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Sample records for methyl anion affinities

  1. Methyl Cation Affinities of Neutral and Anionic Maingroup-Element Hydrides: Trends Across the Periodic Table and Correlation with Proton Affinities

    NARCIS (Netherlands)

    Mulder, R. Joshua; Guerra, Celia Fonseca; Bickelhaupt, F. Matthias

    2010-01-01

    We have computed the methyl cation affinities in the gas phase of archetypal anionic and neutral bases across the periodic table using ZORA-relativistic density functional theory (DFT) at BP86/QZ4P//BP86/TZ2P. The main purpose of this work is to provide the methyl cation affinities (and

  2. Methyl cation affinities of neutral and anionic maingroup-element hydrides: trends across the periodic table and correlation with proton affinities.

    Science.gov (United States)

    Mulder, R Joshua; Guerra, Célia Fonseca; Bickelhaupt, F Matthias

    2010-07-22

    We have computed the methyl cation affinities in the gas phase of archetypal anionic and neutral bases across the periodic table using ZORA-relativistic density functional theory (DFT) at BP86/QZ4P//BP86/TZ2P. The main purpose of this work is to provide the methyl cation affinities (and corresponding entropies) at 298 K of all anionic (XH(n-1)(-)) and neutral bases (XH(n)) constituted by maingroup-element hydrides of groups 14-17 and the noble gases (i.e., group 18) along the periods 2-6. The cation affinity of the bases decreases from H(+) to CH(3)(+). To understand this trend, we have carried out quantitative bond energy decomposition analyses (EDA). Quantitative correlations are established between the MCA and PA values.

  3. Supramolecular Affinity Chromatography for Methylation-Targeted Proteomics.

    Science.gov (United States)

    Garnett, Graham A E; Starke, Melissa J; Shaurya, Alok; Li, Janessa; Hof, Fraser

    2016-04-05

    Proteome-wide studies of post-translationally methylated species using mass spectrometry are complicated by high sample diversity, competition for ionization among peptides, and mass redundancies. Antibody-based enrichment has powered methylation proteomics until now, but the reliability, pan-specificity, polyclonal nature, and stability of the available pan-specific antibodies are problematic and do not provide a standard, reliable platform for investigators. We have invented an anionic supramolecular host that can form host-guest complexes selectively with methyllysine-containing peptides and used it to create a methylysine-affinity column. The column resolves peptides on the basis of methylation-a feat impossible with a comparable commercial cation-exchange column. A proteolyzed nuclear extract was separated on the methyl-affinity column prior to standard proteomics analysis. This experiment demonstrates that such chemical methyl-affinity columns are capable of enriching and improving the analysis of methyllysine residues from complex protein mixtures. We discuss the importance of this advance in the context of biomolecule-driven enrichment methods.

  4. Benzonitrile: Electron affinity, excited states, and anion solvation

    Science.gov (United States)

    Dixon, Andrew R.; Khuseynov, Dmitry; Sanov, Andrei

    2015-10-01

    We report a negative-ion photoelectron imaging study of benzonitrile and several of its hydrated, oxygenated, and homo-molecularly solvated cluster anions. The photodetachment from the unsolvated benzonitrile anion to the X ˜ 1 A 1 state of the neutral peaks at 58 ± 5 meV. This value is assigned as the vertical detachment energy (VDE) of the valence anion and the upper bound of adiabatic electron affinity (EA) of benzonitrile. The EA of the lowest excited electronic state of benzonitrile, a ˜ 3 A 1 , is determined as 3.41 ± 0.01 eV, corresponding to a 3.35 eV lower bound for the singlet-triplet splitting. The next excited state, the open-shell singlet A ˜ 1 A 1 , is found about an electron-volt above the triplet, with a VDE of 4.45 ± 0.01 eV. These results are in good agreement with ab initio calculations for neutral benzonitrile and its valence anion but do not preclude the existence of a dipole-bound state of similar energy and geometry. The step-wise and cumulative solvation energies of benzonitrile anions by several types of species were determined, including homo-molecular solvation by benzonitrile, hydration by 1-3 waters, oxygenation by 1-3 oxygen molecules, and mixed solvation by various combinations of O2, H2O, and benzonitrile. The plausible structures of the dimer anion of benzonitrile were examined using density functional theory and compared to the experimental observations. It is predicted that the dimer anion favors a stacked geometry capitalizing on the π-π interactions between the two partially charged benzonitrile moieties.

