality, ligand exchange, and the cluster transfer chemistry of Saccharomyces cerevisiae Grx3. Systematic perturbations were introduced to the glutathione-binding site by substitution of conserved charged amino acids that form crucial electrostatic contacts with the glutathione molecule. Native Grx3 could also be reconstituted in the absence of glutathione, with either DTT, BME or free L-cysteine as the source of the exogenous Fe-S ligand contact, while retaining full functional reactivity. The delivery of the [2Fe-2S] cluster to Grx3 from cluster donor proteins such as Isa, Nfu, and a [2Fe-2S](GS) 4 complex, revealed that electrostatic contacts are of key importance for positioning the exogenous glutathione that in turn influences the chiral environment of the cluster. All Grx3 derivatives were reconstituted by standard chemical reconstitution protocols and found to transfer cluster to apo ferredoxin 1 (Fdx1) at rates comparable to native protein, even when using DTT, BME or free L-cysteine as a thiol source in place of GSH during reconstitution. Kinetic analysis of cluster transfer from holo derivatives to apo Fdx1 has led to a mechanistic model for cluster transfer chemistry of native holo Grx3, and identification of the likely rate-limiting step for the reaction.

  4. Tetrasubstituted phenanthrolines as highly potent, water-soluble, and selective g-quadruplex ligands

    DEFF Research Database (Denmark)

    Larsen, Anders Foller; Nielsen, Mads Corvinius; Ulven, Trond

    2012-01-01

    Small molecules capable of stabilizing the G-quadruplex (G4) structure are of interest for the development of improved anticancer drugs. Novel 4,7-diamino-substituted 1,10-phenanthroline-2,9-dicarboxamides that represent hybrid structures of known phenanthroline-based ligands have been designed....... An efficient synthetic route to the compounds has been developed and their interactions with various G4 sequences have been evaluated by Förster resonance energy transfer (FRET) melting assays, fluorescent intercalator displacement (FID), electrospray ionization mass spectrometry (ESI-MS), and circular...... dichroism (CD) spectroscopy. The preferred compounds have high aqueous solubility and are strong and potent G4 binders with a high selectivity over duplex DNA; thus, they represent a significant improvement over the lead compounds. Two of the compounds are inhibitors of HeLa and HT1080 cell proliferation....

  5. The ion-exchange obtaining of high purity samarium oxide

    International Nuclear Information System (INIS)

    Brzyska, W.; Soltysiak, I.; Cygan, J.

    1987-01-01

    The use of lactic acid - EDTA mixture as an eluent for the obtaining of high purity samarium oxide was studied. The studies were carried out at room temperature on cation exchange resin Wofatit KPS X 8. The best results were obtained for lactic acid (0,26 mol/dm 3 ) - EDTA (0,013 mol/dm 3 ) mixture at pH 3,3. As the result of 57% samarium concentrate elution with column load 1:3 and flow rate 0,4 cm/min, over 99% pure samarium oxide with 73% yield has been obtained. The yield of spectrally pure Sm 2 O 3 exceeded 45%. (author)

  6. Interaction Entropy: A New Paradigm for Highly Efficient and Reliable Computation of Protein-Ligand Binding Free Energy.

    Science.gov (United States)

    Duan, Lili; Liu, Xiao; Zhang, John Z H

    2016-05-04

    Efficient and reliable calculation of protein-ligand binding free energy is a grand challenge in computational biology and is of critical importance in drug design and many other molecular recognition problems. The main challenge lies in the calculation of entropic contribution to protein-ligand binding or interaction systems. In this report, we present a new interaction entropy method which is theoretically rigorous, computationally efficient, and numerically reliable for calculating entropic contribution to free energy in protein-ligand binding and other interaction processes. Drastically different from the widely employed but extremely expensive normal mode method for calculating entropy change in protein-ligand binding, the new method calculates the entropic component (interaction entropy or -TΔS) of the binding free energy directly from molecular dynamics simulation without any extra computational cost. Extensive study of over a dozen randomly selected protein-ligand binding systems demonstrated that this interaction entropy method is both computationally efficient and numerically reliable and is vastly superior to the standard normal mode approach. This interaction entropy paradigm introduces a novel and intuitive conceptual understanding of the entropic effect in protein-ligand binding and other general interaction systems as well as a practical method for highly efficient calculation of this effect.

  7. The study of development of welded compact plate heat exchanger for high temperature and pressure

    International Nuclear Information System (INIS)

    Park, Jae Hong; Lim, Hyug; Kim, Jung Kyu; Cho, Sung Youl; Kwon, Oh Boong

    2009-01-01

    In view of space saving, the design of more compact heat exchangers is relatively important. Also, to meet the demand for saving energy and resources today, manufacturers are trying to enhance efficiency and reduce the size and weight of heat exchangers. Over the past decade, there has been tremendous advancement in the manufacturing technology of high efficiency heat exchangers. This has allowed the use of smaller and high performance heat exchangers. Consequently, the use of smaller and high performance heat exchanger becomes popular in the design of heat exchangers. Welded compact plate heat exchanger is used in high temperature and pressure. In the design of heat exchanger, it is necessary to understand the heat transfer characteristics, so performance data are provided to help design of this type heat exchanger.

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

    Science.gov (United States)

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

    2012-05-31

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

  9. Focus State Roadway Departure Safety Plans and High Friction Surface Treatments Peer Exchange : an RPSCB Peer Exchange

    Science.gov (United States)

    2014-08-01

    This report summarizes the Focus State Roadway Departure Safety Plans and High Friction Surface Treatments Peer Exchange, held in Birmingham, Alabama, sponsored by the Federal Highway Administration (FHWA) Office of Safetys Roadway Safety Professi...

  10. Carbon dioxide selective adsorption within a highly stable mixed-ligand Zeolitic Imidazolate Framework

    KAUST Repository

    Huang, Lin

    2014-08-01

    A new mixed-ligand Zeolitic Imidazolate Framework Zn4(2-mbIm) 3(bIm)5·4H2O (named JUC-160, 2-mbIm = 2-methylbenzimidazole, bIm = benzimidazole and JUC = Jilin University China) was synthesized with a solvothermal reaction of Zn(NO3) 2·6H2O, bIm and 2-mbIm in DMF solution at 180 °C. Topological analysis indicated that JUC-160 has a zeolite GIS (gismondine) topology. Study of the gas adsorption and thermal and chemical stability of JUC-160 demonstrated its selective adsorption property for carbon dioxide, high thermal stability, and remarkable chemical resistance to boiling alkaline water and organic solvent for up to one week. © 2014 Elsevier B.V.

  11. Self-Assembled Fluorescent Nanoprobe Based on Forster Resonance Energy Transfer for Carbon Monoxide in Living Cells and Animals via Ligand Exchange.

    Science.gov (United States)

    Jia, Ruizhen; Song, Pengfei; Wang, Jingjing; Mai, Hengtang; Li, Sixian; Cheng, Yu; Wu, Song

    2018-05-29

    Carbon monoxide (CO) is recognized as a biologically essential gaseous neurotransmitter that modulates many physiological processes in living subjects. Currently reported fluorescent probes for CO imaging in cells basically utilize palladium related chemistry which requires complicated synthetic work. Herein we provide a new strategy to construct a fluorescent nanoprobe, NanoCO-1, based on the Forster resonance energy transfer (FRET) mechanism by entrapping the existing dirhodium complex as the energy acceptor and the CO recognition part, and a commonly used nitrobenzoxadiazole (NBD) dye as energy donor into a micelle formed by self-assembly. The exchange of ligands in the dirhodium complex by CO in the nanoprobe disrupts the FRET and leads to the turn-on of fluorescence. The merits of NanoCO-1 including good biocompatibility, selectivity, photostability, and low cytotoxity, render this nanoprobe ability to track CO in living cells, zebrafish embryo, and larvae. Our straightforward approach can be extended to establish the CO fluorescent probes based on adsorption of CO on a variety of metal derivatives.

  12. Synthesis and spectroscopic behavior of highly luminescent Eu 3+-dibenzoylmethanate (DBM) complexes with sulfoxide ligands

    Science.gov (United States)

    Niyama, E.; Brito, H. F.; Cremona, M.; Teotonio, E. E. S.; Reyes, R.; Brito, G. E. S.; Felinto, M. C. F. C.

    2005-09-01

    In this paper the synthesis, characterization and photoluminescent behavior of the [RE(DBM) 3L 2] complexes (RE = Gd and Eu) with a variety of sulfoxide ligands; L = benzyl sulfoxide (DBSO), methyl sulfoxide (DMSO), phenyl sulfoxide (DPSO) and p-tolyl sulfoxide (PTSO) have been investigated in solid state. The emission spectra of the Eu 3+-β-diketonate complexes show characteristics narrow bands arising from the 5D 0 → 7F J ( J = 0-4) transitions, which are split according to the selection rule for C n, C nv or C s site symmetries. The experimental Judd-Ofelt intensity parameters ( Ω2 and Ω4), radiative ( Arad) and non-radiative ( Anrad) decay rates, and R02 for the europium complexes have been determined and compared. The highest value of Ω2 (61.9 × 10 -20 cm 2) was obtained to the complex with PTSO ligand, indicating that Eu 3+ ion is in the highly polarizable chemical environment. The higher values of the experimental quantum yield ( q) and emission quantum efficiency of the emitter 5D 0 level ( η) for the Eu-complexes with DMSO, DBSO and PTSO sulfoxides suggest that these complexes are promising Light Conversion Molecular Devices (LCMDs). The lower value of quantum yield ( q = 1%), for the hydrated complex [Eu(DBM) 3(H 2O)], indicates that the luminescence quenching occurs via multiphonon relaxation by coupling with the OH-oscillators from water molecule coordinated to rare earth ion. The pure red emission of the Eu-complexes has been confirmed by ( x, y) color coordinates.

  13. Theoretical characterization and design of highly efficient iridium (III) complexes bearing guanidinate ancillary ligand.

    Science.gov (United States)

    Ren, Xin-Yao; Wu, Yong; Wang, Li; Zhao, Liang; Zhang, Min; Geng, Yun; Su, Zhong-Min

    2014-06-01

    A density functional theory/time-depended density functional theory was used to investigate the synthesized guanidinate-based iridium(III) complex [(ppy)2Ir{(N(i)Pr)2C(NPh2)}] (1) and two designed derivatives (2 and 3) to determine the influences of different cyclometalated ligands on photophysical properties. Except the conventional discussions on geometric relaxations, absorption and emission properties, many relevant parameters, including spin-orbital coupling (SOC) matrix elements, zero-field-splitting parameters, radiative rate constants (kr) and so on were quantitatively evaluated. The results reveal that the replacement of the pyridine ring in the 2-phenylpyridine ligand with different diazole rings cannot only enlarge the frontier molecular orbital energy gaps, resulting in a blue-shift of the absorption spectra for 2 and 3, but also enhance the absorption intensity of 3 in the lower-energy region. Furthermore, it is intriguing to note that the photoluminescence quantum efficiency (ΦPL) of 3 is significantly higher than that of 1. This can be explained by its large SOC value(n=3-4) and large transition electric dipole moment (μS3), which could significantly contribute to a larger kr. Besides, compared with 1, the higher emitting energy (ET1) and smaller (2) value for 3 may lead to a smaller non-radiative decay rate. Additionally, the detailed results also indicate that compared to 1 with pyridine ring, 3 with imidazole ring performs a better hole injection ability. Therefore, the designed complex 3 can be expected as a promising candidate for highly efficient guanidinate-based phosphorescence emitter for OLEDs applications. Copyright © 2014 Elsevier Inc. All rights reserved.

  14. Exchange across the shelf break at high southern latitudes

    Directory of Open Access Journals (Sweden)

    J. M. Klinck

    2010-05-01

    Full Text Available Exchange of water across the Antarctic shelf break has considerable scientific and societal importance due to its effects on circulation and biology of the region, conversion of water masses as part of the global overturning circulation and basal melt of glacial ice and the consequent effect on sea level rise. The focus in this paper is the onshore transport of warm, oceanic Circumpolar Deep Water (CDW; export of dense water from these shelves is equally important, but has been the focus of other recent papers and will not be considered here. A variety of physical mechanisms are described which could play a role in this onshore flux. The relative importance of some processes are evaluated by simple calculations. A numerical model for the Ross Sea continental shelf is used as an example of a more comprehensive evaluation of the details of cross-shelf break exchange. In order for an ocean circulation model to simulate these processes at high southern latitudes, it needs to have high spatial resolution, realistic geometry and bathymetry. Grid spacing smaller than the first baroclinic radius of deformation (a few km is required to adequately represent the circulation. Because of flow-topography interactions, bathymetry needs to be represented at these same small scales. Atmospheric conditions used to force these circulation models also need to be known at a similar small spatial resolution (a few km in order to represent orographically controlled winds (coastal jets and katabatic winds. Significantly, time variability of surface winds strongly influences the structure of the mixed layer. Daily, if not more frequent, surface fluxes must be imposed for a realistic surface mixed layer. Sea ice and ice shelves are important components of the coastal circulation. Ice isolates the ocean from exchange with the atmosphere, especially in the winter. Melting and freezing of both sea ice and glacial ice influence salinity and thereby the character of shelf

  15. High affinity, ligand specific uptake of complexed copper-67 by brain tissue incubated in vitro

    International Nuclear Information System (INIS)

    Barnea, A.; Hartter, D.E.

    1987-01-01

    Copper is an essential metal that is highly concentrated in the brain. The blood, the sole source of tissue Cu, contains 16-20 μM Cu, of which >95% is complexed to proteins and 2 was 10 times greater than that of CuAlbumin or Cu(II). Within the range of 0.2-150μM Cu, multiple uptake sites for CuHis were apparent. Increasing the molar ratio of His:Cu had a differential effect on Cu uptake: enhancing uptake at [Cu] 1 μM. Thus, using a His:Cu ratio of 1000, they observed a high affinity process exhibiting saturating and half saturating values of 5 μM and 1.5 μM Cu, respectively; using a His:Cu ratio of 2, they observed a low affinity process exhibiting saturating and half-saturating values of 100 μM and 40 μM Cu, respectively. Both processes required thermic but not metabolic energy, suggestive of facilitated diffusion. Considering the blood brain barrier for proteins, CuHis appears to be the major substrate for Cu uptake by neuronal tissue. They demonstrate the existence of a ligand specific, high affinity (apparent Km about 1.5 μM Cu) uptake process for CuHis in the brain, operative at the physiological concentration range of CuHis and histidine

  16. New Synthesis and Tritium Labeling of a Selective Ligand for Studying High-Affinity γ-Hydroxybutyrate (GHB) Binding Sites

    DEFF Research Database (Denmark)

    Vogensen, Stine B.; Marek, Ales; Bay, Tina

    2013-01-01

    3-Hydroxycyclopent-1-enecarboxylic acid (HOCPCA, 1) is a potent ligand for the high-affinity GHB binding sites in the CNS. An improved synthesis of 1 together with a very efficient synthesis of [3H]-1 is described. The radiosynthesis employs in situ generated lithium trimethoxyborotritide. Screen...

  17. Purification of optical imaging ligand-Cybesin by high-speed counter-current chromatography

    Science.gov (United States)

    Ma, Zhiyong; Ma, Ying; Sun, Xilin; Ye, Yunpeng; Shen, Baozhong; Chen, Xiaoyuan; Ito, Yoichiro

    2010-01-01

    Fluorescent Cybesin (Cypate-Bombesin Peptide Analogue Conjugate) was synthesized from Indocyanine Green (ICG) and the bombesin receptor ligand as a contrast agent for detecting pancreas tumors. However, the LC–MS analysis indicated that the target compound was only a minor component in the reaction mixture. Since preparative HPLC can hardly separate such a small amount of the target compound directly from the original crude reaction mixture without a considerable adsorptive loss onto the solid support, high-speed counter-current chromatography (HSCCC) was used for purification since the method uses no solid support and promises high sample recovery. A suitable two-phase solvent system composed of hexane/ethyl acetate/methanol/methyl t.-butyl ether/acetonitrile/water) at a volume ratio of 1:1:1:4:4:7 was selected based on the partition coefficient of Cybesin (K ≈ 0.9) determined by LC–MS. The separation was performed in two steps using the same solvent system with lower aqueous mobile phase. From 400 mg of the crude reaction mixture the first separation yielded 7.7 mg of fractions containing the target compound at 12.8% purity, and in the second run 1 mg of Cybesin was obtained at purity of 94.0% with a sample recovery rate of over 95% based on the LC–MS Analysis. PMID:20933483

  18. High photoreactivity in a non-fluorescent photocleavable ligands on gold

    Science.gov (United States)

    Robinson, Hans D.; Daengngam, Chalongrat; Stoianov, Stefan V.; Thorpe, Steven B.; Guo, Xi; Santos, Webster L.; Morris, John R.

    2014-03-01

    We report on the photo-patterning of a gold surface functionalized with a self-assembled monolayer of an o-nitrobenzyl-based photocleavable ligand bound to the gold surface with a thiol anchor. We find that the dose of UV light required to induce the photoreaction on gold is very similar to the dose in an alcohol solution, even though many optical phenomena are strongly suppressed on metal surfaces. We attribute this finding to a combination of the large skin depth in gold at UV wavelengths, the high speed of the photoreaction, and the spatially indirect nature of the lowest excited singlet. Any photoreactive compound where the quantum efficiency of fluorescence is sufficiently low, preferably no larger than about 10-5 in the case of gold surfaces, will show a similarly high photoreactivity in metal-surface monolayers. The implications of this result for optically driven self-assembly in plasmonic systems will be discussed. This work was supported by a grant from the National Science Foundation (DMR-106753).

  19. High Thermal Conductivity Polymer Composites for Low Cost Heat Exchangers

    Energy Technology Data Exchange (ETDEWEB)

    None

    2017-08-01

    This factsheet describes a project that identified and evaluated commercially available and state-of-the-art polymer-based material options for manufacturing industrial and commercial non-metallic heat exchangers. A heat exchanger concept was also developed and its performance evaluated with heat transfer modeling tools.

  20. Benchmarking Ligand-Based Virtual High-Throughput Screening with the PubChem Database

    Directory of Open Access Journals (Sweden)

    Mariusz Butkiewicz

    2013-01-01

    Full Text Available With the rapidly increasing availability of High-Throughput Screening (HTS data in the public domain, such as the PubChem database, methods for ligand-based computer-aided drug discovery (LB-CADD have the potential to accelerate and reduce the cost of probe development and drug discovery efforts in academia. We assemble nine data sets from realistic HTS campaigns representing major families of drug target proteins for benchmarking LB-CADD methods. Each data set is public domain through PubChem and carefully collated through confirmation screens validating active compounds. These data sets provide the foundation for benchmarking a new cheminformatics framework BCL::ChemInfo, which is freely available for non-commercial use. Quantitative structure activity relationship (QSAR models are built using Artificial Neural Networks (ANNs, Support Vector Machines (SVMs, Decision Trees (DTs, and Kohonen networks (KNs. Problem-specific descriptor optimization protocols are assessed including Sequential Feature Forward Selection (SFFS and various information content measures. Measures of predictive power and confidence are evaluated through cross-validation, and a consensus prediction scheme is tested that combines orthogonal machine learning algorithms into a single predictor. Enrichments ranging from 15 to 101 for a TPR cutoff of 25% are observed.

  1. Cyclic GMP-AMP Containing Mixed Phosphodiester Linkages Is An Endogenous High Affinity Ligand for STING

    Science.gov (United States)

    Zhang, Xu; Shi, Heping; Wu, Jiaxi; Zhang, Xuewu; Sun, Lijun; Chen, Chuo; Chen, Zhijian J.

    2013-01-01

    The presence of microbial or self DNA in the cytoplasm of mammalian cells is a danger signal detected by the DNA sensor cyclic-GMP-AMP (cGAMP) synthase (cGAS), which catalyzes the production of cGAMP that in turn serves as a second messenger to activate innate immune responses. Here we show that endogenous cGAMP in mammalian cells contains two distinct phosphodiester linkages, one between 2′-OH of GMP and 5′-phosphate of AMP, and the other between 3′-OH of AMP and 5′-phosphate of GMP. This molecule, termed 2′3′-cGAMP, is unique in that it binds to the adaptor protein STING with a much greater affinity than cGAMP molecules containing other combinations of phosphodiester linkages. The crystal structure of STING bound to 2′3′-cGAMP revealed the structural basis of this high-affinity binding and a ligand-induced conformational change in STING that may underlie its activation. PMID:23747010

  2. A highly conserved tyrosine of Tim-3 is phosphorylated upon stimulation by its ligand galectin-9

    International Nuclear Information System (INIS)

    Weyer, Philipp S. van de; Muehlfeit, Michael; Klose, Christoph; Bonventre, Joseph V.; Walz, Gerd; Kuehn, E. Wolfgang

    2006-01-01

    Tim-3 is a member of the TIM family of proteins (T-cell immunoglobulin mucin) involved in the regulation of CD4+ T-cells. Tim-3 is a T H 1-specific type 1 membrane protein and regulates T H 1 proliferation and the development of tolerance. Binding of galectin-9 to the extracellular domain of Tim-3 results in apoptosis of T H 1 cells, but the intracellular pathways involved in the regulatory function of Tim-3 are unknown. Unlike Tim-1, which is expressed in renal epithelia and cancer, Tim-3 has not been described in cells other than neuronal or T-cells. Using RT-PCR we demonstrate that Tim-3 is expressed in malignant and non-malignant epithelial tissues. We have cloned Tim-3 from an immortalized liver cell carcinoma line and identified a highly conserved tyrosine in the intracellular tail of Tim-3 (Y265). We demonstrate that Y265 is specifically phosphorylated in vivo by the interleukin inducible T cell kinase (ITK), a kinase which is located in close proximity of the TIM genes on the allergy susceptibility locus 5q33.3. Stimulation of Tim-3 by its ligand galectin-9 results in increased phosphorylation of Y265, suggesting that this tyrosine residue plays an important role in downstream signalling events regulating T-cell fate. Given the role of TIM proteins in autoimmunity and cancer, the conserved SH2 binding domain surrounding Y265 could represent a possible target site for pharmacological intervention

  3. Secondary heat exchanger design and comparison for advanced high temperature reactor

    International Nuclear Information System (INIS)

    Sabharwall, P.; Kim, E. S.; Siahpush, A.; McKellar, M.; Patterson, M.

    2012-01-01

    Next generation nuclear reactors such as the advanced high temperature reactor (AHTR) are designed to increase energy efficiency in the production of electricity and provide high temperature heat for industrial processes. The efficient transfer of energy for industrial applications depends on the ability to incorporate effective heat exchangers between the nuclear heat transport system and the industrial process heat transport system. This study considers two different types of heat exchangers - helical coiled heat exchanger and printed circuit heat exchanger - as possible options for the AHTR secondary heat exchangers with distributed load analysis and comparison. Comparison is provided for all different cases along with challenges and recommendations. (authors)

  4. Bis-Indole Derivatives for Polysaccharide Compositional Analysis and Chiral Resolution of D-, L-Monosaccharides by Ligand Exchange Capillary Electrophoresis Using Borate-Cyclodextrin as a Chiral Selector

    Directory of Open Access Journals (Sweden)

    Wen-Bin Yang

    2011-02-01

    Full Text Available A series of aldo-bis-indole derivatives (aldo-BINs was prepared by aromatic C-alkylation reactions of aldoses and indole in acetic acid solution. Common monosaccharides such as glucose, mannose, galactose, fucose, xylose, rhamnose, ribose, arabinose and N-acetylglucosamine were smoothly derivatized to form the UV absorbing aldo-BINs. The use of a capillary electrophoretic method to separate these novel aldo-BIN derivatives was established. The capillary electrophoresis conditions were set by using borate buffer (100 mM at high pH (pH 9.0. The limit of determination was assessed to be 25 nM. The enantioseparation of D, L-pairs of aldo-BINs based on chiral ligand-exchange capillary electrophoresis technology was also achieved by using modified hydroxypropyl-β-cyclodextrin as the chiral selector in the presence of borate buffer. This aldose labeling method was applied successfully to the compositional and configurational analysis of saccharides, exemplified by a rapid and efficient method to simultaneously analyze the composition and configuration of saccharides from the medicinal herbs Cordyceps sinensis and Dendrobium huoshanense.

  5. Improved Oxygen Reduction Activity and Durability of Dealloyed PtCox Catalysts for Proton Exchange Membrane Fuel Cells: Strain, Ligand, and Particle Size Effects

    Science.gov (United States)

    Jia, Qingying; Caldwell, Keegan; Strickland, Kara; Ziegelbauer, Joseph M.; Liu, Zhongyi; Yu, Zhiqiang; Ramaker, David E.; Mukerjee, Sanjeev

    2015-01-01

    The development of active and durable catalysts with reduced platinum content is essential for fuel cell commercialization. Herein we report that the dealloyed PtCo/HSC and PtCo3/HSC nanoparticle (NP) catalysts exhibit the same levels of enhancement in oxygen reduction activity (~4-fold) and durability over pure Pt/C NPs. Surprisingly, ex situ high-angle annular dark field scanning transmission electron microscopy (HAADF STEM) shows that the bulk morphologies of the two catalysts are distinctly different: D-PtCo/HSC catalyst is dominated by NPs with solid Pt shells surrounding a single ordered PtCo core; however, the D-PtCo3/HSC catalyst is dominated by NPs with porous Pt shells surrounding multiple disordered PtCo cores with local concentration of Co. In situ X-ray absorption spectroscopy (XAS) reveals that these two catalysts possess similar Pt–Pt and Pt–Co bond distances and Pt coordination numbers (CNs), despite their dissimilar morphologies. The similar activity of the two catalysts is thus ascribed to their comparable strain, ligand, and particle size effects. Ex situ XAS performed on D-PtCo3/HSC under different voltage cycling stage shows that the continuous dissolution of Co leaves behind the NPs with a Pt-like structure after 30k cycles. The attenuated strain and/or ligand effects caused by Co dissolution are presumably counterbalanced by the particle size effects with particle growth, which likely accounts for the constant specific activity of the catalysts along with voltage cycling. PMID:26413384

  6. Implementing high-speed rail in Wisconsin peer exchange.

    Science.gov (United States)

    2009-01-01

    The Wisconsin Department of Transportation Division of Transportation Investment Management hosted : a peer exchange on June 2 -4, 2009 in Milwaukee, Wisconsin. Representatives from four state DOTs and : two freight railroads joined representatives f...

  7. Application of metal foam heat exchangers for a high-performance liquefied natural gas regasification system

    International Nuclear Information System (INIS)

    Kim, Dae Yeon; Sung, Tae Hong; Kim, Kyung Chun

    2016-01-01

    The intermediate fluid vaporizer has wide applications in the regasification of LNG (liquefied natural gas). The heat exchanger performance is one of the main contributors to the thermodynamic and cost effectiveness of the entire LNG regasification system. Within the paper, the authors discuss a new concept for a compact heat exchanger with a micro-cellular structure medium to minimize volume and mass and to increase thermal efficiency. Numerical calculations have been conducted to design a metal-foam filled plate heat exchanger and a shell-and-tube heat exchanger using published experimental correlations. The geometry of both heat exchangers was optimized using the conditions of thermolators in LNG regasification systems. The heat transfer and pressure drop performance was predicted to compare the heat exchangers. The results show that the metal-foam plate heat exchanger has the best performance at different channel heights and mass flow rates of fluid. In the optimized configurations, the metal-foam plate heat exchanger has a higher heat transfer rate and lower pressure drop than the shell-and-tube heat exchanger as the mass flow rate of natural gas is increased. - Highlights: • A metal foam heat exchanger is proposed for LNG regasification system. • Comparison was made with a shell and tube heat exchanger. • Heat transfer and pressure drop characteristics were estimated. • The geometry of both heat exchangers is optimized for thermolators. • It can be used as a compact and high performance thermolators.

  8. Carbon-11-labelling of a novel, trishomocubane-derived, high affinity and selectivity DAT ligand

    International Nuclear Information System (INIS)

    Dolle, F.; Le Helleix, St.; Peyronneau, M.A.; Saba, W.; Tournier, N.; Valette, H.; Banister, S.; Kassiou, M.

    2011-01-01

    Complete text of publication follows: Objectives: Parkinson's disease, schizophrenia, attention deficit disorder and drug abuse are related to abnormalities within the brain's dopaminergic system. The neuronal dopamine transporter (DAT) plays a key role in regulating the synaptic concentration of dopamine and thus dopamine neurotransmission in the brain. Since the DAT can be considered as a marker of the integrity and number of the presynaptic striatal dopamine-producing neurons, considerable efforts have been spent in recent years on the design and development of DAT-selective radioligands for use in Positron Emission Tomography (PET) studies. Notably, the tropane PE2I and its fluorinated analogue LBT-999 were identified as having high affinity and selectivity for the DAT over the norepinephrine transporter (NET) and the serotonin transporter (SERT). Besides tropanes, only a few bicyclic frameworks, e.g. bicyclo[2.2.2]octanes, have delivered compounds with high affinity for the DAT. Recently, novel poly-carbocyclic DAT ligands with selectivity over the NET and the SERT were reported. The lead compound of this series (1, N-methyl-N-(3-fluoro) benzyl-pentacyclo[5.4.0.0 2, 6 .0 3, 10 .0 5, 9 ] undec-8-ylamine, Ki = 1.2 nM, ≥ 8300-fold selectivity over NET and SERT) was selected as a potential candidate for imaging the DAT with PET and isotopically labelled with carbon-11 using [ 11 C]methyl triflate. Methods: The trishomocubane derivatives 1 (reference) and 2 (precursor for labelling with carbon-11) were prepared from commercially available Cookson's diketone in 6 and 7 steps, respectively. Carbon-11 labelling of 1 was performed using a TRACERLab FX-C Pro synthesizer (GEMS) and comprises (1) trapping at -10 C of [ 11 C]MeOTf in acetone (0.4 mL) containing the nor-derivative 2 (0.6-0.9 mg, free base) and aq. 3N NaOH (8 μL); (2) heating at 110 C for 2 min; (3) concentration to dryness and taking up the residue in 1.0 mL of the HPLC mobile phase; (4) purification

  9. The character of resonant charge exchange involving highly excited atoms

    International Nuclear Information System (INIS)

    Kosarim, A. V.; Smirnov, B. M.; Capitelli, M.; Laricchiuta, A.

    2012-01-01

    We study the process of resonant charge exchange involving excited helium atoms with the principal quantum number n = 5 colliding with the helium ion in the ground state in the collision energy range from thermal up to 10 eV. This information may be important for the analysis of planet atmospheres containing helium, in particular, for Jupiter’s atmosphere, but our basic interest is the transition from the quantum to classical description of this process, where, due to large cross sections, evaluations of the cross sections are possible. For the chosen process, quantum theory allows determining the cross section as a result of a tunnel electron transition, while classical theory accounts for over-barrier electron transitions. The classical theory additionally requires effective transitions between states with close energies. The analysis of these transitions for helium with n = 5 shows that electron momenta and their projections are mixed for a part of the states, while for other states, the mixing is absent. A simple criterion to separate such states is given. In addition, the main contribution to the cross section of resonant charge exchange follows from tunnel electron transitions. As a result, the quantum theory is better for calculating the cross sections of resonant charge exchange than the classical one and also allows finding the partial cross sections of resonant charge exchange, while the classical approach gives the cross section of resonant charge exchange in a simple manner with the accuracy of 20%.

  10. Carbon dioxide selective adsorption within a highly stable mixed-ligand Zeolitic Imidazolate Framework

    KAUST Repository

    Huang, Lin; Xue, Ming; Song, Qingshan; Chen, Siru; Pan, Ying; Qiu, Shilun

    2014-01-01

    A new mixed-ligand Zeolitic Imidazolate Framework Zn4(2-mbIm) 3(bIm)5·4H2O (named JUC-160, 2-mbIm = 2-methylbenzimidazole, bIm = benzimidazole and JUC = Jilin University China) was synthesized with a solvothermal reaction of Zn(NO3) 2·6H2O, b

  11. Preparation of inorganic ion exchangers with high selectivity for lithium isotopes

    International Nuclear Information System (INIS)

    Oi, Takao

    2004-01-01

    Development of ion exchangers that show large lithium isotope effects is hoped for to establish highly efficient chromatographic processes of lithium isotope separation. In this paper, preparation, characterization, ion exchange properties, and lithium isotope selectivity of inorganic materials that have been and still are being studied by my research group at Sophia University are reviewed. They include manganese oxides-based ion exchangers, antimonic acids and titanium/zirconium phosphates-based ion exchangers. As a result, the lithium isotope separation effects that were one order of magnitude larger than those of organic ion exchangers were obtained. Some inorganic ion exchangers were found to show ion exchange rates more than comparable to those of organic ones. (author)

  12. New Synthesis and Tritium Labeling of a Selective Ligand for Studying High-affinity γ-Hydroxybutyrate (GHB) Binding Sites

    Science.gov (United States)

    Vogensen, Stine B.; Marek, Aleš; Bay, Tina; Wellendorph, Petrine; Kehler, Jan; Bundgaard, Christoffer; Frølund, Bente; Pedersen, Martin H.F.; Clausen, Rasmus P.

    2013-01-01

    3-Hydroxycyclopent-1-enecarboxylic acid (HOCPCA, 1) is a potent ligand for the high-affinity GHB binding sites in the CNS. An improved synthesis of 1 together with a very efficient synthesis of [3H]-1 is described. The radiosynthesis employs in situ generated lithium trimethoxyborotritide. Screening of 1 against different CNS targets establishes a high selectivity and we demonstrate in vivo brain penetration. In vitro characterization of [3H]-1 binding shows high specificity to the high-affinity GHB binding sites. PMID:24053696

  13. High-capacity, selective solid sequestrants for innovative chemical separation: Inorganic ion exchange approach

    International Nuclear Information System (INIS)

    Bray, L.

    1995-01-01

    The approach of this task is to develop high-capacity, selective solid inorganic ion exchangers for the recovery of cesium and strontium from nuclear alkaline and acid wastes. To achieve this goal, Pacific Northwest Laboratories (PNL) is collaborating with industry and university participants to develop high capacity, selective, solid ion exchangers for the removal of specific contaminants from nuclear waste streams

  14. Cyclic high temperature heat storage using borehole heat exchangers

    Science.gov (United States)

    Boockmeyer, Anke; Delfs, Jens-Olaf; Bauer, Sebastian

    2016-04-01

    The transition of the German energy supply towards mainly renewable energy sources like wind or solar power, termed "Energiewende", makes energy storage a requirement in order to compensate their fluctuating production and to ensure a reliable energy and power supply. One option is to store heat in the subsurface using borehole heat exchangers (BHEs). Efficiency of thermal storage is increasing with increasing temperatures, as heat at high temperatures is more easily injected and extracted than at temperatures at ambient levels. This work aims at quantifying achievable storage capacities, storage cycle times, injection and extraction rates as well as thermal and hydraulic effects induced in the subsurface for a BHE storage site in the shallow subsurface. To achieve these aims, simulation of these highly dynamic storage sites is performed. A detailed, high-resolution numerical simulation model was developed, that accounts for all BHE components in geometrical detail and incorporates the governing processes. This model was verified using high quality experimental data and is shown to achieve accurate simulation results with excellent fit to the available experimental data, but also leads to large computational times due to the large numerical meshes required for discretizing the highly transient effects. An approximate numerical model for each type of BHE (single U, double U and coaxial) that reduces the number of elements and the simulation time significantly was therefore developed for use in larger scale simulations. The approximate numerical model still includes all BHE components and represents the temporal and spatial temperature distribution with a deviation of less than 2% from the fully discretized model. Simulation times are reduced by a factor of ~10 for single U-tube BHEs, ~20 for double U-tube BHEs and ~150 for coaxial BHEs. This model is then used to investigate achievable storage capacity, injection and extraction rates as well as induced effects for

  15. Improved spacers for high temperature gas-cooled heat exchangers

    Energy Technology Data Exchange (ETDEWEB)

    Nordstroem, L A [Swiss Federal Institute for Reactor Research, Wuerenlingen (Switzerland)

    1984-07-01

    Experimental and analytical investigations in the field of heat exchanger thermohydraulics have been performed at EIR for many years, Basic studies have been carried out on heat transfer and pressure loss for tube bundles of different geometries and tube surfaces. As a part of this overall R+D programme for heat exchangers, investigations have been carried out on spacer pressure loss in bundles with longitudinal flow. An analytical spacer pressure loss model was developed which could handle different types of subchannel within the bundle. The model has been evaluated against experiments, using about 25 spacers of widely differing geometries. In a gas-cooled reactor it is important to keep the pressure loss over the primary circuit heat exchangers to a minimum. In exchangers with grid spacers these contribute a significant proportion of the overall bundle losses. For example, in the HHT Recuperator, with a shell-side pressure loss of 3.5 % of the inlet pressure, the spacers cause about one half of this loss. Reducing the loss to, say, 2.5 % results in an overall increase in plant efficiency by more than 1 % - a significant improvement Preliminary analysis identified 5 geometries in particular which were chosen for experimental evaluation as part of a joint project with the SULZER Company, to develop a low pressure-loss spacer for HHT heat exchangers (longitudinal counter-flow He/He and He/H{sub 2}O designs). The aim of the tests was to verify the low pressure-loss characteristics of these spacer grid types, as well as the quality of the results calculated by the computer code analytical model. The experimental and analytical results are compared in this report.

  16. Fe- and Cu-complex formation with artificial ligands investigated by ultra-high resolution Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS: Implications for natural metal-organic complex studies

    Directory of Open Access Journals (Sweden)

    Hannelore Waska

    2016-07-01

    Full Text Available In recent years, electrospray-ionization mass spectrometry (ESI-MS has been increasingly used to complement the bulk determination of metal-ligand equilibria, for example via competitive ligand exchange-adsorptive cathodic stripping voltammetry (CLE-ACSV. However, ESI-MS speciation analyses may be impacted by instrumental artefacts such as reduction reactions, fragmentation, and adduct formation at the ESI source, changes in the ionization efficiencies of the detected species in relation to sample matrix, and peak overlaps in response to increasing sample complexity. In our study, equilibria of the known artificial ligands citrate, ethylenediaminetetraacetic acid (EDTA, 1-nitroso-2-naphthol (NN, and salicylaldoxime (SA with iron (Fe and copper (Cu were investigated by ultra-high resolution ESI-MS, Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS, under a variety of sample matrix and ionization settings. The acquired mass spectra were compared with metal-ligand equilibrium data from the literature as well as an adapted speciation model. Overall, the mass spectra produced representative species mentioned in previous reports and predicted by the speciation calculations, such as Fe(Cit, Cu(Cit2, Fe(EDTA, Cu(EDTA, Fe(NN3, and Cu(SA2. The analyses furthermore revealed new species which had been hypothesized but not measured directly using other methods, for example ternary complexes of citrate with Fe and Cu, Cu(SA monomers, and the dimer Fe(SA2. Finally, parallel measurements of a Cu+SA calibration series and a Cu+SA+EDTA competition series indicated that FT-ICR-MS can produce linear responses and low detection limits analogous to those of ACSV. We propose that ultra-high resolution FT-ICR-MS can be used as a representative tool to study interactions of trace metals with artificial as well as natural, unknown ligands at the molecular level.

  17. Affinity chromatography with pseudobiospecific ligands on high-performance supports for purification of proteins of biotechnological interest

    Directory of Open Access Journals (Sweden)

    N.B. Iannucci

    2003-03-01

    Full Text Available High-performance affinity matrices were obtained by attaching pseudobiospecific ligands to hollow-fibre membranes. The neutral protease contained in FlavourzymeTM was purified to homogeneity with Yellow 4R-HE affinity hollow-fibre membranes. Immobilisation of Red HE-3B allowed purification of a milk-clotting enzyme obtained by solid-state culture of Mucor bacilliformis. Copper immobilisation through iminodiacetic acid allowed fractionation of Biocon Bioconcentrated PlusTM to separate the pectinesterase-containing fraction. The productivity of the developed processes - 1900, 94 and 750 U/ml.min, respectively - was 10- to 15-fold higher than that achieved with the same ligands immobilised on agarose-based soft gels, mainly due to the shortening of the purification processes.

  18. Biophysical and physicochemical methods differentiate highly ligand-efficient human D-amino acid oxidase inhibitors.

    Science.gov (United States)

    Lange, Jos H M; Venhorst, Jennifer; van Dongen, Maria J P; Frankena, Jurjen; Bassissi, Firas; de Bruin, Natasja M W J; den Besten, Cathaline; de Beer, Stephanie B A; Oostenbrink, Chris; Markova, Natalia; Kruse, Chris G

    2011-10-01

    Many early drug research efforts are too reductionist thereby not delivering key parameters such as kinetics and thermodynamics of target-ligand binding. A set of human D-Amino Acid Oxidase (DAAO) inhibitors 1-6 was applied to demonstrate the impact of key biophysical techniques and physicochemical methods in the differentiation of chemical entities that cannot be adequately distinguished on the basis of their normalized potency (ligand efficiency) values. The resulting biophysical and physicochemical data were related to relevant pharmacodynamic and pharmacokinetic properties. Surface Plasmon Resonance data indicated prolonged target-ligand residence times for 5 and 6 as compared to 1-4, based on the observed k(off) values. The Isothermal Titration Calorimetry-derived thermodynamic binding profiles of 1-6 to the DAAO enzyme revealed favorable contributions of both ΔH and ΔS to their ΔG values. Surprisingly, the thermodynamic binding profile of 3 elicited a substantially higher favorable contribution of ΔH to ΔG in comparison with the structurally closely related fused bicyclic acid 4. Molecular dynamics simulations and free energy calculations of 1, 3, and 4 led to novel insights into the thermodynamic properties of the binding process at an atomic level and in the different thermodynamic signatures of 3 and 4. The presented holistic approach is anticipated to facilitate the identification of compounds with best-in-class properties at an early research stage. Copyright © 2011 Elsevier Masson SAS. All rights reserved.

  19. Hanford high level waste: Sample Exchange/Evaluation (SEE) Program

    International Nuclear Information System (INIS)

    King, A.G.

    1994-08-01

    The Pacific Northwest Laboratory (PNL)/Analytical Chemistry Laboratory (ACL) and the Westinghouse Hanford Company (WHC)/Process Analytical Laboratory (PAL) provide analytical support services to various environmental restoration and waste management projects/programs at Hanford. In response to a US Department of Energy -- Richland Field Office (DOE-RL) audit, which questioned the comparability of analytical methods employed at each laboratory, the Sample Exchange/Exchange (SEE) program was initiated. The SEE Program is a selfassessment program designed to compare analytical methods of the PAL and ACL laboratories using sitespecific waste material. The SEE program is managed by a collaborative, the Quality Assurance Triad (Triad). Triad membership is made up of representatives from the WHC/PAL, PNL/ACL, and WHC Hanford Analytical Services Management (HASM) organizations. The Triad works together to design/evaluate/implement each phase of the SEE Program

  20. Process Heat Exchanger Options for the Advanced High Temperature Reactor

    Energy Technology Data Exchange (ETDEWEB)

    Piyush Sabharwall; Eung Soo Kim; Michael McKellar; Nolan Anderson

    2011-06-01

    The work reported herein is a significant intermediate step in reaching the final goal of commercial-scale deployment and usage of molten salt as the heat transport medium for process heat applications. The primary purpose of this study is to aid in the development and selection of the required heat exchanger for power production and process heat application, which would support large-scale deployment.

  1. Process Heat Exchanger Options for Fluoride Salt High Temperature Reactor

    International Nuclear Information System (INIS)

    Sabharwall, Piyush; Kim, Eung Soo; McKellar, Michael; Anderson, Nolan

    2011-01-01

    The work reported herein is a significant intermediate step in reaching the final goal of commercial-scale deployment and usage of molten salt as the heat transport medium for process heat applications. The primary purpose of this study is to aid in the development and selection of the required heat exchanger for power production and process heat application, which would support large-scale deployment.

  2. Process Heat Exchanger Options for Fluoride Salt High Temperature Reactor

    Energy Technology Data Exchange (ETDEWEB)

    Piyush Sabharwall; Eung Soo Kim; Michael McKellar; Nolan Anderson

    2011-04-01

    The work reported herein is a significant intermediate step in reaching the final goal of commercial-scale deployment and usage of molten salt as the heat transport medium for process heat applications. The primary purpose of this study is to aid in the development and selection of the required heat exchanger for power production and process heat application, which would support large-scale deployment.

  3. Fabrication of High-Temperature Heat Exchangers by Plasma Spraying Exterior Skins on Nickel Foams

    Science.gov (United States)

    Hafeez, P.; Yugeswaran, S.; Chandra, S.; Mostaghimi, J.; Coyle, T. W.

    2016-06-01

    Thermal-sprayed heat exchangers were tested at high temperatures (750 °C), and their performances were compared to the foam heat exchangers made by brazing Inconel sheets to their surface. Nickel foil was brazed to the exterior surface of 10-mm-thick layers of 10 and 40 PPI nickel foam. A plasma torch was used to spray an Inconel coating on the surface of the foil. A burner test rig was built to produce hot combustion gases that flowed over exposed face of the heat exchanger. Cooling air flowed through the foam heat exchanger at rates of up to 200 SLPM. Surface temperature and air inlet/exit temperature were measured. Heat transfer to air flowing through the foam was significantly higher for the thermally sprayed heat exchangers than for the brazed heat exchangers. On an average, thermally sprayed heat exchangers show 36% higher heat transfer than conventionally brazed foam heat exchangers. At low flow rates, the convective resistance is large (~4 × 10-2 m2 K/W), and the effect of thermal contact resistance is negligible. At higher flow rates, the convective resistance decreases (~2 × 10-3 m2 K/W), and the lower contact resistance of the thermally sprayed heat exchanger provides better performance than the brazed heat exchangers.

  4. Design, Synthesis, and Biological Evaluation of Small, High-Affinity Siglec-7 Ligands: Toward Novel Inhibitors of Cancer Immune Evasion.

    Science.gov (United States)

    Prescher, Horst; Frank, Martin; Gütgemann, Stephan; Kuhfeldt, Elena; Schweizer, Astrid; Nitschke, Lars; Watzl, Carsten; Brossmer, Reinhard

    2017-02-09

    Natural killer cells are able to directly lyse tumor cells, thereby participating in the immune surveillance against cancer. Unfortunately, many cancer cells use immune evasion strategies to avoid their eradication by the immune system. A prominent escape strategy of malignant cells is to camouflage themselves with Siglec-7 ligands, thereby recruiting the inhibitory receptor Siglec-7 expressed on the NK cell surface which subsequently inhibits NK-cell-mediated lysis. Here we describe the synthesis and evaluation of the first, high-affinity low molecular weight Siglec-7 ligands to interfere with cancer cell immune evasion. The compounds are Sialic acid derivatives and bind with low micromolar K d values to Siglec-7. They display up to a 5000-fold enhanced affinity over the unmodified sialic acid scaffold αMe Neu5Ac, the smallest known natural Siglec-7 ligand. Our results provide a novel immuno-oncology strategy employing natural immunity in the fight against cancers, in particular blocking Siglec-7 with low molecular weight compounds.

  5. Synthesis of mixed-ligand cobalt complexes and their applications in high cis-1,4-selective butadiene polymerization

    KAUST Repository

    Liu, Wen

    2015-08-03

    Incomplete oxidation of (N-di-tert-butylphosphino)-6-(2-methyl-2’H-benzoimidazole)-2-aminepyridine dichlorocobalt (PN3CoCl2) in DMF results in a unique co-crystal I formed with three parts including DMF, unit A and unit B complex with Co1 and Co2, respectively, (PN3 ligand in unit A: (N-di-tert-butylphosphino)-6-(2’-methyl-2’H-benzoimidazole)-2-aminepyridine, and O=PN3 ligand in unit B: (N-di-tert-butylphosphinoxide)-6-(2’-methyl-2’H-benzoimidazole)-2-aminepyridine) with 1:1:1 molar ratio. Co1 and Co2 complexes both display a five-coordinated distorted-square-pyramidal geometry around the metal center. The Co1 center is coordinated with PN3 ligand via two N atoms from pyridine, benzoimidazole moiety as well as one P atom, and the Co2 center is coordinated with the oxidized ligandO=PN3 via two N atoms from pyridine, benzoimidazole moiety as well as one O atom from DMF molecule, while the oxidized phosphine moiety (O=P) being excluded from the coordination sphere. Activated with AlEt2Cl, the co-crystallized complexes I are able to actively convert butadiene to polybutadiene, affording cis-1,4 polybutadiene with cis-1,4 unit up to 95.5-97.8% and number average molecular weight of cal. 105g/mol. The high cis-1,4 selectivity and monomodal GPC curve of resultant polymer imply that the identical active species generated from two distinctive cobalt centers.

  6. Synthesis of mixed-ligand cobalt complexes and their applications in high cis-1,4-selective butadiene polymerization

    KAUST Repository

    Liu, Wen; Pan, Weijing; Wang, Peng; Li, Wei; Mu, Jingshan; Weng, Gengsheng; Jia, Xiaoyu; Gong, Dirong; Huang, Kuo-Wei

    2015-01-01

    Incomplete oxidation of (N-di-tert-butylphosphino)-6-(2-methyl-2’H-benzoimidazole)-2-aminepyridine dichlorocobalt (PN3CoCl2) in DMF results in a unique co-crystal I formed with three parts including DMF, unit A and unit B complex with Co1 and Co2, respectively, (PN3 ligand in unit A: (N-di-tert-butylphosphino)-6-(2’-methyl-2’H-benzoimidazole)-2-aminepyridine, and O=PN3 ligand in unit B: (N-di-tert-butylphosphinoxide)-6-(2’-methyl-2’H-benzoimidazole)-2-aminepyridine) with 1:1:1 molar ratio. Co1 and Co2 complexes both display a five-coordinated distorted-square-pyramidal geometry around the metal center. The Co1 center is coordinated with PN3 ligand via two N atoms from pyridine, benzoimidazole moiety as well as one P atom, and the Co2 center is coordinated with the oxidized ligandO=PN3 via two N atoms from pyridine, benzoimidazole moiety as well as one O atom from DMF molecule, while the oxidized phosphine moiety (O=P) being excluded from the coordination sphere. Activated with AlEt2Cl, the co-crystallized complexes I are able to actively convert butadiene to polybutadiene, affording cis-1,4 polybutadiene with cis-1,4 unit up to 95.5-97.8% and number average molecular weight of cal. 105g/mol. The high cis-1,4 selectivity and monomodal GPC curve of resultant polymer imply that the identical active species generated from two distinctive cobalt centers.

  7. Domain interplay in the urokinase receptor. Requirement for the third domain in high affinity ligand binding and demonstration of ligand contact sites in distinct receptor domains

    DEFF Research Database (Denmark)

    Behrendt, N; Ronne, E; Dano, K

    1996-01-01

    by chemical cross-linking, but quantitative binding/competition studies showed that the apparent ligand affinity was 100- to 1000-fold lower than that of the intact suPAR. This loss of affinity was comparable with the loss found after cleavage between the first domain (D1) and D(2 + 3), using chymotrypsin...

  8. Using a Potassium Acetate Solution for Cooling High Pressure Hydrogen in a Prototype Heat Exchanger

    DEFF Research Database (Denmark)

    Rothuizen, Erasmus Damgaard; Abel, M.; Rokni, Masoud

    2011-01-01

    is to be delivered at high pressure a heat exchanger was designed and constructed. The paper presents a detailed study of construction of the heat exchanger which has been tested and compared to theory to predict and verify its performance. The method presented by Nellis and Klein for laminar flow in annulus tubes...

  9. Relativistic one-boson-exchange model and elastic electron-deuteron scattering at high momentum transfer

    International Nuclear Information System (INIS)

    Hummel, E.; Tjon, J.A.

    1989-01-01

    Using the one-boson-exchange model a relativistic covariant analysis is carried out of the elastic electromagnetic form factors of the deuteron including the ρπγ and ωεγ mesonic-exchange-current contributions. The theoretical predictions are compared with the recent experimental data at high momentum transfer

  10. Rates of nickel(II) capture from complexes with NTA, EDDA, and related tetradentate chelating agents by the hexadentate chelating agents EDTA and CDTA: Evidence of a "semijunctive" ligand exchange pathway

    Science.gov (United States)

    Boland, Nathan E.; Stone, Alan T.

    2017-09-01

    Many siderophores and metallophores produced by soil organisms, as well as anthropogenic chelating agent soil amendments, rely upon amine and carboxylate Lewis base groups for metal ion binding. UV-visible spectra of metal ion-chelating agent complexes are often similar and, as a consequence, whole-sample absorbance measurements are an unreliable means of monitoring the progress of exchange reactions. In the present work, we employ capillary electrophoresis to physically separate Ni(II)-tetradentate chelating agent complexes (NiL) from Ni(II)-hexadentate chelating agent complexes (NiY) prior to UV detection, such that progress of the reaction NiL + Y → NiY + L can be conveniently monitored. Rates of ligand exchange for Ni(II) are lower than for other +II transition metal ions. Ni(II) speciation in environmental media is often under kinetic rather than equilibrium control. Nitrilotriacetic acid (NTA), with three carboxylate groups all tethered to a central amine Lewis base group, ethylenediamine-N,N‧-diacetic acid (EDDA), with carboxylate-amine-amine-carboxylate groups arranged linearly, plus four structurally related compounds, are used as tetradentate chelating agents. Ethylenediaminetetraacetic acid (EDTA) and the structurally more rigid analog trans-cyclohexaneethylenediaminetetraacetic acid (CDTA) are used as hexadentate chelating agents. Effects of pH and reactant concentration are explored. Ni(II) capture by EDTA was consistently more than an order of magnitude faster than capture by CDTA, and too fast to quantify using our capillary electrophoresis-based technique. Using NiNTA as a reactant, Ni(II) capture by CDTA is independent of CDTA concentration and greatly enhanced by a proton-catalyzed pathway at low pH. Using NiEDDA as reactant, Ni(II) capture by CDTA is first order with respect to CDTA concentration, and the contribution from the proton-catalyzed pathway diminished by CDTA protonation. While the convention is to assign either a disjunctive

  11. Recycle attuned catalytic exchange (RACE) for reliable and low inventory processing of highly tritiated water

    International Nuclear Information System (INIS)

    Iseli, M.; Schaub, M.; Ulrich, D.

    1992-01-01

    The detritiation of highly tritiated water by liquid phase catalytic exchange needs dilution of the feed with water to tritium concentrations suitable for catalyst and safety rules and to assure flow rates large enough for wetting the catalyst. Dilution by recycling detritiated water from within the exchange process has three advantages: the amount and concentration of the water for dilution is controlled within the exchange process, there is no additional water load to processes located downstream RACE, and the ratio of gas to liquid flow rates in the exchange column could be adjusted by using several recycles differing in amount and concentration to avoid an excessively large number of theoretical separation stages. In this paper, the flexibility of the recycle attuned catalytic exchange (RACE) and its effect on the cryogenic distillation are demonstrated for the detritiation of the highly tritiated water from a tritium breeding blanket

  12. Enhanced exchange bias in MnN/CoFe bilayers after high-temperature annealing

    Science.gov (United States)

    Dunz, M.; Schmalhorst, J.; Meinert, M.

    2018-05-01

    We report an exchange bias of more than 2700 Oe at room temperature in MnN/CoFe bilayers after high-temperature annealing. We studied the dependence of exchange bias on the annealing temperature for different MnN thicknesses in detail and found that samples with tMnN > 32nm show an increase of exchange bias for annealing temperatures higher than TA = 400 °C. Maximum exchange bias values exceeding 2000 Oe with reasonably small coercive fields around 600 Oe are achieved for tMnN = 42, 48 nm. The median blocking temperature of those systems is determined to be 180 °C after initial annealing at TA = 525 °C. X-ray diffraction measurements and Auger depth profiling show that the large increase of exchange bias after high-temperature annealing is accompanied by strong nitrogen diffusion into the Ta buffer layer of the stacks.

  13. Hydrophobic and hydrophilic nanosheet catalysts with high catalytic activity and recycling stability through control of the outermost ligand

    Science.gov (United States)

    Ko, Younji; Kim, Donghee; Kwon, Cheong Hoon; Cho, Jinhan

    2018-04-01

    In this study, we introduce hydrophobic and hydrophilic graphene oxide nanosheet (GON) catalysts prepared by consecutive ligand replacement of hydrophobically stabilized magnetic and catalytic nanoparticles (NPs); it exhibits high catalytic activity, fast magnetic response, and good dispersion in both nonpolar and aqueous media, allowing high loading amount of magnetic and catalytic NPs onto GON sheets. More specifically, these GON catalysts showed a high product yield of 66-99% and notable recyclability (93% of the initial product yield after 10 reaction cycles) in a Suzuki-Miyaura reaction in nonpolar media, outperforming the performance of the conventional hydrophilic GON catalysts. Additional coating of a hydrophilic layer onto GON catalysts also showed the notable performance (product yield ∼99%) in catalytic reactions performed in aqueous media. Given that ligand-controlled catalytic NPs adsorbed onto 2D nanosheets can be used as hydrophobic and hydrophilic stabilizers as well as catalysts, our approach can provide a tool for developing and designing 2D-nanosheet catalysts with high performance in nonpolar and polar media.

  14. Computer aided drug discovery of highly ligand efficient, low molecular weight imidazopyridine analogs as FLT3 inhibitors.

    Science.gov (United States)

    Frett, Brendan; McConnell, Nick; Smith, Catherine C; Wang, Yuanxiang; Shah, Neil P; Li, Hong-yu

    2015-04-13

    The FLT3 kinase represents an attractive target to effectively treat AML. Unfortunately, no FLT3 targeted therapeutic is currently approved. In line with our continued interests in treating kinase related disease for anti-FLT3 mutant activity, we utilized pioneering synthetic methodology in combination with computer aided drug discovery and identified low molecular weight, highly ligand efficient, FLT3 kinase inhibitors. Compounds were analyzed for biochemical inhibition, their ability to selectively inhibit cell proliferation, for FLT3 mutant activity, and preliminary aqueous solubility. Validated hits were discovered that can serve as starting platforms for lead candidates. Copyright © 2015 Elsevier Masson SAS. All rights reserved.

  15. Preliminary study on high temperature heat exchanger for nuclear steel making

    Energy Technology Data Exchange (ETDEWEB)

    Mori, Y [Tokyo Inst. of Tech. (Japan); Ikegami, H

    1975-03-01

    In the high temperature heat exchanger as well as the steam reformer, several technical problems should be solved before realizing a nuclear plant complex for iron and steel making. Research has been carried out on heat exchanger between helium and steam, hydrogen permeation through super alloys, hydrogen removal using a titanium sponge, and creep and carburization performance of super alloys. The primary coolant used is helium having a pressure of approximately 12 kg/cm/sup 2/G and a temperature of approximately 1100/sup 0/C measured at the inlet of the high temperature heat exchanger, i.e., the test section. Steam, hydrogen and carbon monoxide are used as secondary coolants.

  16. Photoaffinity labeling of mammalian α1-adrenergic receptors: identification of the ligand binding subunit with a high affinity radioiodinated probe

    International Nuclear Information System (INIS)

    Leeb-Lundberg, L.M.F.; Dickinson, K.E.J.; Heald, S.L.

    1984-01-01

    A description is given of the synthesised and characterization of a novel high affinity radioiodinated α 1 -adrenergic receptor photoaffinity probe, 4-amino-6,7-dimethoxy-2-[4-[5-(4-azido-3-[ 125 I]iodophenyl)pentanoyl]-1-piperazinyl] quinazoline. In the absence of light, this ligand binds with high affinity (K/sub d/ = 130 pm) in a reverisble and saturable manner to sites in rat hepatic plasma membranes. The binding is stereoselective and competitively inhibited by adrenergic agonists and antagonists with an α 1 -adrenergic specificity. Upon photolysis, this ligand incorporates irreversibly into plasma membranes prepared from several mammalian tissues including rat liver, rat, guinea pig, and rabbit spleen, rabbit lung, and rabbit aorta vascular smooth muscle cells, also with typical α 1 -adrenergic specificity. Autoradiograms of such membrane samples subjected to sodium dodecyl sulfate-polyacrylamide gel electrophoresis reveal a major specifically labeled polypeptide at M/sub 4/ = 78,000-85,000, depending on the tissue used, in addition to some lower molecular weight peptides. Protease inhibitors, in particular EDTA, a metalloprotease inhibitor, dramatically increases the predominance of the M/sub r/ = 78,000-85,000 polypeptide while attenuating the labeling of the lower molecular weight bands. This new high affinity radioiodinated photoaffinity probe should be of great value for the molecular characterization of the α 1 -adrenergic receptor

  17. GluVII:06--a highly conserved and selective anchor point for non-peptide ligands in chemokine receptors

    DEFF Research Database (Denmark)

    Rosenkilde, Mette M; Schwartz, Thue W

    2006-01-01

    ligands and that the two peripheral chemical moieties of the ligands from this central point in the receptor structure explore each of the two halves of the main ligand binding pocket. It is envisioned that knowledge of this binding mode can be exploited in structure-based discovery and design of novel...

  18. Laboratory automation of high-quality and efficient ligand-binding assays for biotherapeutic drug development.

    Science.gov (United States)

    Wang, Jin; Patel, Vimal; Burns, Daniel; Laycock, John; Pandya, Kinnari; Tsoi, Jennifer; DeSilva, Binodh; Ma, Mark; Lee, Jean

    2013-07-01

    Regulated bioanalytical laboratories that run ligand-binding assays in support of biotherapeutics development face ever-increasing demand to support more projects with increased efficiency. Laboratory automation is a tool that has the potential to improve both quality and efficiency in a bioanalytical laboratory. The success of laboratory automation requires thoughtful evaluation of program needs and fit-for-purpose strategies, followed by pragmatic implementation plans and continuous user support. In this article, we present the development of fit-for-purpose automation of total walk-away and flexible modular modes. We shared the sustaining experience of vendor collaboration and team work to educate, promote and track the use of automation. The implementation of laboratory automation improves assay performance, data quality, process efficiency and method transfer to CRO in a regulated bioanalytical laboratory environment.

  19. Kinetics of the high temperature oxygen exchange reaction on 238PuO2 powder

    International Nuclear Information System (INIS)

    Whiting, Christofer E.; Du, Miting; Felker, L. Kevin; Wham, Robert M.; Barklay, Chadwick D.; Kramer, Daniel P.

    2015-01-01

    Oxygen exchange reactions performed on PuO 2 suggest the reaction is influenced by at least three mechanisms: an internal chemical reaction, surface mobility of active species/defects, and surface exchange of gaseous oxygen with lattice oxygen. Activation energies for the surface mobility and internal chemical reaction are presented. Determining which mechanism is dominant appears to be a complex function including at least specific surface area and temperature. Thermal exposure may also impact the oxygen exchange reaction by causing reductions in the specific surface area of PuO 2 . Previous CeO 2 surrogate studies exhibit similar behavior, confirming that CeO 2 is a good qualitative surrogate for PuO 2 , in regards to the oxygen exchange reaction. Comparison of results presented here with previous work on the PuO 2 oxygen exchange reaction allows complexities in the previous work to be explained. These explanations allowed new conclusions to be drawn, many of which confirm the conclusions presented here. - Highlights: • PuO 2 Oxygen exchange kinetics can be influenced by at least 3 different mechanisms. • An internal chemical reaction controls the rate at high temperature and large SSA. • Surface mobility and surface exchange influence rate at lower temperatures and SSA. • Exchange temperatures may alter SSA and make data difficult to interpret.

  20. Americium Separations from High-Salt Solutions Using Anion Exchange

    International Nuclear Information System (INIS)

    Barr, Mary E.; Jarvinen, Gordon D.; Stark, Peter C.; Chamberlin, Rebecca M.; Bartsch, Richard A.; Zhang, Z.Y.; Zhao, W.

    2001-01-01

    The aging of the US nuclear stockpile presents a number of challenges, including the increasing radioactivity of plutonium residues due to the ingrowth of 241 Am from the β-decay of 241 Pu. We investigated parameters that affect the sorption of Am onto anion-exchange resins from concentrated effluents derived from nitric acid processing of plutonium residues. These postevaporator wastes are nearly saturated solutions of acidic nitrate salts, and americium removal is complicated by physical factors, such as solution viscosity and particulates, as well as by the presence of large quantities of competing metals and acid. Single- and double-contact batch distribution coefficients for americium and neodymium from simple and complex surrogate solutions are presented. Varied parameters include the nitrate salt concentration and composition and the nitric acid concentration. We find that under these extremely concentrated conditions, Am(III) removal efficiencies can surpass 50% per contact. Distribution coefficients for both neodymium and americium are insensitive to solution acidity and appear to be driven primarily by low water activities of the solutions

  1. Highly conductive side chain block copolymer anion exchange membranes.

    Science.gov (United States)

    Wang, Lizhu; Hickner, Michael A

    2016-06-28

    Block copolymers based on poly(styrene) having pendent trimethyl styrenylbutyl ammonium (with four carbon ring-ionic group alkyl linkers) or benzyltrimethyl ammonium groups with a methylene bridge between the ring and ionic group were synthesized by reversible addition-fragmentation radical (RAFT) polymerization as anion exchange membranes (AEMs). The C4 side chain polymer showed a 17% increase in Cl(-) conductivity of 33.7 mS cm(-1) compared to the benzyltrimethyl ammonium sample (28.9 mS cm(-1)) under the same conditions (IEC = 3.20 meq. g(-1), hydration number, λ = ∼7.0, cast from DMF/1-propanol (v/v = 3 : 1), relative humidity = 95%). As confirmed by small angle X-ray scattering (SAXS), the side chain block copolymers with tethered ammonium cations showed well-defined lamellar morphologies and a significant reduction in interdomain spacing compared to benzyltrimethyl ammonium containing block copolymers. The chemical stabilities of the block copolymers were evaluated under severe, accelerated conditions, and degradation was observed by (1)H NMR. The block copolymer with C4 side chain trimethyl styrenylbutyl ammonium motifs displayed slightly improved stability compared to that of a benzyltrimethyl ammonium-based AEM at 80 °C in 1 M NaOD aqueous solution for 30 days.

  2. Characterisation of powerful antioxidants and synthetic iron ligands, as protective agents against oxidative damages, using new high throughput screening assays

    International Nuclear Information System (INIS)

    Meunier, St.

    2002-12-01

    This work was devoted to the development of pertinent high throughput screening assays in the aim of studying oxidative stress. Three screening assays have been developed for the evaluation of protective agents toward ROS generated by gamma irradiation, UV or by a Fenton-like system. 24 natural extracts and a library of 120 pure compounds, containing among the most powerful antioxidants known to date, have been readily studied using, these new techniques. We found that two pulvinic acid derivatives possess excellent protective properties, and especially a pigment of fungus named norbadione A. Beyond its in vitro activity, this molecule displays remarkable biological properties. In the aim of studying an alternative pathway of protection against oxidation induced by iron, ligands able to modify the redox properties of this metal, have been synthesised. We have developed a parallel synthesis allowing the variation of the architecture, denticity, chelating moieties and hydrophobicity of iron chelates. Using this strategy, 47 potential Fe(III) ligands were obtained. Their protective capacities have been studied using a fourth screening assay, demonstrating the effectiveness of some ligands. Finally, the immunoassay technique called SPI-RAD has been used in order to study a particular consequence of drastic oxidative stress, namely covalent crosslinks between proteins. Our results demonstrate that these linkages occur in the presence of metals (FeII or CuII) and hydrogen peroxide, as well as in the presence of NO . radical. Moreover, it has been demonstrated that tyrosines residues and disulfide bridges play an important role in these phenomena. (author)

  3. Structure, equilibrium and ligand exchange dynamics in the binary and ternary dioxouranium(VI)-ethylenediamine-N,N'-diacetic acid-fluoride system: A potentiometric, NMR and X-ray crystallographic study.

    Science.gov (United States)

    Palladino, Giuseppe; Szabó, Zoltán; Fischer, Andreas; Grenthe, Ingmar

    2006-11-21

    The structure, thermodynamics and kinetics of the binary and ternary uranium(VI)-ethylenediamine-N,N'-diacetate (in the following denoted EDDA) fluoride systems have been studied using potentiometry, 1H, 19F NMR spectroscopy and X-ray diffraction. The UO2(2+)-EDDA system could be studied up to -log[H3O+] = 3.4 where the formation of two binary complexes UO2(EDDA)(aq) and UO2(H3EDDA)3+ were identified, with equilibrium constants logbeta(UO2EDDA) = 11.63 +/- 0.02 and logbeta(UO2H3EDDA3+) = 1.77 +/- 0.04, respectively. In the ternary system the complexes UO2(EDDA)F-, UO2(EDDA)(OH)- and (UO2)2(mu-OH)2(HEDDA)2F2(aq) were identified; the latter through 19F NMR. 1H NMR spectra indicate that the EDDA ligand is chelate bonded in UO2(EDDA)(aq), UO2(EDDA)F- and UO2(EDDA)(OH)- while only one carboxylate group is coordinated in UO2(H3EDDA)3+. The rate and mechanism of the fluoride exchange between UO2(EDDA)F- and free fluoride was studied by 19F NMR spectroscopy. Three reactions contribute to the exchange; (i) site exchange between UO2(EDDA)F- and free fluoride without any net chemical exchange, (ii) replacement of the coordinated fluoride with OH- and (iii) the self dissociation of the coordinated fluoride forming UO2(EDDA)(aq); these reactions seem to follow associative mechanisms. (1)H NMR spectra show that the exchange between the free and chelate bonded EDDA is slow and consists of several steps, protonation/deprotonation and chelate ring opening/ring closure, the mechanism cannot be elucidated from the available data. The structure (UO2)2(EDDA)2(mu-H2EDDA) was determined by single crystal X-ray diffraction and contains two UO2(EDDA) units with tetracoordinated EDDA linked by H2EDDA in the "zwitterion" form, coordinated through a single carboxylate oxygen from each end to the two uranium atoms. The geometry of the complexes indicates that there is no geometric constraint for an associative ligand substitution mechanism.

  4. Moderator's view: High-volume plasma exchange: pro, con and consensus.

    Science.gov (United States)

    Kaplan, Andre A

    2017-09-01

    I have been asked to comment on the pro and con opinions regarding high-volume plasma exchange. The authors of both positions have provided cogent arguments and a reasonable approach to choosing the exchange volume for any given therapeutic plasma exchange. The major issue of relevance in this discussion is the nature of the toxins targeted for removal. These parameters include molecular weight, the apparent volume of distribution, the degree of protein binding, the biologic and chemical half-life, and the severity and rapidity of its toxicity. © The Author 2017. Published by Oxford University Press on behalf of ERA-EDTA. All rights reserved.

  5. Heat exchanger design considerations for high temperature gas-cooled reactor (HTGR) plants

    International Nuclear Information System (INIS)

    McDonald, C.F.; Vrable, D.L.; Van Hagan, T.H.; King, J.H.; Spring, A.H.

    1980-02-01

    Various aspects of the high-temperature heat exchanger conceptual designs for the gas turbine (HTGR-GT) and process heat (HTGR-PH) plants are discussed. Topics include technology background, heat exchanger types, surface geometry, thermal sizing, performance, material selection, mechanical design, fabrication, and the systems-related impact of installation and integration of the units in the prestressed concrete reactor vessel. The impact of future technology developments, such as the utilization of nonmetallic materials and advanced heat exchanger surface geometries and methods of construction, is also discussed

  6. High-performance ion-exchange chromatography of alkali metals with conductivity detection

    International Nuclear Information System (INIS)

    Ahmad, M.; Khan, A.R.

    1981-01-01

    High-performance ion-exchange chromatography of alkali metal and ammonium ions was studied using a conductivity meter as detector. Elution with 0.003 N mitric acid gave excellent resolution. Sensitivity levels, for a 200 micro litre injection, vary from 5 ppm for potassium to 0.1 ppm for lithium. A method to decrease retention times by reducing the exchange capacity of the cation exchange column used by loading it with calciumions, without affecting the resolation, has been described. Application of the method to water, soil and uranium dioxide samples has been demonstrated. (author)

  7. Distinct Iron-binding Ligands in the Upper Water Column at Station ALOHA

    Science.gov (United States)

    Bundy, R.; Boiteau, R.; Repeta, D.

    2016-02-01

    The distribution and chemical properties of iron-binding organic ligands at station ALOHA were examined using a combination of solid phase extraction (SPE) followed by high pressure liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICPMS). HPLC-ICPMS ligand measurements were complemented by competitive ligand exchange adsorptive cathodic stripping voltammetry (CLE-ACSV) analysis using salicylaldoxime as the added ligand. By HPLC-ICPMS, we find enhanced concentrations of distinct naturally-occurring polar iron-binding ligands present at the surface and in the chlorophyll maximum. Lower concentrations were found in the subsurface, where a suite of non-polar ligands was detected. Siderophores were present at the deepest depths sampled at station ALOHA, down to 400m. Incubation studies provided evidence for the production of iron-binding ligands associated with nutrient amended phytoplankton growth in surface waters, and as a result of microbial particle remineralization in the subsurface water column. Ligands classes identified via SPE were then compared to CLE-ACSV ligand measurements, as well as the conditional stability constants measured from model polar and non-polar siderophores, yielding insight to the sources of iron-binding ligands throughout the water column at station ALOHA.

  8. Charge exchange processes of high energy heavy ions channeled in crystals

    International Nuclear Information System (INIS)

    Andriamonje, S.; Dural, J.; Toulemonde, M.; Groeneveld, K.O.; Maier, R.; Quere, Y.

    1990-01-01

    The interaction of moving ions with single crystals is very sensitive to the orientation of the incident beam with respect to the crystalline directions of the target. The experiments show that high energy heavy ion channeling deeply modifies the slowing down and charge exchange processes. In this review, we describe the opportunity offered by channeling conditions to study the charge exchange processes. Some aspects of the charge exchange processes with high energy channeled heavy ions are selected from the extensive literature published over the past few years on this subject. Special attention is given to the work performed at the GANIL facility on the study of Radiative Electron Capture (REG), Electron Impact Ionisation (EII), and convoy electron emission. Finally we emphasize the interest of studying resonant charge exchange processes such as Resonant Coherent Excitation (RCE), Resonant Transfer and Excitation (RTE) or Dielectronic Recombination (DR) and the recently proposed Nuclear Excitation by Electron Capture (NEEC)

  9. Environmental variation, vegetation distribution, carbon dynamics and water/energy exchange at high latitudes

    Science.gov (United States)

    McGuire, A.D.; Wirth, C.; Apps, M.; Beringer, J.; Clein, J.; Epstein, H.; Kicklighter, D.W.; Bhatti, J.; Chapin, F. S.; De Groot, B.; Efremov, D.; Eugster, W.; Fukuda, M.; Gower, T.; Hinzman, L.; Huntley, B.; Jia, G.J.; Kasischke, E.; Melillo, J.; Romanovsky, V.; Shvidenko, A.; Vaganov, E.; Walker, D.

    2002-01-01

    The responses of high latitude ecosystems to global change involve complex interactions among environmental variables, vegetation distribution, carbon dynamics, and water and energy exchange. These responses may have important consequences for the earth system. In this study, we evaluated how vegetation distribution, carbon stocks and turnover, and water and energy exchange are related to environmental variation spanned by the network of the IGBP high latitude transects. While the most notable feature of the high latitude transects is that they generally span temperature gradients from southern to northern latitudes, there are substantial differences in temperature among the transects. Also, along each transect temperature co-varies with precipitation and photosynthetically active radiation, which are also variable among the transects. Both climate and disturbance interact to influence latitudinal patterns of vegetation and soil carbon storage among the transects, and vegetation distribution appears to interact with climate to determine exchanges of heat and moisture in high latitudes. Despite limitations imposed by the data we assembled, the analyses in this study have taken an important step toward clarifying the complexity of interactions among environmental variables, vegetation distribution, carbon stocks and turnover, and water and energy exchange in high latitude regions. This study reveals the need to conduct coordinated global change studies in high latitudes to further elucidate how interactions among climate, disturbance, and vegetation distribution influence carbon dynamics and water and energy exchange in high latitudes.

  10. Characterization of SynCAM surface trafficking using a SynCAM derived ligand with high homophilic binding affinity

    International Nuclear Information System (INIS)

    Breillat, Christelle; Thoumine, Olivier; Choquet, Daniel

    2007-01-01

    In order to better probe SynCAM function in neurons, we produced a fusion protein between the extracellular domain of SynCAM1 and the constant fragment of human IgG (SynCAM-Fc). Whether in soluble form or immobilized on latex microspheres, the chimera bound specifically to the surface of hippocampal neurons and recruited endogenous SynCAM molecules. SynCAM-Fc was also used in combination with Quantum Dots to follow the mobility of transfected SynCAM receptors at the neuronal surface. Both immobile and highly mobile SynCAM were found. Thus, SynCAM-Fc behaves as a high affinity ligand that can be used to study the function of SynCAM at the neuronal membrane

  11. Assessment of commercially available ion exchange materials for cesium removal from highly alkaline wastes

    International Nuclear Information System (INIS)

    Brooks, K.P.; Kim, A.Y.; Kurath, D.E.

    1996-04-01

    Approximately 61 million gallons of nuclear waste generated in plutonium production, radionuclide removal campaigns, and research and development activities is stored on the Department of Energy's Hanford Site, near Richland, Washington. Although the pretreatment process and disposal requirements are still being defined, most pretreatment scenarios include removal of cesium from the aqueous streams. In many cases, after cesium is removed, the dissolved salt cakes and supernates can be disposed of as LLW. Ion exchange has been a leading candidate for this separation. Ion exchange systems have the advantage of simplicity of equipment and operation and provide many theoretical stages in a small space. The organic ion exchange material Duolite trademark CS-100 has been selected as the baseline exchanger for conceptual design of the Initial Pretreatment Module (IPM). Use of CS-100 was chosen because it is considered a conservative, technologically feasible approach. During FY 96, final resin down-selection will occur for IPM Title 1 design. Alternate ion exchange materials for cesium exchange will be considered at that time. The purpose of this report is to conduct a search for commercially available ion exchange materials which could potentially replace CS-100. This report will provide where possible a comparison of these resin in their ability to remove low concentrations of cesium from highly alkaline solutions. Materials which show promise can be studied further, while less encouraging resins can be eliminated from consideration

  12. Assessment of commercially available ion exchange materials for cesium removal from highly alkaline wastes

    Energy Technology Data Exchange (ETDEWEB)

    Brooks, K.P.; Kim, A.Y.; Kurath, D.E.

    1996-04-01

    Approximately 61 million gallons of nuclear waste generated in plutonium production, radionuclide removal campaigns, and research and development activities is stored on the Department of Energy`s Hanford Site, near Richland, Washington. Although the pretreatment process and disposal requirements are still being defined, most pretreatment scenarios include removal of cesium from the aqueous streams. In many cases, after cesium is removed, the dissolved salt cakes and supernates can be disposed of as LLW. Ion exchange has been a leading candidate for this separation. Ion exchange systems have the advantage of simplicity of equipment and operation and provide many theoretical stages in a small space. The organic ion exchange material Duolite{trademark} CS-100 has been selected as the baseline exchanger for conceptual design of the Initial Pretreatment Module (IPM). Use of CS-100 was chosen because it is considered a conservative, technologically feasible approach. During FY 96, final resin down-selection will occur for IPM Title 1 design. Alternate ion exchange materials for cesium exchange will be considered at that time. The purpose of this report is to conduct a search for commercially available ion exchange materials which could potentially replace CS-100. This report will provide where possible a comparison of these resin in their ability to remove low concentrations of cesium from highly alkaline solutions. Materials which show promise can be studied further, while less encouraging resins can be eliminated from consideration.

  13. Heat Exchangers for Utilization of the Heat of High-Temperature Geothermal Brines

    Science.gov (United States)

    Alkhasov, A. B.; Alkhasova, D. A.

    2018-03-01

    The basic component of two-circuit geothermal systems is the heat exchanger. When used in geothermal power systems, conventional shell-and-tube and plate heat exchangers cause problems related to the cleaning of the latter from salt-deposition and corrosion products. Their lifetime does not exceed, as a rule, 1 year. To utilize the heat of high-temperature geothermal brines, a heat exchanger of the "tube-in-tube" type is proposed. A heat exchanger of this design has been operated for several years in Ternair geothermal steam field; in this heat exchanger, the thermal potential of the saline thermal water is transferred to the fresh water of the secondary circuit of the heating system for apartment houses. The reduction in the weight and size characteristics of the heat exchangers is a topical problem that can be solved with the help of heat transfer enhancers. To enhance the heat transfer process in the heat exchanger, longitudinal ribbing of the heat exchange surface is proposed. The increase in the heat exchange surface from the heat carrier side by ribbing results in an increase in the amount of the heat transferred from the heating agent. The heat exchanger is easy to manufacture and is assembled out of components comprised of two concentrically positioned tubes of a definite length, 3-6 m, serially connected with each other. The method for calculation of the impact of the number and the size of the longitudinal ribs on the heat transfer in the well heat exchanger is presented and a criterion for the selection of the optimal number and design parameters of the ribs is formulated. To prevent the corrosion and salt deposition in the heat exchanger, the use of an effective OEDFK (oxyethylidenediphosphonic acid) agent is proposed. This agent has a long-lasting corrosion-inhibiting and antiscaling effect, which is explained by the formation of a strongly adhesive chelate layer difficult to wash off the surface. The passivating OEDFK layer is restored by periodical

  14. A new crystal form of human tear lipocalin reveals high flexibility in the loop region and induced fit in the ligand cavity

    International Nuclear Information System (INIS)

    Breustedt, Daniel A.; Chatwell, Lorenz; Skerra, Arne

    2009-01-01

    The crystal structure of tear lipocalin determined in space group P2 1 revealed large structural deviations from the previously solved X-ray structure in space group C2, especially in the loop region and adjoining parts of the β-barrel which give rise to the ligand-binding site. These findings illustrate a novel mechanism for promiscuity in ligand recognition by the lipocalin protein family. Tear lipocalin (TLC) with the bound artificial ligand 1,4-butanediol has been crystallized in space group P2 1 with four protein molecules in the asymmetric unit and its X-ray structure has been solved at 2.6 Å resolution. TLC is a member of the lipocalin family that binds ligands with diverse chemical structures, such as fatty acids, phospholipids and cholesterol as well as microbial siderophores and the antibiotic rifampin. Previous X-ray structural analysis of apo TLC crystallized in space group C2 revealed a rather large bifurcated ligand pocket and a partially disordered loop region at the entrace to the cavity. Analysis of the P2 1 crystal form uncovered major conformational changes (i) in β-strands B, C and D, (ii) in loops 1, 2 and 4 at the open end of the β-barrel and (iii) in the extended C-terminal segment, which is attached to the β-barrel via a disulfide bridge. The structural comparison indicates high conformational plasticity of the loop region as well as of deeper parts of the ligand pocket, thus allowing adaptation to ligands that differ vastly in size and shape. This illustrates a mechanism for promiscuity in ligand recognition which may also be relevant for some other physiologically important members of the lipocalin protein family

  15. Very High Temperature Test of Alloy617 Compact Heat Exchanger in Helium Experimental Loop

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Chan Soo; Park, Byung-Ha; Kim, Eung-Seon [KAERI, Daejeon (Korea, Republic of)

    2016-05-15

    The Intermediate Heat eXchanger (IHX) is a key-challenged high temperature component which determines the efficiency and the economy of VHTR system. Heat generated in the VHTR fuel block is transferred from the VHTR to the intermediate loop through IHX. In the present, the shell-helical tube heat exchanger is generally used as IHX of the helium cooled reactor. Recently, a Printed Circuit Heat Exchanger (PCHE) is one of the candidates for the IHX in a VHTR because its operation temperature and pressure are larger than any other compact heat exchanger types. These test results show that there is no problem in operation of HELP at the very high temperature experimental condition and the alloy617 compact heat exchanger can be operated in the very high temperature condition above 850℃. In the future, the high temperature structural analysis will be studied to estimate the thermal stress during transient and thermal shock condition. The conditions and evaluation standard for the alloy 617 diffusion bonding will be minutely studied to fabricate the large-scale PCHE for the high temperature condition.

  16. Highly dispersive ion exchangers in the analytical chemistry of uranium, particularly regarding separation methods

    International Nuclear Information System (INIS)

    Schoening, R.

    1975-01-01

    The reaction of water-insoluble polyvinyl pyrrolidon with uranium VI was investigated and a determination method for uranium was worked out in which the polyvinyl pyrrolidon was used as specific exchanger. Good separations of uranium from numerous transition metal ions were achieved here. The application of this exchanger for a fast and simple elution and determination method was of particular importance. A possible sorption mechanism was suggested based on the capacity curve of uranium with polyvinyl pyrrolidon and nitrogen and chloride content at maximum load. The sorption occurs by coordination of the carbonyl oxygen of single pyrrolidon rings with the protons of the complex acides and uranium. This assumption is supported by IR investigations. The sorbability of other inorganic acids was also investigated and possible structures were formulated for the sorption mechanism. In addition to this, ion exchangers were prepared based on cellulose by converting cellulose powder with aziridine and tris-1-aziridinyl-phosphine oxide. A polyethylene imine cellulose of high capacity was obtained in the conversion of cellulose powder with aziridine. This exchanger absorbs cobalt III very strongly. The exchanger loaded with cobalt III was used to separate the uranium as cyanato complex. The exchanger obtained in converting chlorated cellulose with tris-1-aziridinyl phosphine oxide also absorbs uranium VI very strongly. Thus a separation method of high specifity and selectivity was developed. (orig.) [de

  17. Development of a High-Throughput Ion-Exchange Resin Characterization Workflow.

    Science.gov (United States)

    Liu, Chun; Dermody, Daniel; Harris, Keith; Boomgaard, Thomas; Sweeney, Jeff; Gisch, Daryl; Goltz, Bob

    2017-06-12

    A novel high-throughout (HTR) ion-exchange (IEX) resin workflow has been developed for characterizing ion exchange equilibrium of commercial and experimental IEX resins against a range of different applications where water environment differs from site to site. Because of its much higher throughput, design of experiment (DOE) methodology can be easily applied for studying the effects of multiple factors on resin performance. Two case studies will be presented to illustrate the efficacy of the combined HTR workflow and DOE method. In case study one, a series of anion exchange resins have been screened for selective removal of NO 3 - and NO 2 - in water environments consisting of multiple other anions, varied pH, and ionic strength. The response surface model (RSM) is developed to statistically correlate the resin performance with the water composition and predict the best resin candidate. In case study two, the same HTR workflow and DOE method have been applied for screening different cation exchange resins in terms of the selective removal of Mg 2+ , Ca 2+ , and Ba 2+ from high total dissolved salt (TDS) water. A master DOE model including all of the cation exchange resins is created to predict divalent cation removal by different IEX resins under specific conditions, from which the best resin candidates can be identified. The successful adoption of HTR workflow and DOE method for studying the ion exchange of IEX resins can significantly reduce the resources and time to address industry and application needs.

  18. Screening small-molecule compound microarrays for protein ligands without fluorescence labeling with a high-throughput scanning microscope.

    Science.gov (United States)

    Fei, Yiyan; Landry, James P; Sun, Yungshin; Zhu, Xiangdong; Wang, Xiaobing; Luo, Juntao; Wu, Chun-Yi; Lam, Kit S

    2010-01-01

    We describe a high-throughput scanning optical microscope for detecting small-molecule compound microarrays on functionalized glass slides. It is based on measurements of oblique-incidence reflectivity difference and employs a combination of a y-scan galvometer mirror and an x-scan translation stage with an effective field of view of 2 cm x 4 cm. Such a field of view can accommodate a printed small-molecule compound microarray with as many as 10,000 to 20,000 targets. The scanning microscope is capable of measuring kinetics as well as endpoints of protein-ligand reactions simultaneously. We present the experimental results on solution-phase protein reactions with small-molecule compound microarrays synthesized from one-bead, one-compound combinatorial chemistry and immobilized on a streptavidin-functionalized glass slide.

  19. Mechanism of pyridine-ligand exchanges at the different labile sites of 3d heterometallic and mixed valence mu3-oxo trinuclear clusters.

    Science.gov (United States)

    Novitchi, Ghenadie; Riblet, Fabrice; Scopelliti, Rosario; Helm, Lothar; Gulea, Aurelian; Merbach, André E

    2008-11-17

    The syntheses and single crystal X-ray structural analysis of five novel hetero- and homometallic mu 3-oxo trinuclear cluster with the formula [Fe (III) 2M (II)(mu 3-O)(mu-O 2CCH 3) 6(4-Rpy) 3]. x(4-Rpy). y(CH 3CN) where R = Ph for 1(Fe 2Mn), 2(Fe 2Fe), 3(Fe 2Co), 4(Fe 2Ni) and R = CF 3 for 5(Fe 2Co), are reported. The persistence of the structure for compounds 2- 5 in dichloromethane solution in the temperature range 190-320 K is demonstrated by (1)H and (19)F NMR spectroscopy. Even at the lowest temperature, the electron exchange in the homometallic mixed-valence compound 2(Fe 2Fe) is in the fast regime at the NMR time scale. Variable temperature and pressure NMR line broadening allowed quantifying the fast coordinated/free 4-Rpy exchanges at the two labile metal centers in these clusters: 2: Fe (III)( k (298)/10 (3) s (-1) = 16.6; Delta H (++) = 60.32 kJ mol (-1); Delta S (++) = + 34.8 J K (-1) mol (-1); Delta V (++) = + 12.5 cm (3) mol (-1)); 3: Fe (11.9; 58.92; +30.7; +10.6) and Co (2.8; 68.24; +49.8; +13.9); 4: Fe(12.2; 67.91; +61.0; -) and Ni (0.37; 78.62; +67.8; +12.3); 5: Fe (46; 58.21; +39.3; +14.2) and Co (4.7; 55.37; +11.2; +10.9). A limiting D mechanism is assigned to these exchange reactions. This assignment is based on a first-order rate law, the detection of intermediates, the positive and large entropies and volumes of activation. The order of reactivity k (Co) > k (Ni) is expected for a D mechanism at these metal centers: their low exchange rates are due to their strong binding with the 4-Rpy donor. Surrounded by oxygen donors the d (5) iron(III) usually reacts associatively; however, here due to low affinity of this ion for nitrogen the mechanism is D and the rate of exchange is very fast, even faster than on the divalent ions. There is no significant effect of the divalent ion in cluster 2, 3, and 5 on the exchange rates of 4-Phpy at the iron center, which seems to indicate that the specific electronic interactions between the three ions making

  20. Development of composite ion exchanger for separation of cesium from high level liquid waste

    International Nuclear Information System (INIS)

    Kumar, A.; Varshney, L.

    2010-01-01

    137 Cs (t 1/2 = 30 years) is one of the major radioisotope present in high level liquid waste (HLLW) generated during the reprocessing of nuclear fuel. Separation of 137 Cs from HLLW results in reduction of personal radiation exposure during the conditioning, transportation, storage and disposal. In addition, 137 Cs has enormous application as a radiation source in food preservation, sterilization of medical products, brachytherapy, blood irradiation, hygienization of sewage sludge etc. Ammonium molybdophosphate (AMP), an inorganic ion exchanger, has high selectivity and high exchange capacity for Cs. It exits as microcrystalline powder which is not amenable for column operation. ALIX is a composite material in which AMP is physically blended with inert polymeric substrate to improve its column property, exchange kinetics and increase its mechanical strength. The observed excellent properties of the composite are attributed to its engineered structure which is formed during its production. SEM analysis of ALIX shows that AMP crystals embedded in the cavities are not covered by the polymer which greatly enhances its availability for cesium exchange. The highly porous structure of the composite having 49% void volume facilitates faster kinetics of exchange of Cs from the aqueous phase and increased rate of reaction with alkali required during its dissolution

  1. A high field optical-pumping spin-exchange polarized deuterium source

    International Nuclear Information System (INIS)

    Coulter, K.P.; Holt, R.J.; Kinney, E.R.; Kowalczyk, R.S.; Poelker, M.; Potterveld, D.H.; Young, L.; Zeidman, B.; Toporkov, D.

    1992-01-01

    Recent results from a prototype high field optical-pumping spin-exchange polarized deuterium source are presented. Atomic polarization as high as 62% have been observed with an intensity of 6.3 x 10 17 atoms-sec -1 and 65% dissociation fraction

  2. Basic thermo-fluid dynamic problems in high temperature heat exchangers

    International Nuclear Information System (INIS)

    McEligot, D.M.

    1986-01-01

    The authors consider high temperature heat exchangers to be ones where the heat transfer coefficients cannot be predicted confidently by classical analyses for pure forced convection with constant fluid properties. Alternatively, one could consider heat exchangers operating above some arbitrary temperature, say 1000F or 600C perhaps, to be at high temperature conditions. In that case, most common working fluids will be superheated vapors or gases. While some liquid metal heat exchangers are designed to operate in this range, the heat transfer coefficients of liquid metals are usually sufficiently high that the dominant thermal resistance would be due to the second fluid. This paper concentrates on convective heat transfer with gases. Typical applications include modular gas cooled nuclear reactors, proposed nuclear propulsion systems and space power plants, and superheaters in Rankine steam cycles

  3. Sorption of vanillin on highly basic anion exchanger under static conditions

    Science.gov (United States)

    Sholokhova, A. Yu.; Eliseeva, T. V.; Voronyuk, I. V.

    2017-11-01

    The kinetics of the sorption of vanillin by a granulated anion exchanger is studied under static conditions. A comparison of the kinetic curves of the uptake of hydroxybenzaldehyde by gel and macroporous anion exchanger shows that macroporous sorbent has better kinetic characteristics. The effect temperature has on the capacity of an anion exchanger and the time needed to establish sorption equilibrium is found, and the activation energy of vanillin uptake is determined. Studying the effect experimental factors have on the rate of sorption and using the formal kinetics approach, it is established that in the investigated range of concentrations, the limiting stage of the uptake of vanillin by an anion exchanger with the functional groups of a quaternary ammonium base is that of external diffusion. Vanillin sorption by a highly basic anion exchanger in hydroxyl form is characterized by polymolecular uptake best described by a BET isotherm; at the same time, the uptake of sorbate by a chloride form is of a monomolecular character and can be described by a Freindlich isotherm. Structural changes in the anion exchanger sorbed hydroxybenzaldehyde are identified via FTIR spectroscopy.

  4. Unlocking Chain Exchange in Highly Amphiphilic Block Polymer Micellar Systems: Influence of Agitation.

    Science.gov (United States)

    Murphy, Ryan P; Kelley, Elizabeth G; Rogers, Simon A; Sullivan, Millicent O; Epps, Thomas H

    2014-11-18

    Chain exchange between block polymer micelles in highly selective solvents, such as water, is well-known to be arrested under quiescent conditions, yet this work demonstrates that simple agitation methods can induce rapid chain exchange in these solvents. Aqueous solutions containing either pure poly(butadiene- b -ethylene oxide) or pure poly(butadiene- b -ethylene oxide- d 4 ) micelles were combined and then subjected to agitation by vortex mixing, concentric cylinder Couette flow, or nitrogen gas sparging. Subsequently, the extent of chain exchange between micelles was quantified using small angle neutron scattering. Rapid vortex mixing induced chain exchange within minutes, as evidenced by a monotonic decrease in scattered intensity, whereas Couette flow and sparging did not lead to measurable chain exchange over the examined time scale of hours. The linear kinetics with respect to agitation time suggested a surface-limited exchange process at the air-water interface. These findings demonstrate the strong influence of processing conditions on block polymer solution assemblies.

  5. Surfactant Ligand Removal and Rational Fabrication of Inorganically Connected Quantum Dots

    KAUST Repository

    Zhang, Haitao

    2011-12-14

    A novel method is reported to create inorganically connected nanocrystal (NC) assemblies for both II-VI and IV-VI semiconductors by removing surfactant ligands using (NH 4) 2S. This surface modification process differs from ligand exchange methods in that no new surfactant ligands are introduced and the post-treated NC surfaces are nearly bare. The detailed mechanism study shows that the high reactivity between (NH 4) 2S and metal-surfactant ligand complexes enables the complete removal of surfactant ligands in seconds and converts the NC metal-rich shells into metal sulfides. The post-treated NCs are connected through metal-sulfide bonding and form a larger NCs film assembly, while still maintaining quantum confinement. Such "connected but confined" NC assemblies are promising new materials for electronic and optoelectronic devices. © 2011 American Chemical Society.

  6. Molecular Docking Explains Atomic Interaction between Plant-originated Ligands and Oncogenic E7 Protein of High Risk Human Papillomavirus Type 16

    Directory of Open Access Journals (Sweden)

    Satish Kumar

    2014-12-01

    Full Text Available Cervical cancer caused by Human papillomavirus (HPV is one of the leading causes of cancer mortality in women worldwide, particularly in the developing countries. In the last few decades, various compounds from plant origin such as Curcumin, Epigallocatechin gallate (EGCG, Jaceosidin, Resveratrol etc. have been used as anti cancer therapeutic agents. Different studies have shown these plant-originated compounds are able to suppress HPV infection. The E6 and E7 oncoproteins of high-risk HPV play a key role in HPV related cancers. In this study, we explored these ligands from plants origin against E7 oncoprotein of high risk HPV 16, which is known to inactivate tumor suppressor pRb protein. A robust homology model of HPV 16 E7 was built to foresee the interaction mechanism of E7 oncoprotein with these ligands using structure-based drug designing approach. Docking studies demonstrate the interaction of these ligands with pRb binding site of E7 protein by residues Tyr52, Asn53, Val55, Phe57, Cys59, Ser63, Thr64, Thr72, Arg77, Glu80 and Asp81 and help restoration of pRb functioning. This in silico based atomic interaction between these ligands and E7 protein may assist in validating the plant-originated ligands as effective drugs against HPV.

  7. A high pressure study of calmodulin-ligand interactions using small-angle X-ray and elastic incoherent neutron scattering.

    Science.gov (United States)

    Cinar, Süleyman; Al-Ayoubi, Samy; Sternemann, Christian; Peters, Judith; Winter, Roland; Czeslik, Claus

    2018-01-31

    Calmodulin (CaM) is a Ca 2+ sensor and mediates Ca 2+ signaling through binding of numerous target ligands. The binding of ligands by Ca 2+ -saturated CaM (holo-CaM) is governed by attractive hydrophobic and electrostatic interactions that are weakened under high pressure in aqueous solutions. Moreover, the potential formation of void volumes upon ligand binding creates a further source of pressure sensitivity. Hence, high pressure is a suitable thermodynamic variable to probe protein-ligand interactions. In this study, we compare the binding of two different ligands to holo-CaM as a function of pressure by using X-ray and neutron scattering techniques. The two ligands are the farnesylated hypervariable region (HVR) of the K-Ras4B protein, which is a natural binding partner of holo-CaM, and the antagonist trifluoperazine (TFP), which is known to inhibit holo-CaM activity. From small-angle X-ray scattering experiments performed up to 3000 bar, we observe a pressure-induced partial unfolding of the free holo-CaM in the absence of ligands, where the two lobes of the dumbbell-shaped protein are slightly swelled. In contrast, upon binding TFP, holo-CaM forms a closed globular conformation, which is pressure stable at least up to 3000 bar. The HVR of K-Ras4B shows a different binding behavior, and the data suggest the dissociation of the holo-CaM/HVR complex under high pressure, probably due to a less dense protein contact of the HVR as compared to TFP. The elastic incoherent neutron scattering experiments corroborate these findings. Below 2000 bar, pressure induces enhanced atomic fluctuations in both holo-CaM/ligand complexes, but those of the holo-CaM/HVR complex seem to be larger. Thus, the inhibition of holo-CaM by TFP is supported by a low-volume ligand binding, albeit this is not associated with a rigidification of the complex structure on the sub-ns Å-scale.

  8. High-Temperature Test of 800HT Printed Circuit Heat Exchanger in HELP

    International Nuclear Information System (INIS)

    Kim, Chan Soo; Hong, Sung-Deok; Kim, Min Hwan; Shim, Jaesool

    2014-01-01

    Korea Atomic Energy Research Institute has developed high-temperature Printed Circuit Heat Exchangers (PCHE) for a Very High Temperature gas-cooled Reactor and operated a very high temperature Helium Experimental LooP (HELP) to verify the performance of the high temperature heat exchanger at the component level environment. PCHE is one of the candidates for the intermediate heat exchanger in a VHTR, because its design temperature and pressure are larger than any other compact heat exchanger types. High temperature PCHEs in HELP consist of an alloy617 PCHE and an 800HT PCHE. This study presents the high temperature test of an 800HT PCHE in HELP. The experimental data include the pressure drops, the overall heat transfer coefficients, and the surface temperature distributions under various operating conditions. The experimental data are compared with the thermo-hydraulic analysis from COMSOL. In addition, the single channel tests are performed to quantify the friction factor under normal nitrogen and helium inlet conditions. (author)

  9. Heat exchanger for transfering heat produced in a high temperature reactor to an intermediate circuit gas

    International Nuclear Information System (INIS)

    Barchewitz, E.; Baumgaertner, H.

    1985-01-01

    The invention is concerned with improving the arrangement of a heat exchanger designed to transfer heat from the coolant gas circuit of a high temperature reactor to a gas which is to be used for a process heat plant. In the plant the material stresses are to be kept low at high differential pressures and temperatures. According to the invention the tube bundles designed as boxes are fixed within the heat exchanger closure by means of supply pipes having got loops. For conducting the hot gas the heat exchanger has got a central pipe leading out of the reactor vessel through the pod closure and having got only one point of fixation, lying in this closure. Additional advantageous designs are mentioned. (orig./PW)

  10. Minimization of storage and disposal volumes by treatment of liquids by highly selective ion exchangers

    International Nuclear Information System (INIS)

    Tusa, E.; Harjula, R.; Lehto, J.

    2000-01-01

    Novel highly selective inorganic ion exchangers provide new efficient methods for the treatment of nuclear waste liquids. These methods have several advantages compared to conventional technologies such as evaporation, direct solidification or treatment by organic ion exchange resins. Due to high selectivity, the radionuclides can be concentrated to a very small volume even from high-salt effluents. This means that the volume waste will be very small compared to other methods, which brings considerable savings in the cost of intermediate storage and final disposal. Process equipment are highly compact and require little supervision, which brings down the capital and operation costs. The new selective inorganic ion exchangers CsTreat, SrTreat and CoTreat (manufactured by Fortum Engineering Ltd., Finland) have the highest selectivities and processing capacities, exceeding those of zeolites by several orders of magnitude. The materials are now in use in a number of nuclear sites worldwide, including those in the USA, Europe and Japan. Installations include mobile and stationary systems. Considerable experience has been gained in the use of these new materials. Lessons learned, as well as advantages and economic benefits of these highly selective exchangers will be discussed in this paper. (authors)

  11. Steel reinforced composite silicone membranes and its integration to microfluidic oxygenators for high performance gas exchange.

    Science.gov (United States)

    Matharoo, Harpreet; Dabaghi, Mohammadhossein; Rochow, Niels; Fusch, Gerhard; Saraei, Neda; Tauhiduzzaman, Mohammed; Veldhuis, Stephen; Brash, John; Fusch, Christoph; Selvaganapathy, P Ravi

    2018-01-01

    Respiratory distress syndrome (RDS) is one of the main causes of fatality in newborn infants, particularly in neonates with low birth-weight. Commercial extracorporeal oxygenators have been used for low-birth-weight neonates in neonatal intensive care units. However, these oxygenators require high blood volumes to prime. In the last decade, microfluidics oxygenators using enriched oxygen have been developed for this purpose. Some of these oxygenators use thin polydimethylsiloxane (PDMS) membranes to facilitate gas exchange between the blood flowing in the microchannels and the ambient air outside. However, PDMS is elastic and the thin membranes exhibit significant deformation and delamination under pressure which alters the architecture of the devices causing poor oxygenation or device failure. Therefore, an alternate membrane with high stability, low deformation under pressure, and high gas exchange was desired. In this paper, we present a novel composite membrane consisting of an ultra-thin stainless-steel mesh embedded in PDMS, designed specifically for a microfluidic single oxygenator unit (SOU). In comparison to homogeneous PDMS membranes, this composite membrane demonstrated high stability, low deformation under pressure, and high gas exchange. In addition, a new design for oxygenator with sloping profile and tapered inlet configuration has been introduced to achieve the same gas exchange at lower pressure drops. SOUs were tested by bovine blood to evaluate gas exchange properties. Among all tested SOUs, the flat design SOU with composite membrane has the highest oxygen exchange of 40.32 ml/min m 2 . The superior performance of the new device with composite membrane was demonstrated by constructing a lung assist device (LAD) with a low priming volume of 10 ml. The LAD was achieved by the oxygen uptake of 0.48-0.90 ml/min and the CO 2 release of 1.05-2.27 ml/min at blood flow rates ranging between 8 and 48 ml/min. This LAD was shown to increase the

  12. Gamma radiolysis of the highly selective ligands CyMe{sub 4}BTBP and CyMe{sub 4}BTPhen: Qualitative and quantitative investigation of radiolysis product

    Energy Technology Data Exchange (ETDEWEB)

    Schmidt, H.; Wilden, A.; Modolo, G.; Bosbach, D. [Forschungszentrum Juelich GmbH, Institute of Energy and Climate Research IEK-6: Nuclear Waste Management, 52425 Juelich (Germany); Santiago-Schuebel, B.; Hupert, M. [Forschungszentrum Juelich GmbH, Central Institute for Engineering, Analytics - ZEA-3, 52425 Juelich (Germany); Svehla, J.; Gruner, B. [Institute of Inorganic Chemistry, Academy of Sciences, Hlavni 1001, 25068 Husinec-Rez (Czech Republic); Ekberg, C. [Department of Chemical and Biochemical Engineering, Chalmers University of Technology, 41296 Gothenburg (Sweden)

    2016-07-01

    The highly selective nitrogen donor ligands CyMe{sub 4}BTBP and CyMe4{sub B}TPhen where γ-irradiated under identical experimental conditions in 1-octanol with and without contact to nitric acid solution. Subsequently, solvent extraction experiments were carried out to evaluate the stability of the extractants against γ-radiation monitoring Am(III) and Eu(III) distribution ratios. Generally, decreasing distribution ratios with increasing absorbed dose were detected for both molecules. Furthermore, qualitative mass spectrometric analyses were performed and ligand concentrations were determined by HPLC-DAD after irradiation to investigate the radiolysis mechanism. An exponential decrease with increasing absorbed dose was observed for both ligands with a faster rate for CyMe{sub 4}BTPhen. Main radiolysis products indicated the addition of one or more diluent molecules (1-octanol) to the ligand via prior production of α-hydroxy-octyl radicals from diluent radiolysis. The addition of nitric acid during the irradiation lead to a remarkable stabilization of the system, as the extraction of Am(III) and Eu(III) did not change significantly over the whole examined dose range. Quantification of the remaining ligand concentration on the other hand showed decreasing concentrations with increasing absorbed dose. The stabilization of D values is therefore explained by the formation of 1-octanol addition products which are also able to extract the studied metal ions. (authors)

  13. Gamma radiolysis of the highly selective ligands CyMe_4BTBP and CyMe_4BTPhen: Qualitative and quantitative investigation of radiolysis product

    International Nuclear Information System (INIS)

    Schmidt, H.; Wilden, A.; Modolo, G.; Bosbach, D.; Santiago-Schuebel, B.; Hupert, M.; Svehla, J.; Gruner, B.; Ekberg, C.

    2016-01-01

    The highly selective nitrogen donor ligands CyMe_4BTBP and CyMe4_BTPhen where γ-irradiated under identical experimental conditions in 1-octanol with and without contact to nitric acid solution. Subsequently, solvent extraction experiments were carried out to evaluate the stability of the extractants against γ-radiation monitoring Am(III) and Eu(III) distribution ratios. Generally, decreasing distribution ratios with increasing absorbed dose were detected for both molecules. Furthermore, qualitative mass spectrometric analyses were performed and ligand concentrations were determined by HPLC-DAD after irradiation to investigate the radiolysis mechanism. An exponential decrease with increasing absorbed dose was observed for both ligands with a faster rate for CyMe_4BTPhen. Main radiolysis products indicated the addition of one or more diluent molecules (1-octanol) to the ligand via prior production of α-hydroxy-octyl radicals from diluent radiolysis. The addition of nitric acid during the irradiation lead to a remarkable stabilization of the system, as the extraction of Am(III) and Eu(III) did not change significantly over the whole examined dose range. Quantification of the remaining ligand concentration on the other hand showed decreasing concentrations with increasing absorbed dose. The stabilization of D values is therefore explained by the formation of 1-octanol addition products which are also able to extract the studied metal ions. (authors)

  14. High porewater exchange in a mangrove-dominated estuary revealed from short-lived radium isotopes

    Science.gov (United States)

    Sadat-Noori, Mahmood; Santos, Isaac R.; Tait, Douglas R.; Reading, Michael J.; Sanders, Christian J.