  5. AT Base Pair Anions vs. (9-methyl-A)(1-methyl-T) Base Pair Anions

    International Nuclear Information System (INIS)

    Radisic, Dunja; Bowen, Kit H.; Dabkowska, Iwona; Storoniak, Piotr; Rak, Janusz; Gutowski, Maciej S.

    2005-01-01

    The anionic base pairs of adenine and thymine, (AT)-, and 9-methyladenine and 1-methylthymine, (MAMT)-, have been investigated both theoretically and experimentally in a complementary, synergistic study. Calculations on (AT)- found that it had undergone a barrier-free proton transfer (BFPT) similar to that seen in other dimer anion systems and that its structural configuration that was neither Watson-Crick (WC) nor Hoogsteen (HS). The vertical detachment energy (VDE) of (AT)- was determined by anion photoelectron spectroscopy and found to be in agreement with the VDE value predicted by theory for the BFPT mechanism. An AT pair in DNA is structurally immobilized into the WC configuration, in part, by being bonded to the sugars of the double helix. This circumstance was mimicked by methylating the sites on both A and T where these sugars would have been tied, viz., 9-methyladenine and 1-methylthymine. Calculations found no BFPT in (MAMT)- and a resulting (MAMT)- configuration that wa s either HS or WC, with the configurations differing in stability by ca. 2 kcal/mol. The photoelectron spectrum of (MAMT)- occurred at a completely different electron binding energy than had (AT)-. Moreover, the VDE value of (MAMT)- was in agreement with that predicted by theory. The configuration of (MAMT)- and its lack of electron-induced proton transfer are inter-related. While there may be other pathways for electron-induced damage, BFPT in the WC/HS configurations of (AT)- is not feasible

  6. AT base pair anions versus (9-methyl-A)(1-methyl-T) base pair anions.

    Science.gov (United States)

    Radisic, Dunja; Bowen, Kit H; Dabkowska, Iwona; Storoniak, Piotr; Rak, Janusz; Gutowski, Maciej

    2005-05-04

    The anionic base pairs of adenine and thymine, (AT)(-), and 9-methyladenine and 1-methylthymine, (MAMT)(-), have been investigated both theoretically and experimentally in a complementary, synergistic study. Calculations on (AT)(-) found that it had undergone a barrier-free proton transfer (BFPT) similar to that seen in other dimer anion systems and that its structural configuration was neither Watson-Crick (WC) nor Hoogsteen (HS). The vertical detachment energy (VDE) of (AT)(-) was determined by anion photoelectron spectroscopy and found to be in agreement with the VDE value predicted by theory for the BFPT mechanism. An AT pair in DNA is structurally immobilized into the WC configuration, in part, by being bonded to the sugars of the double helix. This circumstance was mimicked by methylating the sites on both A and T where these sugars would have been tied, viz., 9-methyladenine and 1-methylthymine. Calculations found no BFPT in (MAMT)(-) and a resulting (MAMT)(-) configuration that was either HS or WC, with the configurations differing in stability by ca. 2 kcal/mol. The photoelectron spectrum of (MAMT)(-) occurred at a completely different electron binding energy than had (AT)(-). Moreover, the VDE value of (MAMT)(-) was in agreement with that predicted by theory. The configuration of (MAMT)(-) and its lack of electron-induced proton transfer are inter-related. While there may be other pathways for electron-induced DNA alterations, BFPT in the WC/HS configurations of (AT)(-) is not feasible.

  7. Structure-affinity relationship in the interactions of human organic anion transporter 1 with caffeine, theophylline, theobromine and their metabolites.