    2017-10-01

    We hypothesise that mangroves play an important role in groundwater exchange processes in sub-tropical and tropical estuarine waters. To investigate this, multiple high resolution time series measurements of radium across a tidal estuary (Coffs Creek, NSW, Australia) were performed as well as a spatial survey in both bottom and surface layers. Results from the spatial survey revealed increasing radium concentrations in parts of the estuary surrounded by mangroves. The average radium concentration in estuary areas lined with mangroves was 2.5 times higher than the average concentration at the mouth of the estuary and 6.5-fold higher than upstream freshwater areas. Additionally, the area enriched in radium coincided with low dissolved oxygen concentrations, implying that porewater exchange may drive anoxia. A radium mass balance model based on 223Ra and 224Ra isotopes at different sections of the estuary confirmed higher porewater exchange rates from areas fringed with mangrove vegetation. Estimated porewater exchange rates were 27.8 ± 5.3 and 13.6 ± 2.1 cm d-1 (0.8 ± 0.1 and 0.4 ± 0.1 m3 s-1) based on 223Ra and 224Ra isotopes, respectively. The average saline porewater exchange was ∼ 10-fold larger than the upstream surface freshwater inputs to the estuary. We suggest that mangrove environments within subtropical estuaries are hotspots for porewater exchange due to the complex belowground structure of crab burrows and the effect of tidal pumping. Because porewater exchange releases carbon and nitrogen from coastal sediments, development and modification of mangrove areas in subtropical estuaries have a significant effect on coastal biogeochemical cycles.

  15. High Pt utilization PEMFC electrode obtained by alternative ion-exchange/electrodeposition.

    Science.gov (United States)

    Chen, Siguo; Wei, Zidong; Li, Hua; Li, Li

    2010-12-14

    High Pt utilization PEMFC electrodes were prepared by an alternative ion-exchange/electrodeposition (AIEE) technique. The results demonstrated that the MEA employing an AIEE electrode with a Pt loading of 0.014 mg Pt cm(-2) exhibits performance approximately 2.2 times larger than that employing a conventional Nafion-bonded Pt/C electrode with a same Pt loading.

  16. Phosphoric acid doped imidazolium polysulfone membranes for high temperature proton exchange membrane fuel cells

    DEFF Research Database (Denmark)

    Yang, Jingshuai; Li, Qingfeng; Jensen, Jens Oluf

    2012-01-01

    A novel acid–base polymer membrane is prepared by doping of imidazolium polysulfone with phosphoric acid for high temperature proton exchange membrane fuel cells. Polysulfone is first chloromethylated, followed by functionalization of the chloromethylated polysulfone with alkyl imidazoles i.e. me...

  17. Production and application of cation/anion exchange membranes of high performance

    International Nuclear Information System (INIS)

    Xu Zhili; Tan Chunhong; Yang Xiangmin

    1995-01-01

    A third affiliated factory of our university has been established for the production in batches of cation/anion exchange membranes of high performance, trade marks of which are HF-1 and HF-2. Membrane products have been applied in various fields (including industries and research institutions) with great success

  18. Adjuvant effects of mannose-binding lectin ligands on the immune response to infectious bronchitis vaccine in chickens with high or low serum mannose-binding lectin concentrations

    DEFF Research Database (Denmark)

    Kjærup, Rikke Munkholm; Dalgaard, Tina Sørensen; Norup, Liselotte Rothmann

    2014-01-01

    in the pathogenesis of IBV infection and the production of IBV-specific antibodies, which may be exploited in optimising IBV vaccine strategies. The present study shows that MBL has the capability to bind to IBV in vitro. Chickens from two inbred lines (L10H and L10L) selected for high or low MBL serum concentrations......, respectively, were vaccinated against IBV with or without the addition of the MBL ligands mannan, chitosan and fructooligosaccharide (FOS). The addition of MBL ligands to the IBV vaccine, especially FOS, enhanced the production of IBV-specific IgG antibody production in L10H chickens, but not L10L chickens...... to the vaccine, most pronouncedly after the first vaccination. As MBL ligands co-administered with IBV vaccine induced differences between the two chicken lines, these results indirectly suggest that MBL is involved in the immune response to IBV vaccination. Furthermore, the higher antibody response in L10H...

  19. Severe Leptospirosis with Multiple Organ Failure Successfully Treated by Plasma Exchange and High-Volume Hemofiltration

    Directory of Open Access Journals (Sweden)

    Vincent Bourquin

    2011-01-01

    Full Text Available Background. Leptospirosis is a spirochetal zoonosis with complex clinical features including renal and liver failure. Case report. We report the case of a Swiss fisherman presenting with leptospirosis. After initial improvement, refractory septic shock and severe liver and kidney failure developed. The expected mortality was estimated at 90% with clinical scores. The patient underwent plasma exchanges and high-volume hemofiltration (HVHF with complete recovery of hepatic and kidney functions. Discussion. Plasma exchanges and HVHF may confer survival benefit on patients with severe leptospirosis, refractory septic shock, and multiple-organ failure.

  20. High energy charge exchange np and antipp scattering using the dual fermion model

    International Nuclear Information System (INIS)

    Weigt, G.

    1976-01-01

    The five independent helicity amplitudes Phisub(i)(s, t) calculated by Mandelstam from the Neveu-Schwarz-Ramond model for fermion-antifermion scattering are used in the Regge limit for a phenomenological description of high energy np and antipp charge exchange scattering. A forward spike which widens with increasing energy as well as an energy dependence changing from lower to higher energy data are reproduced by these non-evasive dual Born amplitudes using π, A 2 and rho Regge pole t-channel exchanges. (author)

  1. High Temperature Gas-to-Gas Heat Exchanger Based on a Solid Intermediate Medium

    Directory of Open Access Journals (Sweden)

    R. Amirante

    2014-04-01

    Full Text Available This paper proposes the design of an innovative high temperature gas-to-gas heat exchanger based on solid particles as intermediate medium, with application in medium and large scale externally fired combined power plants fed by alternative and dirty fuels, such as biomass and coal. An optimization procedure, performed by means of a genetic algorithm combined with computational fluid dynamics (CFD analysis, is employed for the design of the heat exchanger: the goal is the minimization of its size for an assigned heat exchanger efficiency. Two cases, corresponding to efficiencies equal to 80% and 90%, are considered. The scientific and technical difficulties for the realization of the heat exchanger are also faced up; in particular, this work focuses on the development both of a pressurization device, which is needed to move the solid particles within the heat exchanger, and of a pneumatic conveyor, which is required to deliver back the particles from the bottom to the top of the plant in order to realize a continuous operation mode. An analytical approach and a thorough experimental campaign are proposed to analyze the proposed systems and to evaluate the associated energy losses.

  2. Ligand-enhanced electrokinetic remediation of metal-contaminated marine sediments with high acid buffering capacity.

    Science.gov (United States)

    Masi, Matteo; Iannelli, Renato; Losito, Gabriella

    2016-06-01

    The suitability of electrokinetic remediation for removing heavy metals from dredged marine sediments with high acid buffering capacity was investigated. Laboratory-scale electrokinetic remediation experiments were carried out by applying two different voltage gradients to the sediment (0.5 and 0.8 V/cm) while circulating water or two different chelating agents at the electrode compartments. Tap water, 0.1 M citric acid and 0.1 M ethylenediaminetetraacetic acid (EDTA) solutions were used respectively. The investigated metals were Zn, Pb, V, Ni and Cu. In the unenhanced experiment, the acid front could not propagate due to the high acid buffering capacity of the sediments; the production of OH(-) ions at the cathode resulted in a high-pH environment causing the precipitation of CaCO3 and metal hydroxides. The use of citric acid prevented the formation of precipitates, but solubilisation and mobilisation of metal species were not sufficiently achieved. Metal removal was relevant when EDTA was used as the conditioning agent, and the electric potential was raised up to 0.8 V/cm. EDTA led to the formation of negatively charged complexes with metals which migrated towards the anode compartment by electromigration. This result shows that metal removal from sediments with high acid buffering capacity may be achieved by enhancing the electrokinetic process by EDTA addition when the acidification of the medium is not economically and/or environmentally sustainable.

  3. A class-A GPCR solubilized under high hydrostatic pressure retains its ligand binding ability

    Science.gov (United States)

    The effect of high hydrostatic pressure (HHP) on the solubilization of a class-A G protein-coupled receptor, the silkmoth pheromone biosynthesis-activating neuropeptide receptor (PBANR), was investigated. PBANR was expressed in expresSF+ insect cells as a C-terminal fusion protein with EGFP. The mem...

  4. Effectiveness of high interest rate policy on exchange rates: A reexamination of the Asian financial crisis

    Directory of Open Access Journals (Sweden)

    Chin Diew Lai

    2006-09-01

    Full Text Available One of the most controversial issues in the aftermath of the Asian financial crisis has been the appropriate response of monetary policy to a sharp decline in the value of some currencies. In this paper, we empirically examine the effects on Asian exchange rates of sharply higher interest rates during the Asian financial crisis. Taking account of the currency contagion effect, our results indicate that sharply higher interest rates helped to support the exchange rates of South Korea, the Philippines, and Thailand. For Malaysia, no significant causal relation is found from the rate of interest to exchange rates, as the authorities in Malaysia did not actively adopt a high interest rate policy to defend the currency.

  5. Structures, equilibria and ligand exchange dynamics in the binary and ternary dioxouranium(VI)-ethylenediamine-N-N'-diacetic acid - fluoride system; a potentiometric, NMR and X-ray study

    International Nuclear Information System (INIS)

    Palladino, G.; Szabo, Z.; Fischer, A.; Grenthe, I.

    2005-01-01

    Full text of publication follows: The structure, thermodynamics and kinetics of the binary and ternary Uranyl(VI)- ethylenediamine- N-N'-di-acetate (in the following denoted EDDA) fluoride system have been studied using potentiometry, 1 H, 19 F NMR and a single-crystal X-ray determination. The potentiometric data were obtained using measurements of the free hydrogen ion and fluoride concentrations with glass and fluoride electrodes, respectively. The experimental data were used to deduce stoichiometry and equilibrium constants using a least square refinements programme. The UO 2 2+ - EDDA system could be studied up to -log[H 3 O + ] 3.4, after which a precipitate was formed. The test solutions contained two binary complexes, the uncharged UO 2 (EDDA)(aq) and UO 2 (H 3 EDDA) 3+ , with equilibrium constants log β(UO 2 EDDA) = 11.63 ± 0.02 and log β(UO 2 H 3 EDDA 3+ ) = 1.77 ± 0.04, respectively. By using fluoride as additional ligand the solubility increases because of the formation of very stable ternary complexes that allowed an experimental study over a larger pH range. The structure of the complexes in the ternary system was deduced using a combination of 1 H and 19 F NMR spectroscopy. The 19 F NMR spectra at lower pH, had peaks from the binary fluoride complexes (UO 2 F + , UO 2 F 2 (aq) and UO 2 F 3 - ) that could be used to obtain information on the equilibrium constants in the ternary system; at -log[H 3 O + ] > 4.7 new signals for the complexes (UO 2 ) 2 (EDDA) 2 F 2 2- , and UO 2 (EDDA)F - were observed. The analyses of 1 H NMR spectra indicate clearly that the EDDA ligand is chelate bonded in UO 2 (EDDA)F-. The fluorine exchange between UO 2 (EDDA)F- and UO 2 F 3 - was studied using 19 F NMR line-broadening technique. The experimental rate constant is k obs = k 0 + k 1 [UO 2 F 3 - ], with k 0 (3.24 ± 0.06) 10 2 s -1 and k 1 = (71.2 ± 2.3) 10 3 M -1 s -1 .The rate and the activation parameters for the exchange between UO 2 (EDDA)F - complex and free

  6. Highly stable [mambf6-n(o/h2o)n(ligand)2(solvent)x]n metal organic frameworks

    KAUST Repository

    Eddaoudi, Mohamed; Adil, Karim; Belmabkhout, Youssef; Shekhah, Osama; Bhatt, Prashant M.; Cadiau, Amandine

    2016-01-01

    Provided herein are metal organic frameworks having high selectivity and stability in the present of gases and vapors including H2S, H2O, and CO2. Metal organic frameworks can comprise metal nodes and N-donor organic ligands. Further provided

  7. Biological variation and reference intervals for circulating osteopontin, osteoprotegerin, total soluble receptor activator of nuclear factor kappa B ligand and high-sensitivity C-reactive protein

    DEFF Research Database (Denmark)

    Sennels, H P; Jacobsen, Søren; Jensen, T

    2007-01-01

    Objective. Monitoring inflammatory diseases and osteoclastogenesis with osteopontin (OPN), osteoprotegerin (OPG), total soluble receptor activator of nuclear factor kappa B ligand (total sRANKL) and high-sensitivity C-reactive protein (hsCRP) has recently attracted increased interest. The purpose...

  8. Spiro(phosphoamidite) ligand (SIPHOS)/Cu(OTf)2-catalyzed highly regio-and stereo-selective hydroborations of internal alkynes with diborane in water

    Institute of Scientific and Technical Information of China (English)

    Qing-Qing Xuan; Ya-Hui Wei; Qiu-Ling Song

    2017-01-01

    The highly regio-and stereoselective hydroborations of unactivated internal alkynes with diboron compound catalyzed by Cu(OTf)2 with spiro(phosphoamidite) as ligand in the presence of Cs2CO3 in water was developed.This protocol was applied efficiently in the aqueous synthesis of multi-substituted vinylboranes.

  9. Highly stable [mambf6-n(o/h2o)n(ligand)2(solvent)x]n metal organic frameworks

    KAUST Repository

    Eddaoudi, Mohamed

    2016-10-13

    Provided herein are metal organic frameworks having high selectivity and stability in the present of gases and vapors including H2S, H2O, and CO2. Metal organic frameworks can comprise metal nodes and N-donor organic ligands. Further provided are methods of making metal organic frameworks.

  10. Digital One Disc One Compound Method for High Throughput Discovery of Prostate Cancer Targeting Ligands

    Science.gov (United States)

    2016-12-01

    efficiency of drug discovery and make a potential impact on modern pharmaceutical industries . 15. SUBJECT TERMS ODOC carriers, barcode, split-mix...approach4-7. Array technologies can construct high density of molecules in an array format on a solid substrate (microchip), from which the chemical...and-play microfluidic packaging scheme, known as Microflego – 3D Microfluidic Assembly, to facilely establish complex 3D microfluidic networks using

  11. Preliminary study on high temperature heat exchanger for nuclear steel making

    Energy Technology Data Exchange (ETDEWEB)

    Nakada, T; Ohtomo, A; Yamada, R; Suzuki, K; Narita, Y [Ishikawajima-Harima Heavy Industries Co. Ltd., Tokyo (Japan)

    1975-05-01

    Both in the high temperature heat exchanger and in the steam reformer, there remain several technical problems to be solved before nuclear steel making is actualized. The loop for use with basic studies of those problems was planned by the Iron and Steel Institute of Japan (ISIJ), and its actual design, construction and co-ordination of tests were undertaken by IHI on behalf of ISIJ. The primary coolant used in the loop was helium having a pressure of approx. 12 kg/cm/sup 2/g and a temperature of approx. 1100/sup 0/C at the inlet of the high temperature heat exchanger, i.e., the test section. Steam, hydrogen, and carbon monoxide were used as secondary coolants. Of the technical problems regarding the high temperature heat exchanger for nuclear steel making, which were selected and studied using the loop, the following items are discussed: (1) heat exchange performance using helium and steam; (2) hydrogen permeation of heat resisting alloys; (3) creep and carburization of heat resisting alloys; amd (4) hydrogen absorption performance of the titanium sponge.

  12. Tumorigenesis induced by the HHV8-encoded chemokine receptor requires ligand modulation of high constitutive activity

    DEFF Research Database (Denmark)

    Holst, P J; Rosenkilde, M M; Manfra, D

    2001-01-01

    sarcoma (KS). Here we demonstrate that several lines of mice carrying mutated receptors deficient in either constitutive activity or chemokine regulation fail to develop KS-like disease. In addition, animals expressing a receptor that preserves chemokine binding and constitutive activity but that does...... not respond to agonist stimulation have a much lower incidence of angiogenic lesions and tumors. These results indicate that induction of the KS-like disease in transgenic mice by ORF74 requires not only high constitutive signaling activity but also modulation of this activity by endogenous chemokines....

  13. THE IMPORTANCE OF AFFECT TO BUILD CONSUMER TRUST IN HIGH-CONSEQUENCES EXCHANGES

    Directory of Open Access Journals (Sweden)

    Mellina da Silva Terres

    2012-12-01

    Full Text Available The present article investigates the importance of affect displayed by service provider to build consumer trust in high consequence exchanges. High-consequence exchanges are difficult situations in which the choices present a dilemma that can cause stress and severe emotional reactions (KAHN; LUCE, 2003. In this specific case, trust based on affect seems to become important; mainly because consumers may not have ability to evaluate the cognitive aspects of the situation, and moreover, a medical services failure can be highly problematic or even fatal (LEISEN; HYMAN, 2004. On the other hand, in low-consequence choices, we are predicting that cognition will be more important than affect in building trust. In this kind of situation, patients are more self-confident, less sensitive, and don’t perceive a high probability of loss (KUNREUTHER et al., 2002, and therefore focuses more on the rational outcomes.

  14. Nanostructure-based proton exchange membrane for fuel cell applications at high temperature.

    Science.gov (United States)

    Li, Junsheng; Wang, Zhengbang; Li, Junrui; Pan, Mu; Tang, Haolin

    2014-02-01

    As a clean and highly efficient energy source, the proton exchange membrane fuel cell (PEMFC) has been considered an ideal alternative to traditional fossil energy sources. Great efforts have been devoted to realizing the commercialization of the PEMFC in the past decade. To eliminate some technical problems that are associated with the low-temperature operation (such as catalyst poisoning and poor water management), PEMFCs are usually operated at elevated temperatures (e.g., > 100 degrees C). However, traditional proton exchange membrane (PEM) shows poor performance at elevated temperature. To achieve a high-performance PEM for high temperature fuel cell applications, novel PEMs, which are based on nanostructures, have been developed recently. In this review, we discuss and summarize the methods for fabricating the nanostructure-based PEMs for PEMFC operated at elevated temperatures and the high temperature performance of these PEMs. We also give an outlook on the rational design and development of the nanostructure-based PEMs.

  15. Fe-Binding Dissolved Organic Ligands in the Oxic and Suboxic Waters of the Black Sea

    NARCIS (Netherlands)

    Gerringa, L.J.A.; Rijkenberg, M.J.A.; Bown, J.; Margolin, A.R.; Laan, P.; De Baar, H.J.W.

    2016-01-01

    In the oxygen-rich layer of the Black Sea, above the permanent halocline, the Fe and nitrate concentrations are low where fluorescence is relatively high, indicating uptake by phytoplankton. In this study we used ligand exchange adsorptive cathodic stripping voltammetry (CLE-aCSV), using

  16. Cyclic GMP-AMP containing mixed phosphodiester linkages is an endogenous high-affinity ligand for STING.

    Science.gov (United States)

    Zhang, Xu; Shi, Heping; Wu, Jiaxi; Zhang, Xuewu; Sun, Lijun; Chen, Chuo; Chen, Zhijian J

    2013-07-25

    The presence of microbial or self DNA in the cytoplasm of mammalian cells is a danger signal detected by the DNA sensor cyclic-GMP-AMP (cGAMP) synthase (cGAS), which catalyzes the production of cGAMP that in turn serves as a second messenger to activate innate immune responses. Here we show that endogenous cGAMP in mammalian cells contains two distinct phosphodiester linkages, one between 2'-OH of GMP and 5'-phosphate of AMP, and the other between 3'-OH of AMP and 5'-phosphate of GMP. This molecule, termed 2'3'-cGAMP, is unique in that it binds to the adaptor protein STING with a much greater affinity than cGAMP molecules containing other combinations of phosphodiester linkages. The crystal structure of STING bound to 2'3'-cGAMP revealed the structural basis of this high-affinity binding and a ligand-induced conformational change in STING that may underlie its activation. Copyright © 2013 Elsevier Inc. All rights reserved.

  17. Local antiferromagnetic exchange and collaborative Fermi surface as key ingredients of high temperature superconductors

    Science.gov (United States)

    Hu, Jiangping; Ding, Hong

    2012-01-01

    Cuprates, ferropnictides and ferrochalcogenides are three classes of unconventional high temperature superconductors, who share similar phase diagrams in which superconductivity develops after a magnetic order is suppressed, suggesting a strong interplay between superconductivity and magnetism, although the exact picture of this interplay remains elusive. Here we show that there is a direct bridge connecting antiferromagnetic exchange interactions determined in the parent compounds of these materials to the superconducting gap functions observed in the corresponding superconducting materials: in all high temperature superconductors, the Fermi surface topology matches the form factor of the pairing symmetry favored by local magnetic exchange interactions. We suggest that this match offers a principle guide to search for new high temperature superconductors. PMID:22536479

  18. Study of some ion exchange minerals which can be used in water at high temperature

    International Nuclear Information System (INIS)

    Hure, J.; Platzer, R.; Bittel, R.; Wey, R.

    1958-01-01

    The study of the use of ion exchangers at high temperature has been carried out mainly with a view to purifying water in reactor circuits. The advantages of keeping high resistivity (from many hundreds to a few million ohm-cm) water within a reactor circuit are known; the decreased corrosion reduction in the amount of radiolysis, decreased radioactivity in the circuits and piping, the elements other than those forming water which are carried with the water usually becoming radioactive as they pass through the reactor. If the water circulation takes place at temperatures less than 75 deg. C continuous purification can be easily carried out by using organic ion exchange resins in agitated beds. However at higher temperatures particularly those above 100 deg. C it is not possible to use these media because of the rapid degradation of the high polymers used. Also the action of the radiation, for example that emanating from the products fixed on the ion exchange media permanently destroys the organic chains making up the skeleton of the resins. We have therefore sought after other compounds which are efficient demineralizer, but which have a structure such that high temperature and radiation do not bring about deterioration. We have especially investigated three main types: - natural ion exchangers having an inorganic structure (montmorillonite type clays); - natural inorganic compounds which have been treated to give them ion exchange properties (activated carbons); - synthetic inorganic compounds (salts having a low solubility such as zirconium and thorium phosphates and hydroxides). In this research we have endeavoured to obtain products which are stable in the presence of water at high temperatures, insoluble and not broken down into fine particles (that is to say not polluting the high resistivity water) and which are capable of giving up H + or OH - ions in exchange for the ions contained in the water or at least capable of forming insoluble compounds with these

  19. Fluorescence-based high-throughput functional profiling of ligand-gated ion channels at the level of single cells.

    Directory of Open Access Journals (Sweden)

    Sahil Talwar

    Full Text Available Ion channels are involved in many physiological processes and are attractive targets for therapeutic intervention. Their functional properties vary according to their subunit composition, which in turn varies in a developmental and tissue-specific manner and as a consequence of pathophysiological events. Understanding this diversity requires functional analysis of ion channel properties in large numbers of individual cells. Functional characterisation of ligand-gated channels involves quantitating agonist and drug dose-response relationships using electrophysiological or fluorescence-based techniques. Electrophysiology is limited by low throughput and high-throughput fluorescence-based functional evaluation generally does not enable the characterization of the functional properties of each individual cell. Here we describe a fluorescence-based assay that characterizes functional channel properties at single cell resolution in high throughput mode. It is based on progressive receptor activation and iterative fluorescence imaging and delivers >100 dose-responses in a single well of a 384-well plate, using α1-3 homomeric and αβ heteromeric glycine receptor (GlyR chloride channels as a model system. We applied this assay with transiently transfected HEK293 cells co-expressing halide-sensitive yellow fluorescent protein and different GlyR subunit combinations. Glycine EC50 values of different GlyR isoforms were highly correlated with published electrophysiological data and confirm previously reported pharmacological profiles for the GlyR inhibitors, picrotoxin, strychnine and lindane. We show that inter and intra well variability is low and that clustering of functional phenotypes permits identification of drugs with subunit-specific pharmacological profiles. As this method dramatically improves the efficiency with which ion channel populations can be characterized in the context of cellular heterogeneity, it should facilitate systems

  20. Pressure drop and heat transfer characteristics of a high-temperature printed circuit heat exchanger

    International Nuclear Information System (INIS)

    Chen, Minghui; Sun, Xiaodong; Christensen, Richard N.; Skavdahl, Isaac; Utgikar, Vivek; Sabharwall, Piyush

    2016-01-01

    Highlights: • Pressure drop and heat transfer characteristics of a high-temperature printed circuit heat exchanger have been obtained. • Comparisons of experimental data and available correlations have been performed. • New Fanning friction factor and heat transfer correlations for the test PCHE are developed. - Abstract: Printed circuit heat exchanger (PCHE) is one of the leading intermediate heat exchanger (IHX) candidates to be employed in the very-high-temperature gas-cooled reactors (VHTRs) due to its capability for high-temperature, high-pressure applications. In the current study, a reduced-scale zigzag-channel PCHE was fabricated using Alloy 617 plates for the heat exchanger core and Alloy 800H pipes for the headers. The pressure drop and heat transfer characteristics of the PCHE were investigated experimentally in a high-temperature helium test facility (HTHF) at The Ohio State University. The PCHE helium inlet temperatures and pressures were varied up to 464 °C/2.7 MPa for the cold side and 802 °C/2.7 MPa for the hot side, respectively, while the maximum helium mass flow rates on both sides of the PCHE reached 39 kg/h. The corresponding maximum channel Reynolds number was approximately 3558, covering the laminar flow and laminar-to-turbulent flow transition regimes. New pressure drop and heat transfer correlations for the current zigzag channels with rounded bends were developed based on the experimental data. Comparisons between the experimental data and the results obtained from the available PCHE and straight circular pipe correlations were conducted. Compared to the heat transfer performance in straight circular pipes, the zigzag channels provided little advantage in the laminar flow regime but significant advantage near the transition flow regime.

  1. HIGH ASPECT RATIO ION EXCHANGE RESIN BED - HYDRAULIC RESULTS FOR SPERICAL RESIN BEADS

    International Nuclear Information System (INIS)

    Duignan, M; Charles Nash, C; Timothy Punch, T

    2007-01-01

    A principal role of the DOE Savannah River Site is to safely dispose of a large volume of liquid nuclear waste held in many storage tanks. An in-tank ion exchange unit is being considered for cesium removal to accelerate waste processing. This unit is planned to have a relatively high bed height to diameter ratio (10:1). Complicating the design is the need to cool the ion exchange media; therefore, the ion exchange column will have a central cooling core making the flow path annular. To separate cesium from waste the media being considered is made of resorcinol formaldehyde resin deposited on spherical plastic beads and is a substitute for a previously tested resin made of crystalline silicotitanate. This spherical media not only has an advantage of being mechanically robust, but, unlike its predecessor, it is also reusable, that is, loaded cesium can be removed through elution and regeneration. Resin regeneration leads to more efficient operation and less spent resin waste, but its hydraulic performance in the planned ion exchange column was unknown. Moreover, the recycling process of this spherical resorcinol formaldehyde causes its volume to significantly shrink and swell. To determine the spherical media's hydraulic demand a linearly scaled column was designed and tested. The waste simulant used was prototypic of the wastes' viscosity and density. This paper discusses the hydraulic performance of the media that will be used to assist in the design of a full-scale unit

  2. Final Report for Project titled High Thermal Conductivity Polymer Composites for Low-Cost Heat Exchangers

    Energy Technology Data Exchange (ETDEWEB)

    Thibaud-Erkey, Catherine [United Technologies reserach Center, East Hartford, CT (United States); Alahyari, Abbas [United Technologies reserach Center, East Hartford, CT (United States)

    2016-12-28

    Heat exchangers (HXs) are critical components in a wide range of heat transfer applications, from HVAC (Heating Ventilation and Cooling) to automobiles to manufacturing plants. They require materials capable of transferring heat at high rates while also minimizing thermal expansion over the usage temperature range. Conventionally, metals are used for applications where effective and efficient heat exchange is required, since many metals exhibit thermal conductivity over 100 W/m K. While metal HXs are constantly being improved, they still have some inherent drawbacks due to their metal construction, in particular corrosion. Polymeric material can offer solution to such durability issues and allow designs that cannot be afforded by metal construction either due to complexity or cost. A major drawback of polymeric material is their low thermal conductivity (0.1-0.5? W/mK) that would lead to large system size. Recent improvements in the area of filled polymers have highlighted the possibility to greatly improve the thermal conductivity of polymeric materials while retaining their inherent manufacturing advantage, and have been applied to heat sink applications. Therefore, the objective of this project was to develop a robust review of materials for the manufacturing of industrial and commercial non-metallic heat exchangers. This review consisted of material identification, literature evaluation, as well as empirical and model characterization, resulting in a database of relevant material properties and characteristics to provide guidance for future heat exchanger development.

  3. High Temperature Heat Exchanger Design and Fabrication for Systems with Large Pressure Differentials

    Energy Technology Data Exchange (ETDEWEB)

    Chordia, Lalit [Thar Energy, LLC, Pittsburgh, PA (United States); Portnoff, Marc A. [Thar Energy, LLC, Pittsburgh, PA (United States); Green, Ed [Thar Energy, LLC, Pittsburgh, PA (United States)

    2017-03-31

    The project’s main purpose was to design, build and test a compact heat exchanger for supercritical carbon dioxide (sCO2) power cycle recuperators. The compact recuperator is required to operate at high temperature and high pressure differentials, 169 bar (~2,500 psi), between streams of sCO2. Additional project tasks included building a hot air-to-sCO2 Heater heat exchanger (HX) and design, build and operate a test loop to characterize the recuperator and heater heat exchangers. A novel counter-current microtube recuperator was built to meet the high temperature high differential pressure criteria and tested. The compact HX design also incorporated a number of features that optimize material use, improved reliability and reduced cost. The air-to-sCO2 Heater HX utilized a cross flow, counter-current, micro-tubular design. This compact HX design was incorporated into the test loop and exceeded design expectations. The test loop design to characterize the prototype Brayton power cycle HXs was assembled, commissioned and operated during the program. Both the prototype recuperator and Heater HXs were characterized. Measured results for the recuperator confirmed the predictions of the heat transfer models developed during the project. Heater HX data analysis is ongoing.

  4. Affinity chromatographic purification of tetrodotoxin by use of tetrodotoxin-binding high molecular weight substances in the body fluid of shore crab (Hemigrapsus sanguineus) as ligands.

    Science.gov (United States)

    Shiomi, K; Yamaguchi, S; Shimakura, K; Nagashima, Y; Yamamori, K; Matsui, T

    1993-12-01

    A purification method for tetrodotoxin (TTX), based on affinity chromatography using the TTX-binding high mol. wt substances in the body fluid of shore crab (Hemigrapsus sanguineus) as ligands, was developed. This method was particularly useful for analysis of TTX in biological samples with low concentrations of TTX. The affinity gel prepared was highly specific for TTX, having no ability to bind 4-epi-TTX and anhydro-TTX as well as saxitoxin.

  5. Direct versus ligand-exchange synthesis of [PtAg28(BDT)12(TPP)4]4− nanoclusters: effect of a single-atom dopant on the optoelectronic and chemical properties

    KAUST Repository

    Bootharaju, Megalamane Siddaramappa

    2017-06-07

    Heteroatom doping of atomically precise nanoclusters (NCs) often yields a mixture of doped and undoped products of single-atom difference, whose separation is extremely difficult. To overcome this challenge, novel synthesis methods are required to offer monodisperse doped NCs. For instance, the direct synthesis of PtAg28 NCs produces a mixture of [Ag29(BDT)12(TPP)4]3- and [PtAg28(BDT)12(TPP)4]4- NCs (TPP: triphenylphosphine; BDT: 1,3-benzenedithiolate). Here, we designed a ligand-exchange (LE) strategy to synthesize single-sized, Pt-doped, superatomic Ag NCs [PtAg28(BDT)12(TPP)4]4- by LE of [Pt2Ag23Cl7(TPP)10] NCs with BDTH2 (1,3-benzenedithiol). The doped NCs were thoroughly characterized by optical and photoelectron spectroscopy, mass spectrometry, total electron count, and time-dependent density functional theory (TDDFT). We show that the Pt dopant occupies the center of the PtAg28 cluster, modulates its electronic structure and enhances its photoluminescence intensity and excited-state lifetime, and also enables solvent interactions with the NC surface. Furthermore, doped NCs showed unique reactivity with metal ions - the central Pt atom of PtAg28 could not be replaced by Au, unlike the central Ag of Ag29 NCs. The achieved synthesis of single-sized PtAg28 clusters will facilitate further applications of the LE strategy for the exploration of novel multimetallic NCs.

  6. High Levels of Chemokine C-C Motif Ligand 20 in Human Milk and Its Production by Oral Keratinocytes.

    Science.gov (United States)

    Lourenço, Alan G; Komesu, Marilena C; Duarte, Geraldo; Del Ciampo, Luiz A; Mussi-Pinhata, Marisa M; Yamamoto, Aparecida Y

    2017-03-01

    Chemokine C-C motif ligand 20 (CCL20) is implicated in the formation and function of mucosal lymphoid tissues. Although CCL20 is secreted by many normal human tissues, no studies have evaluated the presence of CCL20 in human milk or its production by oral keratinocytes stimulated by human milk. To evaluate the presence of CCL20 in breast milk and verify CCL20 secretion in vitro by oral keratinocytes stimulated with human and bovine milk, as well as its possible association with breast milk lactoferrin levels. The levels of CCL20 and lactoferrin were measured by enzyme-linked immunosorbent assay in human milk at three different stages of maturation from 74 healthy breastfeeding mothers. In vitro, oral keratinocytes were stimulated with human and bovine milk, and CCL20 was measured in their supernatant. High concentrations of CCL20 were detected in the human breast milk samples obtained during the first week (1,777.07 pg/mL) and second week postpartum (1,523.44 pg/mL), with a significantly low concentration in samples at 3-6 weeks postpartum (238.42 pg/mL; p stimulated higher CCL20 secretion by oral keratinocytes compared with bovine milk (p stimulation had no association with breast milk lactoferrin concentration. CCl20 is present at high levels in human milk, predominantly in the first and second week postpartum, but at significantly lower levels at 3-6 weeks postpartum. Human milk is capable of stimulating CCL20 secretion by oral keratinocytes, and this induction had no association with breast milk lactoferrin concentration.

  7. Multiple direct exchange in a Yang-Mills theory at high energy

    International Nuclear Information System (INIS)

    McCoy, B.M.; Wu, T.T.

    1976-01-01

    For eighth and higher orders, we obtain the leading high-energy behavior of the sum of all one-layer Feynman diagrams in Yang-Mills theory. These are the contributions from Feynman diagrams where the two incident fast particles exchange directly Yang-Mills bosons that are much less energetic. The incident particles may be either bosons or fermions of arbitrary isospin, and the result is also generalized to include the case of the Higgs scalar. The scattering amplitudes in all these cases are closely related, and all behave as s ln/sub n/ -1 s in the 2n + 2 order. Furthermore, in this leading order for n > or = 2, the exchanged isospins are always 0 and 2, no matter how high the isospins of the incident particles are

  8. High Throughput, Label-free Screening Small Molecule Compound Libraries for Protein-Ligands using Combination of Small Molecule Microarrays and a Special Ellipsometry-based Optical Scanner.

    Science.gov (United States)

    Landry, James P; Fei, Yiyan; Zhu, X D

    2011-12-01

    Small-molecule compounds remain the major source of therapeutic and preventative drugs. Developing new drugs against a protein target often requires screening large collections of compounds with diverse structures for ligands or ligand fragments that exhibit sufficiently affinity and desirable inhibition effect on the target before further optimization and development. Since the number of small molecule compounds is large, high-throughput screening (HTS) methods are needed. Small-molecule microarrays (SMM) on a solid support in combination with a suitable binding assay form a viable HTS platform. We demonstrate that by combining an oblique-incidence reflectivity difference optical scanner with SMM we can screen 10,000 small-molecule compounds on a single glass slide for protein ligands without fluorescence labeling. Furthermore using such a label-free assay platform we can simultaneously acquire binding curves of a solution-phase protein to over 10,000 immobilized compounds, thus enabling full characterization of protein-ligand interactions over a wide range of affinity constants.

  9. Dynamic Model of the High Temperature Proton Exchange Membrane Fuel Cell Stack Temperature

    DEFF Research Database (Denmark)

    Andreasen, Søren Juhl; Kær, Søren Knudsen

    2009-01-01

    The present work involves the development of a model for predicting the dynamic temperature of a high temperature proton exchange membrane (HTPEM) fuel cell stack. The model is developed to test different thermal control strategies before implementing them in the actual system. The test system co...... elements for start-up, heat conduction through stack insulation, cathode air convection, and heating of the inlet gases in the manifold. Various measurements are presented to validate the model predictions of the stack temperatures....

  10. One photon exchange processes and the calibration of polarization of high energy protons

    International Nuclear Information System (INIS)

    Margolis, B.; Thomas, G.H.

    1978-01-01

    Polarization phenomena in small momentum transfer high energy one-photon exchange processes in the reaction p + A → X + A where A is a complex nucleus and X is anything are examined. It is shown that these polarizations can be related directly to photoproduction polarization effects in the reaction γ + p → X at low energies. Explicit formulae are written for polarization effects in the case where X → π 0 + p

  11. Development of Highly Nano-Dispersed NiO/GDC Catalysts from Ion Exchange Resin Templates

    Directory of Open Access Journals (Sweden)

    Angel Caravaca

    2017-11-01

    Full Text Available Novel NiO/GDC (Gadolinium-doped Ceria cermet catalysts were developed by the Weak Acid Resin (WAR method using an ion exchange resin template. In addition, the specific surface area of these tunable materials was enhanced by NiO partial dissolution in aqueous acid solution. The whole procedure highly improved the micro-structural properties of these materials compared to previous studies. Catalysts with high metal loadings (≥10%, small Ni nanoparticles (<10 nm, and high specific surface areas (>70 m2/g were achieved. These properties are promising for catalytic applications such as methane steam reforming for H2 production.

  12. Charge-exchange-induced formation of hollow atoms in high-intensity laser-produced plasmas

    Energy Technology Data Exchange (ETDEWEB)

    Rosmej, F.B. [TU-Darmstadt, Institut fuer Kernphysik, Darmstadt (Germany); Faenov, A.Ya.; Pikuz, T.A.; Magunov, A.I.; Skobelev, I.Yu. [Multicharged Ions Spectra Data Center of VNIIFTRI, Mendeleevo (Russian Federation); Auguste, T.; D' Oliveira, P.; Hulin, S.; Monot, P. [Commissariat a lEnergie Atomique DSM/DRECAM/SPAM, Gif-Sur-Yvette Cedex (France); Andreev, N.E.; Chegotov, M.V.; Veisman, M.E. [High Energy Density Research Centre, Institute of High Temperatures of Russian Academy of Sciences, Moscow (Russian Federation)

    1999-03-14

    For the first time registration of high-resolution soft x-ray emission and atomic data calculations of hollow-atom dielectronic satellite spectra of highly charged nitrogen have been performed. Double-electron charge-exchange processes from excited states are proposed for the formation of autoionizing levels nln'l' in high-intensity laser-produced plasmas, when field-ionized ions penetrate into the residual gas. Good agreement is found between theory and experiment. Plasma spectroscopy with hollow ions is proposed and a temperature diagnostic for laser-produced plasmas in the long-lasting recombining regime is developed. (author). Letter-to-the-editor.

  13. Heat exchanger

    International Nuclear Information System (INIS)

    Dostatni, A.W.; Dostatni, Michel.

    1976-01-01

    In the main patent, a description was given of a heat exchanger with an exchange surface in preformed sheet metal designed for the high pressure and temperature service particularly encountered in nuclear pressurized water reactors and which is characterised by the fact that it is composed of at least one exchanger bundle sealed in a containment, the said bundle or bundles being composed of numerous juxtaposed individual compartments whose exchange faces are built of preformed sheet metal. The present addendun certificate concerns shapes of bundles and their positioning methods in the exchanger containment enabling its compactness to be increased [fr

  14. High Pressure ZZ-Exchange NMR Reveals Key Features of Protein Folding Transition States.

    Science.gov (United States)

    Zhang, Yi; Kitazawa, Soichiro; Peran, Ivan; Stenzoski, Natalie; McCallum, Scott A; Raleigh, Daniel P; Royer, Catherine A

    2016-11-23

    Understanding protein folding mechanisms and their sequence dependence requires the determination of residue-specific apparent kinetic rate constants for the folding and unfolding reactions. Conventional two-dimensional NMR, such as HSQC experiments, can provide residue-specific information for proteins. However, folding is generally too fast for such experiments. ZZ-exchange NMR spectroscopy allows determination of folding and unfolding rates on much faster time scales, yet even this regime is not fast enough for many protein folding reactions. The application of high hydrostatic pressure slows folding by orders of magnitude due to positive activation volumes for the folding reaction. We combined high pressure perturbation with ZZ-exchange spectroscopy on two autonomously folding protein domains derived from the ribosomal protein, L9. We obtained residue-specific apparent rates at 2500 bar for the N-terminal domain of L9 (NTL9), and rates at atmospheric pressure for a mutant of the C-terminal domain (CTL9) from pressure dependent ZZ-exchange measurements. Our results revealed that NTL9 folding is almost perfectly two-state, while small deviations from two-state behavior were observed for CTL9. Both domains exhibited large positive activation volumes for folding. The volumetric properties of these domains reveal that their transition states contain most of the internal solvent excluded voids that are found in the hydrophobic cores of the respective native states. These results demonstrate that by coupling it with high pressure, ZZ-exchange can be extended to investigate a large number of protein conformational transitions.

  15. High Frequency of Programmed Death-ligand 1 Expression in Emphysematous Bullae-associated Lung Adenocarcinomas.

    Science.gov (United States)

    Toyokawa, Gouji; Takada, Kazuki; Okamoto, Tatsuro; Kozuma, Yuka; Matsubara, Taichi; Haratake, Naoki; Takamori, Shinkichi; Akamine, Takaki; Katsura, Masakazu; Shoji, Fumihiro; Oda, Yoshinao; Maehara, Yoshihiko

    2017-09-01

    Emphysematous bullae (EB) are known to be associated with a high incidence of lung cancer; however, the reason for this has yet to be elucidated. The objective of the present study was to clarify the prevalence of programmed death-ligand-1 (PD-L1) expression in EB-associated lung adenocarcinomas. A total of 369 patients with resected lung adenocarcinoma whose preoperative computed tomography findings were available for the examination of EB were analyzed for PD-L1 expression by immunohistochemistry and evaluated to determine the association between PD-L1 expression and EB-related adenocarcinomas. Among 369 patients, EB and cancer adjoining EB (Ca-ADJ) were identified in 81 (22.0%) and 50 (13.6%) patients, respectively. EB and Ca-ADJ were significantly associated with male gender, a smoking habit, a decreased forced expiratory volume in 1 second, a relatively higher tumor grade, advanced T status and stage, the presence of pleural and vessel invasion, invasive pathologic subtypes, and wild-type epidermal growth factor receptor. Seventy patients (19.0%) were positive for PD-L1 expression, whereas the remaining 299 patients (81.0%) were negative. Thirty-six (44.4%) and 29 (58.0%) of 81 and 50 patients with EB and Ca-ADJ, respectively, were positive for PD-L1 expression, which was shown to be significant by the Fisher exact test (P < .001 and P < .001, respectively). Among the 81 lung adenocarcinomas with EB, Ca-ADJ was significantly associated with PD-L1 expression (P = .021). In a multivariate analysis, the presence of Ca-ADJ was found to be an independent predictor of PD-L1 expression. EB-associated lung adenocarcinomas express PD-L1 protein more frequently than those without EB. Copyright © 2016 Elsevier Inc. All rights reserved.

  16. Versatile ligands for high-performance liquid chromatography: An overview of ionic liquid-functionalized stationary phases.

    Science.gov (United States)

    Zhang, Mingliang; Mallik, Abul K; Takafuji, Makoto; Ihara, Hirotaka; Qiu, Hongdeng

    2015-08-05

    Ionic liquids (ILs), a class of unique substances composed purely by cation and anions, are renowned for their fascinating physical and chemical properties, such as negligible volatility, high dissolution power, high thermal stability, tunable structure and miscibility. They are enjoying ever-growing applications in a great diversity of disciplines. IL-modified silica, transforming the merits of ILs into chromatographic advantages, has endowed the development of high-performance liquid chromatography (HPLC) stationary phase with considerable vitality. In the last decade, IL-functionalized silica stationary phases have evolved into a series of branches to accommodate to different HPLC modes. An up-to-date overview of IL-immobilized stationary phases is presented in this review, and divided into five parts according to application mode, i.e., ion-exchange, normal-phase, reversed-phase, hydrophilic interaction and chiral recognition. Specific attention is channeled to synthetic strategies, chromatographic behavior and separation performance of IL-functionalized silica stationary phases. Copyright © 2015 Elsevier B.V. All rights reserved.

  17. Effect of radiant heat transfer on the performance of high temperature heat exchanger

    International Nuclear Information System (INIS)

    Mori, Yasuo; Hijikata, Kunio; Yamada, Yukio

    1975-01-01

    The development of high temperature gas-cooled reactors is motivated by the consideration of the application of nuclear heat for industrial uses or direct steelmaking and chemical processes. For these purposes, reliable and efficient heat exchangers should be developed. This report analyzes the effect of radiant heat transfer on the performance of high temperature heat exchangers. The heat transfer model is as follows: the channel composed with two parallel adiabatic walls is divided with one parallel plate between the walls. Non-radiative fluid flows in the two separated channels in opposite direction. Heat transfer equations for this system were obtained, and these equations were solved by some approximate method and numerical analysis. The effect of radiation on heat transfer became larger as the radiant heat transfer between two walls was larger. In the heat exchangers of counter flow type, the thermal efficiency is controlled with three parameters, namely radiation-convection parameter, Stanton number and temperature difference. The thermal efficiency was larger with the increase of these parameters. (Iwase, T.)

  18. Energy loss and charge exchange processes of high energy heavy ions channeled in crystals

    International Nuclear Information System (INIS)

    Poizat, J.C.; Andriamonje, S.; Anne, R.; Faria, N.V.d.C.; Chevallier, M.; Cohen, C.; Dural, J.; Farizon-Mazuy, B.; Gaillard, M.J.; Genre, R.; Hage-Ali, M.; Kirsch, R.; L'hoir, A.; Mory, J.; Moulin, J.; Quere, Y.; Remillieux, J.; Schmaus, D.; Toulemonde, M.

    1990-01-01

    The interaction of moving ions with single crystals is very sensitive to the orientation of the incident beam with respect to the crystalline directions of the target. Our experiments show that high energy heavy ion channeling deeply modifies their slowing down and charge exchange processes. This is due to the fact that channeled ions interact only with outershell target electrons, which means that the electron density they experience is very low and that the binding energy, and then the momentum distribution of these electrons, are quite different from the corresponding average values associated to random incidence. The two experimental studies presented here show the reduction of the energy loss rate for fast channeled heavy ions and illustrate the two aspects of channeling effects on charge exchange, the reduction of electron loss on one hand, and of electron capture on the other hand

  19. Mechanizing the Merc: The Chicago Mercantile Exchange and the Rise of High-Frequency Trading.

    Science.gov (United States)

    MacKenzie, Donald

    2015-07-01

    This article investigates one important strand in the evolution of today's high-frequency trading or HFT (the fast, automated trading of large numbers of financial securities). That strand is the history of the automation of trading on what has become the world's most prominent futures exchange, the Chicago Mercantile Exchange or Merc. The process of the automation of the Merc was episodic, often driven by responses to perceived external threats, and involved both "local" politics and transnational considerations. The article discusses the relationship between the Merc's automation and the embodied, deeply social trading practices of the Merc's open-outcry trading pits, and compares how the Merc was mechanized with the quite different-and in a sense more explicitly "social"-project of automation launched by the Merc's rival, the Chicago Board of Trade.

  20. Cation exchange separation of 16 rare earth metals by microscale high-performance liquid chromatography

    International Nuclear Information System (INIS)

    Ishii, D.; Hirose, A.; Iwasaki, Y.

    1978-01-01

    The separation of rare earth metals has been studied with a microcolumn of 0.5 mm i.d. and 75 mm length, packed with TSK LS-212 high-performance cation exchange resin. A micro-feeder (Model MF-2, from Azumadenki Kogyo) was used to drive carrier and sample solutions through the ion exchange column and detection cell. By combining a 250 μl syringe and a 0.5 mm i.d. sampling tube the micro-feeder, 0.1-1.0 μl rare earth metals were separated within 38 min, using only 304 μl of 0.4M α-hydroxy-isobutyric acid solution adjusted to pH 3.1-6.0 with ammonia solution as gradient carrier solution. The gradient elution was successfully performed by applying a new technique developed for microscale liquid chromatography. (author)

  1. Simulation of high-resolution MFM tip using exchange-spring magnet

    Energy Technology Data Exchange (ETDEWEB)

    Saito, H. [Faculty of Resource Science and Engineering, Akita University, Akita 010-8502 (Japan)]. E-mail: hsaito@ipc.akita-u.ac.jp; Yatsuyanagi, D. [Faculty of Resource Science and Engineering, Akita University, Akita 010-8502 (Japan); Ishio, S. [Faculty of Resource Science and Engineering, Akita University, Akita 010-8502 (Japan); Ito, A. [Nitto Optical Co. Ltd., Misato, Akita 019-1403 (Japan); Kawamura, H. [Nitto Optical Co. Ltd., Misato, Akita 019-1403 (Japan); Ise, K. [Research Institute of Advanced Technology Akita, Akita 010-1623 (Japan); Taguchi, K. [Research Institute of Advanced Technology Akita, Akita 010-1623 (Japan); Takahashi, S. [Research Institute of Advanced Technology Akita, Akita 010-1623 (Japan)

    2007-03-15

    The transfer function of magnetic force microscope (MFM) tips using an exchange-spring trilayer composed of a centered soft magnetic layer and two hard magnetic layers was calculated and the resolution was estimated by considering the thermodynamic noise limit of an MFM cantilever. It was found that reducing the thickness of the centered soft magnetic layer and the magnetization of hard magnetic layer are important to obtain high resolution. Tips using an exchange-spring trilayer with a very thin FeCo layer and isotropic hard magnetic layers, such as CoPt and FePt, are found to be suitable for obtaining a resolution less than 10 nm at room temperature.

  2. Insertion of Guest Molecules into a Mixed Ligand Metal-Organic Framework via Single-Crystal-to-Single Crystal Guest Exchange

    Science.gov (United States)

    2014-07-01

    Research Laboratory (ARL) in the 2012 Summer Intern Program. This research was supported by an appointment to the Research Participation Program at ARL...flexible and different from traditional microporous materials like zeolites, which are fully inorganic and thus lack synthetic flexibility. During...adsorbed into this porous structure. MOFs have a number of useful properties such as large internal surface areas (some as high as 10 3 –10 5 m 2 /g

  3. Carbon dioxide exchange in the High Arctic - examples from terrestrial ecosystems

    DEFF Research Database (Denmark)

    Grøndahl, L.

    of the growing season, which in combination with high temperatures increased uptake rates. The dry heath ecosystem in general gained carbon during the summer season in the order of magnitude -1.4 gCm-2 up to 32 gCm-2. This result is filling out a gap of knowledge on the response of high Arctic ecosystems...... the measurements conducted in the valley to a regional level. Including information on temporal and spatial variability in air temperature and radiation, together with NDVI and a vegetation map a regional estimate of the CO2 exchange during the summer was provided, elaborating the NDVI based estimate on net carbon...

  4. Characterization of protein/ligand interactions by 1H/3H exchange: application to the hAsf1/ histone H3 complex

    International Nuclear Information System (INIS)

    Mousseau, G.

    2007-05-01

    In the first chapter will be exposed the main current methods of identification to high debit of the interactions protein-protein. Then the methods allowing to characterize the surfaces of interaction or to determine the structures of the complexes will be listed by discussing the main advantages and the inconveniences. Our approach of characterization of the zones of interaction protein-protein is a method of 'foot-printing' 1, based on the identification and radicals' quantification formed on the residues of proteins accessible to the water. The second chapter will so discuss the development of this method of radical identification using the atom of tritium as radioactive label. Our approach will finally be validated in the third chapter by applying it to the characterization of amino acids involved in the interaction enter the human protein anti silencing factor 1 (hAsf11-156) and a fragment of the histone H 3 . (N.C.)

  5. Epoxides cross-linked hexafluoropropylidene polybenzimidazole membranes for application as high temperature proton exchange membranes

    International Nuclear Information System (INIS)

    Yang, Jingshuai; Xu, Yixin; Liu, Peipei; Gao, Liping; Che, Quantong; He, Ronghuan

    2015-01-01

    Covalently cross-linked hexafluoropropylidene polybenzimidazole (F 6 PBI) was prepared and used to fabricate high temperature proton exchange membranes with enhanced mechanical strength against thermoplastic distortion. Three different epoxides, i.e. bisphenol A diglycidyl ether (R 1 ), bisphenol A propoxylate diglycidyl ether (R 2 ) and poly(ethylene glycol) diglycidyl ether (R 3 ), were chosen as the cross-linkers to investigate the influence of their structures on the properties of the cross-linked F 6 PBI membranes. All the cross-linked F 6 PBI membranes displayed excellent stability towards the radical oxidation. Comparing with the pure F 6 PBI membrane, the cross-linked F 6 PBI membranes showed high acid doping level but less swelling after doping phosphoric acid at elevated temperatures. The mechanical strength at 130 °C was improved from 0.4 MPa for F 6 PBI membrane to a range of 0.8–2.0 MPa for the cross-linked F 6 PBI membranes with an acid doping level as high as around 14, especially for that crosslinking with the epoxide (R 3 ), which has a long linear structure of alkyl ether. The proton conductivity of the cross-linked membranes was increased accordingly due to the high acid doping levels. Fuel cell tests demonstrated the technical feasibility of the acid doped cross-linked F 6 PBI membranes for high temperature proton exchange membrane fuel cells

  6. Preparation and characterization of zirconium phosphate ion exchanger samples with respect to the separation of highly active actinoid elements

    International Nuclear Information System (INIS)

    Treplan, J.

    1972-01-01

    Inorganic ion exchangers are of growing interest in connection with separation processes of α-radiators of high specific activity, or with high gamma doses, because they have a considerably higher radiation resistance at their disposal compared to the commonly used organic ion exchangers. In opposition to their use, however, are the worse properties regarding capacity, chemical resistivity, exchange rate and reproducibility of the ion exchange bed. In the present work, an attempt has been made to influence the properties of a typical representative of this group, zirconium phosphate (ZP), by systematic changing of the preparation parameters in such a manner that a sufficient capacity is obtained regarding tri-valent ions. In addition, information is to be gathered in order to clarify the connection between exchanger property and structure of the ZP. (orig./LH) [de

  7. Technology Development Roadmap for the Advanced High Temperature Reactor Secondary Heat Exchanger

    Energy Technology Data Exchange (ETDEWEB)

    P. Sabharwall; M. McCllar; A. Siahpush; D. Clark; M. Patterson; J. Collins

    2012-09-01

    This Technology Development Roadmap (TDRM) presents the path forward for deploying large-scale molten salt secondary heat exchangers (MS-SHX) and recognizing the benefits of using molten salt as the heat transport medium for advanced high temperature reactors (AHTR). This TDRM will aid in the development and selection of the required heat exchanger for: power production (the first anticipated process heat application), hydrogen production, steam methane reforming, methanol to gasoline production, or ammonia production. This TDRM (a) establishes the current state of molten salt SHX technology readiness, (b) defines a path forward that systematically and effectively tests this technology to overcome areas of uncertainty, (c) demonstrates the achievement of an appropriate level of maturity prior to construction and plant operation, and (d) identifies issues and prioritizes future work for maturing the state of SHX technology. This study discusses the results of a preliminary design analysis of the SHX and explains the evaluation and selection methodology. An important engineering challenge will be to prevent the molten salt from freezing during normal and off-normal operations because of its high melting temperature (390°C for KF ZrF4). The efficient transfer of energy for industrial applications depends on the ability to incorporate cost-effective heat exchangers between the nuclear heat transport system and industrial process heat transport system. The need for efficiency, compactness, and safety challenge the capabilities of existing heat exchanger technology. The description of potential heat exchanger configurations or designs (such as printed circuit, spiral or helical coiled, ceramic, plate and fin, and plate type) were covered in an earlier report (Sabharwall et al. 2011). Significant future work, much of which is suggested in this report, is needed before the benefits and full potential of the AHTR can be realized. The execution of this TDRM will focuses

  8. 1,2,4-Triazines in the Synthesis of Bipyridine Bisphenolate ONNO Ligands and Their Highly Luminescent Tetradentate Pt(II) Complexes for Solution-Processable OLEDs.

    Science.gov (United States)

    Pander, Piotr; Bulmer, Rachel; Martinscroft, Ross; Thompson, Stuart; Lewis, Frank W; Penfold, Thomas J; Dias, Fernando B; Kozhevnikov, Valery N

    2018-04-02

    This article describes a convenient method for the synthesis of ONNO-type tetradentate 6,6'-bis(2-phenoxy)-2,2'-bipyridine (bipyridine bisphenolate, BpyBph) ligands and their platinum(II) complexes. The methodology includes the synthesis of 1,2,4-triazine precursors followed by their transformation to functionalized pyridines by the Boger reaction. Two complementary routes employing 3,3'- and 5,5'-bis-triazines allow a modification of the central pyridine rings in different positions, which was exemplified by the introduction of cyclopentene rings. The new ligands were used to prepare highly luminescent ONNO-type Pt(II) complexes. The position of the cyclopentene rings significantly influences the solubility and photophysical properties of these complexes. Derivatives with closely positioned cyclopentene rings are soluble in organic solvents and proved to be the best candidate for solution-processable organic light-emitting devices (OLEDs), showing efficient single-dopant candlelight electroluminescence.

  9. Tris-(hydroxyamino)triazines: high-affinity chelating tridentate O,N,O-hydroxylamine ligand for the cis-V(V)O2(+) cation.

    Science.gov (United States)

    Nikolakis, Vladimiros A; Exarchou, Vassiliki; Jakusch, Tamás; Woolins, J Derek; Slawin, Alexandra M Z; Kiss, Tamás; Kabanos, Themistoklis A

    2010-10-14

    The treatment of the trichloro-1,3,5-triazine with N-methylhydroxylamine hydrochloride results in the replacement of the three chlorine atoms of the triazine ring with the function -N(OH)CH(3) yielding the symmetrical tris-(hydroxyamino)triazine ligand H(3)trihyat. Reaction of the ligand H(3)trihyat with NaV(V)O(3) in aqueous solution followed by addition of Ph(4)PCl gave the mononuclear vanadium(V) compound Ph(4)P[V(V)O(2)(Htrihyat)] (1). The structure of compound 1 was determined by X-ray crystallography and indicates that this compound has a distorted square-pyramidal arrangement around vanadium. The ligand Htrihyat(2-) is bonded to vanadium atom in a tridentate fashion at the triazine ring nitrogen atom and the two deprotonated hydroxylamido oxygen atoms. The high electron density of the triazine ring nitrogen atoms, which results from the resonative contribution of electrons of exocyclic nitrogen atoms, leads to a very strong V-N bond. The cis-[V(V)O(2)(Htrihyat)](-) species exhibits high hydrolytic stability in aqueous solution over a wide pH range, 2.5-11.5, as was evidenced by potentiometry.

  10. Ion-exchange preparation of high-purity vanadium acid from industrial liquors

    International Nuclear Information System (INIS)

    Sajdakhmedov, U.A.; Arslanov, Sh.S.; Vulikh, A.I.

    1994-01-01

    The results of investigations on production of special-purity vanadium acid and vanadium oxide directly from process solutions (technical grade liquors) using ionites are presented. Potentiality of thorough purification of vanadium(5) oxide, when producing vanadium acid on the KU-2 cationite with subsequent purification on anionite, is shown. On the basis of the results obtained a principle flowsheet of ion-exchange production of high-purity vanadium(5) oxide from industrial liquors has been developed. 2 refs.; 1 fig.; 4 tabs

  11. Trace elements in migrating high-temperature fluids: Effects of diffusive exchange with the adjoining solid

    Science.gov (United States)

    Kenyon, Patricia M.

    1993-01-01

    Trace element concentrations and isotopic ratios are frequently used to study the behavior of high-temperature fluids in both metamorphic and igneous systems. Many theoretical formulations of the effects of fluid migration on trace elements have assumed instantaneous reequilibration between the migrating fluid and the solid material through which it is passing. This paper investigates the additional effects which arise when equilibration is not instantaneous due to a limited rate of diffusion in the solid, using an analytical steady state solution to a set of partial differential equations describing the exchange of trace elements between the fluid and the solid during the migration of the fluid.

  12. High-throughput preparation and testing of ion-exchanged zeolites

    International Nuclear Information System (INIS)

    Janssen, K.P.F.; Paul, J.S.; Sels, B.F.; Jacobs, P.A.

    2007-01-01

    A high-throughput research platform was developed for the preparation and subsequent catalytic liquid-phase screening of ion-exchanged zeolites, for instance with regard to their use as heterogeneous catalysts. In this system aqueous solutions and other liquid as well as solid reagents are employed as starting materials and 24 samples are prepared on a library plate with a 4 x 6 layout. Volumetric dispensing of metal precursor solutions, weighing of zeolite and subsequent mixing/washing cycles of the starting materials and distributing reaction mixtures to the library plate are automatically performed by liquid and solid handlers controlled by a single common and easy-to-use programming software interface. The thus prepared materials are automatically contacted with reagent solutions, heated, stirred and sampled continuously using a modified liquid handling. The high-throughput platform is highly promising in enhancing synthesis of catalysts and their screening. In this paper the preparation of lanthanum-exchanged NaY zeolites (LaNaY) on the platform is reported, along with their use as catalyst for the conversion of renewables

  13. Effect of radiation heat transfer on the performance of high temperature heat exchanger, (2)

    International Nuclear Information System (INIS)

    Yamada, Yukio; Mori, Yasuo; Hijikata, Kunio.

    1977-01-01

    In high temperature helium gas-cooled reactors, the nuclear energy can be utilized effectively, and the safety is excellent as compared with conventional reactors. They are advantageous also in view of environmental problems. In this report, the high temperature heat exchanger used for heating steam with the helium from a high temperature gas reactor is modeled, and the case that radiating gas flow between parallel plates is considered. Analysis was made on the case of one channel and constant heat flux and on the model for a counter-flow type heat exchanger with two channels, and the effect of radiation on the heat transfer in laminar flow and turbulent flow regions was clarified theoretically. The basic equations, the method of approximate solution and the results of calculation are explained. When one dimensional radiation was considered, the representative temperature Tr regarding fluid radiation was introduced, and its relation to mean mixing temperature Tm was determined. It was clarified that the large error in the result did not arise even if Tr was taken equally to Tm, especially in case of turbulent flow. The error was practically negligible when the rate of forced convection heat transfer in case of radiating medium flow was taken same as that in the case without radiation. (Kako, I.)

  14. Directly patching high-level exchange-correlation potential based on fully determined optimized effective potentials

    Science.gov (United States)

    Huang, Chen; Chi, Yu-Chieh

    2017-12-01

    The key element in Kohn-Sham (KS) density functional theory is the exchange-correlation (XC) potential. We recently proposed the exchange-correlation potential patching (XCPP) method with the aim of directly constructing high-level XC potential in a large system by patching the locally computed, high-level XC potentials throughout the system. In this work, we investigate the patching of the exact exchange (EXX) and the random phase approximation (RPA) correlation potentials. A major challenge of XCPP is that a cluster's XC potential, obtained by solving the optimized effective potential equation, is only determined up to an unknown constant. Without fully determining the clusters' XC potentials, the patched system's XC potential is "uneven" in the real space and may cause non-physical results. Here, we developed a simple method to determine this unknown constant. The performance of XCPP-RPA is investigated on three one-dimensional systems: H20, H10Li8, and the stretching of the H19-H bond. We investigated two definitions of EXX: (i) the definition based on the adiabatic connection and fluctuation dissipation theorem (ACFDT) and (ii) the Hartree-Fock (HF) definition. With ACFDT-type EXX, effective error cancellations were observed between the patched EXX and the patched RPA correlation potentials. Such error cancellations were absent for the HF-type EXX, which was attributed to the fact that for systems with fractional occupation numbers, the integral of the HF-type EXX hole is not -1. The KS spectra and band gaps from XCPP agree reasonably well with the benchmarks as we make the clusters large.

  15. Treatment with constitutive androstane receptor ligand during pregnancy prevents insulin resistance in offspring from high-fat diet-induced obese pregnant mice.

    Science.gov (United States)

    Masuyama, Hisashi; Hiramatsu, Yuji

    2012-07-15

    The constitutive androstane receptor (CAR) has been reported to decrease insulin resistance even during pregnancy, while exposure to a high-fat diet (HFD) in utero in mice can induce a type 2 diabetes phenotype that can be transmitted to the progeny. Therefore, we examined whether treatment with a CAR ligand during pregnancy could prevent hypertension, insulin resistance, and hyperlipidemia in the offspring from HFD-induced obese pregnant mice (OH mice). We employed four groups of offspring from HFD-fed and control diet-fed pregnant mice with or without treatment with a CAR ligand. Treatment with a CAR ligand during pregnancy improved glucose tolerance and the levels of triglyceride and adipocytokine and restored the changes induced by HFD with amelioration of hypertension in the adult OH mice. This treatment also increased adiponectin mRNA expression, suppressed leptin expression in adipose tissues of OH mice, and abolished the effect of HFD on the epigenetic modifications of the genes encoding adiponectin and leptin in the offspring during immaturity and adulthood. Our data suggest that CAR might be a potential therapeutic target to prevent metabolic syndrome in adulthood of offspring exposed to an HFD in utero.

  16. High Efficiency, High Temperature Foam Core Heat Exchanger for Fission Surface Power Systems, Phase II

    Data.gov (United States)

    National Aeronautics and Space Administration — Fission-based power systems with power levels of 30 to ≥100 kWe will be needed for planetary surface bases. Development of high temperature, high efficiency heat...

  17. High-Temperature Structural Analysis Model of the Process Heat Exchanger for Helium Gas Loop (II)

    International Nuclear Information System (INIS)

    Song, Kee Nam; Lee, Heong Yeon; Kim, Chan Soo; Hong, Seong Duk; Park, Hong Yoon

    2010-01-01

    PHE (Process Heat Exchanger) is a key component required to transfer heat energy of 950 .deg. C generated in a VHTR (Very High Temperature Reactor) to the chemical reaction that yields a large quantity of hydrogen. Korea Atomic Energy Research Institute established the helium gas loop for the performance test of components, which are used in the VHTR, and they manufactured a PHE prototype to be tested in the loop. In this study, as part of the high temperature structural-integrity evaluation of the PHE prototype, which is scheduled to be tested in the helium gas loop, we carried out high-temperature structural-analysis modeling, thermal analysis, and thermal expansion analysis of the PHE prototype. The results obtained in this study will be used to design the performance test setup for the PHE prototype

  18. Kinetics of the high temperature oxygen exchange reaction on {sup 238}PuO{sub 2} powder

    Energy Technology Data Exchange (ETDEWEB)

    Whiting, Christofer E., E-mail: chris.whiting@udri.udayton.edu [University of Dayton – Research Institute, 300 College Park, Dayton, OH 45469-0172 (United States); Du, Miting; Felker, L. Kevin; Wham, Robert M. [Oak Ridge National Laboratory, P.O. Box 2008, Oak Ridge, TN 37831 (United States); Barklay, Chadwick D.; Kramer, Daniel P. [University of Dayton – Research Institute, 300 College Park, Dayton, OH 45469-0172 (United States)

    2015-12-15

    Oxygen exchange reactions performed on PuO{sub 2} suggest the reaction is influenced by at least three mechanisms: an internal chemical reaction, surface mobility of active species/defects, and surface exchange of gaseous oxygen with lattice oxygen. Activation energies for the surface mobility and internal chemical reaction are presented. Determining which mechanism is dominant appears to be a complex function including at least specific surface area and temperature. Thermal exposure may also impact the oxygen exchange reaction by causing reductions in the specific surface area of PuO{sub 2}. Previous CeO{sub 2} surrogate studies exhibit similar behavior, confirming that CeO{sub 2} is a good qualitative surrogate for PuO{sub 2}, in regards to the oxygen exchange reaction. Comparison of results presented here with previous work on the PuO{sub 2} oxygen exchange reaction allows complexities in the previous work to be explained. These explanations allowed new conclusions to be drawn, many of which confirm the conclusions presented here. - Highlights: • PuO{sub 2} Oxygen exchange kinetics can be influenced by at least 3 different mechanisms. • An internal chemical reaction controls the rate at high temperature and large SSA. • Surface mobility and surface exchange influence rate at lower temperatures and SSA. • Exchange temperatures may alter SSA and make data difficult to interpret.

  19. Bitopic Ligands and Metastable Binding Sites

    DEFF Research Database (Denmark)

    Fronik, Philipp; Gaiser, Birgit I; Sejer Pedersen, Daniel

    2017-01-01

    of orthosteric binding sites. Bitopic ligands have been employed to address the selectivity problem by combining (linking) an orthosteric ligand with an allosteric modulator, theoretically leading to high-affinity subtype selective ligands. However, it remains a challenge to identify suitable allosteric binding...... that have been reported to date, this type of bitopic ligands would be composed of two identical pharmacophores. Herein, we outline the concept of bitopic ligands, review metastable binding sites, and discuss their potential as a new source of allosteric binding sites....

  20. High spatial and temporal resolution charge exchange recombination spectroscopy on the HL-2A tokamak

    Energy Technology Data Exchange (ETDEWEB)

    Wei, Y. L.; Yu, D. L., E-mail: yudl@swip.ac.cn; Liu, L.; Cao, J. Y.; Sun, A. P.; Ma, Q.; Chen, W. J.; Liu, Yi; Yan, L. W.; Yang, Q. W.; Duan, X. R.; Liu, Yong [Southwestern Institute of Physics, Chengdu 610041 (China); Ida, K. [National Institute for Fusion Science, Toki 509-5292 (Japan); Hellermann, M. von [ITER Diagnostic Team, IO, Route de Vinon sur Verdon, 13115 St Paul lez Durance (France); FOM-Institute for Plasma physics “Rijnhuizen,” Association EURATOM, Trilateral Euregio Cluster, 3430 BE Nieuwegein (Netherlands)

    2014-10-01

    A 32/64-channel charge exchange recombination spectroscopy (CXRS) diagnostic system is developed on the HL-2A tokamak (R = 1.65 m, a = 0.4 m), monitoring plasma ion temperature and toroidal rotation velocity simultaneously. A high throughput spectrometer (F/2.8) and a pitch-controlled fiber bundle enable the temporal resolution of the system up to 400 Hz. The observation geometry and an optimized optic system enable the highest radial resolution up to ~1 cm at the plasma edge. The CXRS system monitors the carbon line emission (C VI, n = 8–7, 529.06 nm) whose Doppler broadening and Doppler shift provide ion temperature and plasma rotation velocity during the neutral beam injection. The composite CX spectral data are analyzed by the atomic data and analysis structure charge exchange spectroscopy fitting (ADAS CXSFIT) code. First experimental results are shown for the case of HL-2A plasmas with sawtooth oscillations, electron cyclotron resonance heating, and edge transport barrier during the high-confinement mode (H-mode)

  1. AMPA receptor ligands

    DEFF Research Database (Denmark)

    Strømgaard, Kristian; Mellor, Ian

    2004-01-01

    Alpha-amino-3-hydroxy-5-methyl-4-isoxazole propionic acid (AMPA) receptors (AMPAR), subtype of the ionotropic glutamate receptors (IGRs), mediate fast synaptic transmission in the central nervous system (CNS), and are involved in many neurological disorders, as well as being a key player in the f......Alpha-amino-3-hydroxy-5-methyl-4-isoxazole propionic acid (AMPA) receptors (AMPAR), subtype of the ionotropic glutamate receptors (IGRs), mediate fast synaptic transmission in the central nervous system (CNS), and are involved in many neurological disorders, as well as being a key player...... in the formation of memory. Hence, ligands affecting AMPARs are highly important for the study of the structure and function of this receptor, and in this regard polyamine-based ligands, particularly polyamine toxins, are unique as they selectively block Ca2+ -permeable AMPARs. Indeed, endogenous intracellular...

  2. Synthesis of aryl-substituted 5-[18F]fluoroalkylbenzamides: High affinity ligands for dopamine D-2 studies

    International Nuclear Information System (INIS)

    Mathis, C.A.; Bishop, J.E.; Gerdes, J.M.; Faggin, B.; Mailman, R.

    1990-01-01

    Recent studies of the structure-activity relationship of benzamides have shown that the 2,3-dimethoxy substitution pattern of (S)-N-[(1-ethyl-2-pyrrolidinyl)methyl]-2,3-dimethoxy-5-iodobenzamide (PDB) resulted in a potent D-2 antagonist. Based upon these results and the concept that the potency of receptor ligands can be preserved when aromatic halogen substituents are replaced by fluoroalkyl functional groups, the authors synthesized a series of aryl-substituted fluoroalkyl PDBs and salicylamides. Synthetic pathways and an in vivo study in rats are outlined

  3. Separation of the lanthanides on high-efficiency bonded phases and conventional ion-exchange resins

    International Nuclear Information System (INIS)

    Elchuk, S.; Cassidy, R.M.

    1979-01-01

    High-performance liquid chromatographic separations (< 20 min) of the lanthanides are illustrated for both 5- and 10-μm bonded-phase strong-acid ion exchangers. The performance of these bonded phase packings is compared with that obtained with a 13-μm styrene-divinylbenzene resin. The eluted metal ions are detected with a variable-wavelength detector after a post-column complexation reaction. The requirements and characteristics of post-column reaction for sensitive metal ion detection after separation on high-performance columns are discussed and the linearity, reproducibility, and sensitivity of the system used in the work are illustrated. The potential of on-column preconcentration for the ultratrace (pg/mL) determination of metal ions is also discussed and illustrated. 7 figures, 2 tables

  4. Improved Electrodes for High Temperature Proton Exchange Membrane Fuel Cells using Carbon Nanospheres.

    Science.gov (United States)

    Zamora, Héctor; Plaza, Jorge; Cañizares, Pablo; Lobato, Justo; Rodrigo, Manuel A

    2016-05-23

    This work evaluates the use of carbon nanospheres (CNS) in microporous layers (MPL) of high temperature proton exchange membrane fuel cell (HT-PEMFC) electrodes and compares the characteristics and performance with those obtained using conventional MPL based on carbon black. XRD, hydrophobicity, Brunauer-Emmett-Teller theory, and gas permeability of MPL prepared with CNS were the parameters evaluated. In addition, a short life test in a fuel cell was carried out to evaluate performance under accelerated stress conditions. The results demonstrate that CNS is a promising alternative to traditional carbonaceous materials because of its high electrochemical stability and good electrical conductivity, suitable to be used in this technology. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Charge exchange as a recombination mechanism in high-temperature plasmas

    International Nuclear Information System (INIS)

    Hulse, R.A.; Post, D.E.; Mikkelsen, D.R.

    1980-03-01

    Charge exchange with neutral hydrogen is examined as a recombination mechanism for multi-charged impurity ions present in high-temperature fusion plasmas. At sufficiently low electron densities, fluxes of atomic hydrogen produced by either the injection of neutral heating beams or the background of thermal neutrals can yield an important or even dominant recombination process for such ions. Equilibrium results are given for selected impurity elements showing the altered ionization balance and radiative cooling rate produced by the presence of various neutral populations. A notable result is that the stripping of impurities to relatively non-radiative ionization states with increasing electron temperature can be postponed or entirely prevented by the application of intense neutral beam heating power. A time dependent calculation modelling the behavior of iron in recent PLT tokamak high power neutral beam heating experiments is also presented

  6. New load cycling strategy for enhanced durability of high temperature proton exchange membrane fuel cell

    DEFF Research Database (Denmark)

    Thomas, Sobi; Jeppesen, Christian; Steenberg, Thomas

    2017-01-01

    The objective of this paper is to develop a new operational strategy to increase the lifetime of a high temperature proton exchange membrane (HT-PEMFCs) fuel cell system by using load cycling patterns to reduce the phosphoric acid loss from the fuel cell. Four single cells were operated under.......8 Acm-2 for the higher end, were selected for the load cycling operation. The relaxation time, which is the period of time spent at low current density operation, is varied to understand how the performance over prolonged period behaves. The duration of the high current density operation is selected...... based on the relaxation time in order to have the same average current density of (0.55 Acm-2 ) for all the cells. Cell 5, with a relaxation time of 2 min performs best and shows lower degradation rate of 36 μVh-1 compared to other load cycling cells with smaller relaxation times. The cell operated...

  7. Application of expert systems to heat exchanger control at the 100-megawatt high-flux isotope reactor

    International Nuclear Information System (INIS)

    Clapp, N.E. Jr.; Clark, F.H.; Mullens, J.A.; Otaduy, P.J.; Wehe, D.K.

    1985-01-01

    The High-Flux Isotope Reactor (HFIR) is a 100-MW pressurized water reactor at the Oak Ridge National Laboratory. It is used to produce isotopes and as a source of high neutron flux for research. Three heat exchangers are used to remove heat from the reactor to the cooling towers. A fourth heat exchanger is available as a spare in case one of the operating heat exchangers malfunctions. It is desirable to maintain the reactor at full power while replacing the failed heat exchanger with the spare. The existing procedures used by the operators form the initial knowledge base for design of an expert system to perform the switchover. To verify performance of the expert system, a dynamic simulation of the system was developed in the MACLISP programming language. 2 refs., 3 figs

  8. Separation and determination of alditols and sugars by high-pH anion-exchange chromatography with pulsed amperometric detection

    DEFF Research Database (Denmark)

    Andersen, Rikke; Sørensen, A.

    2000-01-01

    Carbohydrates such as alditols (polyols or sugar alcohols), monosaccharides and disaccharides are separated as anions by anion-exchange chromatography with a sodium hydroxide eluent, MA1 CarboPac column and pulsed amperometric detection. We report a high-pH anion-exchange chromatographic-pulsed a......Carbohydrates such as alditols (polyols or sugar alcohols), monosaccharides and disaccharides are separated as anions by anion-exchange chromatography with a sodium hydroxide eluent, MA1 CarboPac column and pulsed amperometric detection. We report a high-pH anion-exchange chromatographic......-pulsed amperometric detection (HPAEC-PAD) method that determines all the polyols used as food additives in food products and the most commonly found mono- and disaccharides on a routine basis. The linearity, repeatability, internal reproducibility and accuracy are described. The applicability of the method has been...

  9. Comfortable, high-efficiency heat pump with desiccant-coated, water-sorbing heat exchangers.

    Science.gov (United States)

    Tu, Y D; Wang, R Z; Ge, T S; Zheng, X

    2017-01-12

    Comfortable, efficient, and affordable heating, ventilation, and air conditioning systems in buildings are highly desirable due to the demands of energy efficiency and environmental friendliness. Traditional vapor-compression air conditioners exhibit a lower coefficient of performance (COP) (typically 2.8-3.8) owing to the cooling-based dehumidification methods that handle both sensible and latent loads together. Temperature- and humidity-independent control or desiccant systems have been proposed to overcome these challenges; however, the COP of current desiccant systems is quite small and additional heat sources are usually needed. Here, we report on a desiccant-enhanced, direct expansion heat pump based on a water-sorbing heat exchanger with a desiccant coating that exhibits an ultrahigh COP value of more than 7 without sacrificing any comfort or compactness. The pump's efficiency is doubled compared to that of pumps currently used in conventional room air conditioners, which is a revolutionary HVAC breakthrough. Our proposed water-sorbing heat exchanger can independently handle sensible and latent loads at the same time. The desiccants adsorb moisture almost isothermally and can be regenerated by condensation heat. This new approach opens up the possibility of achieving ultrahigh efficiency for a broad range of temperature- and humidity-control applications.

  10. Improvement of an automated protein crystal exchange system PAM for high-throughput data collection

    International Nuclear Information System (INIS)

    Hiraki, Masahiko; Yamada, Yusuke; Chavas, Leonard M. G.; Wakatsuki, Soichi; Matsugaki, Naohiro

    2013-01-01

    A special liquid-nitrogen Dewar with double capacity for the sample-exchange robot has been created at AR-NE3A at the Photon Factory, allowing continuous fully automated data collection. In this work, this new system is described and the stability of its calibration is discussed. Photon Factory Automated Mounting system (PAM) protein crystal exchange systems are available at the following Photon Factory macromolecular beamlines: BL-1A, BL-5A, BL-17A, AR-NW12A and AR-NE3A. The beamline AR-NE3A has been constructed for high-throughput macromolecular crystallography and is dedicated to structure-based drug design. The PAM liquid-nitrogen Dewar can store a maximum of three SSRL cassettes. Therefore, users have to interrupt their experiments and replace the cassettes when using four or more of them during their beam time. As a result of investigation, four or more cassettes were used in AR-NE3A alone. For continuous automated data collection, the size of the liquid-nitrogen Dewar for the AR-NE3A PAM was increased, doubling the capacity. In order to check the calibration with the new Dewar and the cassette stand, calibration experiments were repeatedly performed. Compared with the current system, the parameters of the novel system are shown to be stable

  11. Improvement of an automated protein crystal exchange system PAM for high-throughput data collection

    Energy Technology Data Exchange (ETDEWEB)

    Hiraki, Masahiko, E-mail: masahiko.hiraki@kek.jp; Yamada, Yusuke; Chavas, Leonard M. G. [High Energy Accelerator Research Organization, 1-1 Oho, Tsukuba, Ibaraki 305-0801 (Japan); Wakatsuki, Soichi [High Energy Accelerator Research Organization, 1-1 Oho, Tsukuba, Ibaraki 305-0801 (Japan); SLAC National Accelerator Laboratory, 2575 Sand Hill Road, MS 69, Menlo Park, CA 94025-7015 (United States); Stanford University, Beckman Center B105, Stanford, CA 94305-5126 (United States); Matsugaki, Naohiro [High Energy Accelerator Research Organization, 1-1 Oho, Tsukuba, Ibaraki 305-0801 (Japan)

    2013-11-01

    A special liquid-nitrogen Dewar with double capacity for the sample-exchange robot has been created at AR-NE3A at the Photon Factory, allowing continuous fully automated data collection. In this work, this new system is described and the stability of its calibration is discussed. Photon Factory Automated Mounting system (PAM) protein crystal exchange systems are available at the following Photon Factory macromolecular beamlines: BL-1A, BL-5A, BL-17A, AR-NW12A and AR-NE3A. The beamline AR-NE3A has been constructed for high-throughput macromolecular crystallography and is dedicated to structure-based drug design. The PAM liquid-nitrogen Dewar can store a maximum of three SSRL cassettes. Therefore, users have to interrupt their experiments and replace the cassettes when using four or more of them during their beam time. As a result of investigation, four or more cassettes were used in AR-NE3A alone. For continuous automated data collection, the size of the liquid-nitrogen Dewar for the AR-NE3A PAM was increased, doubling the capacity. In order to check the calibration with the new Dewar and the cassette stand, calibration experiments were repeatedly performed. Compared with the current system, the parameters of the novel system are shown to be stable.

  12. A high temperature ceramic heat exchanger element for a solar thermal receiver

    Science.gov (United States)

    Strumpf, H. J.; Kotchick, D. M.; Coombs, M. G.

    1982-01-01

    The development of a high-temperature ceramic heat exchanger element to be integrated into a solar receiver producing heated air was studied. A number of conceptual designs were developed for heat exchanger elements of differing configuration. These were evaluated with respect to thermal performance, pressure drop, structural integrity, and fabricability. The final design selection identified a finned ceramic shell as the most favorable concept. The shell is surrounded by a larger metallic shell. The flanges of the two shells are sealed to provide a leak-tight pressure vessel. The ceramic shell is to be fabricated by a innovative combination of slip casting the receiver walls and precision casting the heat transfer finned plates. The fins are bonded to the shell during firing. The unit is sized to produce 2150 F air at 2.7 atm pressure, with a pressure drop of about 2 percent of the inlet pressure. This size is compatible with a solar collector providing a receiver input of 85 kw(th). Fabrication of a one-half scale demonstrator ceramic receiver was completed.

  13. High-temperature ceramic heat exchanger element for a solar thermal receiver

    Science.gov (United States)

    Strumpf, H. J.; Kotchick, D. M.; Coombs, M. G.

    1982-01-01

    A study was performed by AiResearch Manufacturing Company, a division of The Garrett Corporation, on the development a high-temperature ceramic heat exchanger element to be integrated into a solar receiver producing heated air. A number of conceptual designs were developed for heat exchanger elements of differing configuration. These were evaluated with respect to thermal performance, pressure drop, structural integrity, and fabricability. The final design selection identified a finned ceramic shell as the most favorable concept. The shell is surrounded by a larger metallic shell. The flanges of the two shells are sealed to provide a leak-tight pressure vessel. The ceramic shell is to be fabricated by an innovative combination of slip casting the receiver walls and precision casting the heat transfer finned plates. The fins are bonded to the shell during firing. The unit is sized to produce 2150 F ar at 2.7 atm pressure, with a pressure drop of about 2 percent of the inlet pressure. This size is compatible with a solar collector providing a receiver input of 85 kw(th). Fabrication of a one-half scale demonstrator ceramic receiver has been completed.

  14. High temperature series expansions with a multiple-exchange Hamiltonian for the bcc and hcp phases of solid 3He

    International Nuclear Information System (INIS)

    Roger, M.; Suaudeau, E.; Bernier, M.E.R.

    1987-08-01

    High temperature series expansions with a multiple-exchange Hamiltonian are performed to fourth order in arbitrary magnetic field for both phases of solid 3 He. The susceptibility series are analysed with Pade approximants and compared with recent experimental results. For the hcp phase we estimate the ferromagnetic ordering temperature from susceptibility series and discuss the influence of four-particle exchange in lowering the transition

  15. Are polynuclear superhalogens without halogen atoms probable? A high-level ab initio case study on triple-bridged binuclear anions with cyanide ligands

    Science.gov (United States)

    Yin, Bing; Li, Teng; Li, Jin-Feng; Yu, Yang; Li, Jian-Li; Wen, Zhen-Yi; Jiang, Zhen-Yi

    2014-03-01

    The first theoretical exploration of superhalogen properties of polynuclear structures based on pseudohalogen ligand is reported here via a case study on eight triply-bridged [Mg2(CN)5]- clusters. From our high-level ab initio results, all these clusters are superhalogens due to their high vertical electron detachment energies (VDE), of which the largest value is 8.67 eV at coupled-cluster single double triple (CCSD(T)) level. Although outer valence Green's function results are consistent with CCSD(T) in most cases, it overestimates the VDEs of three anions dramatically by more than 1 eV. Therefore, the combined usage of several theoretical methods is important for the accuracy of purely theoretical prediction of superhalogen properties of new structures. Spatial distribution of the extra electron of high-VDE anions here indicates two features: remarkable aggregation on bridging CN units and non-negligible distribution on every CN unit. These two features lower the potential and kinetic energies of the extra electron respectively and thus lead to high VDE. Besides superhalogen properties, the structures, relative stabilities and thermodynamic stabilities with respect to detachment of CN-1 were also investigated for these anions. The collection of these results indicates that polynuclear structures based on pseudohalogen ligand are promising candidates for new superhalogens with enhanced properties.

  16. Are polynuclear superhalogens without halogen atoms probable? A high-level ab initio case study on triple-bridged binuclear anions with cyanide ligands

    International Nuclear Information System (INIS)

    Yin, Bing; Wen, Zhen-Yi; Li, Teng; Li, Jin-Feng; Yu, Yang; Li, Jian-Li; Jiang, Zhen-Yi

    2014-01-01

    The first theoretical exploration of superhalogen properties of polynuclear structures based on pseudohalogen ligand is reported here via a case study on eight triply-bridged [Mg 2 (CN) 5 ] − clusters. From our high-level ab initio results, all these clusters are superhalogens due to their high vertical electron detachment energies (VDE), of which the largest value is 8.67 eV at coupled-cluster single double triple (CCSD(T)) level. Although outer valence Green's function results are consistent with CCSD(T) in most cases, it overestimates the VDEs of three anions dramatically by more than 1 eV. Therefore, the combined usage of several theoretical methods is important for the accuracy of purely theoretical prediction of superhalogen properties of new structures. Spatial distribution of the extra electron of high-VDE anions here indicates two features: remarkable aggregation on bridging CN units and non-negligible distribution on every CN unit. These two features lower the potential and kinetic energies of the extra electron respectively and thus lead to high VDE. Besides superhalogen properties, the structures, relative stabilities and thermodynamic stabilities with respect to detachment of CN −1 were also investigated for these anions. The collection of these results indicates that polynuclear structures based on pseudohalogen ligand are promising candidates for new superhalogens with enhanced properties

  17. Are polynuclear superhalogens without halogen atoms probable? A high-level ab initio case study on triple-bridged binuclear anions with cyanide ligands

    Energy Technology Data Exchange (ETDEWEB)

    Yin, Bing, E-mail: rayinyin@gmail.com; Wen, Zhen-Yi [MOE Key Laboratory of Synthetic and Natural Functional Molecule Chemistry, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, College of Chemistry and Materials Science, Northwest University, Xi' an 710069 (China); Institute of Modern Physics, Northwest University, Xi' an 710069 (China); Li, Teng; Li, Jin-Feng; Yu, Yang; Li, Jian-Li [MOE Key Laboratory of Synthetic and Natural Functional Molecule Chemistry, Shaanxi Key Laboratory of Physico-Inorganic Chemistry, College of Chemistry and Materials Science, Northwest University, Xi' an 710069 (China); Jiang, Zhen-Yi [Institute of Modern Physics, Northwest University, Xi' an 710069 (China)

    2014-03-07

    The first theoretical exploration of superhalogen properties of polynuclear structures based on pseudohalogen ligand is reported here via a case study on eight triply-bridged [Mg{sub 2}(CN){sub 5}]{sup −} clusters. From our high-level ab initio results, all these clusters are superhalogens due to their high vertical electron detachment energies (VDE), of which the largest value is 8.67 eV at coupled-cluster single double triple (CCSD(T)) level. Although outer valence Green's function results are consistent with CCSD(T) in most cases, it overestimates the VDEs of three anions dramatically by more than 1 eV. Therefore, the combined usage of several theoretical methods is important for the accuracy of purely theoretical prediction of superhalogen properties of new structures. Spatial distribution of the extra electron of high-VDE anions here indicates two features: remarkable aggregation on bridging CN units and non-negligible distribution on every CN unit. These two features lower the potential and kinetic energies of the extra electron respectively and thus lead to high VDE. Besides superhalogen properties, the structures, relative stabilities and thermodynamic stabilities with respect to detachment of CN{sup −1} were also investigated for these anions. The collection of these results indicates that polynuclear structures based on pseudohalogen ligand are promising candidates for new superhalogens with enhanced properties.

  18. Novel high-performance nanocomposite proton exchange membranes based on poly (ether sulfone)

    Energy Technology Data Exchange (ETDEWEB)

    Hasani-Sadrabadi, Mohammad Mahdi [Polymer Engineering Department, Amirkabir University of Technology, Tehran (Iran); Biomedical Engineering Department, Amirkabir University of Technology, Tehran (Iran); Dashtimoghadam, Erfan; Ghaffarian, Seyed Reza [Polymer Engineering Department, Amirkabir University of Technology, Tehran (Iran); Hasani Sadrabadi, Mohammad Hossein [Faculty of Social and Economics Science, Alzahra University, Tehran (Iran); Heidari, Mahdi [Graduate School of Management and Economics, Sharif University of Technology, Tehran (Iran); Moaddel, Homayoun [Department of Materials Science and Engineering, University of California, Los Angeles, CA (United States)

    2010-01-15

    In the present research, proton exchange membranes based on partially sulfonated poly (ether sulfone) (S-PES) with various degrees of sulfonation were synthesized. It was found that the increasing of sulfonation degree up to 40% results in the enhancement of water uptake, ion exchange capacity and proton conductivity properties of the prepared membranes to 28.1%, 1.59 meq g{sup -1}, and 0.145 S cm{sup -1}, respectively. Afterwards, nanocomposite membranes based on S-PES (at the predetermined optimum sulfonation degree) containing various loading weights of organically treated montmorillonite (OMMT) were prepared via the solution intercalation technique. X-ray diffraction patterns revealed the exfoliated structure of OMMT in the macromolecular matrices. The S-PES nanocomposite membrane with 3.0 wt% of OMMT content showed the maximum selectivity parameter of about 520,000 S s cm{sup -3} which is related to the high conductivity of 0.051 S cm{sup -1} and low methanol permeability of 9.8 x 10{sup -8} cm{sup 2} s{sup -1}. Furthermore, single cell DMFC fuel cell performance test with 4 molar methanol concentration showed a high power density (131 mW cm{sup -2}) of the nanocomposite membrane at the optimum composition (40% of sulfonation and 3.0 wt% of OMMT loading) compared to the Nafion {sup registered} 117 membrane (114 mW cm{sup -2}). Manufactured nanocomposite membranes thanks to their high selectivity, ease of preparation and low cost could be suggested as the ideal candidate for the direct methanol fuel cell applications. (author)

  19. High-heat-flux testing of helium-cooled heat exchangers for fusion applications

    International Nuclear Information System (INIS)

    Youchison, D.L.; Izenson, M.G.; Baxi, C.B.; Rosenfeld, J.H.

    1996-01-01

    High-heat-flux experiments on three types of helium-cooled divertor mock-ups were performed on the 30-kW electron beam test system and its associated helium flow loop at Sandia National Laboratories. A dispersion-strengthened copper alloy (DSCu) was used in the manufacture of all the mock-ups. The first heat exchanger provides for enhanced heat transfer at relatively low flow rates and much reduced pumping requirements. The Creare sample was tested to a maximum absorbed heat flux of 5.8 MW/m 2 . The second used low pressure drops and high mass flow rates to achieve good heat removal. The GA specimen was tested to a maximum absorbed heat flux of 9 MW/m 2 while maintaining a surface temperature below 400 degree C. A second experiment resulted in a maximum absorbed heat flux of 34 MW/m 2 and surface temperatures near 533 degree C. The third specimen was a DSCu, axial flow, helium-cooled divertor mock-up filled with a porous metal wick which effectively increases the available heat transfer area. Low mass flow and high pressure drop operation at 4.0 MPa were characteristic of this divertor module. It survived a maximum absorbed heat flux of 16 MW/m 2 and reached a surface temperature of 740 degree C. Thermacore also manufactured a follow-on, dual channel porous metal-type heat exchanger, which survived a maximum absorbed heat flux of 14 MW/m 2 and reached a maximum surface temperature of 690 degree C. 11refs., 20 figs., 3 tabs

  20. Insights into an original pocket-ligand pair classification: a promising tool for ligand profile prediction.

    Directory of Open Access Journals (Sweden)

    Stéphanie Pérot

    Full Text Available Pockets are today at the cornerstones of modern drug discovery projects and at the crossroad of several research fields, from structural biology to mathematical modeling. Being able to predict if a small molecule could bind to one or more protein targets or if a protein could bind to some given ligands is very useful for drug discovery endeavors, anticipation of binding to off- and anti-targets. To date, several studies explore such questions from chemogenomic approach to reverse docking methods. Most of these studies have been performed either from the viewpoint of ligands or targets. However it seems valuable to use information from both ligands and target binding pockets. Hence, we present a multivariate approach relating ligand properties with protein pocket properties from the analysis of known ligand-protein interactions. We explored and optimized the pocket-ligand pair space by combining pocket and ligand descriptors using Principal Component Analysis and developed a classification engine on this paired space, revealing five main clusters of pocket-ligand pairs sharing specific and similar structural or physico-chemical properties. These pocket-ligand pair clusters highlight correspondences between pocket and ligand topological and physico-chemical properties and capture relevant information with respect to protein-ligand interactions. Based on these pocket-ligand correspondences, a protocol of prediction of clusters sharing similarity in terms of recognition characteristics is developed for a given pocket-ligand complex and gives high performances. It is then extended to cluster prediction for a given pocket in order to acquire knowledge about its expected ligand profile or to cluster prediction for a given ligand in order to acquire knowledge about its expected pocket profile. This prediction approach shows promising results and could contribute to predict some ligand properties critical for binding to a given pocket, and conversely

  1. Insights into an original pocket-ligand pair classification: a promising tool for ligand profile prediction.

    Science.gov (United States)

    Pérot, Stéphanie; Regad, Leslie; Reynès, Christelle; Spérandio, Olivier; Miteva, Maria A; Villoutreix, Bruno O; Camproux, Anne-Claude

    2013-01-01

    Pockets are today at the cornerstones of modern drug discovery projects and at the crossroad of several research fields, from structural biology to mathematical modeling. Being able to predict if a small molecule could bind to one or more protein targets or if a protein could bind to some given ligands is very useful for drug discovery endeavors, anticipation of binding to off- and anti-targets. To date, several studies explore such questions from chemogenomic approach to reverse docking methods. Most of these studies have been performed either from the viewpoint of ligands or targets. However it seems valuable to use information from both ligands and target binding pockets. Hence, we present a multivariate approach relating ligand properties with protein pocket properties from the analysis of known ligand-protein interactions. We explored and optimized the pocket-ligand pair space by combining pocket and ligand descriptors using Principal Component Analysis and developed a classification engine on this paired space, revealing five main clusters of pocket-ligand pairs sharing specific and similar structural or physico-chemical properties. These pocket-ligand pair clusters highlight correspondences between pocket and ligand topological and physico-chemical properties and capture relevant information with respect to protein-ligand interactions. Based on these pocket-ligand correspondences, a protocol of prediction of clusters sharing similarity in terms of recognition characteristics is developed for a given pocket-ligand complex and gives high performances. It is then extended to cluster prediction for a given pocket in order to acquire knowledge about its expected ligand profile or to cluster prediction for a given ligand in order to acquire knowledge about its expected pocket profile. This prediction approach shows promising results and could contribute to predict some ligand properties critical for binding to a given pocket, and conversely, some key pocket

  2. Murine CMV Expressing the High Affinity NKG2D Ligand MULT-1: A Model for the Development of Cytomegalovirus-Based Vaccines

    Directory of Open Access Journals (Sweden)

    Lea Hiršl

    2018-05-01

    Full Text Available The development of a vaccine against human cytomegalovirus (CMV has been a subject of long-term medical interest. The research during recent years identified CMV as an attractive vaccine vector against infectious diseases and tumors. The immune response to CMV persists over a lifetime and its unique feature is the inflationary T cell response to certain viral epitopes. CMV encodes numerous genes involved in immunoevasion, which are non-essential for virus growth in vitro. The deletion of those genes results in virus attenuation in vivo, which enables us to dramatically manipulate its virulence and the immune response. We have previously shown that the murine CMV (MCMV expressing RAE-1γ, one of the cellular ligands for the NKG2D receptor, is highly attenuated in vivo but retains the ability to induce a strong CD8+ T cell response. Here, we demonstrate that recombinant MCMV expressing high affinity NKG2D ligand murine UL16 binding protein-like transcript (MULT-1 (MULT-1MCMV inserted in the place of its viral inhibitor is dramatically attenuated in vivo in a NK cell-dependent manner, both in immunocompetent adult mice and in immunologically immature newborns. MULT-1MCMV was more attenuated than the recombinant virus expressing RAE-1γ. Despite the drastic sensitivity to innate immune control, MULT-1MCMV induced an efficient CD8+ T cell response to viral and vectored antigens. By using in vitro assay, we showed that similar to RAE-1γMCMV, MULT-1 expressing virus provided strong priming of CD8+ T cells. Moreover, MULT-1MCMV was able to induce anti-viral antibodies, which after passing the transplacental barrier protect offspring of immunized mothers from challenge infection. Altogether, this study further supports the concept that CMV expressing NKG2D ligand possesses excellent characteristics to serve as a vaccine or vaccine vector.

  3. Dependence of cancer cell adhesion kinetics on integrin ligand surface density measured by a high-throughput label-free resonant waveguide grating biosensor.

    Science.gov (United States)

    Orgovan, Norbert; Peter, Beatrix; Bősze, Szilvia; Ramsden, Jeremy J; Szabó, Bálint; Horvath, Robert

    2014-02-07

    A novel high-throughput label-free resonant waveguide grating (RWG) imager biosensor, the Epic® BenchTop (BT), was utilized to determine the dependence of cell spreading kinetics on the average surface density (v(RGD)) of integrin ligand RGD-motifs. v(RGD) was tuned over four orders of magnitude by co-adsorbing the biologically inactive PLL-g-PEG and the RGD-functionalized PLL-g-PEG-RGD synthetic copolymers from their mixed solutions onto the sensor surface. Using highly adherent human cervical tumor (HeLa) cells as a model system, cell adhesion kinetic data of unprecedented quality were obtained. Spreading kinetics were fitted with the logistic equation to obtain the spreading rate constant (r) and the maximum biosensor response (Δλmax), which is assumed to be directly proportional to the maximum spread contact area (Amax). r was found to be independent of the surface density of integrin ligands. In contrast, Δλmax increased with increasing RGD surface density until saturation at high densities. Interpreting the latter behavior with a simple kinetic mass action model, a 2D dissociation constant of 1753 ± 243 μm(-2) (corresponding to a 3D dissociation constant of ~30 μM) was obtained for the binding between RGD-specific integrins embedded in the cell membrane and PLL-g-PEG-RGD. All of these results were obtained completely noninvasively without using any labels.

  4. Catalyst Degradation in High Temperature Proton Exchange Membrane Fuel Cells Based on Acid Doped Polybenzimidazole Membranes

    DEFF Research Database (Denmark)

    Cleemann, Lars Nilausen; Buazar, F.; Li, Qingfeng

    2013-01-01

    and multi‐walled carbon nanotubes were used as supports for electrode catalysts and evaluated in accelerated durability tests under potential cycling at 150 °C. Measurements of open circuit voltage, area specific resistance and hydrogen permeation through the membrane were carried out, indicating little...... contribution of the membrane degradation to the performance losses during the potential cycling tests. As the major mechanism of the fuel cell performance degradation, the electrochemical active area of the cathodic catalysts showed a steady decrease in the cyclic voltammetric measurements, which was also......Degradation of carbon supported platinum catalysts is a major failure mode for the long term durability of high temperature proton exchange membrane fuel cells based on phosphoric acid doped polybenzimidazole membranes. With Vulcan carbon black as a reference, thermally treated carbon black...

  5. High temperature heat exchanger application in power engineering and energy-technological processes

    International Nuclear Information System (INIS)

    Shpilrain, E.E.

    1986-01-01

    The possibilities for intensification of various processes in metallurgy and chemical technology, the prospects for enhancing power plant efficiency are often linked with temperature increase of reagents, heat carriers and working fluids. In some cases elevated temperatures give the opportunity to use new and principally different technologies, enhance capacities of power production units and technological apparatuses, improve their economical performance. The variety of problems where high temperature heat exchangers are or can be used are extremely wide. It is therefore impossible to overview all of them in one lecture. Therefore the author tries to consider only some examples which are typical and gives an impression of what kind of problems arise in these cases

  6. A highly selective fluorescent chemosensor for CN- based on a novel bis(salamo)-type tetraoxime ligand

    Science.gov (United States)

    Wang, Fei; Gao, Lei; Zhao, Qing; Zhang, Yang; Dong, Wen-Kui; Ding, Yu-Jie

    2018-02-01

    The optical properties of a novel chemosensor for cyanide anions based on a symmetric bis(salamo)-type ligand (H3L) were investigated by UV-Vis and fluorescence spectroscopy in MeOH/H2O (1:1 v/v) solution. Sensor H3L can selectively sense CN- based on prominent color changes among other anions. The chemosensor exhibits an apparent fluorescence enhancement at 482 nm to CN- which because cyanide ions interact with Cdbnd N bonds. Combining the corrected Benesi-Hildebrand formula, the binding constant of the formed host-guest complex was calculated as 2.42 × 105 M- 1. Meanwhile, the detection limit of the sensor toward CN- was 8.91 × 10- 7 M. It is worth noting that the designed sensor can be used for rapid detection of cyanide anions in basic pH range, and has great practical value.

  7. Use of Novel Highly Selective Ion Exchange Media for Minimizing the Waste Arising from Different NPP and Other Liquids

    International Nuclear Information System (INIS)

    Tusa, Esko; Harjula, Risto; Lehto, Jukka

    2003-01-01

    Highly selective inorganic ion exchangers give new possibilities to implement and operate new innovative treatment systems for radioactive liquids. Because of high selectivity these ion exchangers can be used even in liquids of high salt concentrations. Only selected target nuclides will be separated and inactive salts are left in the liquid, which can be released or recategorized. Thus, it is possible to reduce the volume of radioactive waste dramatically. On the other hand, only a small volume of highly selective material is required in applications, which makes it possible to design totally new types of compact treatment systems. The major benefit of selective ion exchange media comes from the very large volume reduction of radioactive waste in final disposal. It is also possible to save in investment costs, because small ion exchanger volumes can be used and handled in a very small facility. This paper describes different applications of these highly selective ion exchangers, both commercial fullscale applications and laboratory tests, to give the idea of their efficiency for different liquids

  8. Leak detection in a high-pressure heat exchanger system in a refinery using radiotracer technique

    International Nuclear Information System (INIS)

    Samantray, J.S.; Sunil Goswami; Sharma, V.K.; Jayashree Biswal; Pant, H.J.

    2014-01-01

    A radiotracer investigation was carried out in a diesel hydrotreater (DHDT) unit in a refinery for leak detection in a breech-lock heat exchanger system. The main objectives of the study were to identify the leaking heat exchanger in a system with six heat exchangers and estimate the leak rate. Bromine-82 as dibromobiphenyl was selected and used as radiotracer for the investigation. The radiotracer was instantaneously injected into the suction end of the feed pump line to the heat exchanger of the DHDT unit. The movement of the tracer was measured at strategically selected locations using NaI(Tl) scintillation detectors. Based upon the results of the radiotracer investigation, it was found that out of six heat exchangers, exchanger E-1F was leaking. (author)

  9. Synthesis and characterization of [{sup 76}Br]-labeled high-affinity A{sub 3} adenosine receptor ligands for positron emission tomography

    Energy Technology Data Exchange (ETDEWEB)

    Kiesewetter, Dale O. [Positron Emission Tomography Radiochemistry Group, NIBIB, Clinical Center, National Institutes of Health, Bethesda, MD 20892 (United States)], E-mail: dk7k@nih.gov; Lang Lixin; Ma Ying; Bhattacharjee, Abesh Kumar [Positron Emission Tomography Radiochemistry Group, NIBIB, Clinical Center, National Institutes of Health, Bethesda, MD 20892 (United States); Gao, Zhan-Guo; Joshi, Bhalchandra V.; Melman, Artem; Castro, Sonia de; Jacobson, Kenneth A. [Molecular Recognition Section, Laboratory of Bioorganic Chemistry, National Institute of Diabetes and Digestive and Kidney Diseases, National Institutes of Health, Bethesda, MD 20892 (United States)

    2009-01-15

    Introduction: Bromine-76-radiolabeled analogues of previously reported high-affinity A{sub 3} adenosine receptor (A{sub 3}AR) nucleoside ligands have been prepared as potential radiotracers for positron emission tomography. Methods: The radiosyntheses were accomplished by oxidative radiobromination on the N{sup 6}-benzyl moiety of trimethyltin precursors. Biodistribution studies of the kinetics of uptake were conducted in awake rats. Results: We prepared an agonist ligand {l_brace}[{sup 76}Br](1'S,2'R,3'S,4'R,5'S)-4'-{l_brace}2-chloro-6-[(3-bromophenylmethyl)amino] purin-9-yl{r_brace}-1'-(methylaminocarbonyl)bicyclo[3.1.0]hexane-2',3'-diol (MRS3581){r_brace} in 59% radiochemical yield with a specific activity of 19.5 GBq/{mu}mol and an antagonist ligand {l_brace}[{sup 76}Br](1'R,2'R,3'S,4'R,5'S)-4'-(6-(3-bromobenzylamino) -2-chloro-9H-purin-9-yl)bicyclo[3.1.0]hexane-2',3'-diol (MRS5147){r_brace} in 65% radiochemical yield with a specific activity of 22 GBq/{mu}mol. The resultant products exhibited the expected high affinity (K{sub i}{approx}0.6 nM) and specific binding at the human A{sub 3}AR in vitro. Biodistribution studies in the rat showed uptake in the organs of excretion and metabolism. The antagonist MRS5147 exhibited increasing uptake in testes, an organ that contains significant quantities of A{sub 3}AR, over a 2-h time course, which suggests the presence of a specific A{sub 3}AR retention mechanism. Conclusion: We were able to compare uptake of the [{sup 76}Br]-labeled antagonist MRS5147 to [{sup 76}Br]agonist MRS3581. The antagonist MRS5147 shows increasing uptake in the testes, an A{sub 3}AR-rich tissue, suggesting that this ligand may have promise as a molecular imaging agent.

  10. Ligand design for alkali-metal-templated self-assembly of unique high-nuclearity CuII aggregates with diverse coordination cage units: crystal structures and properties.

    Science.gov (United States)

    Du, Miao; Bu, Xian-He; Guo, Ya-Mei; Ribas, Joan

    2004-03-19

    The construction of two unique, high-nuclearity Cu(II) supramolecular aggregates with tetrahedral or octahedral cage units, [(mu(3)-Cl)[Li subset Cu(4)(mu-L(1))(3)](3)](ClO(4))(8)(H(2)O)(4.5) (1) and [[Na(2) subset Cu(12)(mu-L(2))(8)(mu-Cl)(4)](ClO(4))(8)(H(2)O)(10)(H(3)O(+))(2)](infinity) (2) by alkali-metal-templated (Li(+) or Na(+)) self-assembly, was achieved by the use of two newly designed carboxylic-functionalized diazamesocyclic ligands, N,N'-bis(3-propionyloxy)-1,4-diazacycloheptane (H(2)L(1)) or 1,5-diazacyclooctane-N,N'-diacetate acid (H(2)L(2)). Complex 1 crystallizes in the trigonal R3c space group (a = b = 20.866(3), c = 126.26(4) A and Z = 12), and 2 in the triclinic P1 space group (a = 13.632(4), b = 14.754(4), c = 19.517(6) A, alpha = 99.836(6), beta = 95.793(5), gamma = 116.124(5) degrees and Z = 1). By subtle variation of the ligand structures and the alkali-metal templates, different polymeric motifs were obtained: a dodecanuclear architecture 1 consisting of three Cu(4) tetrahedral cage units with a Li(+) template, and a supramolecular chain 2 consisting of two crystallographically nonequivalent octahedral Cu(6) polyhedra with a Na(+) template. The effects of ligand functionality and alkali metal template ions on the self-assembly processes of both coordination supramolecular aggregates, and their magnetic behaviors are discussed in detail.

  11. Air-sea exchange over Black Sea estimated from high resolution regional climate simulations

    Science.gov (United States)

    Velea, Liliana; Bojariu, Roxana; Cica, Roxana

    2013-04-01

    Black Sea is an important influencing factor for the climate of bordering countries, showing cyclogenetic activity (Trigo et al, 1999) and influencing Mediterranean cyclones passing over. As for other seas, standard observations of the atmosphere are limited in time and space and available observation-based estimations of air-sea exchange terms present quite large ranges of uncertainty. The reanalysis datasets (e.g. ERA produced by ECMWF) provide promising validation estimates of climatic characteristics against the ones in available climatic data (Schrum et al, 2001), while cannot reproduce some local features due to relatively coarse horizontal resolution. Detailed and realistic information on smaller-scale processes are foreseen to be provided by regional climate models, due to continuous improvements of physical parameterizations and numerical solutions and thus affording simulations at high spatial resolution. The aim of the study is to assess the potential of three regional climate models in reproducing known climatological characteristics of air-sea exchange over Black Sea, as well as to explore the added value of the model compared to the input (reanalysis) data. We employ results of long-term (1961-2000) simulations performed within ENSEMBLE project (http://ensemblesrt3.dmi.dk/) using models ETHZ-CLM, CNRM-ALADIN, METO-HadCM, for which the integration domain covers the whole area of interest. The analysis is performed for the entire basin for several variables entering the heat and water budget terms and available as direct output from the models, at seasonal and annual scale. A comparison with independent data (ERA-INTERIM) and findings from other studies (e.g. Schrum et al, 2001) is also presented. References: Schrum, C., Staneva, J., Stanev, E. and Ozsoy, E., 2001: Air-sea exchange in the Black Sea estimated from atmospheric analysis for the period 1979-1993, J. Marine Systems, 31, 3-19 Trigo, I. F., T. D. Davies, and G. R. Bigg (1999): Objective

  12. Septide and neurokinin A are high-affinity ligands on the NK-1 receptor: evidence from homologous versus heterologous binding analysis.

    Science.gov (United States)

    Hastrup, H; Schwartz, T W

    1996-12-16

    The three main tachykinins, substance P, neurokinin A (NKA), and neurokinin B, are believed to be selective ligands for respectively the NK-1, NK-2 and NK-3 receptors. However, NKA also has actions which cannot be mediated through its normal NK-2 receptor and the synthetic peptide [pGlu6,Pro9]-Substance P9-11--called septide--is known to have tachykinin-like actions despite its apparent lack of binding to any known tachykinin receptor. In the cloned NK-1 receptor expressed in COS-7 cells NKA and septide as expected were poor competitors for radiolabeled substance P. However, by using radiolabeled NKA and septide directly, it was found that both peptides in homologous binding assays as well as in competition against each other in fact bound to the NK-1 receptor with high affinity: Kd values of 0.51 +/- 0.15 nM (NKA) and 0.55 +/- 0.03 nM (septide). It is concluded that NKA and septide are high-affinity ligands for the NK-1 receptor but that they are poor competitors for substance P, which in contrast competes very well for binding with both NKA and septide.

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

    Science.gov (United States)

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

    2014-10-21

    Proteins are dynamic molecules that exhibit conformational flexibility to function properly. Well-known examples of this are allosteric regulation of protein activity and ligand-induced conformational changes in protein receptors. Detailed knowledge of the conformational properties of proteins is therefore pertinent to both basic and applied research, including drug development, since the majority of drugs target protein receptors and a growing number of drugs introduced to the market are therapeutic peptides or proteins. X-ray crystallography provides a static picture at atomic resolution of the lowest-energy structure of the native ensemble. There is a growing need for sensitive analytical tools to explore all of the significant molecular structures in the conformational landscape of proteins. Hydrogen/deuterium exchange monitored by mass spectrometry (HDX-MS) has recently emerged as a powerful method for characterizing protein conformational dynamics. The basis of this method is the fact that backbone amides in stable hydrogen-bonded structures (e.g., α-helices and β-sheets) are protected against exchange with the aqueous solvent. All protein structures are dynamic, however, and eventually all of the protecting hydrogen bonds will transiently break as the protein--according to thermodynamic principles--cycles through partially unfolded states that correspond to excited free energy levels. As a result, all of the backbone amides will eventually become temporarily solvent-exposed and exchange-competent over time. Consequently, a folded protein in D2O will gradually incorporate deuterium into its backbone amides, and the kinetics of the process can be readily monitored by mass spectrometry. The deuterium uptake kinetics for the intact protein (global exchange kinetics) represents the sum of the exchange kinetics for the individual backbone amides. Local exchange kinetics is typically achieved by using pepsin digestion under quench conditions (i.e., under cold

  14. High-volume plasma exchange in patients with acute liver failure: An open randomised controlled trial.

    Science.gov (United States)

    Larsen, Fin Stolze; Schmidt, Lars Ebbe; Bernsmeier, Christine; Rasmussen, Allan; Isoniemi, Helena; Patel, Vishal C; Triantafyllou, Evangelos; Bernal, William; Auzinger, Georg; Shawcross, Debbie; Eefsen, Martin; Bjerring, Peter Nissen; Clemmesen, Jens Otto; Hockerstedt, Krister; Frederiksen, Hans-Jørgen; Hansen, Bent Adel; Antoniades, Charalambos G; Wendon, Julia

    2016-01-01

    Acute liver failure (ALF) often results in cardiovascular instability, renal failure, brain oedema and death either due to irreversible shock, cerebral herniation or development of multiple organ failure. High-volume plasma exchange (HVP), defined as exchange of 8-12 or 15% of ideal body weight with fresh frozen plasma in case series improves systemic, cerebral and splanchnic parameters. In this prospective, randomised, controlled, multicentre trial we randomly assigned 182 patients with ALF to receive either standard medical therapy (SMT; 90 patients) or SMT plus HVP for three days (92 patients). The baseline characteristics of the groups were similar. The primary endpoint was liver transplantation-free survival during hospital stay. Secondary-endpoints included survival after liver transplantation with or without HVP with intention-to-treat analysis. A proof-of-principle study evaluating the effect of HVP on the immune cell function was also undertaken. For the entire patient population, overall hospital survival was 58.7% for patients treated with HVP vs. 47.8% for the control group (hazard ratio (HR), with stratification for liver transplantation: 0.56; 95% confidence interval (CI), 0.36-0.86; p=0.0083). HVP prior to transplantation did not improve survival compared with patients who received SMT alone (CI 0.37 to 3.98; p=0.75). The incidence of severe adverse events was similar in the two groups. Systemic inflammatory response syndrome (SIRS) and sequential organ failure assessment (SOFA) scores fell in the treated group compared to control group, over the study period (pHVP improves outcome in patients with ALF by increasing liver transplant-free survival. This is attributable to attenuation of innate immune activation and amelioration of multi-organ dysfunction. Copyright © 2015 European Association for the Study of the Liver. Published by Elsevier B.V. All rights reserved.

  15. High temperature corrosion of advanced ceramic materials for hot gas filters and heat exchangers

    Energy Technology Data Exchange (ETDEWEB)

    Crossland, C.E.; Shelleman, D.L.; Spear, K.E. [Pennsylvania State Univ., University Park, PA (United States)] [and others

    1996-08-01

    A vertical flow-through furnace has been built to study the effect of corrosion on the morphology and mechanical properties of ceramic hot gas filters. Sections of 3M Type 203 and DuPont Lanxide SiC-SiC filter tubes were sealed at one end and suspended in the furnace while being subjected to a simulated coal combustion environment at 870{degrees}C. X-ray diffraction and electron microscopy is used to identify phase and morphology changes due to corrosion while burst testing determines the loss of mechanical strength after exposure to the combustion gases. Additionally, a thermodynamic database of gaseous silicon compounds is currently being established so that calculations can be made to predict important products of the reaction of the environment with the ceramics. These thermodynamic calculations provide useful information concerning the regimes where the ceramic may be degraded by material vaporization. To verify the durability and predict lifetime performance of ceramic heat exchangers in coal combustion environments, long-term exposure testing of stressed (internally pressurized) tubes must be performed in actual coal combustion environments. The authors have designed a system that will internally pressurize 2 inch OD by 48 inch long ceramic heat exchanger tubes to a maximum pressure of 200 psi while exposing the outer surface of the tubes to coal combustion gas at the Combustion and Environmental Research Facility (CERF) at the Pittsburgh Energy and Technology Center. Water-cooled, internal o-ring pressure seals were designed to accommodate the existing 6 inch by 6 inch access panels of the CERF. Tubes will be exposed for up to a maximum of 500 hours at temperatures of 2500 and 2600{degrees}F with an internal pressure of 200 psi. If the tubes survive, their retained strength will be measured using the high temperature tube burst test facility at Penn State University. Fractographic analysis will be performed to identify the failure source(s) for the tubes.

  16. Highly Stable Anion Exchange Membranes for High-Voltage Redox-Flow Batteries

    Energy Technology Data Exchange (ETDEWEB)

    Yan, Yushan [Univ. of Delaware, Newark, DE (United States)

    2018-02-26

    membrane in the sulfuric acid system was also achieved due to the high acid doping ability of the polymer structure. The cationic 9MeOTTP+-F6PBI PTFE reinforced membrane shows a cerium (IV) permeability that is 27-fold lower than that of Nafion 212. Excellent voltage and energy efficiencies with a 9MeOTTP+-F6PBI PTFE reinforced membrane were demonstrated in an all-vanadium redox flow battery (VRFB).

  17. Combined low temperature-high light effects on gas exchange properties of jojoba leaves.

    Science.gov (United States)

    Loreto, F; Bongi, G

    1989-12-01

    Jojoba (Simmondsia chinensis [Link] Schneider) is an important crop in desert climates. A relatively high frequency of periods of chilling and high photon flux density (PFD) in this environment makes photoinhibition likely, resulting in a reduction of assimilation capacity in overwintering leaves. This could explain the low net photosynthesis found in shoots from the field (4-6 micromoles per square meter per second) when compared to greenhouse grown plants (12-15 micromoles per square meter per second). The responses of photosynthesis and stomatal conductance to changes in absorbed PFD and in substomatal partial pressure of CO(2) were measured on jojoba leaves recovering from chilling temperature (4 degrees C) in high or low PFD. No measurable gas exchange was found immediately after chilling in either high or low PFD. For leaves chilled in low PFD, the original quantum yield was restored after 24 hours. The time course of recovery from chilling in high PFD was much longer. Quantum yield recovered to 60% of its original value in 72 hours but failed to recover fully after 1 week. Measurements of PSII chlorophyll fluorescence at 77 K showed that the reduced quantum yield was caused by photoinhibition. The ratio of variable to maximal fluorescence fell from a control level of 0.82 to 0.41 after the photoinhibitory treatment and recovery was slow. We also found a large increase in net assimilation rate and little closure of stomata as CO(2) was increased from ambient partial pressure of 35 to 85 pascals. For plants grown in full light, the increase in net assimilation rate was 100%. The photosynthetic response at high CO(2) concentration may constitute an ecological advantage of jojoba as a crop in the future.

  18. Combined Low Temperature-High Light Effects on Gas Exchange Properties of Jojoba Leaves 1

    Science.gov (United States)

    Loreto, Francesco; Bongi, Guido

    1989-01-01

    Jojoba (Simmondsia chinensis [Link] Schneider) is an important crop in desert climates. A relatively high frequency of periods of chilling and high photon flux density (PFD) in this environment makes photoinhibition likely, resulting in a reduction of assimilation capacity in overwintering leaves. This could explain the low net photosynthesis found in shoots from the field (4-6 micromoles per square meter per second) when compared to greenhouse grown plants (12-15 micromoles per square meter per second). The responses of photosynthesis and stomatal conductance to changes in absorbed PFD and in substomatal partial pressure of CO2 were measured on jojoba leaves recovering from chilling temperature (4°C) in high or low PFD. No measurable gas exchange was found immediately after chilling in either high or low PFD. For leaves chilled in low PFD, the original quantum yield was restored after 24 hours. The time course of recovery from chilling in high PFD was much longer. Quantum yield recovered to 60% of its original value in 72 hours but failed to recover fully after 1 week. Measurements of PSII chlorophyll fluorescence at 77 K showed that the reduced quantum yield was caused by photoinhibition. The ratio of variable to maximal fluorescence fell from a control level of 0.82 to 0.41 after the photoinhibitory treatment and recovery was slow. We also found a large increase in net assimilation rate and little closure of stomata as CO2 was increased from ambient partial pressure of 35 to 85 pascals. For plants grown in full light, the increase in net assimilation rate was 100%. The photosynthetic response at high CO2 concentration may constitute an ecological advantage of jojoba as a crop in the future. PMID:16667220

  19. Transient changes in milk production efficiency and bacterial community composition resulting from near-total exchange of ruminal contents between high- and low-efficiency Holstein cows

    Science.gov (United States)

    The objectives of this study were to determine if milk production efficiency (MPE) is altered by near-total exchange of ruminal contents between high- (HE) and low-MPE (LE) cows and to characterize ruminal bacterial community composition (BCC) prior to exchange and over time post-exchange. Three pai...

  20. CR4056, a new analgesic I2 ligand, is highly effective against bortezomib-induced painful neuropathy in rats

    Directory of Open Access Journals (Sweden)

    Meregalli C

    2012-06-01

    Full Text Available Cristina Meregalli,1 Cecilia Ceresa,1 Annalisa Canta,1 Valentina Alda Carozzi,1 Alessia Chiorazzi,1 Barbara Sala,1 Norberto Oggioni,1 Marco Lanza,2 Ornella Letar,i2 Flora Ferrari,2 Federica Avezza,1 Paola Marmiroli,1 GianFranco Caselli,2 Guido Cavaletti11Department of Neuroscience and Biomedical Technologies, University of Milan-Bicocca, 2Pharmacology and Toxicology Department, Rottapharm | Madaus Research Center, Monza, ItalyAbstract: Although bortezomib (BTZ is the frontline treatment for multiple myeloma, its clinical use is limited by the occurrence of painful peripheral neuropathy, whose treatment is still an unmet clinical need. Previous studies have shown chronic BTZ administration (0.20 mg/kg intravenously three times a week for 8 weeks to female Wistar rats induced a peripheral neuropathy similar to that observed in humans. In this animal model of BTZ-induced neurotoxicity, the present authors evaluated the efficacy of CR4056, a novel I2 ligand endowed with a remarkable efficacy in several animal pain models. CR4056 was administered in a wide range of doses (0.6–60 mg/kg by gavage every day for 2–3 weeks in comparison with buprenorphine (Bupre (28.8 µg/kg subcutaneously every day for 2 weeks and gabapentin (Gaba (100 mg/kg by gavage every day for 3 weeks. Chronic administration of BTZ reduced nerve conduction velocity and induced allodynia. CR4056, Bupre, or Gaba did not affect the impaired nerve conduction velocity. Conversely, CR4056 dose-dependently reversed BTZ-induced allodynia (minimum effective dose 0.6 mg/kg. The optimal dose found, 6 mg/kg, provided a constant pain relief throughout the treatment period and without rebound after suspension, being effective when coadministered with BTZ, starting before or after allodynia was established, or when administered alone after BTZ cessation. A certain degree of tolerance was seen after 7 days of administration, but only at the highest doses (20 and 60 mg/kg. Bupre was effective

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  2. Radiochemical neutron activation analysis of high pure palladium and platinum by ion exchange chromatography

    International Nuclear Information System (INIS)

    Sadikov, I.I.; Zinov'ev, V.G.; Sadikova, Z.O.; Salimov, M.I.

    2006-01-01

    Full text: The palladium and platinum are widely used for jewel manufacture because of their beautiful white color. However the most part of these metals are widely adopted in the world as catalysts. Many works on analytical chemistry of platinum group elements published during last years are devoted to determination of platinum and palladium in other materials. There are no articles on analysis technique of the palladium and platinum purity published during last 20 years. Available publications are very old and are published till 70th of the last century, and implement chemical and spectral methods. At the same time, the palladium and platinum are very suitable for NAA. Therefore the purpose of our research was development of high-sensitivity and multielement techniques of radiochemical neutron activation analysis of a high pure palladium and platinum. Research of nuclear characteristics of palladium and platinum has shown that radioactive nuclides with different yields are formed under the reactor neutrons. 109 , 111 , 111m Pd, 109m , 111 Ag, 191 , 197 , 199 Pt, 199 Au are the most important among them. 109Pd separation factor is equal to 1*10 5 at palladium analysis, whereas 197 Pt and 199 Au separation factor is equal to 1*10 4 at the platinum analysis every other day after irradiation. Palladium and platinum can be separated by precipitation, extraction and ion exchange methods. For separation of radioactive nuclide of the matrix elements from the impurity elements we used ion exchange chromatography system Dowex-1x8 - 1 M HNO 3 for palladium and Dowex-1x8 - 0.1 M HNO 3 for platinum. At the HNO 3 acid concentrations variation from 0,1 M to 1 M more then 25 elements have distribution factors less than 1 and 10 elements have distribution factors 5 while matrix elements have distribution factors higher than 100. It allows an effective separation of these elements from palladium and platinum. Optimum sizes of the chromatographic column and the column effluent

  3. High-yield synthesis of brookite TiO.sub.2 nanoparticles

    Science.gov (United States)

    Huber, Dale L [Albuquerque, NM; Monson, Todd C [Albuquerque, NM

    2011-05-17

    A method for forming non-agglomerated brookite TiO.sub.2 nanoparticles without the use of expensive organic surfactants or high temperature processing. Embodiments of this invention use titanium isopropoxide as the titanium precursor and isopropanol as both the solvent and ligand for ligand-stabilized brookite-phase titania. Isopropanol molecules serve as the ligands interacting with the titania surfaces that stabilize the titania nanoparticles. The isopropanol ligands can be exchanged with other alcohols and other ligands during or after the nanoparticle formation reaction.

  4. Reduction of dinitrogen ligands

    International Nuclear Information System (INIS)

    Richards, R.L.

    1983-01-01

    Processes of dinitrogen ligand reduction in complexes of transition metals are considered. The basic character of the dinitrogen ligand is underlined. Data on X-ray photoelectronic spectroscopy and intensities of bands ν (N 2 ) in IR-spectra of nitrogen complexes are given. The mechanism of protonation of an edge dinitrogen ligand is discussed. Model systems and mechanism of nitrogenogenase are compared

  5. Preparation of highly-oxidized starch using hydrogen peroxide and its application as a novel ligand for zirconium tanning of leather.

    Science.gov (United States)

    Yu, Yue; Wang, Ya-Nan; Ding, Wei; Zhou, Jianfei; Shi, Bi

    2017-10-15

    A series of highly-oxidized starch (HOS) were prepared using H 2 O 2 and a copper-iron catalyst as a desired ligand for zirconium tanning of leather. The effects of catalyst and H 2 O 2 dosages, and reaction temperature on the oxidation degree (OD, represented as the amount of carbonyl and carboxyl groups derived) of starch were investigated. The OD reached 76.2% when oxidation was conducted using 60% H 2 O 2 and 0.015% catalyst at 98°C for 2h. 13 C NMR and FT-IR illustrated carbonyl and carboxyl groups were formed in HOS after oxidation. GPC and laser particle size analyses indicated the decrease of HOS molecular size with increasing H 2 O 2 dosage and OD. HOS with moderate OD and molecular weight was able to coordinate with zirconium and remarkably improve tanning process. Leather tanned by Zr complexes using HOS-60 (60% H 2 O 2 , Mn 3516g/mol) as ligand presented considerably better physical and organoleptic properties than those of traditional Zr-tanned leather. Copyright © 2017 Elsevier Ltd. All rights reserved.

  6. A viral, transporter associated with antigen processing (TAP)-independent, high affinity ligand with alternative interactions endogenously presented by the nonclassical human leukocyte antigen E class I molecule.

    Science.gov (United States)

    Lorente, Elena; Infantes, Susana; Abia, David; Barnea, Eilon; Beer, Ilan; García, Ruth; Lasala, Fátima; Jiménez, Mercedes; Mir, Carmen; Morreale, Antonio; Admon, Arie; López, Daniel

    2012-10-12

    The transporter associated with antigen processing (TAP) enables the flow of viral peptides generated in the cytosol by the proteasome and other proteases to the endoplasmic reticulum, where they complex with nascent human leukocyte antigen (HLA) class I. Later, these peptide-HLA class I complexes can be recognized by CD8(+) lymphocytes. Cancerous cells and infected cells in which TAP is blocked, as well as individuals with unusable TAP complexes, are able to present peptides on HLA class I by generating them through TAP-independent processing pathways. Here, we identify a physiologically processed HLA-E ligand derived from the D8L protein in TAP-deficient vaccinia virus-infected cells. This natural high affinity HLA-E class I ligand uses alternative interactions to the anchor motifs previously described to be presented on nonclassical HLA class I molecules. This octameric peptide was also presented on HLA-Cw1 with similar binding affinity on both classical and nonclassical class I molecules. In addition, this viral peptide inhibits HLA-E-mediated cytolysis by natural killer cells. Comparison between the amino acid sequences of the presenting HLA-E and HLA-Cw1 alleles revealed a shared structural motif in both HLA class molecules, which could be related to their observed similar cross-reactivity affinities. This motif consists of several residues located on the floor of the peptide-binding site. These data expand the role of HLA-E as an antigen-presenting molecule.

  7. Atomic resolution mechanistic studies of ribocil: A highly selective unnatural ligand mimic of the E. coli FMN riboswitch

    Energy Technology Data Exchange (ETDEWEB)

    Howe, John A.; Xiao, Li; Fischmann, Thierry O.; Wang, Hao; Tang, Haifeng; Villafania, Artjohn; Zhang, Rumin; Barbieri, Christopher M.; Roemer, Terry (Merck)

    2016-08-02

    Bacterial riboswitches are non-coding RNA structural elements that direct gene expression in numerous metabolic pathways. The key regulatory roles of riboswitches, and the urgent need for new classes of antibiotics to treat multi-drug resistant bacteria, has led to efforts to develop small-molecules that mimic natural riboswitch ligands to inhibit metabolic pathways and bacterial growth. Recently, we reported the results of a phenotypic screen targeting the riboflavin biosynthesis pathway in the Gram-negative bacteria Escherichia coli that led to the identification of ribocil, a small molecule inhibitor of the flavin mononucleotide (FMN) riboswitch controlling expression of this biosynthetic pathway. Although ribocil is structurally distinct from FMN, ribocil functions as a potent and highly selective synthetic mimic of the natural ligand to repress riboswitch-mediated ribB gene expression and inhibit bacterial growth both in vitro and in vivo. Herein, we expand our analysis of ribocil; including mode of binding in the FMN binding pocket of the riboswitch, mechanisms of resistance and structure-activity relationship guided efforts to generate more potent analogs.

  8. Highly porous polytriazole ion exchange membranes cast from solutions in non-toxic cosolvents

    KAUST Repository

    Chisca, Stefan

    2017-04-04

    The development of highly functionalized porous materials for protein separation is important for biotech processes. We report the preparation of highly porous polytriazole with sulfonic acid functionalization. The resulting ion exchange membranes are selective for protein adsorption. The starting material was a hydroxyl-functionalized polytriazole, which is an advantageous platform for further modification. The polymer was dissolved in a mixture of 1-ethyl-3-methylimidazolium acetate ([C2mim]OAc) and dimethyl carbonate (DMC), which can be both considered green solvents. The polymer solubilization was only possible due to an interesting effect of cosolvency, which is discussed, based in phase diagrams. Membranes were prepared by solution casting, followed by immersion in a non-solvent bath. We then grafted sulfone groups on the membranes, by reacting the hydroxyl groups with 1,3-propane sultone and 1,4-butane sultone. Lysozyme adsorption was successfully evaluated. Membranes modified with 1,4-butane sultone adsorbed more protein than those with 1,3-propane sultone.

  9. Status of Charge Exchange Cross Section Measurements for Highly Charged Ions on Atomic Hydrogen

    Science.gov (United States)

    Draganic, I. N.; Havener, C. C.; Schultz, D. R.; Seely, D. G.; Schultz, P. C.

    2011-05-01

    Total cross sections of charge exchange (CX) for C5+, N6+, and O7+ ions on ground state atomic hydrogen are measured in an extended collision energy range of 1 - 20,000 eV/u. Absolute CX measurements are performed using an improved merged-beams technique with intense highly charged ion beams extracted from a 14.5 GHz ECR ion source mounted on a high voltage platform. In order to improve the problematic H+ signal collection for these exoergic CX collisions at low relative energies, a new double focusing electrostatic analyzer was installed. Experimental CX data are in good agreement with all previous H-oven relative measurements at higher collision energies. We compare our results with the most recent molecular orbital close-coupling (MOCC) and atomic orbital close-coupling (AOCC) theoretical calculations. Work supported by the NASA Solar & Heliospheric Physics Program NNH07ZDA001N, the Office of Fusion Energy Sciences and the Division of Chemical Sciences, Geosciences, and Biosciences, and the Office of Basic Energy Sciences of the U.S. DoE.

  10. High-temperature process heat reactor with solid coolant and radiant heat exchange

    International Nuclear Information System (INIS)

    Alekseev, A.M.; Bulkin, Yu.M.; Vasil'ev, S.I.

    1984-01-01

    The high temperature graphite reactor with the solid coolant in which heat transfer is realized by radiant heat exchange is described. Neutron-physical and thermal-technological features of the reactor are considered. The reactor vessel is made of sheet carbon steel in the form of a sealed rectangular annular box. The moderator is a set of graphite blocks mounted as rows of arched laying Between the moderator rows the solid coolant annular layings made of graphite blocks with high temperature nuclear fuel in the form of coated microparticles are placed. The coolant layings are mounted onto ring movable platforms, the continuous rotation of which is realizod by special electric drives. Each part of the graphite coolant laying consecutively passes through the reactor core neutron cut-off zones and technological zone. In the core the graphite is heated up to the temperature of 1350 deg C sufficient for effective radiant heat transfer. In the neutron cut-off zone the chain reaction and further graphite heating are stopped. In the technological zone the graphite transfers the accumulated heat to the walls of technological channels in which the working medium moves. The described reactor is supposed to be used in nuclear-chemical complex for ammonia production by the method of methane steam catalytic conversion

  11. Affinity-based, biophysical methods to detect and analyze ligand binding to recombinant proteins: matching high information content with high throughput.

    Science.gov (United States)

    Holdgate, Geoff A; Anderson, Malcolm; Edfeldt, Fredrik; Geschwindner, Stefan

    2010-10-01

    Affinity-based technologies have become impactful tools to detect, monitor and characterize molecular interactions using recombinant target proteins. This can aid the understanding of biological function by revealing mechanistic details, and even more importantly, enables the identification of new improved ligands that can modulate the biological activity of those targets in a desired fashion. The selection of the appropriate technology is a key step in that process, as each one of the currently available technologies offers a characteristic type of biophysical information about the ligand-binding event. Alongside the indisputable advantages of each of those technologies they naturally display diverse restrictions that are quite frequently related to the target system to be studied but also to the affinity, solubility and molecular size of the ligands. This paper discusses some of the theoretical and experimental aspects of the most common affinity-based methods, what type of information can be gained from each one of those approaches, and what requirements as well as limitations are expected from working with recombinant proteins on those platforms and how those can be optimally addressed.

  12. Open-cycle magnetohydrodynamic power plant based upon direct-contact closed-loop high-temperature heat exchanger

    Science.gov (United States)

    Berry, G.F.; Minkov, V.; Petrick, M.

    1981-11-02

    A magnetohydrodynamic (MHD) power generating system is described in which ionized combustion gases with slag and seed are discharged from an MHD combustor and pressurized high temperature inlet air is introduced into the combustor for supporting fuel combustion at high temperatures necessary to ionize the combustion gases, and including a heat exchanger in the form of a continuous loop with a circulating heat transfer liquid such as copper oxide. The heat exchanger has an upper horizontal channel for providing direct contact between the heat transfer liquid and the combustion gases to cool the gases and condense the slag which thereupon floats on the heat transfer liquid and can be removed from the channel, and a lower horizontal channel for providing direct contact between the heat transfer liquid and pressurized air for preheating the inlet air. The system further includes a seed separator downstream of the heat exchanger.

  13. Abiotic and biotic determinants of leaf carbon exchange capacity from tropical to high boreal biomes

    Science.gov (United States)

    Smith, N. G.; Dukes, J. S.

    2016-12-01

    Photosynthesis and respiration on land represent the two largest fluxes of carbon dioxide between the atmosphere and the Earth's surface. As such, the Earth System Models that are used to project climate change are high sensitive to these processes. Studies have found that much of this uncertainty is due to the formulation and parameterization of plant photosynthetic and respiratory capacity. Here, we quantified the abiotic and biotic factors that determine photosynthetic and respiratory capacity at large spatial scales. Specifically, we measured the maximum rate of Rubisco carboxylation (Vcmax), the maximum rate of Ribulose-1,5-bisphosphate regeneration (Jmax), and leaf dark respiration (Rd) in >600 individuals of 98 plant species from the tropical to high boreal biomes of Northern and Central America. We also measured a bevy of covariates including plant functional type, leaf nitrogen content, short- and long-term climate, leaf water potential, plant size, and leaf mass per area. We found that plant functional type and leaf nitrogen content were the primary determinants of Vcmax, Jmax, and Rd. Mean annual temperature and mean annual precipitation were not significant predictors of these rates. However, short-term climatic variables, specifically soil moisture and air temperature over the previous 25 days, were significant predictors and indicated that heat and soil moisture deficits combine to reduce photosynthetic capacity and increase respiratory capacity. Finally, these data were used as a model benchmarking tool for the Community Land Model version 4.5 (CLM 4.5). The benchmarking analyses determined errors in the leaf nitrogen allocation scheme of CLM 4.5. Under high leaf nitrogen levels within a plant type the model overestimated Vcmax and Jmax. This result suggested that plants were altering their nitrogen allocation patterns when leaf nitrogen levels were high, an effect that was not being captured by the model. These data, taken with models in mind

  14. High infection control rate and function after routine one-stage exchange for chronically infected TKA.

    Science.gov (United States)

    Jenny, Jean-Yves; Barbe, Bruno; Gaudias, Jeannot; Boeri, Cyril; Argenson, Jean-Noël

    2013-01-01

    Many surgeons consider two-stage exchange the gold standard for treating chronic infection after TKA. One-stage exchange is an alternative for infection control and might provide better knee function, but the rates of infection control and levels of function are unclear. We asked whether a one-stage exchange protocol would lead to infection control rates and knee function similar to those after two-stage exchange. We followed all 47 patients with chronically infected TKAs treated with one-stage exchange between July 2004 and February 2007. We monitored for recurrence of infection and obtained Knee Society Scores. We followed patients a minimum of 3 years or until death or infection recurrence. Three of the 47 patients (6%) experienced a persistence or recurrence of the index infection with the same pathogen isolated. Three patients (6%) had control of the index infection but between 6 and 17 months experienced an infection with another pathogen. The 3-year survival rates were 87% for being free of any infection and 91% for being healed of the index infection. Twenty-five of the 45 patients (56%) had a Knee Society Score of more than 150 points. While routine one-stage exchange was not associated with a higher rate of infection recurrence failure, knee function was not improved compared to that of historical patients having two-stage exchange. One stage-exchange may be a reasonable alternative in chronically infected TKA as a more convenient approach for patients without the risks of two operations and hospitalizations and for reducing costs. The ideal one stage-exchange candidate should be identified in future studies.

  15. Natural Deposition Strategy for Interfacial, Self-Assembled, Large-Scale, Densely Packed, Monolayer Film with Ligand-Exchanged Gold Nanorods for In Situ Surface-Enhanced Raman Scattering Drug Detection.

    Science.gov (United States)

    Mao, Mei; Zhou, Binbin; Tang, Xianghu; Chen, Cheng; Ge, Meihong; Li, Pan; Huang, Xingjiu; Yang, Liangbao; Liu, Jinhuai

    2018-03-15

    Liquid interfacial self-assembly of metal nanoparticles holds great promise for its various applications, such as in tunable optical devices, plasmonics, sensors, and catalysis. However, the construction of large-area, ordered, anisotropic, nanoparticle monolayers and the acquisition of self-assembled interface films are still significant challenges. Herein, a rapid, validated method to fabricate large-scale, close-packed nanomaterials at the cyclohexane/water interface, in which hydrophilic cetyltrimethylammonium bromide coated nanoparticles and gold nanorods (AuNRs) self-assemble into densely packed 2D arrays by regulating the surface ligand and suitable inducer, is reported. Decorating AuNRs with polyvinylpyrrolidone not only extensively decreases the charge of AuNRs, but also diminishes repulsive forces. More importantly, a general, facile, novel technique to transfer an interfacial monolayer through a designed in situ reaction cell linked to a microfluidic chip is revealed. The self-assembled nanofilm can then automatically settle on the substrate and be directly detected in the reaction cell in situ by means of a portable Raman spectrometer. Moreover, a close-packed monolayer of self-assembled AuNRs provides massive, efficient hotspots to create great surface-enhanced Raman scattering (SERS) enhancement, which provides high sensitivity and reproducibility as the SERS-active substrate. Furthermore, this strategy was exploited to detect drug molecules in human urine for cyclohexane-extracted targets acting as the oil phase to form an oil/water interface. A portable Raman spectrometer was employed to detect methamphetamine down to 100 ppb levels in human urine, exhibiting excellent practicability. As a universal platform, handy tool, and fast pretreatment method with a good capability for drug detection in biological systems, this technique shows great promise for rapid, credible, and on-spot drug detection. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Separation of the potential G-quadruplex ligands from the butanol extract of Zanthoxylum ailanthoides Sieb. & Zucc. by countercurrent chromatography and preparative high performance liquid chromatography.

    Science.gov (United States)

    Han, Tian; Cao, Xueli; Xu, Jing; Pei, Hairun; Zhang, Hong; Tang, Yalin

    2017-07-21

    G-quadruplex DNA structure is considered to be a very attractive target for antitumor drug design due to its unique role in maintaining telomerase activities. Therefore, discovering ligands with high stability of G-quadruplex structure is of great interest. In this paper, pH-zone refining counter current chromatography (CCC) and preparative high performance liquid chromatography (HPLC) were employed for the separation of potent G-quadruplex ligands from the n-butanol fraction of the crude extract of Zanthoxylum ailanthoides, which is a traditional Chinese medicine recently found to display high inhibitory activity against several human cancer cells. The 75% aqueous ethanol extract of the stem bark of Z. ailanthoides and its fractions with petroleum ether, ethyl acetate and n-butanol displayed almost the same G-quadruplex stabilization ability. Here, pH-zone refining CCC was used for the separation of the alkaloids from the n-butanol fraction by a seldom used solvent system composed of dichloromethane-methanol-water (4:1:2.5) with 10mM TEA in the organic stationary phase as retainer and 10mM HCl in the aqueous mobile phase as eluter. Compounds I, II and III were obtained, with purity greater than 95%, in the quantities of 31.2, 94.0, and 26.4mg respectively from 300mg of lipophilic fraction within 80min, which were identified as three tetrahydroprotoberberines isolated for the first time in this plant. In addition, a phenylpropanoid glycoside compound IV (Syringin), an isoquinoline (Magnoflorine, V), and two lignin isomers (+)-lyoniresiol-3α-O-β-d-glucopyranoside (VI) and (-)-lyoniresinol -3α-O-β-D -glucopyranoside (VII) were isolated by traditional CCC together with preparative HPLC. Compounds IV, V, VI and VII were obtained, with purity greater than 95%, in the quantities of 4.0, 13.2, 6.7, and 6.5mg respectively from 960mg of hydrophilic fraction. Among the seven isolated compounds, tetrahydroprotoberberine I, II and III were found to display remarkable

  17. High Molar Extinction Coefficient Ru(II-Mixed Ligand Polypyridyl Complexes for Dye Sensitized Solar Cell Application

    Directory of Open Access Journals (Sweden)

    Malapaka Chandrasekharam

    2011-01-01

    Full Text Available Two new ruthenium(II mixed ligand terpyridine complexes, “Ru(Htcterpy(NCS(L1 (N(C4H94, mLBD1” and Ru(Htcterpy(NCS(L2(N(C4H94, mLBD2 were synthesized and fully characterized by UV-Vis, emission, cyclic voltammogram, and other spectroscopic means, and the structures of the compounds are confirmed by 1H-NMR, ESI-MASS, and FT-IR spectroscopes. The influence of the substitution of L1 and L2 on solar-to-electrical energy conversion efficiency (η of dye-sensitized solar cells (DSSCs was evaluated relative to reference black dye. The dyes showed molar extinction coefficients of 17600 M−1 cm−1 for mLBD1 and 21300 M−1 cm−1 for mLBD2 both at λ maximum of 512 nm, while black dye has shown 8660 M−1 cm−1 at λ maximum of 615 nm. The monochromatic incident photon-to-collected electron conversion efficiencies of 60.71% and 75.89% were obtained for mLBD1 and mLBD2 dyes, respectively. The energy conversion efficiencies of mLBD1 and mLBD2 dyes are 3.15% (SC=11.86 mA/cm2, OC=613 mV, ff=0.4337 and 3.36% (SC=12.71 mA/cm2, OC=655 mV, ff=0.4042, respectively, measured at the AM1.5G conditions, the reference black dye-sensitized solar cell, fabricated and evaluated under identical conditions exhibited η-value of 2.69% (SC=10.95 mA/cm2, OC=655 mV, ff=0.3750.

  18. Ligands in PSI structures

    International Nuclear Information System (INIS)

    Kumar, Abhinav; Chiu, Hsiu-Ju; Axelrod, Herbert L.; Morse, Andrew; Elsliger, Marc-André; Wilson, Ian A.; Deacon, Ashley

    2010-01-01

    A survey of the types and frequency of ligands that are bound to PSI structures is analyzed as well as their utility in functional annotation of previously uncharacterized proteins. Approximately 65% of PSI structures report some type of ligand(s) that is bound in the crystal structure. Here, a description is given of how such ligands are handled and analyzed at the JCSG and a survey of the types, variety and frequency of ligands that are observed in the PSI structures is also compiled and analyzed, including illustrations of how these bound ligands have provided functional clues for annotation of proteins with little or no previous experimental characterization. Furthermore, a web server was developed as a tool to mine and analyze the PSI structures for bound ligands and other identifying features

  19. Net Ecosystem Exchange of CO2 with Rapidly Changing High Arctic Landscapes

    Science.gov (United States)

    Emmerton, C. A.

    2015-12-01

    High Arctic landscapes are expansive and changing rapidly. However our understanding of their functional responses and potential to mitigate or enhance anthropogenic climate change is limited by few measurements. We collected eddy covariance measurements to quantify the net ecosystem exchange (NEE) of CO2 with polar semidesert and meadow wetland landscapes at the highest-latitude location measured to date (82°N). We coupled these rare data with ground and satellite vegetation production measurements (Normalized Difference Vegetation Index; NDVI) to evaluate the effectiveness of upscaling local to regional NEE. During the growing season, the dry polar semidesert landscape was a near zero sink of atmospheric CO2 (NEE: -0.3±13.5 g C m-2). A nearby meadow wetland accumulated over two magnitudes more carbon (NEE: -79.3±20.0 g C m-2) than the polar semidesert landscape, and was similar to meadow wetland NEE at much more southern latitudes. Polar semidesert NEE was most influenced by moisture, with wetter surface soils resulting in greater soil respiration and CO2 emissions. At the meadow wetland, soil heating enhanced plant growth, which in turn increased CO2 uptake. Our upscaling assessment found that polar semidesert NDVI measured on site was low (mean: 0.120-0.157) and similar to satellite measurements (mean: 0.155-0.163). However, weak plant growth resulted in poor satellite NDVI-NEE relationships and created challenges for remotely-detecting changes in the cycling of carbon on the polar semidesert landscape. The meadow wetland appeared more suitable to assess plant production and NEE via remote-sensing, however high Arctic wetland extent is constrained by topography to small areas that may be difficult to resolve with large satellite pixels. We predict that until summer precipitation and humidity increases substantially, climate-related changes of dry high Arctic landscapes may be restricted by poor soil moisture retention, and therefore have some inertia against

  20. Identification of a hydrolyzable tannin, oenothein B, as an aluminum-detoxifying ligand in a highly aluminum-resistant tree, Eucalyptus camaldulensis.

    Science.gov (United States)

    Tahara, Ko; Hashida, Koh; Otsuka, Yuichiro; Ohara, Seiji; Kojima, Katsumi; Shinohara, Kenji

    2014-02-01

    Eucalyptus camaldulensis is a tree species in the Myrtaceae that exhibits extremely high resistance to aluminum (Al). To explore a novel mechanism of Al resistance in plants, we examined the Al-binding ligands in roots and their role in Al resistance of E. camaldulensis. We identified a novel type of Al-binding ligand, oenothein B, which is a dimeric hydrolyzable tannin with many adjacent phenolic hydroxyl groups. Oenothein B was isolated from root extracts of E. camaldulensis by reverse-phase high-performance liquid chromatography and identified by nuclear magnetic resonance and mass spectrometry analyses. Oenothein B formed water-soluble or -insoluble complexes with Al depending on the ratio of oenothein B to Al and could bind at least four Al ions per molecule. In a bioassay using Arabidopsis (Arabidopsis thaliana), Al-induced inhibition of root elongation was completely alleviated by treatment with exogenous oenothein B, which indicated the capability of oenothein B to detoxify Al. In roots of E. camaldulensis, Al exposure enhanced the accumulation of oenothein B, especially in EDTA-extractable forms, which likely formed complexes with Al. Oenothein B was localized mostly in the root symplast, in which a considerable amount of Al accumulated. In contrast, oenothein B was not detected in three Al-sensitive species, comprising the Myrtaceae tree Melaleuca bracteata, Populus nigra, and Arabidopsis. Oenothein B content in roots of five tree species was correlated with their Al resistance. Taken together, these results suggest that internal detoxification of Al by the formation of complexes with oenothein B in roots likely contributes to the high Al resistance of E. camaldulensis.

  1. Numerical simulation of proton exchange membrane fuel cells at high operating temperature

    Science.gov (United States)

    Peng, Jie; Lee, Seung Jae

    A three-dimensional, single-phase, non-isothermal numerical model for proton exchange membrane (PEM) fuel cell at high operating temperature (T ≥ 393 K) was developed and implemented into a computational fluid dynamic (CFD) code. The model accounts for convective and diffusive transport and allows predicting the concentration of species. The heat generated from electrochemical reactions, entropic heat and ohmic heat arising from the electrolyte ionic resistance were considered. The heat transport model was coupled with the electrochemical and mass transport models. The product water was assumed to be vaporous and treated as ideal gas. Water transportation across the membrane was ignored because of its low water electro-osmosis drag force in the polymer polybenzimidazole (PBI) membrane. The results show that the thermal effects strongly affect the fuel cell performance. The current density increases with the increasing of operating temperature. In addition, numerical prediction reveals that the width and distribution of gas channel and current collector land area are key optimization parameters for the cell performance improvement.

  2. Numerical simulation of proton exchange membrane fuel cells at high operating temperature

    Energy Technology Data Exchange (ETDEWEB)

    Peng, Jie; Lee, Seung Jae [Energy Lab, Samsung Advanced Institute of Technology, Mt. 14-1 Nongseo-Dong, Giheung-Gu, Yongin-Si, Gyeonggi-Do 446-712 (Korea, Republic of)

    2006-11-22

    A three-dimensional, single-phase, non-isothermal numerical model for proton exchange membrane (PEM) fuel cell at high operating temperature (T>=393K) was developed and implemented into a computational fluid dynamic (CFD) code. The model accounts for convective and diffusive transport and allows predicting the concentration of species. The heat generated from electrochemical reactions, entropic heat and ohmic heat arising from the electrolyte ionic resistance were considered. The heat transport model was coupled with the electrochemical and mass transport models. The product water was assumed to be vaporous and treated as ideal gas. Water transportation across the membrane was ignored because of its low water electro-osmosis drag force in the polymer polybenzimidazole (PBI) membrane. The results show that the thermal effects strongly affect the fuel cell performance. The current density increases with the increasing of operating temperature. In addition, numerical prediction reveals that the width and distribution of gas channel and current collector land area are key optimization parameters for the cell performance improvement. (author)

  3. Synthesis of high capacity cation exchangers from a low-grade Chinese natural zeolite

    International Nuclear Information System (INIS)

    Wang Yifei; Lin Feng

    2009-01-01

    The Chinese natural zeolite, in which clinoptilolite coexists with quartz was treated hydrothermally with NaOH solutions, either with or without fusion with NaOH powder as pretreatment. Zeolite Na-P, Na-Y and analcime were identified as the reacted products, depending on the reaction conditions such as NaOH concentration, reaction time and hydrothermal temperature. The products were identified by X-ray diffraction, and characterized by Fourier transform IR and ICP. With hydrothermal treatment after fusion of natural zeolite with NaOH, high purity of zeolite Na-Y and Na-P can be selectively formed, their cation exchange capacity (CEC) are 275 and 355 meq/100 g respectively, which are greatly higher than that of the natural zeolite (97 meq/100 g). Furthermore, the ammonium removal by the synthetic zeolite Na-P in aqueous solution was also studied. The equilibrium isotherms have been got and the influence of other cations present in water upon the ammonia uptake suggested an order of preference Ca 2+ > K + > Mg 2+ .

  4. Highly fluorinated comb-shaped copolymer as proton exchange membranes (PEMs): Fuel cell performance

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Dae Sik; Guiver, Michael D.; Ding, Jianfu [Institute for Chemical Process and Environmental Technology, National Research Council, 1200 Montreal Road, Ottawa, Ontario K1A 0R6 (Canada); Kim, Yu.Seung; Pivovar, Bryan S. [Materials Physics and Applications, Sensors and Electrochemical Devices Group, Los Alamos National Laboratory, Los Alamos, NM 87545 (United States)

    2008-07-15

    The fuel cell performance (DMFC and H{sub 2}/air) of highly fluorinated comb-shaped copolymer is reported. The initial performance of membrane electrode assemblies (MEAs) fabricated from comb-shaped copolymer containing a side-chain weight fraction of 22% are compared with those derived from Nafion and sulfonated polysulfone (BPSH-35) under DMFC conditions. The low water uptake of comb copolymer enabled an increase in proton exchange site concentrations in the hydrated polymer, which is a desirable membrane property for DMFC application. The comb-shaped copolymer architecture induces phase separated morphology between the hydrophobic fluoroaromatic backbone and the polysulfonic acid side chains. The initial performance of the MEAs using BPSH-35 and Comb 22 copolymer were comparable and higher than that of the Nafion MEA at all methanol concentrations. For example, the power density of the MEA using Comb 22 copolymer at 350 mA cm{sup -2} and 0.5 M methanol was 145 mW cm{sup -2}, whereas the power densities of MEAs using BPSH-35 were 136 mW cm{sup -2}. The power density of the MEA using Comb 22 copolymer at 350 mA cm{sup -2} and 2.0 M methanol was 144.5 mW cm{sup -2}, whereas the power densities of MEAs using BPSH-35 were 143 mW cm{sup -2}. (author)

  5. Characterisation of brewpub beer carbohydrates using high performance anion exchange chromatography coupled with pulsed amperometric detection.

    Science.gov (United States)

    Arfelli, Giuseppe; Sartini, Elisa

    2014-01-01

    High performance anion exchange chromatography (HPAEC) coupled with pulsed amperometric detection (PAD) was optimised in order to quantify mannose, maltose, maltotriose, maltotetraose, maltopentaose, maltohexaose and maltoheptaose content of beer. The method allows the determination of above mentioned oligosaccharides, in a single chromatographic run, without any pre-treatment. Limit of detection and limit of quantification were suitable for beer. Accuracy and repeatability were good for the entire amount considered. Once optimised HPAEC PAD for the specific matrix, the second goal of this research was to verify the possibility to discriminate beers, depending on their style. The carbohydrates content of brewpub commercial beers was very variable, ranging from 19.3 to 1469mg/L (mannose), 34.5 to 2882mg/L (maltose), 141.9 to 20731mg/L (maltotriose), 168.5 to 7650mg/L (maltotetraose), 20.1 to 2537mg/L (maltopentaose), 22.9 to 3295mg/L (maltohexaose), 8.5 to 2492mg/L (maltoeptaose), even in the same style of beer. However, the carbohydrates content was useful, jointed with other compounds amount, to discriminate different styles of beer. As a matter of fact, principal component analysis put in evidence beer differences considering some fermentation conditions and colour. Copyright © 2013 Elsevier Ltd. All rights reserved.

  6. Covalent magnetism, exchange interactions and anisotropy of the high temperature layered antiferromagnet MnB₂.

    Science.gov (United States)

    Khmelevskyi, S; Mohn, P

    2012-01-11

    The investigation of the electronic structure and magnetism for the compound MnB(2) with crystal structure type AlB(2) has been revisited to resolve contradictions between various experimental and theoretical results present in the literature. We find that MnB(2) exhibits an interesting example of a Kübler's covalent magnetism (Williams et al 1981 J. Appl. Phys. 52 2069). The covalent magnetism also appears to be the source of some disagreement between the calculated values of the magnetic moments and those given by neutron diffraction experiments. We show that this shortcoming is due to the atomic sphere approximation applied in earlier calculations. The application of the disordered local moment approach and the calculation of the inter-atomic exchange interactions within the Liechtenstein formalism reveal strong local moment antiferromagnetism with a high Néel temperature predicted from Monte Carlo simulations. A fully relativistic band structure calculation and then the application of the torque method yields a strong in-plane anisotropy of the Mn magnetic moments. The agreement of these results with neutron diffraction studies rules out any possible weak itinerant electron magnetism scenarios as proposed earlier for MnB(2).

  7. Novel silica-based ion exchange resin

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1997-11-01

    Eichrom`s highly successful Diphonixo resin resembles a conventional ion exchange resin in its use of sulfonic acid ligands on a styrene- divinylbenzene matrix. Diphonix resin exhibits rapid exchange kinetics that allow economical operation of ion exchange systems. Unlike conventional resins, Diphonix resin contains chelating ligands that are diphosphonic acid groups that recognize and remove the targeted metals and reject the more common elements such as sodium, calcium and magnesium. This latter property makes Diphonix ideal for many industrial scale applications, including those involving waste treatment. For treatment of low-level, transuranic (TRU) and high- level radioactive wastes, Diphonix`s polystyrene backbone hinders its application due to radiolytic stability of the carbon-hydrogen bonds and lack of compatibility with expected vitrification schemes. Polystyrene-based Diphonix is approximately 60% carbon- hydrogen. In response to an identified need within the Department of Energy for a resin with the positive attributes of Diphonix that also exhibits greater radiolytic stability and final waste form compatibility, Eichrom has successfully developed a new, silica-based resin version of Diphonix. Target application for this new resin is for use in environmental restoration and waste management situations involving the processing of low-level, transuranic and high-level radioactive wastes. The resin can also be used for processing liquid mixed waste (waste that contains low level radioactivity and hazardous constituents) including mixed wastes contaminated with organic compounds. Silica-based Diphonix is only 10% carbon-hydrogen, with the bulk of the matrix silica.

  8. Annual CO2 budget and seasonal CO2 exchange signals at a high Arctic permafrost site on Spitsbergen, Svalbard archipelago

    DEFF Research Database (Denmark)

    Luërs, J.; Westermann, Signe; Piel, K.

    2014-01-01

    -lasting snow cover, and several months of darkness. This study presents a complete annual cycle of the CO2 net ecosystem exchange (NEE) dynamics for a high Arctic tundra area at the west coast of Svalbard based on eddy covariance flux measurements. The annual cumulative CO2 budget is close to 0 g C m-2 yr-1...

  9. Fractionation of whey proteins with high-capacity superparamagnetic ion-exchangers

    DEFF Research Database (Denmark)

    Heebøll-Nielsen, Anders; Justesen, S.F.L.; Thomas, Owen R. T.

    2004-01-01

    to particles activated in sequential reactions with allyl bromide and N-bromosuccinimide yielded a maximum bovine serum albumin binding capacity of 156 mg g(-1) combined with a dissociation constant of 0.60 muM, whereas ion-exchangers created by linking polyethylene imine through superficial aldehydes bound up...... was then contacted with the anion-exchanger. For both adsorbent classes of ion-exchanger, desorption selectivity was subsequently studied by sequentially increasing the concentration of NaCl in the elution buffer. In the initial cation-exchange step quantitative removal of lactoferrin (LF) and lactoperoxidase (LPO......) was achieved with some simultaneous binding of immunoglobulins (1g). The immunoglobulins were separated from the other two proteins by desorbing with a low concentration of NaCl (less than or equal to0.4 M), whereas lactoferrin and lactoperoxidase were co-eluted in significantly purer form, e...

  10. High-capacity cation-exchange column for enhanced resolution of adjacent peaks of cations in ion chromatography.

    Science.gov (United States)

    Rey, M A

    2001-06-22

    One of the advantages of ion chromatography [Anal Chem. 47 (1975) 1801] as compared to other analytical techniques is that several ions may be analyzed simultaneously. One of the most important contributions of cation-exchange chromatography is its sensitivity to ammonium ion, which is difficult to analyze by other techniques [J. Weiss, in: E.L. Johnson (Ed.), Handbook of Ion Chromatography, Dionex, Sunnyvale, CA, USA]. The determination of low concentrations of ammonium ion in the presence of high concentrations of sodium poses a challenge in cation-exchange chromatography [J. Weiss, Ion Chromatography, VCH, 2nd Edition, Weinheim, 1995], as both cations have similar selectivities for the common stationary phases containing either sulfonate or carboxylate functional groups. The task was to develop a new cation-exchange stationary phase (for diverse concentration ratios of adjacent peaks) to overcome limitations experienced in previous trails. Various cation-exchange capacities and column body formats were investigated to optimize this application and others. The advantages and disadvantages of two carboxylic acid columns of different cation-exchange capacities and different column formats will be discussed.

  11. Rapid Preparation of Biosorbents with High Ion Exchange Capacity from Rice Straw and Bagasse for Removal of Heavy Metals

    Directory of Open Access Journals (Sweden)

    Supitcha Rungrodnimitchai

    2014-01-01

    Full Text Available This work describes the preparation of the cellulose phosphate with high ion exchange capacity from rice straw and bagasse for removal of heavy metals. In this study, rice straw and bagasse were modified by the reaction with phosphoric acid in the presence of urea. The introduced phosphoric group is an ion exchangeable site for heavy metal ions. The reaction by microwave heating yielded modified rice straw and modified bagasse with greater ion exchange capacities (∼3.62 meq/g and shorter reaction time (1.5–5.0 min than the phosphorylation by oil bath heating. Adsorption experiments towards Pb2+, Cd2+, and Cr3+ ions of the modified rice straw and the modified bagasse were performed at room temperature (heavy metal concentration 40 ppm, adsorbent 2.0 g/L. The kinetics of adsorption agreed with the pseudo-second-order model. It was shown that the modified rice straw and the modified bagasse could adsorb heavy metal ions faster than the commercial ion exchange resin (Dowax. As a result of Pb2+ sorption test, the modified rice straw (RH-NaOH 450W removed Pb2+ much faster in the initial step and reached 92% removal after 20 min, while Dowax (commercial ion exchange resin took 90 min for the same removal efficiency.

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

    Science.gov (United States)

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

    2016-11-01

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

  13. Creep-Data Analysis of Alloy 617 for High Temperature Reactor Intermediate Heat Exchanger

    International Nuclear Information System (INIS)

    Kim, Woo Gon; Ryu, Woo Seog; Kim, Yong Wan; Yin, Song Nan

    2006-01-01

    The design of the metallic components such as hot gas ducts, intermediate heat exchanger (IHX) tube, and steam reformer tubes of very high temperature reactor (VHTR) is principally determined by the creep properties, because an integrity of the components should be preserved during a design life over 30 year life at the maximum operating temperature up to 1000 .deg. C. For designing the time dependent creep of the components, a material database is needed, and an allowable design stress at temperature should be determined by using the material database. Alloy 617, a nicked based superalloy with chromium, molybdenum and cobalt additions, is considered as a prospective candidate material for the IHX because it has the highest design temperature. The alloy 617 is approved to 982 .deg. C (1800 .deg. F) and other alloys approved to 898 .deg. C (1650 .deg. C), such as alloy 556, alloy 230, alloy HX, alloy 800. Also, the alloy 617 exhibits the highest level of creep strength at high temperatures. Therefore, it is needed to collect the creep data for the alloy 617 and the creep-rupture life at the given conditions of temperature and stress should be predicted for the IHX construction. In this paper, the creep data for the alloy 617 was collected through literature survey. Using the collected data, the creep life for the alloy 617 was predicted based on the Larson-Miller parameter. Creep master curves with standard deviations were presented for a safety design, and failure probability for the alloy 617 was obtained with a time coefficient

  14. Charge Exchange of Highly Charged Ne and Mg Ions with H and He

    Science.gov (United States)

    Lyons, D.; Cumbee, R. S.; Stancil, P. C.

    2017-10-01

    Cross sections for single electron capture (SEC), or charge exchange (CX), in collisions of Ne(8-10)+ and Mg(8-12)+ with H and He, are computed using an approximate multichannel Landau-Zener (MCLZ) formalism. Final-state-resolved cross sections for the principal (n), orbital angular momentum (ℓ), and where appropriate, total spin angular momentum (S) quantum numbers are explicitly computed, except for the incident bare ions Ne10+ and Mg12+. In the latter two cases, n{\\ell }-resolution is obtained from analytical ℓ-distribution functions applied to n-resolved MCLZ cross sections. In all cases, the cross sections are computed over the collision energy range 1 meV/u to 50 keV/u with LZ parameters estimated from atomic energies obtained from experiment, theory, or, in the case of high-lying Rydberg levels, estimated with a quantum defect approach. Errors in the energy differences in the adiabatic potentials at the avoided crossing distances give the largest contribution to the uncertainties in the cross sections, which are expected to increase with decreasing cross section magnitude. The energy differences are deduced here with the Olson-Salop-Tauljberg radial coupling model. Proper selection of an ℓ-distribution function for bare ion collisions introduces another level of uncertainty into the results. Comparison is made to existing experimental or theoretical results when available, but such data are absent for most considered collision systems. The n{\\ell }S-resolved SEC cross sections are used in an optically thin cascade simulation to predict X-ray spectra and line ratios that will aid in modeling the X-ray emission in environments where CX is an important mechanism. Details on a MCLZ computational package, Stueckelberg, are also provided.

  15. Quantitative autoradiography of the binding sites for [125I] iodoglyburide, a novel high-affinity ligand for ATP-sensitive potassium channels in rat brain

    International Nuclear Information System (INIS)

    Gehlert, D.R.; Gackenheimer, S.L.; Mais, D.E.; Robertson, D.W.

    1991-01-01

    We have developed a high specific activity ligand for localization of ATP-sensitive potassium channels in the brain. When brain sections were incubated with [ 125 I]iodoglyburide (N-[2-[[[(cyclohexylamino)carbonyl]amino]sulfonyl]ethyl]-5- 125 I-2- methoxybenzamide), the ligand bound to a single site with a KD of 495 pM and a maximum binding site density of 176 fmol/mg of tissue. Glyburide was the most potent inhibitor of specific [ 125 I]iodoglyburide binding to rat forebrain sections whereas iodoglyburide and glipizide were slightly less potent. The binding was also sensitive to ATP which completely inhibited binding at concentrations of 10 mM. Autoradiographic localization of [ 125 I]iodoglyburide binding indicated a broad distribution of the ATP-sensitive potassium channel in the brain. The highest levels of binding were seen in the globus pallidus and ventral pallidum followed by the septohippocampal nucleus, anterior pituitary, the CA2 and CA3 region of the hippocampus, ventral pallidum, the molecular layer of the cerebellum and substantia nigra zona reticulata. The hilus and dorsal subiculum of the hippocampus, molecular layer of the dentate gyrus, cerebral cortex, lateral olfactory tract nucleus, olfactory tubercle and the zona incerta contained relatively high levels of binding. A lower level of binding (approximately 3- to 4-fold) was found throughout the remainder of the brain. These results indicate that the ATP-sensitive potassium channel has a broad presence in the rat brain and that a few select brain regions are enriched in this subtype of neuronal potassium channels

  16. Development of plate-fin heat exchanger for intermediate heat exchanger of high-temperature gas cooled reactor. Fabrication process, high-temperature strength and creep-fatigue life prediction of plate-fin structure made of Hastelloy X

    International Nuclear Information System (INIS)

    Mizokami, Yorikata; Igari, Toshihide; Nakashima, Keiichi; Kawashima, Fumiko; Sakakibara, Noriyuki; Kishikawa, Ryouji; Tanihira, Masanori

    2010-01-01

    The helium/helium heat exchanger (i.e., intermediate heat exchanger: IHX) of a high-temperature gas-cooled reactor (HTGR) system with nuclear heat applications is installed between a primary system and a secondary system. IHX is operated at the highest temperature of 950degC and has a high capacity of up to 600 MWt. A plate-fin-type heat exchanger is the most suitable for IHX to improve construction cost. The purpose of this study is to develop an ultrafine plate-fin-type heat exchanger with a finer pitch fin than a conventional technology. In the first step, fabrication conditions of the ultrafine plate fin were optimized by press tests. In the second step, a brazing material was selected from several candidates through brazing tests of rods, and brazing conditions were optimized for plate-fin structures. In the third step, tensile strength, creep rupture, fatigue, and creep-fatigue tests were performed as typical strength tests for plate-fin structures. The obtained data were compared with those of the base metal and plate-fin element fabricated from SUS316. Finally, the accuracy of the creep-fatigue life prediction using both the linear cumulative damage rule and the equivalent homogeneous solid method was confirmed through the evaluation of creep-fatigue test results of plate-fin structures. (author)

  17. Highly Efficient Perovskite-Quantum-Dot Light-Emitting Diodes by Surface Engineering

    KAUST Repository

    Pan, Jun; Quan, Li Na; Zhao, Yongbiao; Peng, Wei; Banavoth, Murali; Sarmah, Smritakshi P.; Yuan, Mingjian; Sinatra, Lutfan; AlYami, Noktan; Liu, Jiakai; Yassitepe, Emre; Yang, Zhenyu; Voznyy, Oleksandr; Comin, Riccardo; Hedhili, Mohamed N.; Mohammed, Omar F.; Lu, Zheng Hong; Kim, Dong Ha; Sargent, Edward H.; Bakr, Osman

    2016-01-01

    A two-step ligand-exchange strategy is developed, in which the long-carbon-chain ligands on all-inorganic perovskite (CsPbX3, X = Br, Cl) quantum dots (QDs) are replaced with halide-ion-pair ligands. Green and blue light-emitting diodes made from the halide-ion-paircapped quantum dots exhibit high external quantum efficiencies compared with the untreated QDs.

  18. Highly Efficient Perovskite-Quantum-Dot Light-Emitting Diodes by Surface Engineering

    KAUST Repository

    Pan, Jun

    2016-08-16

    A two-step ligand-exchange strategy is developed, in which the long-carbon-chain ligands on all-inorganic perovskite (CsPbX3, X = Br, Cl) quantum dots (QDs) are replaced with halide-ion-pair ligands. Green and blue light-emitting diodes made from the halide-ion-paircapped quantum dots exhibit high external quantum efficiencies compared with the untreated QDs.

  19. High Temperature Magnetic Properties of Indirect Exchange Spring FePt/M(Cu,C/Fe Trilayer Thin Films

    Directory of Open Access Journals (Sweden)

    Anabil Gayen

    2013-01-01

    Full Text Available We report the investigation of temperature dependent magnetic properties of FePt and FePt(30/M(Cu,C/Fe(5 trilayer thin films prepared by using magnetron sputtering technique at ambient temperature and postannealed at different temperatures. L10 ordering, hard magnetic properties, and thermal stability of FePt films are improved with increasing postannealing temperature. In FePt/M/Fe trilayer, the formation of interlayer exchange coupling between magnetic layers depends on interlayer materials and interface morphology. In FePt/C/Fe trilayer, when the C interlayer thickness was about 0.5 nm, a strong interlayer exchange coupling between hard and soft layers was achieved, and saturation magnetization was enhanced considerably after using interlayer exchange coupling with Fe. In addition, incoherent magnetization reversal process observed in FePt/Fe films changes into coherent switching process in FePt/C/Fe films giving rise to a single hysteresis loop. High temperature magnetic studies up to 573 K reveal that the effective reduction in the coercivity decreases largely from 34 Oe/K for FePt/Fe film to 13 Oe/K for FePt/C(0.5/Fe film demonstrating that the interlayer exchange coupling seems to be a promising approach to improve the stability of hard magnetic properties at high temperatures, which is suitable for high-performance magnets and thermally assisted magnetic recording media.

  20. Structural Studies of NH4-exchanged Natrolites at Ambient Conditions and High Temperature

    Energy Technology Data Exchange (ETDEWEB)

    Y Lee; D Seoung; Y Jang; J Bai; Y Lee

    2011-12-31

    We report here for the first time that fully and partially NH{sub 4}-exchanged natrolites can be prepared in hydrated states using the solution exchange method with potassium-natrolite. The structural models of the as-prepared hydrated phases and their dehydrated forms at elevated temperature were refined in space group Fdd2 using in situ synchrotron X-ray powder diffraction data and Rietveld methods. The unit-cell volumes of the hydrated NH{sub 4}-exchanged natrolites at ambient conditions, (NH{sub 4}){sub 16(2)}Al{sub 16}Si{sub 24}O{sub 80}{center_dot}14.1(9)H{sub 2}O and (NH{sub 4}){sub 5.1(1)}K{sub 10.9(1)}Al{sub 16}Si{sub 24}O{sub 80}{center_dot}15.7(3)H{sub 2}O, are found to be larger than that the original sodium-natrolite by ca. 15.6% and 12.8%, respectively. Upon temperature increase, the fully NH{sub 4}-exchanged natrolite undergoes dehydration at ca. 150 C with ca. 16.4% contraction in the unit-cell volume. The dehydrated phase of the fully NH{sub 4}-exchanged natrolite exhibits marginal volume expansion up to 425 C and then becomes amorphized during temperature decrease and exposure to atmospheric condition. In the case of the partially NH{sub 4}-exchanged natrolite, the dehydration starts from ca. 175 C with {approx}15.1% volume contraction and leads to a partial phase separation to show a phase related to the dehydrated K-natrolite. The degree of the phase separation decreases with temperature increase up to 475 C, concomitant to the gradual volume contraction occurring in the partially NH{sub 4}-exchanged natrolite in the dehydrared state. Upon temperature decrease and exposure to atmospheric condition, only the dehydrated K-natrolite is recovered as a crystalline phase from the partially NH{sub 4}-exchanged natrolite. In the hydrated model of the fully NH{sub 4}-exchanged natrolite, the ammonium cations and water molecules are statistically distributed along the elliptical channels, similar to the disordered pattern observed in natrolites exchanged

  1. Brief Report: Randomized Test of the Efficacy of Picture Exchange Communication System on Highly Generalized Picture Exchanges in Children with ASD

    OpenAIRE

    Yoder, Paul J.; Lieberman, Rebecca G.

    2010-01-01

    A randomized control trial comparing two social-communication interventions in young children with autism examined far-transfer of the use of picture exchange to communicate. Thirty-six children were randomly assigned to one of two treatment conditions, one of which was the Picture Exchange Communication System (PECS). All children had access to picture symbols during assessments. Post-treatment measurement of the number of picture exchanges in a far-transfer, assessment context favored the P...

  2. Performance evaluation of an air-breathing high-temperature proton exchange membrane fuel cell

    International Nuclear Information System (INIS)

    Wu, Qixing; Li, Haiyang; Yuan, Wenxiang; Luo, Zhongkuan; Wang, Fang; Sun, Hongyuan; Zhao, Xuxin; Fu, Huide

    2015-01-01

    Highlights: • An air-breathing HT-PEMFC was designed and evaluated experimentally. • The peak power density of the air-breathing HT-PEMFC was 220.5 mW cm"−"2 at 200 °C. • Break-in behavior and effects of temperature and anodic stoichiometry were studied. • The effect of cell orientations on the performance was investigated. • The degradation rate of the air-breathing HT-PEMFC was around 58.32 μV h"−"1. - Abstract: The air-breathing proton exchange membrane fuel cell (PEMFC) is of great interest in mobile power sources because of its simple system design and low parasitic power consumption. Different from previous low-temperature air-breathing PEMFCs, a high-temperature PEMFC with a phosphoric acid doped polybenzimidazole (PBI) membrane as the polymer electrolyte is designed and investigated under air-breathing conditions. The preliminary results show that a peak power density of 220.5 mW cm"−"2 at 200 °C can be achieved without employing any water managements, which is comparable to those with conventional Nafion® membranes operated at low temperatures. In addition, it is found that with the present cell design, the limiting current density arising from the oxygen transfer limitation is around 700 mA cm"−"2 even at 200 °C. The short-term durability test at 200 mA cm"−"2 and 180 °C reveals that all the cells exhibit a gradual decrease in the voltage along with a rise in the internal resistance. The degradation rate of continuous operation is around 58.32 μV h"−"1, which is much smaller than those of start/stop cycling operations.

  3. Quantitative analysis of protein-ligand interactions by NMR.

    Science.gov (United States)

    Furukawa, Ayako; Konuma, Tsuyoshi; Yanaka, Saeko; Sugase, Kenji

    2016-08-01

    Protein-ligand interactions have been commonly studied through static structures of the protein-ligand complex. Recently, however, there has been increasing interest in investigating the dynamics of protein-ligand interactions both for fundamental understanding of the underlying mechanisms and for drug development. NMR is a versatile and powerful tool, especially because it provides site-specific quantitative information. NMR has widely been used to determine the dissociation constant (KD), in particular, for relatively weak interactions. The simplest NMR method is a chemical-shift titration experiment, in which the chemical-shift changes of a protein in response to ligand titration are measured. There are other quantitative NMR methods, but they mostly apply only to interactions in the fast-exchange regime. These methods derive the dissociation constant from population-averaged NMR quantities of the free and bound states of a protein or ligand. In contrast, the recent advent of new relaxation-based experiments, including R2 relaxation dispersion and ZZ-exchange, has enabled us to obtain kinetic information on protein-ligand interactions in the intermediate- and slow-exchange regimes. Based on R2 dispersion or ZZ-exchange, methods that can determine the association rate, kon, dissociation rate, koff, and KD have been developed. In these approaches, R2 dispersion or ZZ-exchange curves are measured for multiple samples with different protein and/or ligand concentration ratios, and the relaxation data are fitted to theoretical kinetic models. It is critical to choose an appropriate kinetic model, such as the two- or three-state exchange model, to derive the correct kinetic information. The R2 dispersion and ZZ-exchange methods are suitable for the analysis of protein-ligand interactions with a micromolar or sub-micromolar dissociation constant but not for very weak interactions, which are typical in very fast exchange. This contrasts with the NMR methods that are used

  4. Receptor for advanced glycation end products and its ligand high-mobility group box-1 mediate allergic airway sensitization and airway inflammation.

    Science.gov (United States)

    Ullah, Md Ashik; Loh, Zhixuan; Gan, Wan Jun; Zhang, Vivian; Yang, Huan; Li, Jian Hua; Yamamoto, Yasuhiko; Schmidt, Ann Marie; Armour, Carol L; Hughes, J Margaret; Phipps, Simon; Sukkar, Maria B

    2014-08-01

    The receptor for advanced glycation end products (RAGE) shares common ligands and signaling pathways with TLR4, a key mediator of house dust mite (Dermatophagoides pteronyssinus) (HDM) sensitization. We hypothesized that RAGE and its ligand high-mobility group box-1 (HMGB1) cooperate with TLR4 to mediate HDM sensitization. To determine the requirement for HMGB1 and RAGE, and their relationship with TLR4, in airway sensitization. TLR4(-/-), RAGE(-/-), and RAGE-TLR4(-/-) mice were intranasally exposed to HDM or cockroach (Blatella germanica) extracts, and features of allergic inflammation were measured during the sensitization or challenge phase. Anti-HMGB1 antibody and the IL-1 receptor antagonist Anakinra were used to inhibit HMGB1 and the IL-1 receptor, respectively. The magnitude of allergic airway inflammation in response to either HDM or cockroach sensitization and/or challenge was significantly reduced in the absence of RAGE but not further diminished in the absence of both RAGE and TLR4. HDM sensitization induced the release of HMGB1 from the airway epithelium in a biphasic manner, which corresponded to the sequential activation of TLR4 then RAGE. Release of HMGB1 in response to cockroach sensitization also was RAGE dependent. Significantly, HMGB1 release occurred downstream of TLR4-induced IL-1α, and upstream of IL-25 and IL-33 production. Adoptive transfer of HDM-pulsed RAGE(+/+)dendritic cells to RAGE(-/-) mice recapitulated the allergic responses after HDM challenge. Immunoneutralization of HMGB1 attenuated HDM-induced allergic airway inflammation. The HMGB1-RAGE axis mediates allergic airway sensitization and airway inflammation. Activation of this axis in response to different allergens acts to amplify the allergic inflammatory response, which exposes it as an attractive target for therapeutic intervention. Copyright © 2014 American Academy of Allergy, Asthma & Immunology. Published by Mosby, Inc. All rights reserved.

  5. High-Flux Zeolitic Imidazolate Framework Membranes for Propylene/Propane Separation by Postsynthetic Linker Exchange.

    Science.gov (United States)

    Lee, Moon Joo; Kwon, Hyuk Taek; Jeong, Hae-Kwon

    2018-01-02

    While zeolitic imidazolate framework, ZIF-8, membranes show impressive propylene/propane separation, their throughput needs to be greatly improved for practical applications. A method is described that drastically reduces the effective thickness of ZIF-8 membranes, thereby substantially improving their propylene permeance (that is, flux). The new strategy is based on a controlled single-crystal to single-crystal linker exchange of 2-methylimidazole in ZIF-8 membrane grains with 2-imidazolecarboxaldehyde (ZIF-90 linker), thereby enlarging the effective aperture size of ZIF-8. The linker-exchanged ZIF-8 membranes showed a drastic increase in propylene permeance by about four times, with a negligible loss in propylene/propane separation factor when compared to as-prepared membranes. The linker-exchange effect depends on the membrane synthesis method. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Quantifying hyporheic exchange dynamics in a highly regulated large river reach.

    Energy Technology Data Exchange (ETDEWEB)

    Hammond, Glenn Edward; Zhou, T; Huang, M; Hou, Z; Bao, J; Arntzen, E; Mackley, R; Harding, S; Titzler, S; Murray, C; Perkins, W; Chen, X; Stegen, J; Thorne, P; Zachara, J

    2017-03-01

    Hyporheic exchange is an important mechanism taking place in riverbanks and riverbed sediments, where river water and shallow groundwater mix and interact with each other. The direction, magnitude, and residence time of the hyporheic flux that penetrates the river bed are critical for biogeochemical processes such as carbon and nitrogen cycling, and biodegradation of organic contaminants. Many approaches including field measurements and numerical methods have been developed to quantify the hyporheic exchanges in relatively small rivers. However, the spatial and temporal distributions of hyporheic exchanges in a large, regulated river reach remain less explored due to the large spatial domains, complexity of geomorphologic features and subsurface properties, and the great pressure gradient variations at the riverbed created by dam operations.

  7. DeVelopment of the high-intensity polarized H- source with proton charge exchange on sodium optically oriented atoms

    International Nuclear Information System (INIS)

    Zelenskij, A.N.; Kokhanovskij, S.A.

    1982-01-01

    The results of experimental study on the source of polarized H - ions at polarized electron capture by proton from optically oriented sodium atoms are presented. Circular-polarized dye laser radiation with lamp pumping is used for polarization of highly dense sodium vapors in the pulsed mode. A facility for polarization measurement in the ion source is described. Dependence of the counting rate of metastables for the right and left circular radiation polarization in respect to wave length is presented. The results of measuring the degree of polarization under change of sodium density are revealed. The measurements have disclosed that obtaining of high polarization degree at 20-30% charge exchange effectiveness is possible but large radiation power is required. Use of a dense charge exchange target provides high effectiveness of hte whole polarization process. Yield of polarized H - ions can approach 10 μA/1 mA of the initial proton current

  8. Isolation of transplutonium elements on ion exchangers from solutions of high salt concentration

    International Nuclear Information System (INIS)

    Guseva, L.I.; Tikhomirova, G.S.; Stepushkina, V.V.

    1985-01-01

    The behaviour of transplutonium elements (TPE) on cation and anion exchangers in aqueous alcoholic solutions of chlorides and nitrates of some alkali and alkaline earth metals depending on different factors: salt concentration, content of alcohol and of acid in the solution as well as the nature of a cation was studied. The data obtained were used to determine the optimal conditions of concentration of TPE on ion exchangers from solutions containing great quantities of salts. The advantages of the use of aqueous alcoholic solutions of nitric acid in the isolation of TPE are shown. (author)

  9. Spin spring behavior in exchange coupled soft and high-coercivity hard ferromagnets.

    Energy Technology Data Exchange (ETDEWEB)

    Shull, R. D.; Shapiro, A. J.; Gornakov, V. S.; Nikitenko, V. I.; Jiang, J. S.; Kaper, H.; Leaf, G.; Bader, S. D.

    2000-11-01

    The magnetization reversal processes in an epitaxial Fe/Sm{sub 2}Co{sub 7} structure were investigated using the magneto-optical indicator film technique. The dependence of the magnitude and the orientation of the structure average magnetization have been studied on both cycling and rotating the external magnetic field. It was discovered that the magnetization reversal of the soft ferromagnet can proceed by formation of not only one-dimensional, but also two-dimensional, exchange spin springs. Experimental data is compared with a theoretical estimation of the rotational hysteresis loop for a spin system containing a one-dimensional exchange spring.

  10. Brief Report: Randomized Test of the Efficacy of Picture Exchange Communication System on Highly Generalized Picture Exchanges in Children with ASD

    Science.gov (United States)

    Yoder, Paul J.; Lieberman, Rebecca G.

    2010-01-01

    A randomized control trial comparing two social-communication interventions in young children with autism examined far-transfer of the use of picture exchange to communicate. Thirty-six children were randomly assigned to one of two treatment conditions, one of which was the Picture Exchange Communication System (PECS). All children had access to…

  11. Study on the optical properties of CdSe QDs with different ligands in specific matrix

    International Nuclear Information System (INIS)

    Lin Wei; Zou Wei; Du Zhongjie; Li Hangquan; Zhang Chen

    2013-01-01

    Different ligand structures of CdSe quantum dots were designed and synthesized for the specific matrix and the effect of the ligands on the photoluminescence and optical properties were further investigated. Ligand exchange reaction was used to synthesize thioglycolic acid-capped CdSe QDs and the process was characterized by FT-IR and titration. The influence of environmental pH value and storing time on the properties of thioglycolic acid-capped CdSe QDs in aqueous solution were studied by absorption and photoluminescence spectra. It was found that alkaline environment was more beneficial for the application of CdSe QDs. Therefore, the amino ligands with different molecular weight were grafted onto CdSe QDs for improving the compatibility with epoxy matrix and then amino-capped CdSe QDs/epoxy nanocomposites were fabricated. The morphologies and properties of the nanocomposites were characterized by DLS, HR-TEM, UV–Vis spectra, and photoluminescence spectra. As a result, amino ligands with short-molecular chain-capped CdSe QDs/epoxy nanocomposites exhibited good dispersion, high transparency and photoluminescence, and would be suitable for potential application in light-emitting diode device.

  12. Demonstration on endurance of ion exchange membrane immersed in high-concentration tritiated water under the Broader Approach Activities

    Energy Technology Data Exchange (ETDEWEB)

    Iwai, Yasunori, E-mail: iwai.yasunori@jaea.go.jp; Sato, Katsumi; Kawamura, Yoshinori; Yamanishi, Toshihiko

    2013-10-15

    Highlights: • Endurance of Nafion ion exchange membrane immersed in 1.38 × 10{sup 12} Bq/kg of highly concentrated tritiated water was demonstrated. • Degradation of Nafion backbone structure by tritium beta was similar to that by gamma rays and electron beams at an equivalent dose. • Degradation directly by radiation was dominant at room temperature compared with that by reactions with radicals produced from water radiolysis. -- Abstract: The Nafion{sup ®} ion exchange membrane is a key material for electrolysis cells of the water detritiation system. Endurance of Nafion ion exchange membrane immersed in 1.38 × 10{sup 12} Bq/kg of highly concentrated tritiated water has been demonstrated at room temperature for up to 2 years under the Broader Approach Activities. The curves of percent elongation at break vs. dose and tensile strength vs. dose for the Nafion membranes immersed in tritiated water were well consistent with those for Nafion membranes irradiated to an equivalent dose with gamma rays and electron beams. This shows that the degradation of Nafion backbone structure by tritium beta is similar to that by gamma rays and electron beams. The results of ferric Fenton test indicated that the degradation directly by radiation was dominant at room temperature compared with that by reactions with radicals produced from water radiolysis. The curve of ion exchange capacity vs. dose for the Nafion membranes immersed in tritiated water was also well consistent with that for Nafion membranes irradiated to an equivalent dose with gamma rays and electron beams. These results showed irradiation tests with gamma rays and electron beams were alternative for predicting degradation of ion exchange membrane by tritium beta.

  13. Annual CO2 budget and seasonal CO2 exchange signals at a High Arctic permafrost site on Spitsbergen, Svalbard archipelago

    Science.gov (United States)

    Lüers, J.; Westermann, S.; Piel, K.; Boike, J.

    2014-01-01

    The annual variability of CO2 exchange in most ecosystems is primarily driven by the activities of plants and soil microorganisms. However, little is known about the carbon balance and its controlling factors outside the growing season in arctic regions dominated by soil freeze/thaw-processes, long-lasting snow cover, and several months of darkness. This study presents a complete annual cycle of the CO2 net ecosystem exchange (NEE) dynamics for a High Arctic tundra area on the west coast of Svalbard based on eddy-covariance flux measurements. The annual cumulative CO2 budget is close to zero grams carbon per square meter per year, but shows a very strong seasonal variability. Four major CO2 exchange seasons have been identified. (1) During summer (ground snow-free), the CO2 exchange occurs mainly as a result of biological activity, with a predominance of strong CO2 assimilation by the ecosystem. (2) The autumn (ground snow-free or partly snow-covered) is dominated by CO2 respiration as a result of biological activity. (3) In winter and spring (ground snow-covered), low but persistent CO2 release occur, overlain by considerable CO2 exchange events in both directions associated with changes of air masses and air and atmospheric CO2 pressure. (4) The snow melt season (pattern of snow-free and snow-covered areas), where both, meteorological and biological forcing, resulting in a visible carbon uptake by the high arctic ecosystem. Data related to this article are archived under: http://doi.pangaea.de/10.1594/PANGAEA.809507.

  14. Multicomponent ion transport in a mono and bilayer cation-exchange membrane at high current density

    NARCIS (Netherlands)

    Moshtari Khah, S.; Oppers, N.A.W.; de Groot, M.T.; Keurentjes, J.T.F.; Schouten, J.C.; van der Schaaf, J.

    2017-01-01

    This work describes a model for bilayer cation-exchange membranes used in the chlor-alkali process. The ion transport inside the membrane is modeled with the Nernst–Planck equation. A logistic function is used at the boundary between the two layers of the bilayer membrane to describe the change in

  15. Distributions of Low- and High-LET Radiation-Induced Breaks in Chromosomes are Associated with Inter- and Intrachromosome Exchanges

    Science.gov (United States)

    Hada, Megumi; Zhang, Ye; Feiveson, Alan; Cucinotta, Francis A.; Wu, Honglu

    2010-01-01

    To study the breakpoint along the length of the chromosome induced by low- and high-LET radiations, we exposed human epithelial cells in vitro to Cs-137 rays at both low and high dose rates, secondary neutrons at a low dose rate, and 600 MeV/u Fe ions at a high dose rate. The location of the breaks was identified using the multicolor banding in situ hybridization (mBAND) that paints Chromosome 3 in 23 different colored bands. The breakpoint distributions were found to be similar between rays of low and high dose rates and between the two high-LET radiation types. Detailed analysis of the chromosome break ends involved in inter- and intrachromosome exchanges revealed that only the break ends participating in interchromosome exchanges contributed to the hot spots found for low-LET. For break ends participating in intrachromosome exchanges, the distributions for all four radiation scenarios were similar with clusters of breaks found in three regions. Analysis of the locations of the two break ends in Chromosome 3 that joined to form an intrachromosome exchange demonstrated that two breaks with a greater genomic separation may be more likely to rejoin than two closer breaks, indicating that chromatin folding can play an important role in the rejoining of chromosome breaks. Our study demonstrated that the gene-rich regions do not necessarily contain more breaks. The breakpoint distribution depends more on the likelihood that a break will join with another break in the same chromosome or in a different chromosome.

  16. Ligand sphere conversions in terminal carbide complexes

    DEFF Research Database (Denmark)

    Morsing, Thorbjørn Juul; Reinholdt, Anders; Sauer, Stephan P. A.

    2016-01-01

    Metathesis is introduced as a preparative route to terminal carbide complexes. The chloride ligands of the terminal carbide complex [RuC(Cl)2(PCy3)2] (RuC) can be exchanged, paving the way for a systematic variation of the ligand sphere. A series of substituted complexes, including the first...... example of a cationic terminal carbide complex, [RuC(Cl)(CH3CN)(PCy3)2]+, is described and characterized by NMR, MS, X-ray crystallography, and computational studies. The experimentally observed irregular variation of the carbide 13C chemical shift is shown to be accurately reproduced by DFT, which also...... demonstrates that details of the coordination geometry affect the carbide chemical shift equally as much as variations in the nature of the auxiliary ligands. Furthermore, the kinetics of formation of the sqaure pyramidal dicyano complex, trans-[RuC(CN)2(PCy3)2], from RuC has been examined and the reaction...

  17. Schiff base ligand

    Indian Academy of Sciences (India)

    Unknown

    Low-temperature stoichiometric Schiff base reaction in air in 3 : 1 mole ratio between benz- aldehyde and triethylenetetramine (trien) in methanol yields a novel tetraaza µ-bis(bidentate) acyclic ligand L. It was .... electrochemical work was performed as reported in ..... change in ligand shape through change in oxidation.

  18. Novel high-affinity and selective biaromatic 4-substituted ¿-hydroxybutyric acid (GHB) analogues as GHB ligands

    DEFF Research Database (Denmark)

    Høg, Signe; Wellendorph, Petrine; Nielsen, Birgitte

    2008-01-01

    Gamma-hydroxybutyrate (GHB) is a metabolite of gamma-aminobutyric acid (GABA) and has been proposed to function as a neurotransmitter or neuromodulator. GHB is used in the treatment of narcolepsy and is a drug of abuse. GHB binds to both GABA(B) receptors and specific high-affinity GHB sites...

  19. CC12, a high-affinity ligand for [3H]cimetidine binding, is an improgan antagonist

    NARCIS (Netherlands)

    Hough, L.H.; Nalwalk, J.B.; Phillips, J.R.; Kern, B.; Shan, Z.; Wentland, M.; de Esch, I.J.P.; Janssen, EA; Barr, T.; Stadel, R.

    2007-01-01

    Improgan, a chemical congener of cimetidine, is a highly effective non-opioid analgesic when injected into the CNS. Despite extensive characterization, neither the improgan receptor, nor a pharmacological antagonist of improgan has been previously described. Presently, the specific binding of [

  20. Selectivity in ligand binding to uranyl compounds: A synthetic, structural, thermodynamic and computational study

    Energy Technology Data Exchange (ETDEWEB)

    Arnold, John [Univ. of California, Berkeley, CA (United States)

    2015-01-21

    The uranyl cation (UO₂²⁺) is the most abundant form of uranium on the planet. It is estimated that 4.5 billion tons of uranium in this form exist in sea water. The ability to bind and extract the uranyl cation from aqueous solution while separating it from other elements would provide a limitless source of nuclear fuel. A large body of research concerns the selective recognition and extraction of uranyl. A stable molecule, the cation has a linear O=U=O geometry. The short U-O bonds (1.78 Å) arise from the combination of uranium 5f/6d and oxygen 2p orbitals. Due to the oxygen moieties being multiply bonded, these sites were not thought to be basic enough for Lewis acidic coordination to be a viable approach to sequestration. The goal of this research is thus to broaden the coordination chemistry of the uranyl ion by studying new ligand systems via synthetic, structural, thermodynamic and computational methods. It is anticipated that this fundamental science will find use beyond actinide separation technologies in areas such as nuclear waste remediation and nuclear materials. The focus of this study is to synthesize uranyl complexes incorporating amidinate and guanidinate ligands. Both synthetic and computational methods are used to investigate novel equatorial ligand coordination and how this affects the basicity of the oxo ligands. Such an understanding will later apply to designing ligands incorporating functionalities that can bind uranyl both equatorially and axially for highly selective sequestration. Efficient and durable chromatography supports for lanthanide separation will be generated by (1) identifying robust peptoid-based ligands capable of binding different lanthanides with variable affinities, and (2) developing practical synthetic methods for the attachment of these ligands to Dowex ion exchange resins.

  1. Selectivity in ligand binding to uranyl compounds: A synthetic, structural, thermodynamic and computational study

    International Nuclear Information System (INIS)

    Arnold, John

    2015-01-01

    The uranyl cation (UO 2 2+ ) is the most abundant form of uranium on the planet. It is estimated that 4.5 billion tons of uranium in this form exist in sea water. The ability to bind and extract the uranyl cation from aqueous solution while separating it from other elements would provide a limitless source of nuclear fuel. A large body of research concerns the selective recognition and extraction of uranyl. A stable molecule, the cation has a linear O=U=O geometry. The short U-O bonds (1.78 Å) arise from the combination of uranium 5f/6d and oxygen 2p orbitals. Due to the oxygen moieties being multiply bonded, these sites were not thought to be basic enough for Lewis acidic coordination to be a viable approach to sequestration. The goal of this research is thus to broaden the coordination chemistry of the uranyl ion by studying new ligand systems via synthetic, structural, thermodynamic and computational methods. It is anticipated that this fundamental science will find use beyond actinide separation technologies in areas such as nuclear waste remediation and nuclear materials. The focus of this study is to synthesize uranyl complexes incorporating amidinate and guanidinate ligands. Both synthetic and computational methods are used to investigate novel equatorial ligand coordination and how this affects the basicity of the oxo ligands. Such an understanding will later apply to designing ligands incorporating functionalities that can bind uranyl both equatorially and axially for highly selective sequestration. Efficient and durable chromatography supports for lanthanide separation will be generated by (1) identifying robust peptoid-based ligands capable of binding different lanthanides with variable affinities, and (2) developing practical synthetic methods for the attachment of these ligands to Dowex ion exchange resins.

  2. Hydrogen exchange

    DEFF Research Database (Denmark)

    Jensen, Pernille Foged; Rand, Kasper Dyrberg

    2016-01-01

    Hydrogen exchange (HX) monitored by mass spectrometry (MS) is a powerful analytical method for investigation of protein conformation and dynamics. HX-MS monitors isotopic exchange of hydrogen in protein backbone amides and thus serves as a sensitive method for probing protein conformation...... and dynamics along the entire protein backbone. This chapter describes the exchange of backbone amide hydrogen which is highly quenchable as it is strongly dependent on the pH and temperature. The HX rates of backbone amide hydrogen are sensitive and very useful probes of protein conformation......, as they are distributed along the polypeptide backbone and form the fundamental hydrogen-bonding networks of basic secondary structure. The effect of pressure on HX in unstructured polypeptides (poly-dl-lysine and oxidatively unfolded ribonuclease A) and native folded proteins (lysozyme and ribonuclease A) was evaluated...

  3. Thermotechnical comparison of possible operation variants for air conditioning system of mine air with high pressure heat exchanger and hydrodistributor

    OpenAIRE

    Korsun, F. O.

    2015-01-01

    Problem. There are vast losses of cold that take place during the transition of cold to deep horizons of shafts by the mine air conditioning system (MASC) with high pressure heat exchanger. Cold is transferred by the recuperative way. Vast losses of cold mean vast losses of electricity to in order to supply it. Any enterprise requires the reduction of electricity consumption. This article gives proposals on how to replace HPHE into hydrodistributor which will considerably reduce cold losses. ...

  4. Interplay of metalloligand and organic ligand to tune micropores within isostructural mixed-metal organic frameworks (M'MOFs) for their highly selective separation of chiral and achiral small molecules

    NARCIS (Netherlands)

    Das, M. C.; Guo, Q.; He, Y.; Kim, J.; Zhao, C.-G.; Hong, K.; Xiang, S.; Zhang, Z.; Thomas, K. M.; Krishna, R.; Chen, B.

    2012-01-01

    Four porous isostructural mixed-metal-organic frameworks (M′MOFs) have been synthesized and structurally characterized. The pores within these M′MOFs are systematically tuned by the interplay of both the metalloligands and organic ligands which have enabled us not only to direct their highly

  5. Divided-evolution-based pulse scheme for quantifying exchange processes in proteins: powerful complement to relaxation dispersion experiments.

    Science.gov (United States)

    Bouvignies, Guillaume; Hansen, D Flemming; Vallurupalli, Pramodh; Kay, Lewis E

    2011-02-16

    A method for quantifying millisecond time scale exchange in proteins is presented based on scaling the rate of chemical exchange using a 2D (15)N, (1)H(N) experiment in which (15)N dwell times are separated by short spin-echo pulse trains. Unlike the popular Carr-Purcell-Meiboom-Gill (CPMG) experiment where the effects of a radio frequency field on measured transverse relaxation rates are quantified, the new approach measures peak positions in spectra that shift as the effective exchange time regime is varied. The utility of the method is established through an analysis of data recorded on an exchanging protein-ligand system for which the exchange parameters have been accurately determined using alternative approaches. Computations establish that a combined analysis of CPMG and peak shift profiles extends the time scale that can be studied to include exchanging systems with highly skewed populations and exchange rates as slow as 20 s(-1).

  6. The ketamine analogue methoxetamine and 3- and 4-methoxy analogues of phencyclidine are high affinity and selective ligands for the glutamate NMDA receptor.

    Directory of Open Access Journals (Sweden)

    Bryan L Roth

    Full Text Available In this paper we determined the pharmacological profiles of novel ketamine and phencyclidine analogues currently used as 'designer drugs' and compared them to the parent substances via the resources of the National Institute of Mental Health Psychoactive Drug Screening Program. The ketamine analogues methoxetamine ((RS-2-(ethylamino-2-(3-methoxyphenylcyclohexanone and 3-MeO-PCE (N-ethyl-1-(3-methoxyphenylcyclohexanamine and the 3- and 4-methoxy analogues of phencyclidine, (1-[1-(3-methoxyphenylcyclohexyl]piperidine and 1-[1-(4-methoxyphenylcyclohexyl]piperidine, were all high affinity ligands for the PCP-site on the glutamate NMDA receptor. In addition methoxetamine and PCP and its analogues displayed appreciable affinities for the serotonin transporter, whilst the PCP analogues exhibited high affinities for sigma receptors. Antagonism of the NMDA receptor is thought to be the key pharmacological feature underlying the actions of dissociative anaesthetics. The novel ketamine and PCP analogues had significant affinities for the NMDA receptor in radioligand binding assays, which may explain their psychotomimetic effects in human users. Additional actions on other targets could be important for delineating side-effects.

  7. Development of a High-Throughput Fluorescence Polarization Assay to Identify Novel Ligands of Glutamate Carboxypeptidase II

    Czech Academy of Sciences Publication Activity Database

    Alquicer, Glenda; Sedlák, David; Byun, Y.; Pavlíček, Jiří; Stathis, M.; Rojas, C.; Slusher, B.; Pomper, M.G.; Bartůněk, Petr; Bařinka, Cyril

    2012-01-01

    Roč. 17, č. 8 (2012), s. 1030-1040 ISSN 1087-0571 R&D Projects: GA MŠk(CZ) ME10031; GA MŠk(CZ) LC06077 Institutional research plan: CEZ:AV0Z50520701 Institutional support: RVO:68378050 Keywords : fluorescence polarization * glutamate carboxypeptidase II * high-throughput screening Subject RIV: EB - Genetics ; Molecular Biology Impact factor: 2.207, year: 2012

  8. I. Exchange currents in electron scattering from light nuclei. II. Heavy-ion scattering at intermediate and high energy

    International Nuclear Information System (INIS)

    Dubach, J.F.

    1976-01-01

    The purpose of this work is to develop a formalism that will allow one to search the wide variety of transitions presented by nuclei in order to locate situations in which the exchange-current effects are important or dominant and thus allow one to study the contributions of the meson exchanges to the electromagnetic densities within the nucleus. The nuclei studied are assumed to be described in a shell model using harmonic oscillator wave functions. The formalism needed to allow one to do a multipole analysis of these exchange currents within 1s and 1p nuclei is developed. This formalism is then applied to an examination of electron scattering from a series of light nuclei: 3 He, 6 Li, 7 Li, 9 Be, and 10 B. Three significant effects due to the inclusion of exchange currents are seen: (1) The exchange currents can often introduce new structure into the form factors. (2) At larger momentum transfer (700 to 1000 MeV/c) the exchange current contributions to the form factor dominate the simpler one-body form factor by a few orders of magnitude. (3) The exchange currents can excite E4 and M5 multipoles in the p shell which are forbidden to the simpler one-body currents. The elastic scattering of two heavy ions at intermediate and high energies (compared to the Coulomb barrier) is examined in the formalism of the WKB and ''Glauber theory'' approximations. As a concrete example, the scattering of 16 O from 60 Ni is studied assuming an optical-model potential that fits elastic scattering data at low energies. One immediate result is that the WKB approximation agrees quite well with ''exact'' numerical calculations at energies as low as 60 MeV. The Glauber theory fails below about 1 GeV but correction terms are developed that can extend the usefulness of the Glauber theory to much lower energies. The model problem of scattering from a black-sphere model of the nucleus is briefly examined

  9. The next chapter in MOF pillaring strategies: Trigonal heterofunctional ligands to access targeted high-connected three dimensional nets, isoreticular platforms

    KAUST Repository

    Eubank, Jarrod F.

    2011-11-09

    A new pillaring strategy, based on a ligand-to-axial approach that combines the two previous common techniques, axial-to-axial and ligand-to-ligand, and permits design, access, and construction of higher dimensional MOFs, is introduced and validated. Trigonal heterofunctional ligands, in this case isophthalic acid cores functionalized at the 5-position with N-donor (e.g., pyridyl- or triazolyl-type) moieties, are designed and utilized to pillar pretargeted two-dimensional layers (supermolecular building layers, SBLs). These SBLs, based on edge transitive Kagomé and square lattices, are cross-linked into predicted three-dimensional MOFs with tunable large cavities, resulting in isoreticular platforms. © 2011 American Chemical Society.

  10. The next chapter in MOF pillaring strategies: Trigonal heterofunctional ligands to access targeted high-connected three dimensional nets, isoreticular platforms

    KAUST Repository

    Eubank, Jarrod F.; Wojtas, Łukasz; Hight, Matthew R.; Bousquet, Till; Kravtsov, Victor Ch H; Eddaoudi, Mohamed

    2011-01-01

    A new pillaring strategy, based on a ligand-to-axial approach that combines the two previous common techniques, axial-to-axial and ligand-to-ligand, and permits design, access, and construction of higher dimensional MOFs, is introduced and validated. Trigonal heterofunctional ligands, in this case isophthalic acid cores functionalized at the 5-position with N-donor (e.g., pyridyl- or triazolyl-type) moieties, are designed and utilized to pillar pretargeted two-dimensional layers (supermolecular building layers, SBLs). These SBLs, based on edge transitive Kagomé and square lattices, are cross-linked into predicted three-dimensional MOFs with tunable large cavities, resulting in isoreticular platforms. © 2011 American Chemical Society.

  11. Effect of organic ligands on the sorption of europium on TiO2 and cement at high pH

    International Nuclear Information System (INIS)

    Dario, Maarten; Molera, Mireia; Allard, Bert

    2004-01-01

    Cement and cement-based materials are used as matrices and as containers for various categories of low-level and medium-level waste. The cement generally contains additives of various kinds, usually organic polymers that will act as plasticisers (up to a few percent). The degradation of these agents will, with time, generate low molecular organics and, eventually, carbon dioxide. The fraction of organic matter (ion exchange resins, filter materials, cellulose, cleaning agents etc) in the cement matrix will be therefore substantial. It can not be ruled out that these agents may act as metal complexing agents with ability to enhance the solubility and mobility of radionuclides from the radioactive waste within or in contact with the cement. Laboratory studies were performed to assess the potential effects of cement additives, spent organic adsorbent resins and some organic cleaning agents in a cement/concrete system on the mobility and distribution of radionuclides using Eu(III) as a model element (for lanthanides as well as actinides in the trivalent state). Batch distribution studies were conducted in the following systems: Solid adsorbents: Standard Portland cement, TiO 2 . Water phase: 0.3 M NaCl equilibrated with cement or TiO 2 ; 0 or 2 mM Ca (for the TiO 2 -systems); pH 12.5. Organic ligands: EDTA, DTPA, NTA, citric acid, D-gluconic acid, oxalic acid, fulvic acid, isosaccharinic acid, acetyl acetone, TTA. Cement additives: Sikament 10, Sikament 210, Peramin Conpac 30, Peramin F, Glenium 51, Cementa Melcrete, Mighty 150. Cleaning agents: Clax Delta Balans, Industrikombi, Prefect Citron. Organics: Dissolved organic matter from the degradation of two solid organic components: an ion exchange resin and a filter aid (Acrisorb LSR 33 and Ricem UP2). Element: Eu (10 -8 M). The distribution of Eu was measured radiometrically (constant solid/liquid ratio, 1g/L) as a function of time (up to 420 d) and additive concentration (0.001-10% of water phase) or as TOC

  12. Effect of organic ligands on the sorption of europium on TiO{sub 2} and cement at high pH

    Energy Technology Data Exchange (ETDEWEB)

    Dario, Maarten [Linkoeping Univ. (Sweden); Molera, Mireia [Royal Inst. of Technology, Stockholm (Sweden); Allard, Bert [Oerebro Univ. (Sweden)

    2004-01-01

    Cement and cement-based materials are used as matrices and as containers for various categories of low-level and medium-level waste. The cement generally contains additives of various kinds, usually organic polymers that will act as plasticisers (up to a few percent). The degradation of these agents will, with time, generate low molecular organics and, eventually, carbon dioxide. The fraction of organic matter (ion exchange resins, filter materials, cellulose, cleaning agents etc) in the cement matrix will be therefore substantial. It can not be ruled out that these agents may act as metal complexing agents with ability to enhance the solubility and mobility of radionuclides from the radioactive waste within or in contact with the cement. Laboratory studies were performed to assess the potential effects of cement additives, spent organic adsorbent resins and some organic cleaning agents in a cement/concrete system on the mobility and distribution of radionuclides using Eu(III) as a model element (for lanthanides as well as actinides in the trivalent state). Batch distribution studies were conducted in the following systems: Solid adsorbents: Standard Portland cement, TiO{sub 2}. Water phase: 0.3 M NaCl equilibrated with cement or TiO{sub 2}; 0 or 2 mM Ca (for the TiO{sub 2}-systems); pH 12.5. Organic ligands: EDTA, DTPA, NTA, citric acid, D-gluconic acid, oxalic acid, fulvic acid, isosaccharinic acid, acetyl acetone, TTA. Cement additives: Sikament 10, Sikament 210, Peramin Conpac 30, Peramin F, Glenium 51, Cementa Melcrete, Mighty 150. Cleaning agents: Clax Delta Balans, Industrikombi, Prefect Citron. Organics: Dissolved organic matter from the degradation of two solid organic components: an ion exchange resin and a filter aid (Acrisorb LSR 33 and Ricem UP2). Element: Eu (10{sup -8} M). The distribution of Eu was measured radiometrically (constant solid/liquid ratio, 1g/L) as a function of time (up to 420 d) and additive concentration (0.001-10% of water phase) or

  13. Performance of technical indicators in forecasting high-frequency foreign exchange rates

    Directory of Open Access Journals (Sweden)

    Václav Mastný

    2004-01-01

    Full Text Available This paper deals with technical analysis and its forecasting ability in the intradaily foreign exchange market. The objective of this study is to investigate whether technical indicators are able to provide prediction superior to „buy and hold“ strategy. Each indicator is tested with series of parameters in time series of different frequency (5, 15, 30, 60 min. The profitability of each indicator is examined in simple trading modell.

  14. A Highly Efficient Catalyst for Oxime Ligation and Hydrazone-Oxime Exchange Suitable for Bioconjugation

    OpenAIRE

    Rashidian, Mohammad; Mahmoodi, Mohammad M.; Shah, Rachit; Dozier, Jonathan K.; Wagner, Carston R.; Distefano, Mark D.

    2013-01-01

    Imine-based reactions are useful for a wide range of bioconjugation applications. Although aniline is known to catalyze the oxime ligation reaction under physiological conditions, it suffers from slow reaction kinetics, specifically when a ketone is being used or when hydrazone-oxime exchange is performed. Here, we report on the discovery of a new catalyst that is up to 15 times more efficient than aniline. That catalyst, m-phenylenediamine (mPDA), was initially used to analyze the kinetics o...

  15. Experimental Results For Hydrocarbon Refrigerant Vaporization In Brazed Plate Heat Exchangers at High Pressure

    OpenAIRE

    Desideri, Adriano; Schmidt Ommen, Torben; Wronski, Jorrit; Quoilin, Sylvain; Lemort, Vincent; Haglind, Fredrik

    2016-01-01

    In this contribution, the experimental heat transfer coefficient  and the pressure drop measured during HFC refrigerants vaporization inside small brazed plate heat exchanger (PHE) at typical evaporation temperature for organic Rankine cycle systems for low thermal energy quality applications are presented. Scientific work focusing on the heat transfer in PHEs has been carried out since the late 19th century. More recent publications have been focusing on vaporization and condensation of ref...

  16. Experimental results for hydrocarbon refrigerant vaporization in brazed plate heat exchangers at high pressure

    OpenAIRE

    Desideri, Adriano; Rhyl Kaern, Martin; Ommen Schmidt, Torben; Wronski, Jorrit; Quoilin, Sylvain; Lemort, Vincent; Haglind, Fredrik

    2016-01-01

    In recent years the interest in small capacity organic Rankine cycle (ORC) power systems for harvesting low quality waste thermal energy from industrial processes has been steadily growing. Micro ORC systems are normally equipped with brazed plate heat exchangers which allows for efficient heat transfer with a compact design. An accurate prediction of the heat transfer process characterizing these devices is required from the design phase to the development of model- based control strategies....

  17. Two high-affinity ligand binding states of uterine estrogen receptor distinguished by modulation of hydrophobic environment

    International Nuclear Information System (INIS)

    Hutchens, T.W.; Li, C.M.; Zamah, N.M.; Besch, P.K.

    1987-01-01

    The steroid binding function of soluble (cytosolic) estrogen receptors from calf uteri was evaluated under conditions known to modify the extent of hydrophobic interaction with receptor-associated proteins. Receptor preparations were equilibrated into 6 M urea buffers and control buffers by chromatography through small columns of Sephadex G-25 or by dialysis at 0.6 0 C. Equilibrium dissociation constants (K/sub d/) and binding capacities (n) of experimental and control receptor preparations were determined by 13-point Scatchard analyses using concentrations of 17β-[ 3 H]estradiol from 0.05 to 10 nM. Nonspecific binding was determined at each concentration by parallel incubations with a 200-fold molar excess of the receptor-specific competitor diethylstilbestrol. The control receptor population was consistently found to be a single class of binding sites with a high affinity for estradiol which was unaffected by G-25 chromatography, by dialysis, by dilution, or by the presence of 0.4 M KCl. However, equilibration into 6 M urea induced a discrete (10-fold) reduction in receptor affinity to reveal a second, thermodynamically stable, high-affinity binding state. The presence of 0.4 M KCl did not significantly influence the discrete change in receptor affinity induced by urea. The effects of urea on both receptor affinity and binding capacity were reversible, suggesting a lack of covalent modification. These results demonstrate nonenzymatic means by which not only the binding capacity but also the affinity of receptor for estradiol can be reversibly controlled, suggesting that high concentrations of urea might be more effectively utilized during the physicochemical characterization and purification of steroid receptor proteins

  18. Screening small-molecule compound microarrays for protein ligands without fluorescence labeling with a high-throughput scanning microscope

    OpenAIRE

    Fei, Yiyan; Landry, James P.; Sun, Yungshin; Zhu, Xiangdong; Wang, Xiaobing; Luo, Juntao; Wu, Chun-Yi; Lam, Kit S.

    2010-01-01

    We describe a high-throughput scanning optical microscope for detecting small-molecule compound microarrays on functionalized glass slides. It is based on measurements of oblique-incidence reflectivity difference and employs a combination of a y-scan galvometer mirror and an x-scan translation stage with an effective field of view of 2 cm×4 cm. Such a field of view can accommodate a printed small-molecule compound microarray with as many as 10,000 to 20,000 targets. The scanning microscope is...

  19. Critical validity assessment of theoretical models: charge-exchange at intermediate and high energies

    Science.gov (United States)

    Belkić, Dževad

    1999-06-01

    Exact comprehensive computations are carried out by means of four leading second-order approximations yielding differential cross sections dQ/ dΩ for the basic charge exchange process H ++H(1s)→H(1s)+H + at intermediate and high energies. The obtained extensive set of results is thoroughly tested against all the existing experimental data with the purpose of critically assessing the validity of the boundary corrected second-Born (CB2), continuum-distorted wave (CDW), impulse approximation (IA) and the reformulated impulse approximation (RIA). The conclusion which emerges from this comparative study clearly indicates that the RIA agrees most favorably with the measurements available over a large energy range 25 keV-5 MeV. Such a finding reaffirms the few-particle quantum scattering theory which imposes several strict conditions on adequate second-order methods. These requirements satisfied by the RIA are: (i) normalisations of all the scattering wave functions, (ii) correct boundary conditions in both entrance and exit channels, (iii) introduction of a mathematically justified two-center continuum state for the sum of an attractive and a repulsive Coulomb potential with the same interaction strength, (iv) inclusion of the multiple scattering effects neglected in the IA, (v) a proper description of the Thomas double scattering in good agreement with the experiments and without any unobserved peak splittings. Nevertheless, the performed comparative analysis of the above four approximations indicates that none of the methods is free from some basic shortcomings. Despite its success, the RIA remains essentially a high-energy model like the other three methods under study. More importantly, their perturbative character leaves virtually no room for further systematic improvements, since the neglected higher-order terms are prohibitively tedious for practical purposes and have never been computed exactly. To bridge this gap, we presently introduce the variational Pad

  20. Critical validity assessment of theoretical models: charge-exchange at intermediate and high energies

    International Nuclear Information System (INIS)

    Belkic, Dzevad

    1999-01-01

    Exact comprehensive computations are carried out by means of four leading second-order approximations yielding differential cross sections dQ/dΩ for the basic charge exchange process H + +H(1s)→H(1s)+H + at intermediate and high energies. The obtained extensive set of results is thoroughly tested against all the existing experimental data with the purpose of critically assessing the validity of the boundary corrected second-Born (CB2), continuum-distorted wave (CDW), impulse approximation (IA) and the reformulated impulse approximation (RIA). The conclusion which emerges from this comparative study clearly indicates that the RIA agrees most favorably with the measurements available over a large energy range 25 keV-5 MeV. Such a finding reaffirms the few-particle quantum scattering theory which imposes several strict conditions on adequate second-order methods. These requirements satisfied by the RIA are: (i) normalisations of all the scattering wave functions, (ii) correct boundary conditions in both entrance and exit channels, (iii) introduction of a mathematically justified two-center continuum state for the sum of an attractive and a repulsive Coulomb potential with the same interaction strength, (iv) inclusion of the multiple scattering effects neglected in the IA, (v) a proper description of the Thomas double scattering in good agreement with the experiments and without any unobserved peak splittings. Nevertheless, the performed comparative analysis of the above four approximations indicates that none of the methods is free from some basic shortcomings. Despite its success, the RIA remains essentially a high-energy model like the other three methods under study. More importantly, their perturbative character leaves virtually no room for further systematic improvements, since the neglected higher-order terms are prohibitively tedious for practical purposes and have never been computed exactly. To bridge this gap, we presently introduce the variational Pade

  1. Pharmacokinetics and biodistribution of a radioiodine labeled peptidomimetic ligand for high-affinity nerve growth factor receptors

    Energy Technology Data Exchange (ETDEWEB)

    Jung, K. H.; Kim, D. H.; Paik, J. Y.; Koh, B. H.; Bae, J. S.; Choe, Y. S.; Lee, K. H.; Kim, B. T. [Samsung Medical Center, Seoul (Korea, Republic of)

    2005-07-01

    Some of the obstacles for the clinical application of whole nerve growth factor (NGF) may be overcome by utilizing small molecule mimetics. We thus investigated the in vivo pharmacokinetics and biodistribution of a small cyclic peptide derived from NGF-[C(92-96)] with high receptor binding affinity. I-125 C(92-96) was labeled with the Bolton-Hunter method, and binding to TrkA/IgG chimeric protein was confirmed on a polyacrylamide gel after cross-linking. Pharmacokinetic analysis was performed in normal ICR mice intravenously injected with 0.5 MBq I-125 C(92-96) containing varying doses of C(92-96). Biodistribution studies were done at 6 h after injection. Cross-linkage analysis confirmed binding of I-125 C(92-96) to the high affinity NGF receptor, TrkA. Intravenously injected I-125 C(92-96) was cleared from the blood in a biexponential manner with an early T1/2{alpha} of 5.2 min and late T1/2{beta} of 121.3 min. Log blood-concentration decreased over time with a k-slope of 0.0025, clearance of 11.8{+-}0.5 ml/min, T1/2 of 4.1{+-}0.4 hr, and volume of distribution of 69.7{+-}4.6 ml. The pattern of elimination from the blood remained essentially unchanged regardless of the dose of added C(92-96), with dose-proportionate increases in AUCs and peak concentrations consistent with linear pharmacokinetics. Biodistribution studies demonstrated high kidney activity suggesting renal excretion of I-125 C(92-96). There were moderate levels of accumulation in the spleen, lungs and liver, followed by the myocardium and skeletal muscle, whereas brain uptake was low (< 0.2 %ID/gm). Intravenously administered C(92-96) follows linear pharmacokinetics, and is cleared from the circulation at a rate comparable to whole NGF despite its substantially smaller size. Although intravenous C(92-96) does not adequately reach brain tissue, clinically relevant doses can achieve major organ accumulation levels that may be sufficient to elicit biologic responses through NGF receptors.

  2. Pharmacokinetics and biodistribution of a radioiodine labeled peptidomimetic ligand for high-affinity nerve growth factor receptors

    International Nuclear Information System (INIS)

    Jung, K. H.; Kim, D. H.; Paik, J. Y.; Koh, B. H.; Bae, J. S.; Choe, Y. S.; Lee, K. H.; Kim, B. T.

    2005-01-01

    Some of the obstacles for the clinical application of whole nerve growth factor (NGF) may be overcome by utilizing small molecule mimetics. We thus investigated the in vivo pharmacokinetics and biodistribution of a small cyclic peptide derived from NGF-[C(92-96)] with high receptor binding affinity. I-125 C(92-96) was labeled with the Bolton-Hunter method, and binding to TrkA/IgG chimeric protein was confirmed on a polyacrylamide gel after cross-linking. Pharmacokinetic analysis was performed in normal ICR mice intravenously injected with 0.5 MBq I-125 C(92-96) containing varying doses of C(92-96). Biodistribution studies were done at 6 h after injection. Cross-linkage analysis confirmed binding of I-125 C(92-96) to the high affinity NGF receptor, TrkA. Intravenously injected I-125 C(92-96) was cleared from the blood in a biexponential manner with an early T1/2α of 5.2 min and late T1/2β of 121.3 min. Log blood-concentration decreased over time with a k-slope of 0.0025, clearance of 11.8±0.5 ml/min, T1/2 of 4.1±0.4 hr, and volume of distribution of 69.7±4.6 ml. The pattern of elimination from the blood remained essentially unchanged regardless of the dose of added C(92-96), with dose-proportionate increases in AUCs and peak concentrations consistent with linear pharmacokinetics. Biodistribution studies demonstrated high kidney activity suggesting renal excretion of I-125 C(92-96). There were moderate levels of accumulation in the spleen, lungs and liver, followed by the myocardium and skeletal muscle, whereas brain uptake was low (< 0.2 %ID/gm). Intravenously administered C(92-96) follows linear pharmacokinetics, and is cleared from the circulation at a rate comparable to whole NGF despite its substantially smaller size. Although intravenous C(92-96) does not adequately reach brain tissue, clinically relevant doses can achieve major organ accumulation levels that may be sufficient to elicit biologic responses through NGF receptors

  3. High-resolution structure of AKR1a4 in the apo form and its interaction with ligands

    International Nuclear Information System (INIS)

    Faucher, Frédérick; Jia, Zongchao

    2012-01-01

    Despite its high affinity for NADPH, AKR1a4 crystallized in the apo form, which is very rare for aldo-keto reductase enzymes. Aldo-keto reductase 1a4 (AKR1a4; EC 1.1.1.2) is the mouse orthologue of human aldehyde reductase (AKR1a1), the founding member of the AKR family. As an NADPH-dependent enzyme, AKR1a4 catalyses the conversion of d-glucuronate to l-gulonate. AKR1a4 is involved in ascorbate biosynthesis in mice, but has also recently been found to interact with SMAR1, providing a novel mechanism of ROS regulation by ATM. Here, the crystal structure of AKR1a4 in its apo form at 1.64 Å resolution as well as the characterization of the binding of AKR1a4 to NADPH and P44, a peptide derived from SMAR1, is presented

  4. Externally fired gas turbine cycles with high temperature heat exchangers utilising Fe-based ODS alloy tubing

    International Nuclear Information System (INIS)

    Olsson, F.; Svensson, S.-A.; Duncan, R.

    2001-01-01

    This work is part of the BRITE / EuRAM Project 'Development of Torsional Grain Structures to Improve Biaxial Creep Performance of Fe-based ODS Alloy Tubing for Biomass Power Plant'. The main goal of this project is to heat exchanger tubes working at 1100 o C and above. The paper deals with design implications of a biomass power plant, using an indirectly fired gas turbine with a high temperature heat exchanger containing Fe-based ODS alloy tubing. In the current heat exchanger design, ODS alloy tubing is used in a radiant section, using a bayonet type tube arrangement. This enables the use of straight sections of ODS tubing and reduces the amount of material required. In order to assess the potential of the power plant system, thermodynamic calculations have been conducted. Both co-generation and condensing applications are studied and results so far indicate that the electrical efficiency is high, compared to values reached by conventional steam cycle power plants of the same size (approx. 5 MW e ). (author)

  5. The nature of the exchange coupling between high-spin Fe(III) heme o3 and CuBII in Escherichia coli quinol oxidase, cytochrome bo3: MCD and EPR studies.

    Science.gov (United States)

    Cheesman, Myles R; Oganesyan, Vasily S; Watmough, Nicholas J; Butler, Clive S; Thomson, Andrew J

    2004-04-07

    Fully oxidized cytochrome bo3 from Escherichia coli has been studied in its oxidized and several ligand-bound forms using electron paramagnetic resonance (EPR) and magnetic circular dichroism (MCD) spectroscopies. In each form, the spin-coupled high-spin Fe(III) heme o3 and CuB(II) ion at the active site give rise to similar fast-relaxing broad features in the dual-mode X-band EPR spectra. Simulations of dual-mode spectra are presented which show that this EPR can arise only from a dinuclear site in which the metal ions are weakly coupled by an anisotropic exchange interaction of J 1 cm-1. A variable-temperature and magnetic field (VTVF) MCD study is also presented for the cytochrome bo3 fluoride and azide derivatives. New methods are used to extract the contribution to the MCD of the spin-coupled active site in the presence of strong transitions from low-spin Fe(III) heme b. Analysis of the MCD data, independent of the EPR study, also shows that the spin-coupling within the active site is weak with J approximately 1 cm-1. These conclusions overturn a long-held view that such EPR signals in bovine cytochrome c oxidase arise from an S' = 2 ground state resulting from strong exchange coupling (J > 10(2) cm-1) within the active site.

  6. Covalent labeling of the beta-adrenergic ligand-binding site with para-(bromoacetamidyl)benzylcarazolol. A highly potent beta-adrenergic affinity label

    International Nuclear Information System (INIS)

    Dickinson, K.E.; Heald, S.L.; Jeffs, P.W.; Lefkowitz, R.J.; Caron, M.G.

    1985-01-01

    Para-(Bromoacetamidyl)benzylcarazolol (pBABC) was synthesized and found to be an extremely potent affinity label for beta-adrenergic receptors. Its interaction with mammalian (rabbit and hamster lung) and nonmammalian (turkey and frog erythrocyte) beta-adrenergic receptors was similar, displaying EC 50 values of 400-900 pM for inhibiting 125 I-cyanopindolol binding to these receptors. pBABC reduced the number of beta-adrenergic receptors in frog erythrocyte membranes, without any change in the affinity of the remaining sites for [ 125 I]iodocyanopindolol. pBABC has been radioiodinated. As assessed by sodium dodecyl sulfate-polyacrylamide gel electrophoresis, this affinity probe specifically labeled the beta-adrenergic peptide of a purified preparation of hamster lung, with high efficiency (approximately 40%) and with a pharmacological specificity characteristic of an interaction at the beta 2-adrenergic receptor ligand-binding site. Comparison of the proteolyzed products derived from purified receptor labeled with [ 125 I]pBABC and with the photoaffinity agent [ 125 I]p-azidobenzylcarazolol suggested that covalent labeling of the beta-adrenergic receptor by these probes occurs at similar domains of the beta-adrenergic receptor

  7. Highly Efficient Interception and Precipitation of Uranium(VI) from Aqueous Solution by Iron-Electrocoagulation Combined with Cooperative Chelation by Organic Ligands.

    Science.gov (United States)

    Li, Peng; Zhun, Bao; Wang, Xuegang; Liao, PingPing; Wang, Guanghui; Wang, Lizhang; Guo, Yadan; Zhang, Weimin

    2017-12-19

    A new strategy combining iron-electrocoagulation and organic ligands (OGLs) cooperative chelation was proposed to screen and precipitate low concentrations (0-18.52 μmol/L) of uranium contaminant in aqueous solution. We hypothesized that OGLs with amino, hydroxyl, and carboxyl groups hydrophobically/hydrophilically would realize precuring of uranyl ion at pH electrocoagulation would achieve faster and more efficient uranium precipitation. Experimentally, the strategy demonstrated highly efficient uranium(VI) precipitation efficiency, especially with hydrophilic macromolecular OGLs. The uranium removal efficiency at optimized experimental condition reached 99.65%. The decrease of zeta potential and the lattice enwrapping between U-OGLs chelates and flocculation precursor were ascribed to the enhanced uranium precipitation activity. Uranium was precipitated as oxides of U(VI) or higher valences that were easily captured in aggregated micelles under low operation current potential. The actual uranium tailing wastewater was treated, and a satisfied uranium removal efficiency of 99.02% was discovered. After elution of the precipitated flocs, a concentrated uranium solution (up to 106.52 μmol/L) with very few other metallic impurities was obtained. Therefore, the proposed strategy could remove uranium and concentrate it concurrently. This work could provide new insights into the purification and recovery of uranium from aqueous solutions in a cost-effective and environmentally friendly process.

  8. Investigation on degradation mechanism of ion exchange membrane immersed in highly concentrated tritiated water under the Broader Approach Activities

    Energy Technology Data Exchange (ETDEWEB)

    Iwai, Yasunori, E-mail: iwai.yasunori@jaea.go.jp; Sato, Katsumi; Yamanishi, Toshihiko

    2014-10-15

    Highlights: • Endurance of Nafion ion exchange membrane immersed into 1.38 × 10{sup 12} Bq/kg of highly concentrated tritiated water has been demonstrated. • The formation of free hydrophobic free products by reactions between radicals on the membrane and oxygen caused the decrease in ionic conductivity. • From the {sup 19}F NMR spectrum, no distinctive degradation in the membrane structure by interaction with tritium was measured. - Abstract: The ion exchange membrane is a key material for electrolysis cells of the water detritiation system. Durability of ion exchange membrane has been demonstrated under the Broader Approach Activities. Long-term exposure of Nafion{sup ®} ion exchange membrane in 1.38 × 10{sup 12} Bq/kg of tritiated water was conducted at room temperature for up to 2 years. The ionic conductivity of Nafion{sup ®} membrane after immersed in tritiated water was changed. The change in color of membrane from colorless to yellowish was caused by reactions of radicals on the polymer and oxygen molecules in air. Infrared Fourier transform spectrum of a yellowish membrane revealed a small peak for bending vibration of C-H situated at 1437 cm{sup −1}, demonstrating the formation of hydrophobic functional group in the membrane. The hydrophilic network in Nafion{sup ®} membrane was partially obstructed by the hydrophobic free products. This caused the decrease in ionic conductivity. The peak for bending vibration was clearly eliminated in the spectrum of the membrane after treatment by acid for removal of free products. The high-resolution solid state {sup 19}F NMR spectrum of a membrane after immersed in tritiated water was similar to that of a membrane irradiated with gamma-rays. From the {sup 19}F NMR spectrum, no distinctive degradation in the membrane structure by interaction with tritium was measured.

  9. Investigation on degradation mechanism of ion exchange membrane immersed in highly concentrated tritiated water under the Broader Approach Activities

    International Nuclear Information System (INIS)

    Iwai, Yasunori; Sato, Katsumi; Yamanishi, Toshihiko

    2014-01-01

    Highlights: • Endurance of Nafion ion exchange membrane immersed into 1.38 × 10 12 Bq/kg of highly concentrated tritiated water has been demonstrated. • The formation of free hydrophobic free products by reactions between radicals on the membrane and oxygen caused the decrease in ionic conductivity. • From the 19 F NMR spectrum, no distinctive degradation in the membrane structure by interaction with tritium was measured. - Abstract: The ion exchange membrane is a key material for electrolysis cells of the water detritiation system. Durability of ion exchange membrane has been demonstrated under the Broader Approach Activities. Long-term exposure of Nafion ® ion exchange membrane in 1.38 × 10 12 Bq/kg of tritiated water was conducted at room temperature for up to 2 years. The ionic conductivity of Nafion ® membrane after immersed in tritiated water was changed. The change in color of membrane from colorless to yellowish was caused by reactions of radicals on the polymer and oxygen molecules in air. Infrared Fourier transform spectrum of a yellowish membrane revealed a small peak for bending vibration of C-H situated at 1437 cm −1 , demonstrating the formation of hydrophobic functional group in the membrane. The hydrophilic network in Nafion ® membrane was partially obstructed by the hydrophobic free products. This caused the decrease in ionic conductivity. The peak for bending vibration was clearly eliminated in the spectrum of the membrane after treatment by acid for removal of free products. The high-resolution solid state 19 F NMR spectrum of a membrane after immersed in tritiated water was similar to that of a membrane irradiated with gamma-rays. From the 19 F NMR spectrum, no distinctive degradation in the membrane structure by interaction with tritium was measured

  10. Analysis of human milk oligosaccharides using high-performance anion-exchange chromatography with pulsed amperometric detection

    DEFF Research Database (Denmark)

    Lie, Aleksander; Pedersen, Lars Haastrup

    ) and lacto-N-neotetraose (Galβ1-4GlcNAcβ1-3Galβ1-4Glc), among others. High-performance anion-exchange chromatography (HPAE) with pulsed amperometric detection (PAD) is an analysis method highly suited for carbohydrates. HPAE with alkaline eluents results in retention of neutral carbohydrates depending...... on the number of charged group in the molecule, pH and concentration of competing anions, while the PAD has sensitivity for carbohydrates in the pmol-range (Lee 1990). As a basis for the development and optimisation of HPAE elution methods, the parameter space was investigated in terms of eluent concentrations...

  11. Separation of human milk oligosaccharides using high-performance anion-exchange chromatography with pulsed amperometric detection

    DEFF Research Database (Denmark)

    Lie, Aleksander; Pedersen, Lars Haastrup

    individual mothers is considerable, ranging from as few as 23 and up to 130 different oligosaccharides. HMOs are known as beneficial for infant health and development, and have received increasing attention in recent years (Bode & Jantscher-Krenn 2012). High-performance anion-exchange chromatography (HPAE......) with pulsed amperometric detection (PAD) is an analysis method highly suited for carbohydrates. HPAE with alkaline eluents results in retention of neutral carbohydrates depending on the number of charged groups in the molecule, pH and concentration of competing anions, while PAD has sensitivity...

  12. LigandRFs: random forest ensemble to identify ligand-binding residues from sequence information alone

    KAUST Repository

    Chen, Peng

    2014-12-03

    Background Protein-ligand binding is important for some proteins to perform their functions. Protein-ligand binding sites are the residues of proteins that physically bind to ligands. Despite of the recent advances in computational prediction for protein-ligand binding sites, the state-of-the-art methods search for similar, known structures of the query and predict the binding sites based on the solved structures. However, such structural information is not commonly available. Results In this paper, we propose a sequence-based approach to identify protein-ligand binding residues. We propose a combination technique to reduce the effects of different sliding residue windows in the process of encoding input feature vectors. Moreover, due to the highly imbalanced samples between the ligand-binding sites and non ligand-binding sites, we construct several balanced data sets, for each of which a random forest (RF)-based classifier is trained. The ensemble of these RF classifiers forms a sequence-based protein-ligand binding site predictor. Conclusions Experimental results on CASP9 and CASP8 data sets demonstrate that our method compares favorably with the state-of-the-art protein-ligand binding site prediction methods.

  13. Identification of the ligand-binding subunit of the human 5-hydroxytryptamine1A receptor with N-(p-azido-m-[125I] iodophenethyl)spiperone, a high affinity radioiodinated photoaffinity probe

    International Nuclear Information System (INIS)

    Raymond, J.R.; Fargin, A.; Lohse, M.J.; Regan, J.W.; Senogles, S.E.; Lefkowitz, R.J.; Caron, M.G.

    1989-01-01

    The ligand-binding subunit of the human 5-hydroxytryptamine1A (5-HT1A) receptor transiently expressed in COS-7 cells and of the native human 5-HT1A receptor derived from hippocampus and frontal cortex were identified by photoaffinity labeling with N-(p-azido-m-[125I]iodophenethyl)spiperone [( 125I]N3-NAPS), previously characterized as a high affinity radioiodinated D2-dopamine receptor probe. The identity of the ligand-binding subunit was confirmed by immunoprecipitation with an antipeptide rabbit antiserum, JWR21, raised against a synthetic peptide derived from the predicted amino acid sequence of the putative third intracellular loop of the human 5-HT1A receptor. In transiently transfected COS-7 cells expressing 14 +/- 3 pmol/mg of protein human 5-HT1A receptors, a single broad 75-kDa band was photoaffinity labeled by [125I]N3-NAPS. This band displayed the expected pharmacology of the 5-HT1A receptor, as evidenced by the ability of a series of competing ligands to block [125I]N3-NAPS photoincorporation. Moreover, antiserum JWR21 specifically and quantitatively immunoprecipitated the 75-kDa photoaffinity-labeled band from a soluble extract of the transfected COS-7 cell membranes, further confirming its identity. Finally, utilizing a combination of photoaffinity labeling and immunoprecipitation, the native ligand-binding subunit of 62-64 kDa was identified in human hippocampus and frontal cortex. The availability of the high specific activity, high affinity, photoaffinity ligand [125I]N3-NAPS and of a potent immunoprecipitating antiserum (JWR21) should greatly facilitate the biochemical characterization of the human 5-HT1A receptor

  14. A Versatile Dinucleating Ligand Containing Sulfonamide Groups

    DEFF Research Database (Denmark)

    Sundberg, Jonas; Witt, Hannes; Cameron, Lisa

    2014-01-01

    ligand can be prepared in aqueous solutions using only divalent metal ions. Two of the copper(II) complexes, [Cu2(psmp)(OH)] and [Cu2(psmp)(OAc)2]-, demonstrate the anticipated 1:2 ligand/metal stoichiometry and show that the dimetallic binding site created for exogenous ligands possesses high inherent...... of antiferromagnetic coupling. This is corroborated computationally by broken-symmetry density functional theory, which for isotropic modeling of the coupling predicts an antiferromagnetic coupling strength of J = 70.5 cm-1....

  15. Hydrogen content, interfacial exchange and hydrogen diffusion in high-temperature protonic conductors based on strontium and barium cerates

    International Nuclear Information System (INIS)

    Vdovin, G.K.; Kurumchin, Eh.Kh.

    2004-01-01

    The hydrogen content and kinetics of the hydrogen exchange in the barium and strontium doped cerates are studied in the reduction atmosphere through the methods of isotope counterbalancing and isotope exchange. The measurements are carried out at 500-840 Deg C and hydrogen pressure of 2.7-16 gPa. It is established, that the hydrogen interfacial exchange proceeds at high velocities through the dissociative-type mechanisms. The effective activation energy of the hydrogen heteroexchange is determined. The coefficient of the hydrogen diffusion in BaCe 0.95 Nd 0.5 O 3-δ is calculated. The hydrogen content per formula unit constituted (0.48±0.05) in the SrCe 0.95 Y 0.05 O 3-δ and (0.60±0.05) in the BaCe 0.95 Nd 0.5 O 3-δ at 550 and 720 Deg C correspondingly and hydrogen pressure of 6.7 gPa [ru

  16. High Temperature Degradation Behavior and its Mechanical Properties of Inconel 617 alloy for Intermediate Heat Exchanger of VHTR

    International Nuclear Information System (INIS)

    Jo, Tae Sun; Kim, Se Hoon; Kim, Young Do; Park, Ji Yeon

    2008-01-01

    Inconel 617 alloy is a candidate material of intermediate heat exchanger (IHX) and hot gas duct (HGD) for very high temperature reactor (VHTR) because of its excellent strength, creep-rupture strength, stability and oxidation resistance at high temperature. Among the alloying elements in Inconel 617, chromium (Cr) and aluminum (Al) can form dense oxide that act as a protective surface layer against degradation. This alloy supports severe operating conditions of pressure over 8 MPa and 950 .deg. C in He gas with some impurities. Thus, high temperature stability of Inconel 617 is very important. In this work, the oxidation behavior of Inconel 617 alloy was studied by exposure at high temperature and was discussed the high temperature degradation behavior with microstructural changes during the surface oxidation

  17. High-frequency data and the effectiveness of the spot exchange rate EUR/USD

    Directory of Open Access Journals (Sweden)

    Petr Zeman

    2013-01-01

    Full Text Available The boom of information technology in recent years significantly influenced the development of the financial markets. Financial markets have become accessible to the public, and increased demand for financial instruments is inevitably reflected in the advanced menu of securities dealers who currently offer a wide variety of investment in the underlying assets and through financial leverage allows investors to profit from tiny price changes of the underlying asset. Shortening of trading period and increasing the frequency of the trades clearly contributes to the growth of profits of securities dealers. The question remains whether this trading method offers the advantage to the investor himself, and whether the investor is able to take advantage of potential market inefficiencies to achieve above-average profits in the short term period. Therefore, this paper analyzes the behaviour of the spot exchange rate EUR/USD within a day, and through statistical tests examining the validity of the random walk hypothesis for the 5-minute, hourly, 4-hourly and daily changes in the spot exchange rate of the currency pair EUR/USD.

  18. High temperature technological heat exchangers and steam generators with helical coil assembly tube bundle

    International Nuclear Information System (INIS)

    Korotaev, O.J.; Mizonov, N.V.; Nikolaevsky, V.B.; Nazarov, E.K.

    1990-01-01

    Analysis of thermal hydraulics characteristics of nuclear steam generators with different tube bundle arrangements and waste heat boilers for ammonia production units was performed on the basis of operating experience results and research and development data. The present report involves the obtained information. The estimations of steam generator performances and repair-ability are given. The significant temperature profile of the primary and secondary coolant flows are attributed to all steam generator designs. The intermediate mixing is found to be an effective means of temperature profile overcoming. At present the only means to provide an effective mixing in heat exchangers of the following types: straight tubes, field tubes, platen tubes and multibank helical coil tubes (with complicated bend distribution along their length) are section arrangements in series in conjunction with forced and natural mixing in connecting lines. Development of the unificated system from mini helical coil assemblies allows to design and manufacture heat exchangers and steam generators within the wide range of operating conditions without additional expenses on the research and development work

  19. Impact of protein and ligand impurities on ITC-derived protein-ligand thermodynamics.

    Science.gov (United States)

    Grüner, Stefan; Neeb, Manuel; Barandun, Luzi Jakob; Sielaff, Frank; Hohn, Christoph; Kojima, Shun; Steinmetzer, Torsten; Diederich, François; Klebe, Gerhard

    2014-09-01

    The thermodynamic characterization of protein-ligand interactions by isothermal titration calorimetry (ITC) is a powerful tool in drug design, giving valuable insight into the interaction driving forces. ITC is thought to require protein and ligand solutions of high quality, meaning both the absence of contaminants as well as accurately determined concentrations. Ligands synthesized to deviating purity and protein of different pureness were titrated by ITC. Data curation was attempted also considering information from analytical techniques to correct stoichiometry. We used trypsin and tRNA-guanine transglycosylase (TGT), together with high affinity ligands to investigate the effect of errors in protein concentration as well as the impact of ligand impurities on the apparent thermodynamics. We found that errors in protein concentration did not change the thermodynamic properties obtained significantly. However, most ligand impurities led to pronounced changes in binding enthalpy. If protein binding of the respective impurity is not expected, the actual ligand concentration was corrected for and the thus revised data compared to thermodynamic properties obtained with the respective pure ligand. Even in these cases, we observed differences in binding enthalpy of about 4kJ⋅mol(-1), which is considered significant. Our results indicate that ligand purity is the critical parameter to monitor if accurate thermodynamic data of a protein-ligand complex are to be recorded. Furthermore, artificially changing fitting parameters to obtain a sound interaction stoichiometry in the presence of uncharacterized ligand impurities may lead to thermodynamic parameters significantly deviating from the accurate thermodynamic signature. Copyright © 2014 Elsevier B.V. All rights reserved.

  20. High-throughput screening using the differential radial capillary action of ligand assay identifies ebselen as an inhibitor of diguanylate cyclases.

    Science.gov (United States)

    Lieberman, Ori J; Orr, Mona W; Wang, Yan; Lee, Vincent T

    2014-01-17

    The rise of bacterial resistance to traditional antibiotics has motivated recent efforts to identify new drug candidates that target virulence factors or their regulatory pathways. One such antivirulence target is the cyclic-di-GMP (cdiGMP) signaling pathway, which regulates biofilm formation, motility, and pathogenesis. Pseudomonas aeruginosa is an important opportunistic pathogen that utilizes cdiGMP-regulated polysaccharides, including alginate and pellicle polysaccharide (PEL), to mediate virulence and antibiotic resistance. CdiGMP activates PEL and alginate biosynthesis by binding to specific receptors including PelD and Alg44. Mutations that abrogate cdiGMP binding to these receptors prevent polysaccharide production. Identification of small molecules that can inhibit cdiGMP binding to the allosteric sites on these proteins could mimic binding defective mutants and potentially reduce biofilm formation or alginate secretion. Here, we report the development of a rapid and quantitative high-throughput screen for inhibitors of protein-cdiGMP interactions based on the differential radial capillary action of ligand assay (DRaCALA). Using this approach, we identified ebselen as an inhibitor of cdiGMP binding to receptors containing an RxxD domain including PelD and diguanylate cyclases (DGC). Ebselen reduces diguanylate cyclase activity by covalently modifying cysteine residues. Ebselen oxide, the selenone analogue of ebselen, also inhibits cdiGMP binding through the same covalent mechanism. Ebselen and ebselen oxide inhibit cdiGMP regulation of biofilm formation and flagella-mediated motility in P. aeruginosa through inhibition of diguanylate cyclases. The identification of ebselen provides a proof-of-principle that a DRaCALA high-throughput screening approach can be used to identify bioactive agents that reverse regulation of cdiGMP signaling by targeting cdiGMP-binding domains.

  1. A General Ligand Design for Gold Catalysis allowing Ligand-Directed Anti Nucleophilic Attack of Alkynes

    Science.gov (United States)

    Wang, Yanzhao; Wang, Zhixun; Li, Yuxue; Wu, Gongde; Cao, Zheng; Zhang, Liming

    2014-01-01

    Most homogenous gold catalyses demand ≥0.5 mol % catalyst loading. Due to the high cost of gold, these reactions are unlikely to be applicable in medium or large scale applications. Here we disclose a novel ligand design based on the privileged biphenyl-2-phosphine framework that offers a potentially general approach to dramatically lowering catalyst loading. In this design, an amide group at the 3’ position of the ligand framework directs and promotes nucleophilic attack at the ligand gold complex-activated alkyne, which is unprecedented in homogeneous gold catalysis considering the spatial challenge of using ligand to reach antiapproaching nucleophile in a linear P-Au-alkyne centroid structure. With such a ligand, the gold(I) complex becomes highly efficient in catalyzing acid addition to alkynes, with a turnover number up to 99,000. Density functional theory calculations support the role of the amide moiety in directing the attack of carboxylic acid via hydrogen bonding. PMID:24704803

  2. High construal level can help negotiators to reach integrative agreements: The role of information exchange and judgement accuracy.

    Science.gov (United States)

    Wening, Stefanie; Keith, Nina; Abele, Andrea E

    2016-06-01

    In negotiations, a focus on interests (why negotiators want something) is key to integrative agreements. Yet, many negotiators spontaneously focus on positions (what they want), with suboptimal outcomes. Our research applies construal-level theory to negotiations and proposes that a high construal level instigates a focus on interests during negotiations which, in turn, positively affects outcomes. In particular, we tested the notion that the effect of construal level on outcomes was mediated by information exchange and judgement accuracy. Finally, we expected the mere mode of presentation of task material to affect construal levels and manipulated construal levels using concrete versus abstract negotiation tasks. In two experiments, participants negotiated in dyads in either a high- or low-construal-level condition. In Study 1, high-construal-level dyads outperformed dyads in the low-construal-level condition; this main effect was mediated by information exchange. Study 2 replicated both the main and mediation effects using judgement accuracy as mediator and additionally yielded a positive effect of a high construal level on a second, more complex negotiation task. These results not only provide empirical evidence for the theoretically proposed link between construal levels and negotiation outcomes but also shed light on the processes underlying this effect. © 2015 The British Psychological Society.

  3. Collecting performance of an evacuated tubular solar high-temperature air heater with concentric tube heat exchanger

    International Nuclear Information System (INIS)

    Wang, Ping-Yang; Li, Shuang-Fei; Liu, Zhen-Hua

    2015-01-01

    Highlights: • A novel evacuated tube solar high temperature air heater is designed. • The solar air heater system consists of 30 linked collecting units. • Every unit consisted of a evacuated tube, a simplified CPC and concentric tube. • The flow air is heated over temperature of 200 °C. - Abstract: A set of evacuated tube solar high temperature air heaters with simplified CPC (compound parabolic concentrator) and concentric tube heat exchanger is designed to provide flow air with a temperature of 150–230 °C for industrial production. The solar air heater system consists of 30 linked collecting units. Each unit includes a simplified CPC and an all-glass evacuated tube absorber with a concentric copper tube heat exchanger installed inside. A stainless steel mesh layer with high thermal conductivity is filled between the evacuated tube and the concentric copper tube. Air passes through each collecting unit, and its temperature increases progressively. An experimental investigation of the thermal performance of the air heater is performed, and the experimental results demonstrate the presented high-temperature solar air heater has excellent collecting performance and large output power, even in the winter. The measured thermal efficiency corresponding to the air temperature of 70 °C reaches 0.52. With the increase of air temperature, thermal efficiency reaches 0.35 at an air temperature of 150 °C, and 0.21 at an air temperature of 220 °C.

  4. Reprocessing and Recycling of Highly Cross-Linked Ion-Conducting Networks through Transalkylation Exchanges of C-N Bonds.

    Science.gov (United States)

    Obadia, Mona M; Mudraboyina, Bhanu P; Serghei, Anatoli; Montarnal, Damien; Drockenmuller, Eric

    2015-05-13

    Exploiting exchangeable covalent bonds as dynamic cross-links recently afforded a new class of polymer materials coined as vitrimers. These permanent networks are insoluble and infusible, but the network topology can be reshuffled at high temperatures, thus enabling glasslike plastic deformation and reprocessing without depolymerization. We disclose herein the development of functional and high-value ion-conducting vitrimers that take inspiration from poly(ionic liquid)s. Tunable networks with high ionic content are obtained by the solvent- and catalyst-free polyaddition of an α-azide-ω-alkyne monomer and simultaneous alkylation of the resulting poly(1,2,3-triazole)s with a series of difunctional cross-linking agents. Temperature-induced transalkylation exchanges of C-N bonds between 1,2,3-triazolium cross-links and halide-functionalized dangling chains enable recycling and reprocessing of these highly cross-linked permanent networks. They can also be recycled by depolymerization with specific solvents able to displace the transalkylation equilibrium, and they display a great potential for applications that require solid electrolytes with excellent mechanical performances and facile processing such as supercapacitors, batteries, fuel cells, and separation membranes.

  5. Exchange of Na+ and K+ between water vapor and feldspar phases at high temperature and low vapor pressure

    Science.gov (United States)

    Fournier, R.O.

    1976-01-01

    In order to determine whether gas (steam) containing a small amount of dissolved alkali chloride is effective in promoting base exchange of Na+ and K+ among alkali feldspars and coexisting brine or brine plus solid salt, experiments were carried out at 400-700??C and steam densities ranging down to less than 0.05. For bulk compositions rich in potassium, the low pressure results are close to previous high-pressure results in composition of the fluid and coexisting solid phase. However, when the bulk composition is more sodic, alkali feldspars are relatively richer in potassium at low pressure than at high pressure. This behaviour corresponds to enrichment of potassium in the gas phase relative to coexisting brine and precipitation of solid NaCl when the brine plus gas composition becomes moderately sodic. The gas phase is very effective in promoting base exchange between coexisting alkali feldspars at high temperature and low water pressure. This suggests that those igneous rocks which contain coexisting alkali feldspars out of chemical equilibrium either remained very dry during the high-temperature part of their cooling history or that the pore fluid was a gas containing very little potassium relative to sodium. ?? 1976.

  6. Ligand-regulated peptide aptamers.

    Science.gov (United States)

    Miller, Russell A

    2009-01-01

    The peptide aptamer approach employs high-throughput selection to identify members of a randomized peptide library displayed from a scaffold protein by virtue of their interaction with a target molecule. Extending this approach, we have developed a peptide aptamer scaffold protein that can impart small-molecule control over the aptamer-target interaction. This ligand-regulated peptide (LiRP) scaffold, consisting of the protein domains FKBP12, FRB, and GST, binds to the cell-permeable small-molecule rapamycin and the binding of this molecule can prevent the interaction of the randomizable linker region connecting FKBP12 with FRB. Here we present a detailed protocol for the creation of a peptide aptamer plasmid library, selection of peptide aptamers using the LiRP scaffold in a yeast two-hybrid system, and the screening of those peptide aptamers for a ligand-regulated interaction.

  7. High power uv metal vapor ion lasers pumped by thermal energy charge exchange

    International Nuclear Information System (INIS)

    Kan, T.

    1975-01-01

    The requirement for efficient and scalable laser sources for laser isotope separation (LIS) has recently been brought into sharp focus. The lack of suitable coherent sources is particularly severe in the uv, a spectral region of interest for more efficient and advanced isotope separation schemes. This report explores the general class of metal vapor ion lasers pumped by thermal energy charge exchange (TECX) as possible scalable coherent sources for LIS with the following potential characteristics: (1) availability of discrete wavelengths spanning the wavelength region between 2000 A less than lambda less than 8000 A, (2) pulsed or cw operation in the multi-kilowatt average power levels, (3) overall device efficiencies approaching one percent, and (4) the engineering of practical laser devices using relatively benign electron beam technology. (U.S.)

  8. Observation of High Transformer Ratio of Shaped Bunch Generated by an Emittance-Exchange Beam Line.

    Science.gov (United States)

    Gao, Q; Ha, G; Jing, C; Antipov, S P; Power, J G; Conde, M; Gai, W; Chen, H; Shi, J; Wisniewski, E E; Doran, D S; Liu, W; Whiteford, C E; Zholents, A; Piot, P; Baturin, S S

    2018-03-16

    Collinear wakefield acceleration has been long established as a method capable of generating ultrahigh acceleration gradients. Because of the success on this front, recently, more efforts have shifted towards developing methods to raise the transformer ratio (TR). This figure of merit is defined as the ratio of the peak acceleration field behind the drive bunch to the peak deceleration field inside the drive bunch. TR is always less than 2 for temporally symmetric drive bunch distributions and therefore recent efforts have focused on generating asymmetric distributions to overcome this limitation. In this Letter, we report on using the emittance-exchange method to generate a shaped drive bunch to experimentally demonstrate a TR≈5 in a dielectric wakefield accelerator.

  9. Interrogating the Molecular Basis for Substrate Recognition in Serotonin and Dopamine Transporters with High-Affinity Substrate-Based Bivalent Ligands

    DEFF Research Database (Denmark)

    Andersen, Jacob; Ladefoged, Lucy Kate; Kristensen, Trine N. Bjerre

    2016-01-01

    insight into substrate recognition in SERT and DAT. An optimized bivalent ligand comprising two serotonin moieties binds SERT with 3,800-fold increased affinity compared to that of serotonin, suggesting that the human transporters have two distinct substrate binding sites. We show that the bivalent...... ligands are inhibitors of SERT and an experimentally validated docking model suggests that the bivalent compounds bind with one substrate moiety in the central binding site (the S1 site), whereas the other substrate moiety binds in a distinct binding site (the S2 site). A systematic study of nonconserved...

  10. An evaluation of multiple-schedule variations to reduce high-rate requests in the picture exchange communication system.

    Science.gov (United States)

    Landa, Robin; Hanley, Gregory P

    2016-06-01

    Using procedures similar to those of Tiger, Hanley, and Heal (2006), we compared two multiple-schedule variations (S+/S- and S+ only) to treat high-rate requests for edible items in the Picture Exchange Communication System (PECS). Two individuals with autism participated, after they showed persistent requests for edible items after PECS training. Stimulus control was achieved only with the multiple schedule that involved presentation of a discriminative stimulus during reinforcement components and its removal during extinction components (S+ only). Discriminated requests were maintained for the 1 participant who experienced schedule thinning. © 2016 Society for the Experimental Analysis of Behavior.

  11. Effect of chloride impurities on the performance and durability of polybenzimidazole-based high temperature proton exchange membrane fuel cells

    DEFF Research Database (Denmark)

    Ali, Syed Talat; Li, Qingfeng; Pan, Chao

    2011-01-01

    The effect of chloride as an air impurity and as a catalyst contaminant on the performance and durability of polybenzimidazole (PBI)-based high temperature proton exchange membrane fuel cell (HT-PEMFC) was studied. The ion chromatographic analysis reveals the existence of chloride contaminations....... The performance loss was recovered when switching from the HCl solution back to pure water in the air humidifier. Under an accelerated aging performance test conducted through potential cycling between 0.9 V and 1.2 V, the PBI-based fuel cell initially containing 0.5 NaCl mg cm−2 on the cathode catalyst layer...

  12. Recovery of nitric acid from simulated acidic high level radioactive waste using pore-filled anion exchange membranes

    International Nuclear Information System (INIS)

    Chavan, Vivek; Agarwal, Chhavi; Pandey, A.K.; Goswami, A.

    2014-01-01

    Acidic waste is generated at different stages of nuclear fuel cycle. The waste contains minor amounts of actinides ( 241 Am, Pu, Np) along with large number of long-lived radionuclides such as 137 Cs, 90 Sr, 106 Ru etc. Before disposal or storage, the overall activity of the waste needs to be reduced. Along with this, the high amount of acid present in the waste needs to be removed. In this study, DD has been used to recover nitric acid from acidic solutions with compositions similar to radioactive waste using pore-filled anion exchange membranes

  13. Performance of water source heat pump system using high-density polyethylene tube heat exchanger wound with square copper wire

    Directory of Open Access Journals (Sweden)

    Xin Wen Zhang

    2015-07-01

    Full Text Available Surface water source heat pump system is an energy-efficient heat pump system. Surface water heat exchanger is an important part of heat pump system that can affect the performance of the system. In order to enhance the performance of the system, the overall heat transfer coefficient (U value of the water exchanger using a 32A square copper coiled high-density polyethylene tube was researched. Comparative experiments were conducted between the performance of the coiled high-density polyethylene tube and the 32A smooth high-density polyethylene tube. At the same time, the coefficient of performance of the heat pump was investigated. According to the result, the U value of the coiled tube was 18% higher than that of the smooth tube in natural convection and 19% higher in forced convection. The coefficient of performance of the heat pump with the coiled tube is higher than that with the smooth tube. The economic evaluation of the coiled tube was also investigated.

  14. Extended high-frequency partial liquid ventilation in lung injury: gas exchange, injury quantification, and vapor loss.

    Science.gov (United States)

    Doctor, Allan; Al-Khadra, Eman; Tan, Puay; Watson, Kenneth F; Diesen, Diana L; Workman, Lisa J; Thompson, John E; Rose, Charles E; Arnold, John H

    2003-09-01

    High-frequency oscillatory ventilation with perflubron (PFB) reportedly improves pulmonary mechanics and gas exchange and attenuates lung injury. We explored PFB evaporative loss kinetics, intrapulmonary PFB distribution, and dosing strategies during 15 h of high-frequency oscillation (HFO)-partial liquid ventilation (PLV). After saline lavage lung injury, 15 swine were rescued with high-frequency oscillatory ventilation (n = 5), or in addition received 10 ml/kg PFB delivered to dependent lung [n = 5, PLV-compartmented (PLV(C))] or 10 ml/kg distributed uniformly within the lung [n = 5, PLV(U)]. In the PLV(C) group, PFB vapor loss was replaced. ANOVA revealed an unsustained improvement in oxygenation index in the PLV(U) group (P = 0.04); the reduction in oxygenation index correlated with PFB losses. Although tissue myeloperoxidase activity was reduced globally by HFO-PLV (P PFB distribution optimized gas exchange during HFO-PLV; additionally, monitoring PFB evaporative loss appears necessary to stabilize intrapulmonary PFB volume.

  15. Case reports of the use of immunoadsorption or plasma exchange in high-risk pregnancies of women with antiphospholipid syndrome.

    Science.gov (United States)

    Bortolati, Maria; Marson, Piero; Chiarelli, Silvia; Tison, Tiziana; Facchinetti, Myriam; Gervasi, Maria Teresa; De Silvestro, Giustina; Ruffatti, Amelia

    2009-04-01

    Conventional treatment of antiphospholipid syndrome (APS) pregnancies with aspirin and/or heparin is sometimes unable to counteract maternal and/or fetal complications. In this article we report the cases of two patients who were unresponsive to conventional treatment for APS during their first pregnancy, and who were treated in the following pregnancy with plasma exchange and immunoadsorption respectively, in addition to conventional therapy. Both patients had a history of thrombotic events, a previous pregnancy loss at the 11th week of gestation and the same antiphospholipid antibody profile (lupus anticoagulant activity and high titers of immunoglobulin G (IgG) anti-beta2 glycoprotein I and IgG anticardiolipin antibodies). Patient 1 was treated from the fourth week of her second pregnancy with weekly plasma exchange. Due to fetal growth restriction and oligohydramnios in the 26th week she delivered, by cesarean section, a healthy female infant weighing 730 g who survived. Patient 2 was treated from the seventh week of her second pregnancy with twice a week protein A immunoadsorption. The pregnancy proceeded normally until the 36th week, when, due to slight intrauterine growth restriction, she delivered a healthy baby girl weighing 2375 g by cesarean section. Anti-beta2 glycoprotein I antibody trends were similar during both types of treatment. On the basis of our findings obtained from only two cases it is impossible to define the best aphaeretic treatment of APS high risk pregnancies. Nevertheless, as a whole these data suggest better disease control using the immunoadsorption technique as compared to plasma exchange, despite their apparently similar anti-beta2 glycoprotein I antibody removal capabilities.

  16. Metallic materials for heat exchanger components and highly stressed internal of HTR reactors for nuclear process heat generation

    International Nuclear Information System (INIS)

    1982-01-01

    The programme was aimed at the development and improvement of materials for the high-temperature heat exchanger components of a process steam HTR. The materials must have high resistance to corrosion, i.e. carburisation and internal oxidation, and high long-term toughness over a wide range of temperatures. They must also meet the requirements set in the nuclear licensing procedure, i.e. resistance to cyclic stress and irradiation, non-destructive testing, etc. Initially, it was only intended to improve and qualify commercial alloys. Later on an alloy development programme was initiated in which new, non-commercial alloys were produced and modified for use in a nuclear process heat facility. Separate abstracts were prepared for 19 pays of this volume. (orig./IHOE) [de

  17. Highly recoverable pyridinium-tagged Hoveyda-Grubbs pre-catalyst for olefin metathesis. Design of the boomerang ligand toward the optimal compromise between activity and reusability.

    Science.gov (United States)

    Rix, Diane; Caïjo, Fréderic; Laurent, Isabelle; Gulajski, Lukasz; Grela, Karol; Mauduit, Marc

    2007-09-28

    Whereas the boomerang ligand of Hoveyda-Grubbs pre-catalysts can be modified by attachment of a pyridinium tag to its benzylidene moiety, a precise adjustment of the length of the spacer allows the optimum balance to be reached between the activity of the catalyst and its recoverability, exceeding 98% after 6 catalytic runs in the best case.

  18. High-Temperature Transitions in Metallopolymers Crosslinked With 2,6-bis(1’-methylbenzimidazolyl)pyridine Metal-Ligand Complex

    Science.gov (United States)

    2013-10-01

    Beck, J. B. Metal–Ligand Induced Supramolecular Polymerization: A Route To Responsive Materials. Faraday Discuss. 2005, 128, 43–53. 29. Ilavsky, J...X-ray Photoelectron Study of the Electrocatalytically Active Cobalt(I) Cage Complexes and the Clathrochelate Cobalt(II)- and Cobalt(III)- Containing

  19. Sodium-calcium ion exchange on clay minerals at moderate to high ionic strengths

    International Nuclear Information System (INIS)

    Rogers, W.J.

    1979-12-01

    Sodium-calcium ion exchange on several clay minerals was studied at ionic strengths ranging from 0.01 to above 1.0. The minerals studied included attapulgite, illite, kaolin, and several montmorillonites. Distribution coefficients of calcium and sodium were obtained for the minerals over a wide range of solution conditions at pH five and equilibrium constants were calculated. The distribution coefficient of calcium, D/sub Ca/, was studied as a function of time, solution pH, loading, sodium concentration, and ionic strength fraction of sodium in constant ionic strength solutions. The distribution coefficient of sodium, D/sub Na/, was also studied as a function of time, loading, and sodium ionic strength fraction in constant total ionic strength solutions. Values of equilibrium constants calculated from distribution coefficients for solutions of constant ionic strength scattered bwteen 2 and 10 kg/kg for the montmorillonites and attapulgite while equilibrium constants for illite ranged from 5 to 10 kg/kg. No equilibrium constants for kaolin were calculated since distribution coefficients of sodium on this clay were too small to be measured. It was found that equilibrium constants at trace sodium loading were generally lower than those for higher sodium loadings by an order of magnitude or more due to the sensitivity of sodium distribution coefficients to the concentration of sodium in the clay at low loadings. Theoretical and experimental treatments of ion exclusion were included

  20. Cell-specific targeting by heterobivalent ligands.

    Science.gov (United States)

    Josan, Jatinder S; Handl, Heather L; Sankaranarayanan, Rajesh; Xu, Liping; Lynch, Ronald M; Vagner, Josef; Mash, Eugene A; Hruby, Victor J; Gillies, Robert J

    2011-07-20

    Current cancer therapies exploit either differential metabolism or targeting to specific individual gene products that are overexpressed in aberrant cells. The work described herein proposes an alternative approach--to specifically target combinations of cell-surface receptors using heteromultivalent ligands ("receptor combination approach"). As a proof-of-concept that functionally unrelated receptors can be noncovalently cross-linked with high avidity and specificity, a series of heterobivalent ligands (htBVLs) were constructed from analogues of the melanocortin peptide ligand ([Nle(4), dPhe(7)]-α-MSH) and the cholecystokinin peptide ligand (CCK-8). Binding of these ligands to cells expressing the human Melanocortin-4 receptor and the Cholecystokinin-2 receptor was analyzed. The MSH(7) and CCK(6) were tethered with linkers of varying rigidity and length, constructed from natural and/or synthetic building blocks. Modeling data suggest that a linker length of 20-50 Å is needed to simultaneously bind these two different G-protein coupled receptors (GPCRs). These ligands exhibited up to 24-fold enhancement in binding affinity to cells that expressed both (bivalent binding), compared to cells with only one (monovalent binding) of the cognate receptors. The htBVLs had up to 50-fold higher affinity than that of a monomeric CCK ligand, i.e., Ac-CCK(6)-NH(2). Cell-surface targeting of these two cell types with labeled heteromultivalent ligand demonstrated high avidity and specificity, thereby validating the receptor combination approach. This ability to noncovalently cross-link heterologous receptors and target individual cells using a receptor combination approach opens up new possibilities for specific cell targeting in vivo for therapy or imaging.

  1. Hydrothermal synthesis of superparamagnetic and red luminescent bifunctional Fe{sub 3}O{sub 4}@Mn{sup 2+}-doped NaYF{sub 4}:Yb/Er core@shell monodisperse nanoparticles and their subsequent ligand exchange in water

    Energy Technology Data Exchange (ETDEWEB)

    Qin, Zhenli; Du, Sinan; Luo, Yang; Liao, Zhijian; Zuo, Fang, E-mail: polymerzf@swun.cn; Luo, Jianbin; Liu, Dong

    2016-08-15

    Graphical abstract: An efficient hydrothermal method was used to fabricate the superparamagnetic and red luminescent bifunctional Fe{sub 3}O{sub 4}@Mn{sup 2(*)+}-doped NaYF{sub 4}:Yb/Er nanoparticles (NPs) with core@shell structures through a seed-growth procedure. Then using PEG phosphate ligand to displace oleate from the as-synthesized NPs, hydrophilic Fe{sub 3}O{sub 4}@Mn{sup 2+}-doped NaYF{sub 4}:Yb/Er NPs with good water solubility are obtained. - Highlights: • Homogeneous size distribution of magnetic-upconversion core@shell structured nanoparticles (NPs) were synthesized. • The core@shell nanostructures were obtained by seed-growth method. • The oleic acid coated Fe{sub 3}O{sub 4} NPs were used as seeds and cores. • The magnetic-upconversion NPs emitted red luminescence under a 980 nm laser. • Synthesized magnetic-upconversion NPs were phase transferred using ligand exchange process. - Abstract: We report the use of an efficient hydrothermal method to synthesize superparamagnetic and red luminescent bifunctional Fe{sub 3}O{sub 4}@Mn{sup 2+}-doped NaYF{sub 4}:Yb/Er nanoparticles (NPs) with core@shell structures via a seed-growth procedure. Oleic acid coated Fe{sub 3}O{sub 4} (OA-Fe{sub 3}O{sub 4}) NPs were initially synthesized using a coprecipitation method. The as-synthesized OA-Fe{sub 3}O{sub 4} NPs were then used as seeds, on which the red upconversion luminescent shell (Mn{sup 2+}-doped NaYF{sub 4}:Yb/Er) was formed. Furthermore, hydrophobic to hydrophilic surface modification of the Fe{sub 3}O{sub 4}@Mn{sup 2+}-doped NaYF{sub 4}:Yb/Er NPs was achieved via a ligand exchange method where oleic acid was displaced by a PEG phosphate ligand [PEG = poly(ethylene glycol)]. These materials were characterized by means of transmission electron microscopy (TEM), X-ray diffraction (XRD), photoluminescence (PL) spectroscopy, and vibrating sample magnetometry (VSM). The Fe{sub 3}O{sub 4} cores were uniformly coated with a Mn{sup 2+}-doped NaYF{sub 4}:Yb

  2. Labeling by ( sup 3 H)1,3-di(2-tolyl)guanidine of two high affinity binding sites in guinea pig brain: Evidence for allosteric regulation by calcium channel antagonists and pseudoallosteric modulation by sigma ligands

    Energy Technology Data Exchange (ETDEWEB)

    Rothman, R.B.; Reid, A.; Mahboubi, A.; Kim, C.H.; De Costa, B.R.; Jacobson, A.E.; Rice, K.C. (National Institute of Mental Health, Bethesda, MD (USA))

    1991-02-01

    Equilibrium binding studies with the sigma receptor ligand ({sup 3}H)1,3-di(2-tolyl)guanidine (({sup 3}H)DTG) demonstrated two high affinity binding sites in membranes prepared from guinea pig brain. The apparent Kd values of DTG for sites 1 and 2 were 11.9 and 37.6 nM, respectively. The corresponding Bmax values were 1045 and 1423 fmol/mg of protein. Site 1 had high affinity for (+)-pentazocine, haloperidol, (R)-(+)-PPP, carbepentane, and other sigma ligands, suggesting a similarity with the dextromethorphan/sigma 1 binding site described by Musacchio et al. (Life Sci. 45:1721-1732 (1989)). Site 2 had high affinity for DTG and haloperidol (Ki = 36.1 nM) and low affinity for most other sigma ligands. Kinetic experiments demonstrated that ({sup 3}H)DTG dissociated in a biphasic manner from both site 1 and site 2. DTG and haloperidol increased the dissociation rate of ({sup 3}H)DTG from site 1 and site 2, demonstrating the presence of pseudoallosteric interactions. Inorganic calcium channel blockers such as Cd2+ selectively increased the dissociation rate of ({sup 3}H)DTG from site 2, suggesting an association of this binding site with calcium channels.

  3. Labeling by [3H]1,3-di(2-tolyl)guanidine of two high affinity binding sites in guinea pig brain: Evidence for allosteric regulation by calcium channel antagonists and pseudoallosteric modulation by sigma ligands

    International Nuclear Information System (INIS)

    Rothman, R.B.; Reid, A.; Mahboubi, A.; Kim, C.H.; De Costa, B.R.; Jacobson, A.E.; Rice, K.C.

    1991-01-01

    Equilibrium binding studies with the sigma receptor ligand [ 3 H]1,3-di(2-tolyl)guanidine ([ 3 H]DTG) demonstrated two high affinity binding sites in membranes prepared from guinea pig brain. The apparent Kd values of DTG for sites 1 and 2 were 11.9 and 37.6 nM, respectively. The corresponding Bmax values were 1045 and 1423 fmol/mg of protein. Site 1 had high affinity for (+)-pentazocine, haloperidol, (R)-(+)-PPP, carbepentane, and other sigma ligands, suggesting a similarity with the dextromethorphan/sigma 1 binding site described by Musacchio et al. [Life Sci. 45:1721-1732 (1989)]. Site 2 had high affinity for DTG and haloperidol (Ki = 36.1 nM) and low affinity for most other sigma ligands. Kinetic experiments demonstrated that [ 3 H]DTG dissociated in a biphasic manner from both site 1 and site 2. DTG and haloperidol increased the dissociation rate of [ 3 H]DTG from site 1 and site 2, demonstrating the presence of pseudoallosteric interactions. Inorganic calcium channel blockers such as Cd2+ selectively increased the dissociation rate of [ 3 H]DTG from site 2, suggesting an association of this binding site with calcium channels

  4. Influence of inhaled nitric oxide on gas exchange during normoxic and hypoxic exercise in highly trained cyclists.

    Science.gov (United States)

    Sheel, A W; Edwards, M R; Hunte, G S; McKenzie, D C

    2001-03-01

    This study tested the effects of inhaled nitric oxide [NO; 20 parts per million (ppm)] during normoxic and hypoxic (fraction of inspired O(2) = 14%) exercise on gas exchange in athletes with exercise-induced hypoxemia. Trained male cyclists (n = 7) performed two cycle tests to exhaustion to determine maximal O(2) consumption (VO(2 max)) and arterial oxyhemoglobin saturation (Sa(O(2)), Ohmeda Biox ear oximeter) under normoxic (VO(2 max) = 4.88 +/- 0.43 l/min and Sa(O(2)) = 90.2 +/- 0.9, means +/- SD) and hypoxic (VO(2 max) = 4.24 +/- 0.49 l/min and Sa(O(2)) = 75.5 +/- 4.5) conditions. On a third occasion, subjects performed four 5-min cycle tests, each separated by 1 h at their respective VO(2 max), under randomly assigned conditions: normoxia (N), normoxia + NO (N/NO), hypoxia (H), and hypoxia + NO (H/NO). Gas exchange, heart rate, and metabolic parameters were determined during each condition. Arterial blood was drawn at rest and at each minute of the 5-min test. Arterial PO(2) (Pa(O(2))), arterial PCO(2), and Sa(O(2)) were determined, and the alveolar-arterial difference for PO(2) (A-aDO(2)) was calculated. Measurements of Pa(O(2)) and Sa(O(2)) were significantly lower and A-aDO(2) was widened during exercise compared with rest for all conditions (P 0.05). We conclude that inhalation of 20 ppm NO during normoxic and hypoxic exercise has no effect on gas exchange in highly trained cyclists.

  5. Deviation from the trans -Effect in Ligand-Exchange Reactions of Zeise’s Ions PtCl3(C2H4)- with Heavier Halides (Br, I- )

    Energy Technology Data Exchange (ETDEWEB)

    Hou, Gao-Lei [Physical; Govind, Niranjan [Environmental; Xantheas, Sotiris S. [Advanced; Department; Wang, Xue-Bin [Physical

    2018-01-16

    Four new Zeise’s family ions with mixed-halide ligands, i.e., PtClnX3-n(C2H4)- (X = Br, I; n = 1, 2), were synthesized via ligand-exchange reactions of KX salts with KPtCl3(C2H4) in aqueous solutions, and were detected in vacuum via electrospray ionization mass spectrometry. Their photoelectron spectra reveal a series of well-resolved spectral peaks with their electron binding energies (EBEs) decreasing with increasing halide size, with I having a much stronger effect than Br, i.e., 4.57 (–Cl3) > 4.56 (–Cl2Br) > 4.53 (–ClBr2) > 4.34 (–Cl2I) > 4.30 eV (–ClI2). Ab initio electronic structure calculations including spin-orbit coupling (SOC) predict that the cis- and trans-isomers are nearly isoenergetic with the cis-isomer for –Cl2X, and the trans-isomer for –ClX2 slightly favored, respectively. Excited-state spectra calculated with time-dependent density functional theory (TDDFT), and their comparison with the observed ones, suggest that for each species, both the cis- and trans-configurations coexist in the experiments and contribute to the observed spectra, a fact that clearly violates the prediction of the widely accepted trans-effect, which suggests that only one isomer would have formed.

  6. Detection of site-specific binding and co-binding of ligands to macromolecules using 19F NMR

    International Nuclear Information System (INIS)

    Jenkins, B.G.

    1991-01-01

    Study of ligand-macromolecular interactions by 19 F nuclear magnetic resonance (NMR) spectroscopy affords many opportunities for obtaining molecular biochemical and pharmaceutical information. This is due to the absence of a background fluorine signal, as well as the relatively high sensitivity of 19 F NMR. Use of fluorine-labeled ligands enables one to probe not only binding and co-binding phenomena to macromolecules, but also can provide data on binding constants, stoichiometries, kinetics, and conformational properties of these complexes. Under conditions of slow exchange and macromolecule-induced chemical shifts, multiple 19 F NMR resonances can be observed for free and bound ligands. These shifted resonances are a direct correlate of the concentration of ligand bound in a specific state rather than the global concentrations of bound or free ligand which are usually determined using other techniques such as absorption spectroscopy or equilibrium dialysis. Examples of these interactions are demonstrated both from the literature and from interactions of 5-fluorotryptophan, 5-fluorosalicylic acid, flurbiprofen, and sulindac sulfide with human serum albumin. Other applications of 19 F NMR to study of these interactions in vivo, as well for receptor binding and metabolic tracing of fluorinated drugs and proteins are discussed

  7. Design of a multi-dopamine-modified polymer ligand optimally suited for interfacing magnetic nanoparticles with biological systems.

    Science.gov (United States)

    Wang, Wentao; Ji, Xin; Na, Hyon Bin; Safi, Malak; Smith, Alexandra; Palui, Goutam; Perez, J Manuel; Mattoussi, Hedi

    2014-06-03

    We have designed a set of multifunctional and multicoordinating polymer ligands that are optimally suited for surface functionalizing iron oxide and potentially other magnetic nanoparticles (NPs) and promoting their integration into biological systems. The amphiphilic polymers are prepared by coupling (via nucleophilic addition) several amine-terminated dopamine anchoring groups, poly(ethylene glycol) moieties, and reactive groups onto a poly(isobutylene-alt-maleic anhydride) (PIMA) chain. This design greatly benefits from the highly efficient and reagent-free one-step reaction of maleic anhydride groups with amine-containing molecules. The availability of several dopamine groups in the same ligand greatly enhances the ligand affinity, via multiple coordination, to the magnetic NPs, while the hydrophilic and reactive groups promote colloidal stability in buffer media and allow subsequent conjugation with target biomolecules. Iron oxide nanoparticles ligand exchanged with these polymer ligands have a compact hydrodynamic size and exhibit enhanced long-term colloidal stability over the pH range of 4-12 and in the presence of excess electrolytes. Nanoparticles ligated with terminally reactive polymers have been easily coupled to target dyes and tested in live cell imaging with no measurable cytotoxicity. Finally, the resulting hydrophilic nanoparticles exhibit large and size-dependent r2 relaxivity values.

  8. Numerical analysis of steady state and transient analysis of high temperature ceramic plate-fin heat exchanger

    International Nuclear Information System (INIS)

    Nagarajan, Vijaisri; Chen, Yitung; Wang, Qiuwang; Ma, Ting

    2014-01-01

    Highlights: • Rip saw fin design is considered to be the best because it has thin fins and has higher heat transfer coefficient. • Minimum principal stress and maximum safety factor are obtained for the inverted bolt fin design. • Maximum principal stress and minimum safety factor are obtained for triangular fin design. • Thermal stress has significant impact than mechanical stress. • High principal stress is found at the startup and shutdown stage. - Abstract: In this study three-dimensional model of ceramic plate-fin high temperature heat exchanger with different fin designs and arrangements is analyzed numerically using ANSYS FLUENT and ANSYS structural module. The ability of ceramics to withstand high temperature and corrosion makes silicon carbide (SiC) suitable candidate material to be used in high temperature heat exchanger. The operating temperature of heat exchanger is 950 °C and the operating pressure is 1.5 MPa. The working fluids are helium, sulfur trioxide, sulfur dioxide, oxygen and the water vapor. Fluid flow and heat transfer analysis are carried out for steady and transient state in FLUENT. The obtained thermal and pressure load for the steady and transient state from ANSYS FLUENT are imported to ANSYS structural module to obtain the principal stress and the factor of safety. Different arrangements of rectangular fins, triangular fins, inverted bolt fins and ripsaw fins are studied. From the results it is found that the minimum stress and the maximum safety factor are obtained for inverted bolt fins. The triangular fins have the maximum principal stress and minimum factor of safety. However, the fluid flow and heat transfer analysis show inverted bolt fins and triangular fins produce higher pressure drop and friction factor. The steady state maximum principal stress is 10.08 MPa, 9.90 MPa and 11.43 MPa for straight, staggered and top and bottom ripsaw fin arrangement. The corresponding safety factors are 21.80, 21.95 and 19

  9. Performance test of silver ion-exchanged zeolite for the removal of gaseous radioactive methyl iodide at high temperature condition

    International Nuclear Information System (INIS)

    Byung-Seon Choi; Geun-Il Park; Jung-Won Lee; Ho-Yeon Yang; Seung-Kon Ryu

    2003-01-01

    Performance tests of silver ion-exchanged zeolite (AgX) adsorbent for the control of radioiodine gas generated from a high-temperature process were carried out using both non-radioactive and a radioactive methyl iodide tracers. From the identification of SEM-EDAX analysis, an experimental result of silver ion-exchanged ratio containing 10∼30 wt% of Ag was fit to that calculated by the weight increment, and it was confirmed that the silver was uniformly distributed inside the pores of the adsorbent. Demonstration test of AgX-10 adsorbent using radioactive methyl iodide tracer was performed. The removal efficiency of radioiodine with AgX-10 in the temperature ranges of 150 to 300 deg C was in the ranges of 99.9% to 99.99%, except for 300 deg C. The influence of the long-term weathering and the poisoning with NO 2 gas (200 ppm) on adsorption capacity of AgX-10 was also analyzed. The removal efficiency of radioactive methyl iodide by AgX-10 weathered for 14 weeks was 99.95%. Long-term poisoning test showed that the adsorption efficiency of methyl iodide started to decrease after 10 weeks, and the removal efficiency of radioiodine by AgX-10, poisoned for 16 weeks, was 99% (DF=100). (author)

  10. Ammonia formation by metal-ligand cooperative hydrogenolysis of a nitrido ligand

    Science.gov (United States)

    Askevold, Bjorn; Nieto, Jorge Torres; Tussupbayev, Samat; Diefenbach, Martin; Herdtweck, Eberhardt; Holthausen, Max C.; Schneider, Sven

    2011-07-01

    Bioinspired hydrogenation of N2 to ammonia at ambient conditions by stepwise nitrogen protonation/reduction with metal complexes in solution has experienced remarkable progress. In contrast, the highly desirable direct hydrogenation with H2 remains difficult. In analogy to the heterogeneously catalysed Haber-Bosch process, such a reaction is conceivable via metal-centred N2 splitting and unprecedented hydrogenolysis of the nitrido ligands to ammonia. We report the synthesis of a ruthenium(IV) nitrido complex. The high nucleophilicity of the nitrido ligand is demonstrated by unusual N-C coupling with π-acidic CO. Furthermore, the terminal nitrido ligand undergoes facile hydrogenolysis with H2 at ambient conditions to produce ammonia in high yield. Kinetic and quantum chemical examinations of this reaction suggest cooperative behaviour of a phosphorus-nitrogen-phosphorus pincer ligand in rate-determining heterolytic hydrogen splitting.

  11. Glutamate receptor ligands

    DEFF Research Database (Denmark)

    Guldbrandt, Mette; Johansen, Tommy N; Frydenvang, Karla Andrea

    2002-01-01

    Homologation and substitution on the carbon backbone of (S)-glutamic acid [(S)-Glu, 1], as well as absolute stereochemistry, are structural parameters of key importance for the pharmacological profile of (S)-Glu receptor ligands. We describe a series of methyl-substituted 2-aminoadipic acid (AA...

  12. High Br- Content CsPb(Cl yBr1- y)3 Perovskite Nanocrystals with Strong Mn2+ Emission through Diverse Cation/Anion Exchange Engineering.

    Science.gov (United States)

    Li, Fei; Xia, Zhiguo; Pan, Caofeng; Gong, Yue; Gu, Lin; Liu, Quanlin; Zhang, Jin Z

    2018-04-11

    The unification of tunable band edge (BE) emission and strong Mn 2+ doping luminescence in all-inorganic cesium lead halide perovskite nanocrystals (NCs) CsPbX 3 (X = Cl and Br) is of fundamental importance in fine tuning their optical properties. Herein, we demonstrate that benefiting from the differentiation of the cation/anion exchange rate, ZnBr 2 and preformed CsPb 1- x Cl 3 : xMn 2+ NCs can be used to obtain high Br - content Cs(Pb 1- x- z Zn z )(Cl y Br 1- y ) 3 : xMn 2+ perovskite NCs with strong Mn 2+ emission, and the Mn 2+ substitution ratio can reach about 22%. More specifically, the fast anion exchange could be realized by the soluble halide precursors, leading to anion exchange within a few seconds as observed from the strong BE emission evolution, whereas the cation exchange instead generally required at least a few hours; moreover, their exchange mechanism and dynamics process have been evaluated. The Mn 2+ emission intensity could be further varied by controlling the replacement of Mn 2+ by Zn 2+ with prolonged ion exchange reaction time. White light emission of the doped perovskite NCs via this cation/anion synergistic exchange strategy has been realized, which was also successfully demonstrated in a prototype white light-emitting diode (LED) device based on a commercially available 365 nm LED chip.

  13. Efficient preparation of {sup 99m}Tc(III) '4+1' mixed-ligand complexes for peptide labeling with high specific activity

    Energy Technology Data Exchange (ETDEWEB)

    Kunstler, Jens-Uwe [Biotectid GmbH, Deutscher Platz 5c, 04103 Leipzig (Germany); Seidel, Gesine [Institute of Radiopharmacy, Forschungszentrum Dresden-Rossendorf, P.O. Box 510 119, 01314 Dresden (Germany); Pietzsch, Hans-Jurgen, E-mail: h.j.pietzsch@fzd.d [Institute of Radiopharmacy, Forschungszentrum Dresden-Rossendorf, P.O. Box 510 119, 01314 Dresden (Germany)

    2010-09-15

    An improved labeling procedure for peptides attached to organometallic {sup 99m}Tc(III) '4+1' mixed-ligand complexes in which the radiometal is coordinated by a tripodal tetradentate chelator 2,2',2''-nitrilotriethanethiol (NS{sub 3}) and a monodentate isocyanide ligand is presented. The labeling procedure was evaluated by the synthesis of [{sup 99m}Tc(NS{sub 3})(L2-RGD)]. The containing radiopharmaceutically interesting RGD-peptide cyclo[Arg-Gly-Asp-D-Tyr-Lys] was modified with 4-isocyanobutanoic acid (L2) as linker conjugated to N{sup 6}-Lys to get the monodentate ligand L2-RGD. The structural identity of the {sup 99m}Tc-conjugate was confirmed by comparison to a Re reference compound. The Tc- and Re-conjugates had matching retention times under identical HPLC conditions. The {sup 99m}Tc-labeling was performed in a novel one-step procedure using the eluate of a {sup 99}Mo/{sup 99m}Tc generator, NS{sub 3}, the isocyanide modified peptide, SnCl{sub 2}, Na{sub 2}EDTA, mannitol and ascorbic acid in the reaction mixture. Using optimized reagents it is possible to label 50 nmol peptide with {sup 99m}Tc within 60 min at room temperature with a radiochemical yield higher than 95% and a specific activity of {approx}20 GBq/{mu}mol.

  14. The thermodynamic principles of ligand binding in chromatography and biology

    DEFF Research Database (Denmark)

    Mollerup, Jørgen

    2007-01-01

    the general thermodynamic principles of ligand binding. Models of the multi-component adsorption in ion-exchange and hydrophobic chromatography, HIC and RPLC, are developed. The parameters in the models have a well-defined physical significance. The models are compared to the Langmuir model...

  15. Impedance characterization of high temperature proton exchange membrane fuel cell stack under the influence of carbon monoxide and methanol vapor

    DEFF Research Database (Denmark)

    Jeppesen, Christian; Polverino, Pierpaolo; Andreasen, Søren Juhl

    2017-01-01

    This work presents a comprehensive mapping of electrochemical impedance measurements under the influence of CO and methanol vapor contamination of the anode gas in a high temperature proton exchange membrane fuel cell, at varying load current. Electrical equivalent circuit model parameters based...... effects are similar for all the test cases, namely, CO alone, methanol alone and a mix of the two, suggesting that effects of methanol may include oxidation into CO on the catalyst layer....... on experimental evaluation of electrochemical impedance spectroscopy measurements were used to quantify the changes caused by different contamination levels. The changes are generally in good agreement with what is found in the literature. It is shown that an increased level of CO contamination resulted...

  16. Effects of Novel Fin Shape of High Temperature Heat Exchanger on 1 kW Class Stirling Engine

    Energy Technology Data Exchange (ETDEWEB)

    Ahn, Joon; Kim, Seok Yeon [Kookmin Univ., Seoul (Korea, Republic of)

    2017-08-15

    In this research, numerical analysis was carried out on novel and existing fins, adjusted in terms of factors such as length, spacing, and angle, of a high-temperature heat exchanger for a 1 kW class Stirling engine, designed as a prime mover for a domestic cogeneration system. The performance improvement as a result of shape optimization was confirmed with numerical analysis by including the air preheater, which was not considered during optimization. However, a negative heat flux was observed in the cylinder head portion. This phenomenon was clarified by analyzing the exhaust gas and wall surface temperature of the combustion chamber. Furthermore, assuming an ideal cycle, the effects of heat transfer enhancement on the thermodynamic cycle and system performance were predicted.

  17. Sister chromatid exchanges (SCEs) in lymphocytes of inhabitants in high background radiation area

    International Nuclear Information System (INIS)

    Li Jinsheng; Zheng Qiaoling

    1985-01-01

    Blood samples were taken from 126 students of 15-16 years old, living in the high background radiation area, and from 124 controls of the same age range, living in the normal background radiation area. All students were interviewed for evaluation of their health status. Whole blood cultures were done with RPMI 1640 medium supplemented with 20% fetal calf serum and antibiotics, The culture were incubated for 54-56 h in the presence of BrdU (10 μg/ml). Metaphases were stained for SCE using a modified techniqu of perry and Wolff. From each person 20 second division metaphases were analysed for SCEs. The average frequencies of SCEs observed in the high background group and the control group are presented. More SCEs were observed in the high background group than in the control with a statistically signigicant difference. In regard to the sex factor, it was found that the SCE frequencies in both sexes of the high background group were slightly higher than those in the control group. These findings suggest that continuous low-level irradiation by the high background radiation may induce increased frequency of SCEs

  18. Progress in understanding of land surface/atmosphere exchanges at high latitudes

    DEFF Research Database (Denmark)

    Harding, R.J.; Gryning, Sven-Erik; Halldin, S.

    2001-01-01

    This paper summarises some of the key results from two European field programmes, WINTEX and LAPP, undertaken in the Boreal/Arctic regions in 1996-98. Both programmes have illustrated the very important role that snow plays within these areas, not only in the determination of energy, water...... and carbon fluxes in the winter, but also in controlling the length of the summer active season, and hence the overall carbon budget. These studies make a considerable advance in our knowledge of the fluxes from snow-covered landscape and the interactions between snow and vegetation. Also some of the first...... desert in the high arctic. The overall annual budgets are everywhere limited by the very short active season in these regions. The heat flux over a high latitude boreal forest during late winter was found to be high. At low solar angles the forest shades most of the snow surface, therefore an important...

  19. High-Temperature Structural Analysis of a Small-Scale Prototype of a Process Heat Exchanger (IV) - Macroscopic High-Temperature Elastic-Plastic Analysis -

    International Nuclear Information System (INIS)

    Song, Kee Nam; Hong, Sung Deok; Park, Hong Yoon

    2011-01-01

    A PHE (Process Heat Exchanger) is a key component required to transfer heat energy of 950 .deg. C generated in a VHTR (Very High Temperature Reactor) to a chemical reaction that yields a large quantity of hydrogen. A small-scale PHE prototype made of Hastelloy-X was scheduled for testing in a small-scale gas loop at the Korea Atomic Energy Research Institute. In this study, as a part of the evaluation of the high-temperature structural integrity of the PHE prototype, high-temperature structural analysis modeling, and macroscopic thermal and elastic-plastic structural analysis of the PHE prototype were carried out under the gas-loop test conditions as a preliminary qwer123$ study before carrying out the performance test in the gas loop. The results obtained in this study will be used to design the performance test setup for the modified PHE prototype

  20. Distribution and air-sea exchange of current-use pesticides (CUPs) from East Asia to the high Arctic Ocean.

    Science.gov (United States)

    Zhong, Guangcai; Xie, Zhiyong; Cai, Minghong; Möller, Axel; Sturm, Renate; Tang, Jianhui; Zhang, Gan; He, Jianfeng; Ebinghaus, Ralf

    2012-01-03

    Surface seawater and marine boundary layer air samples were collected on the ice-breaker R/V Xuelong (Snow Dragon) from the East China Sea to the high Arctic (33.23-84.5° N) in July to September 2010 and have been analyzed for six current-use pesticides (CUPs): trifluralin, endosulfan, chlorothalonil, chlorpyrifos, dacthal, and dicofol. In all oceanic air samples, the six CUPs were detected, showing highest level (>100 pg/m(3)) in the Sea of Japan. Gaseous CUPs basically decreased from East Asia (between 36.6 and 45.1° N) toward Bering and Chukchi Seas. The dissolved CUPs in ocean water ranged widely from air. Trifluralin in seawater was relatively high in the Sea of Japan (35.2° N) and evenly distributed between 36.9 and 72.5° N, but it remained below the detection limit at the highest northern latitudes in Chukchi Sea. In contrast with other CUPs, concentrations of chlorothalonil and dacthal were more abundant in Chukchi Sea and in East Asia. The air-sea gas exchange of CUPs was generally dominated by net deposition. Latitudinal trends of fugacity ratios of α-endosulfan, chlorothalonil, and dacthal showed stronger deposition of these compounds in East Asia than in Chukchi Sea, while trifluralin showed stronger deposition in Chukchi Sea (-455 ± 245 pg/m(2)/day) than in the North Pacific (-241 ± 158 pg/m(2)/day). Air-sea gas exchange of chlorpyrifos varied from net volatilizaiton in East Asia (<40° N) to equilibrium or net deposition in the North Pacific and the Arctic.

  1. Quantification of the Pyrrolizidine Alkaloid Jacobine in Crassocephalum crepidioides by Cation Exchange High-Performance Liquid Chromatography.

    Science.gov (United States)

    Rozhon, Wilfried; Kammermeier, Lukas; Schramm, Sebastian; Towfique, Nayeem; Adebimpe Adedeji, N; Adesola Ajayi, S; Poppenberger, Brigitte

    2018-01-01

    Pyrrolizidine alkaloids (PAs) are secondary plant metabolites with considerable hepatoxic, tumorigenic and genotoxic potential. For separation, reversed phase chromatography is commonly used because of its excellent compatibility with detection by mass spectrometry. However, reversed phase chromatography has a low selectivity for PAs. The objective of this work was to investigate the suitability of cation exchange chromatography for separation of PAs and to develop a rapid method for quantification of jacobine in Crassocephalum crepidioides that is suitable for analysis of huge sample numbers as required for mutant screening procedures. We demonstrate that cation exchange chromatography offers excellent selectivity for PAs allowing their separation from most other plant metabolites. Due to the high selectivity, plant extracts can be directly analysed after simple sample preparation. Detection with UV at 200 nm instead of mass spectrometry can be applied, which makes the method very simple and cost-effective. The recovery rate of the method exceeded 95%, the intra-day and inter-day standard deviations were below 7% and the limit of detection and quantification were 1 mg/kg and 3 mg/kg, respectively. The developed method is sufficiently sensitive for reproducible detection of jacobine in C. crepidioides. Simple sample preparation and rapid separation allows for quantification of jacobine in plant material in a high-throughput manner. Thus, the method is suitable for genetic screenings and may be applicable for other plant species, for instance Jacobaea maritima. In addition, our results show that C. crepidioides cannot be considered safe for human consumption. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

  2. Room-temperature synthesis of pure perovskite-related Cs4PbBr6 nanocrystals and their ligand-mediated evolution into highly luminescent CsPbBr3 nanosheets

    Science.gov (United States)

    Yang, Liu; Li, Dongmei; Wang, Cong; Yao, Wei; Wang, Hao; Huang, Kaixiang

    2017-07-01

    Currently, all-inorganic cesium lead-halide perovskite nanocrystals have attracted enormous attentions owing to their excellent optical performances. While great efforts have been devoted to CsPbBr3 nanocrystals, the perovskite-related Cs4PbBr6 nanocrystals, which were newly reported, still remained poorly understood. Here, we reported a novel room-temperature reaction strategy to synthesize pure perovskite-related Cs4PbBr6 nanocrystals. Size of the products could be adjusted through altering the amount of ligands, simply. A mixture of two good solvents with different polarity was innovatively used as precursor solvent, being one key to the high-yield Cs4PbBr6 nanocrystals synthesis. Other two keys were Cs+ precursor concentration and surface ligands. Ingenious experiments were designed to reveal the underlying reaction mechanism. No excitonic emission was observed from the prepared Cs4PbBr6 nanocrystals in our work. We considered the green emission which was observed in other reports originated from the avoidless transformation of Cs4PbBr6 into CsPbBr3 nanocrystals. Indeed, the new-prepared Cs4PbBr6 nanocrystals could transform into CsPbBr3 nanosheets with surface ligands mediated. The new-transformed two-dimensional CsPbBr3 nanosheets could evolve into large-size nanosheets. The influences of surface ligand density on the fluorescent intensity and stability of transformed CsPbBr3 nanosheets were also explained. Notably, the photoluminescence quantum yield of the as-transformed CsPbBr3 nanosheets could reach as high as 61.6% in the form of thin film. The fast large-scale synthesis of Cs4PbBr6 nanocrystals and their ligand-mediated transformation into high-fluorescent CsPbBr3 nanosheets will be beneficial to the future optoelectronic applications. Our work provides new approaches to understand the structural evolution and light-emitting principle of perovskite nanocrystals. [Figure not available: see fulltext.

  3. Syntheses, X-ray structures, solid state high-field electron paramagnetic resonance, and density-functional theory investigations on chloro and aqua Mn(II) mononuclear complexes with amino-pyridine pentadentate ligands.

    Science.gov (United States)

    Hureau, Christelle; Groni, Sihem; Guillot, Régis; Blondin, Geneviève; Duboc, Carole; Anxolabéhère-Mallart, Elodie

    2008-10-20

    The two pentadentate amino-pyridine ligands L5(2) and L5(3) (L5(2) and L5(3) stand for the N-methyl-N,N',N'-tris(2-pyridylmethyl)ethane-1,2-diamine and the N-methyl-N,N',N'-tris(2-pyridylmethyl)propane-1,3-diamine, respectively) were used to synthesize four mononuclear Mn(II) complexes, namely [(L5(2))MnCl](PF6) (1(PF6)), [(L5(3))MnCl](PF6) (2(PF6)), [(L5(2))Mn(OH2)](BPh4)2 (3(BPh4)2), and [(L5(3))Mn(OH2)](BPh4)2 (4(BPh4)2). The X-ray diffraction studies revealed different configurations for the ligand L5(n) (n = 2, 3) depending on the sixth exogenous ligand and/or the counterion. Solid state high-field electron paramagnetic resonance spectra were recorded on complexes 1-4 as on previously described mononuclear Mn(II) systems with tetra- or hexadentate amino-pyridine ligands. Positive and negative axial zero-field splitting (ZFS) parameters D were determined whose absolute values ranged from 0.090 to 0.180 cm(-1). Density-functional theory calculations were performed unraveling that, in contrast with chloro systems, the spin-spin and spin-orbit coupling contributions to the D-parameter are comparable for mixed N,O-coordination sphere complexes.

  4. New polymer-supported ion-complexing agents: Design, preparation and metal ion affinities of immobilized ligands

    International Nuclear Information System (INIS)

    Alexandratos, Spiro D.

    2007-01-01

    Polymer-supported reagents are comprised of crosslinked polymer networks that have been modified with ligands capable of selective metal ion complexation. Applications of these polymers are in environmental remediation, ion chromatography, sensor technology, and hydrometallurgy. Bifunctional polymers with diphosphonate/sulfonate ligands have a high selectivity for actinide ions. The distribution coefficient for the uranyl ion from 1 M nitric acid is 70,000, compared to 900 for the monophosphonate/sulfonate polymer and 200 for the sulfonic acid ion-exchange resin. A bifunctional trihexyl/triethylammonium polymer has a high affinity and selectivity for pertechnetate and perchlorate anions from groundwater. In one example, its distribution coefficient for perchlorate ions in the presence of competing anions is 3,300,000, compared to 203,180 for a commercially available anion-exchange resin. Polystyrene modified with N-methyl-D-glucamine ligands is capable of selectively complexing arsenate from groundwater. It complexes 99% of the arsenate present in a solution of 100 mg/L arsenate with 560 mg/L sulfate ions. Its selectivity is retained even in the presence of 400 mg/L phosphate. There is no affinity for arsenate above pH 9, allowing for the polymer to be regenerated with moderate alkali solution. In studies aimed at developing a Hg(II)-selective resin, simple amine resins were found to have a high Hg(II) affinity and that affinity is dependent upon the solution pH and the counterion

  5. Strong Ligand-Protein Interactions Derived from Diffuse Ligand Interactions with Loose Binding Sites.

    Science.gov (United States)

    Marsh, Lorraine

    2015-01-01

    Many systems in biology rely on binding of ligands to target proteins in a single high-affinity conformation with a favorable ΔG. Alternatively, interactions of ligands with protein regions that allow diffuse binding, distributed over multiple sites and conformations, can exhibit favorable ΔG because of their higher entropy. Diffuse binding may be biologically important for multidrug transporters and carrier proteins. A fine-grained computational method for numerical integration of total binding ΔG arising from diffuse regional interaction of a ligand in multiple conformations using a Markov Chain Monte Carlo (MCMC) approach is presented. This method yields a metric that quantifies the influence on overall ligand affinity of ligand binding to multiple, distinct sites within a protein binding region. This metric is essentially a measure of dispersion in equilibrium ligand binding and depends on both the number of potential sites of interaction and the distribution of their individual predicted affinities. Analysis of test cases indicates that, for some ligand/protein pairs involving transporters and carrier proteins, diffuse binding contributes greatly to total affinity, whereas in other cases the influence is modest. This approach may be useful for studying situations where "nonspecific" interactions contribute to biological function.

  6. Enhancing the Performance of CdSe/CdS Dot-in-Rod Light-Emitting Diodes via Surface Ligand Modification.

    Science.gov (United States)

    Rastogi, Prachi; Palazon, Francisco; Prato, Mirko; Di Stasio, Francesco; Krahne, Roman

    2018-02-14

    The surface ligands on colloidal nanocrystals (NCs) play an important role in the performance of NC-based optoelectronic devices such as photovoltaic cells, photodetectors, and light-emitting diodes (LEDs). On one hand, the NC emission depends critically on the passivation of the surface to minimize trap states that can provide nonradiative recombination channels. On the other hand, the electrical properties of NC films are dominated by the ligands that constitute the barriers for charge transport from one NC to its neighbor. Therefore, surface modifications via ligand exchange have been employed to improve the conductance of NC films. However, in LEDs, such surface modifications are more critical because of their possible detrimental effects on the emission properties. In this work, we study the role of surface ligand modifications on the optical and electrical properties of CdSe/CdS dot-in-rods (DiRs) in films and investigate their performance in all-solution-processed LEDs. The DiR films maintain high photoluminescence quantum yield, around 40-50%, and their electroluminescence in the LED preserves the excellent color purity of the photoluminescence. In the LEDs, the ligand exchange boosted the luminance, reaching a fourfold increase from 2200 cd/m 2 for native surfactants to 8500 cd/m 2 for the exchanged aminoethanethiol (AET) ligands. Moreover, the efficiency roll-off, operational stability, and shelf life are significantly improved, and the external quantum efficiency is modestly increased from 5.1 to 5.4%. We relate these improvements to the increased conductivity of the emissive layer and to the better charge balance of the electrically injected carriers. In this respect, we performed ultraviolet photoelectron spectroscopy (UPS) to obtain a deeper insight into the band alignment of the LED structure. The UPS data confirm similar flat-band offsets of the emitting layer to the electron- and hole-transport layers in the case of AET ligands, which translates to

  7. Porous polybenzimidazole membranes doped with phosphoric acid: Preparation and application in high-temperature proton-exchange-membrane fuel cells

    International Nuclear Information System (INIS)

    Li, Jin; Li, Xiaojin; Yu, Shuchun; Hao, Jinkai; Lu, Wangting; Shao, Zhigang; Yi, Baolian

    2014-01-01

    Highlights: • Porous polybenzimidazole membrane was prepared with glucose as porogen. • Phosphoric acid content was as high as 15.7 mol H 3 PO 4 per PBI repeat unit. • 200 h Constant current density test was carried out at 150 °C. • Degradation was due to the gap between membrane and catalyst layer. - Abstract: In this paper, the preparation and characterization of porous polybenzimidazole membranes doped with phosphoric acid were reported. For the preparation of porous polybenzimidazole membranes, glucose and saccharose were selected as porogen and added into PBI resin solution before solvent casting. The prepared porous PBI membranes had high proton conductivity and high content of acid doping at room temperature with 15.7 mol H 3 PO 4 per PBI repeat unit, much higher than pure PBI membrane at the same condition. Further, the performance and stability of the porous PBI membrane in high-temperature proton-exchange-membrane fuel cells was tested. It was found that the cell performance remained stable during 200 h stability test under a constant current discharge of 0.5 A cm −2 except for the last fifty hours. The decay in the last fifty hours was ascribed to the delamination between the catalyst layer and membrane increasing the charge-transfer resistance

  8. Field test of radioactive high efficiency filter and filter exchange techniques of fuel cycle examination facility

    International Nuclear Information System (INIS)

    Hwang, Yong Hwa; Lee, Hyung Kwon; Chun, Young Bum; Park, Dae Gyu; Ahn, Sang Bok; Chu, Yong Sun; Kim, Eun Ka.

    1997-12-01

    The development of high efficiency filter was started to protect human beings from the contamination of radioactive particles, toxic gases and bacillus, and its gradual performance increment led to the fabrication of Ultra Low Penetration Air Filter (ULPA) today. The application field of ULPA has been spread not only to the air conditioning of nuclear power facilities, semiconductor industries, life science, optics, medical care and general facilities but also to the core of ultra-precision facilities. Periodic performance test on the filters is essential to extend its life-time through effective maintenance. Especially, the bank test on HEPA filter of nuclear facilities handling radioactive materials is required for environmental safety. Nowadays, the bank test technology has been reached to the utilization of a minimized portable detecting instruments and the evaluation techniques can provide high confidence in the area of particle distribution and leakage test efficiency. (author). 16 refs., 13 tabs., 14 figs

  9. Non-linear and non-symmetric exchange-rate adjustment: new evidence from medium and high inflation countries

    OpenAIRE

    Arghyrou, MG; Boinet, V; Martin, C

    2003-01-01

    This paper analyses a model of non-linear exchange rate adjustment that extends the literature by allowing asymmetric responses to over- and under-valuations. Applying the model to Greece and Turkey, we find that adjustment is asymmetric and that exchange rates depend on the sign as well as the magnitude of deviations, being more responsive to over-valuations than under-valuations. Our findings support and extend the argument that non-linear models of exchange rate adjustment c...

  10. The πNN coupling from high precision np charge exchange at 162 MeV

    International Nuclear Information System (INIS)

    Nilsson, J.; Blomgren, J.; Conde, H.; Elmgren, K.; Olsson, N.; Ericson, T.E.O.; Uppsala Univ.; Jonsson, O.; Nilsson, L.; Loiseau, B.; Ringbom, A.

    1995-02-01

    Differential cross sections for unpolarized neutrons of 162 MeV have been measured to high precision with particular attention to the absolute normalisation. These data can be extrapolated precisely and model-independently to the pion pole and give a πNN coupling constant g 2 =14.6±0.3 or f 2 =0.0808±0.0017. This is higher than recently suggested values. (author) 24 refs.; 3 figs.; 1 tab

  11. Characteristics of summer-time energy exchange in a high Arctic tundra heath 2000–2010

    Directory of Open Access Journals (Sweden)

    Magnus Lund

    2014-07-01

    Full Text Available Global warming will bring about changes in surface energy balance of Arctic ecosystems, which will have implications for ecosystem structure and functioning, as well as for climate system feedback mechanisms. In this study, we present a unique, long-term (2000–2010 record of summer-time energy balance components (net radiation, R n; sensible heat flux, H; latent heat flux, LE; and soil heat flux, G from a high Arctic tundra heath in Zackenberg, Northeast Greenland. This area has been subjected to strong summer-time warming with increasing active layer depths (ALD during the last decades. We observe high energy partitioning into H, low partitioning into LE and high Bowen ratio (β=H/LE compared with other Arctic sites, associated with local climatic conditions dominated by onshore winds, slender vegetation with low transpiration activity and relatively dry soils. Surface saturation vapour pressure deficit (D s was found to be an important variable controlling within-year surface energy partitioning. Throughout the study period, we observe increasing H/R n and LE/R n and decreasing G/R n and β, related to increasing ALD and decreasing soil wetness. Thus, changes in summer-time surface energy balance partitioning in Arctic ecosystems may be of importance for the climate system.

  12. Phosphoric acid distribution in the membrane electrode assembly of high temperature proton exchange membrane fuel cells

    International Nuclear Information System (INIS)

    Kwon, Kyungjung; Park, Jung Ock; Yoo, Duck Young; Yi, Jung S.

    2009-01-01

    The ionomer content in electrode is one of the most important parameters for the high performance of fuel cells. The high temperature PEMFC based on phosphoric acid (PA)-doped polymer membrane with unhumidified reactant gases has a difficulty in controlling the liquid state PA ionomer content in electrode. To evaluate the PA content in electrode, the three techniques of cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and acid-base titration (ABT) are carried out in situ or ex situ. The properties of membrane electrode assembly (MEA) such as electrochemical surface area (ESA), ohmic resistance, charge transfer resistance, double layer capacitance and the amount of PA in MEA components (anode, cathode and membrane) are extracted by each technique. Ex situ CV with the usage of dry gases has a limitation in assessing the reliable ESA of unhumidified PEMFC. While in situ EIS presents some informative values of resistance and capacitance for understanding the PA distribution in MEA, its sensitivity to the PA content in MEA components needs to be higher for detecting a subtle change in PA distribution. Ex situ ABT supplies a clear PA distribution in MEA at room temperature but does not seem to reflect the operating state well at high temperatures. However, it can be used as a detection tool for the loss of the initial acid content in membrane during a long-term MEA durability study.

  13. Phosphoric acid distribution in the membrane electrode assembly of high temperature proton exchange membrane fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Kwon, Kyungjung [Fuel Cell Group, Energy Lab, SAIT, Samsung Electronics Co., Ltd., San 14-1, Nongseo-dong, Giheung-gu, Yongin-si, Gyeonggi-do, 446-712 (Korea, Republic of)], E-mail: kfromberk@gmail.com; Park, Jung Ock; Yoo, Duck Young; Yi, Jung S. [Fuel Cell Group, Energy Lab, SAIT, Samsung Electronics Co., Ltd., San 14-1, Nongseo-dong, Giheung-gu, Yongin-si, Gyeonggi-do, 446-712 (Korea, Republic of)

    2009-11-01

    The ionomer content in electrode is one of the most important parameters for the high performance of fuel cells. The high temperature PEMFC based on phosphoric acid (PA)-doped polymer membrane with unhumidified reactant gases has a difficulty in controlling the liquid state PA ionomer content in electrode. To evaluate the PA content in electrode, the three techniques of cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and acid-base titration (ABT) are carried out in situ or ex situ. The properties of membrane electrode assembly (MEA) such as electrochemical surface area (ESA), ohmic resistance, charge transfer resistance, double layer capacitance and the amount of PA in MEA components (anode, cathode and membrane) are extracted by each technique. Ex situ CV with the usage of dry gases has a limitation in assessing the reliable ESA of unhumidified PEMFC. While in situ EIS presents some informative values of resistance and capacitance for understanding the PA distribution in MEA, its sensitivity to the PA content in MEA components needs to be higher for detecting a subtle change in PA distribution. Ex situ ABT supplies a clear PA distribution in MEA at room temperature but does not seem to reflect the operating state well at high temperatures. However, it can be used as a detection tool for the loss of the initial acid content in membrane during a long-term MEA durability study.

  14. Neutron spectroscopic investigations on crystalline-electric-field and exchange interactions on high-Tc superconductors

    International Nuclear Information System (INIS)

    Staub, U.

    1993-05-01

    It is well known that in the high temperature superconductors of the type RBa 2 Cu 3 O x (123), with R=Y and most of the rare earths, superconductivity is believed to be controlled by the density of mobile charges in the copper oxide (CuO 2 ) planes. In particular, the charge transfer process from the chains to the planes seems to play an important role. In the 123, RBa 2 Cu 4 O 8 (1248) and the Bi 2 Sr 2 Ca 1-x Ho x Cu 2 O 8+δ (Bi2212) systems, the R ions are sandwiched between the CuO 2 planes, thus the crystalline electric field (CEF) interaction at the R sites constitutes an ideal probe of the local symmetry and the charge distribution of the superconducting planes. The (2J+1)-fold degeneracy of the ground-state J-multiplet of the rare earth ions will be partially lifted under the action of the CEF potential. By means of inelastic neutron scattering experiments it is possible to observe directly the transitions between the CEF states. Therefrom we obtain useful information on both the structure and the charge distribution in the vicinity of the R ion. In order to quantify the charge transfer process from the chains to the planes, we performed a detailed analysis of the CEF of Ho 3+ in the 123, 1248 and Bi2212 systems. In addition, we present some experiments on a Cl doped 123 sample and some external pressure experiments on the 123 system. In nearly all high-T c compounds RBa 2 Cu 3 O 7-δ superconductivity and magnetic ordering of the R ion sublattice coexist at low temperatures. In order to understand the interplay of magnetism and superconductivity in these systems, information on both the electronic ground state of the R 3+ ions and the coupling mechanisms between the R 3+ ions is highly desirable. (author) figs., tabs., 73 refs

  15. High temperature proton exchange membranes based on polybenzimidazoles for fuel cells

    DEFF Research Database (Denmark)

    Li, Qingfeng; Jensen, Jens Oluf; Savinell, Robert F

    2009-01-01

    -term durability with a degradation rate of 5Vh−1 has been achieved under continuous operation with hydrogen and air at 150–160 ◦C. With load or thermal cycling, a performance loss of 300V per cycle or 40Vh−1 per operating hour was observed. Further improvement should be done by, e.g. optimizing the thermal...... in recent years motivated extensive research activities with great progress. This treatise is devoted to updating the development, covering polymer synthesis, membrane casting, physicochemical characterizations and fuel cell technologies. To optimize the membrane properties, high molecular weight polymers...

  16. The 3rd CARISMA international conference on medium and high temperature proton exchange membrane fuel cells: Three approaches to better platinum catalysts at biannual conference

    DEFF Research Database (Denmark)

    Jensen, Jens Oluf; Cleemann, Lars Nilausen; Li, Qingfeng

    2013-01-01

    exchange membrane fuel cells (PEMFCs) to be operated at intermediate and high temperatures. The conference series was initiated by the European CARISMA Coordination Action for Research on Intermediate and High Temperature Specialized Membrane Electrode Assemblies. The 2012 event in Copenhagen had around...

  17. I. Cis-dichlorodiammineplatinum(II). Aquation equilibria and isotopic exchange of chloride ligands with free chloride and tetrachloroplatinate(II). II. The Szilard--Chalmers effect in solid-state systems containing the octa-μ3-chloro-octahedro-hexamolybdenum(II) cluster

    International Nuclear Information System (INIS)

    Lee, K.W.

    1976-06-01

    A titration technique was utilized to determine the equilibrium quotients for the first and second aquation steps of cis-Pt(NH 3 ) 2 Cl 2 . At 25.0 0 C and an ionic strength of 0.318 M the first and second aquation equilibrium constants are: K 1 = 3.63 +- 0.22 x 10 -3 M, ΔH 1 0 = 3.4 kcal and K 2 = 1.11 +- 0.14 x 10 -4 M, ΔH 2 0 = 10 kcal. In the ternary system, cis-Pt(NH 3 ) 2 Cl 2 :PtCl 4 2- :Cl - , the kinetics of isotopic exchange of chlorine was investigated. In addition to the expected route of exchange via aquation, a direct exchange of chlorine ligands between cis-Pt(NH 3 ) 2 Cl 2 and PtCl 4 2- occurred which is described by the rate expression. Separation procedures were devised for partial resolution of component yields resulting from dissolving a neutron-irradiated sample of (H 3 O) 2 [(Mo 6 Cl 8 )Cl 6 ] . 6H 2 O in 1.5 N HCl. A recrystallization procedure was formulated to determine the retention of activity in the parent compound of molybdenum(II) chloride clusters after neutron irradiation. The retention found in an aqueous 1.5 N HCl solution containing 1 percent (H 3 O) 2 [(Mo 6 Cl 8 )Cl 6 ] . 6H 2 O is 0.64 percent. For a solid sample of (H 3 O) 2 [(Mo 6 Cl 8 )Cl 6 ] . 6H 2 O aged 24 hours in Dry Ice after neutron irradiation, a retention of 7.0 percent was observed. Under the same conditions, a sample of (Mo 6 Cl 8 )Cl 4 with 0.8 percent and 2.7 percent water had retentions of 25.0 percent and 11.1 percent, respectively. Effects of thermal annealing and gamma ray treatment on solid samples of [(Mo 6 Cl 8 )Cl 4 ] . 2H 2 O were investigated

  18. A high-efficiency spin-resolved photoemission spectrometer combining time-of-flight spectroscopy with exchange-scattering polarimetry

    Energy Technology Data Exchange (ETDEWEB)

    Jozwiak, Chris M.; Graff, Jeff; Lebedev, Gennadi; Andresen, Nord; Schmid, Andreas; Fedorov, Alexei; El Gabaly, Farid; Wan, Weishi; Lanzara, Alessandra; Hussain, Zahid

    2010-04-13

    We describe a spin-resolved electron spectrometer capable of uniquely efficient and high energy resolution measurements. Spin analysis is obtained through polarimetry based on low-energy exchange scattering from a ferromagnetic thin-film target. This approach can achieve a similar analyzing power (Sherman function) as state-of-the-art Mott scattering polarimeters, but with as much as 100 times improved efficiency due to increased reflectivity. Performance is further enhanced by integrating the polarimeter into a time-of-flight (TOF) based energy analysis scheme with a precise and flexible electrostatic lens system. The parallel acquisition of a range of electron kinetic energies afforded by the TOF approach results in an order of magnitude (or more) increase in efficiency compared to hemispherical analyzers. The lens system additionally features a 90 degrees bandpass filter, which by removing unwanted parts of the photoelectron distribution allows the TOF technique to be performed at low electron drift energy and high energy resolution within a wide range of experimental parameters. The spectrometer is ideally suited for high-resolution spin- and angle-resolved photoemission spectroscopy (spin-ARPES), and initial results are shown. The TOF approach makes the spectrometer especially ideal for time-resolved spin-ARPES experiments.

  19. Highly Luminescent Dinuclear Platinum(II) Complexes Incorporating Bis-Cyclometallating Pyrazine-Based Ligands: A Versatile Approach to Efficient Red Phosphors

    OpenAIRE

    Culham, Stacey; Lanoe, Pierre-Henri; Whittle, Victoria; Durrant, Marcus; Williams, Gareth; Kozhevnikov, Valery

    2013-01-01

    A series of luminescent dinuclear platinum(II) complexes incorporating diphenylpyrazine-based bridging ligands ((LH2)-H-n) has been prepared. Both 2,5-diphenylpyrazine ((LH2)-H-2) and 2,3-diphenylpyrazine ((LH2)-H-3) are able to undergo cyclometalation of the two phenyl rings, with each metal ion binding to the two nitrogen atoms of the central heterocycle, giving, after treatment with the anion of dipivaloyl methane (dpm), complexes of formula \\{Pt(dpm)\\}(2)L-n. These compounds are isomers o...

  20. Radiobiology with DNA ligands

    International Nuclear Information System (INIS)

    Weinreich, R.; Argentini, M.; Guenther, I.; Koziorowski, J.; Larsson, B.; Nievergelt-Egido, M.C.; Salt, C.; Wyer, L.; Dos Santos, D.F.; Hansen, H.J.

    1997-01-01

    The paper deals with the following topics: labelling of DNA ligands and other tumour-affinic compounds with 4.15-d 124 I, radiotoxicity of Hoechst 33258 and 33342 and of iodinated Hoechst 33258 in cell cultures, preparation of 76 Br-, 123 I-, and 221 At-labelled 5-halo-2'-deoxyuridine, chemical syntheses of boron derivatives of Hoechst 33258.III., Gadolinium neutron capture therapy