    Science.gov (United States)

    Sugawara, Mitsuru; Mochizuki, Takahiro; Takekuma, Yoh; Miyazaki, Katsumi

    2005-08-15

    It is well known that human organic anion transporter 1 (hOAT1) transports many kinds of drugs, endogenous compounds, and toxins. However, little is known about the structure-affinity relationship. The aim of this study was to elucidate the structure-affinity relationship using a series of structurally related compounds that interact with hOAT1. Inhibitory effects of xanthine- and uric acid-related compounds on the transport of p-aminohippuric acid were examined using CHO-K1 cells stably expressing hOAT1. The order of potency for the inhibitory effects of xanthine-related compounds on PAH uptake was 1-methyl derivative>7-methyl derivative>3-methyl derivative falling dotsxanthine>1,3,7-trimethyl derivative (caffeine). The order of potency of the inhibition was 1,3,7-trimethyluric acid>1,3-dimethyluric acid>1,7-dimethyluric acid>1-methyluric acid>uric acid. A significant correlation between inhibitory potency and lipophilicity of the tested uric acid-related compounds was observed. The main determinant of the affinity of xanthine-related compounds is the position of the methyl group. On the other hand, lipophilicity is the main determinant of the affinity of uric acid-related compounds.

  8. Electron affinities, molecular structures, and thermochemistry of the fluorine, chlorine and bromine substituted methyl radicals

    Science.gov (United States)

    Li, Qian-Shu; Zhao, Jun-Fang; Xie, Yaoming; Schaefer, Henry F., III

    Four independent density functional theory (DFT) methods have been employed to study the structures and electron affinities of the methyl and F-, Cl- and Br-substituted methyl radicals and their anions. The methods used have been carefully calibrated against a comprehensive tabulation of experimental electron affinities (Chemical Reviews, 2002, 102, 231). The first dissociation energies together with the vibrational frequencies of these species are also reported. The basis sets used in this work are of double- ζ plus polarization quality with additional s- and p-type diffuse functions, labelled as DZP++. Previously observed trends in the prediction of bond lengths by the DFT methods are also demonstrated for the F-, Cl- and Br-substituted methyl radicals and their anions. Generally, the Hartree-Fock/DFT hybrid methods predict shorter and more reliable bond lengths than the pure DFT methods. Neutral-anion energy differences reported in this work are the adiabatic electron affinity (EAad), the vertical electron affinity (EAvert), and the vertical detachment energy (VDE). Compared with the available experimental electron affinities, the BHLYP method predicts much lower values, while the other methods predict values (EAad, EAvert, VDE) close to each other and almost within the experimental range. For those systems without reliable experimental measurements, our best adiabatic EAs predicted by BLYP are 0.78 (CHF2), 1.23 (CHFCl), 1.44 (CHFBr), 1.61 (CHClBr), 2.24 (CF2Cl), 2.42 (CF2Br), 2.56 (CFBr2), 2.36 (CCl2Br), 2.46 (CClBr2), and 2.44 eV (CFClBr). The most striking feature of these predictions is that they display an inverse relationship between halogen electronegativity and EA. The DZP++ B3LYP method determines the vibrational frequencies in best agreement with available experimental results for this series, with an average relative error of ~2%. The value of using a variety of DFT methods is observed in that BHLYP does best for geometries, BLYP for electron

  9. Alkali Metal Cation versus Proton and Methyl Cation Affinities: Structure and Bonding Mechanism.

    Science.gov (United States)

    Boughlala, Zakaria; Fonseca Guerra, Célia; Bickelhaupt, F Matthias

    2016-06-01

    We have analyzed the structure and bonding of gas-phase Cl-X and [HCl-X](+) complexes for X(+)= H(+), CH3 (+), Li(+), and Na(+), using relativistic density functional theory (DFT). We wish to establish a quantitative trend in affinities of the anionic and neutral Lewis bases Cl(-) and HCl for the various cations. The Cl-X bond becomes longer and weaker along X(+) = H(+), CH3 (+), Li(+), and Na(+). Our main purpose is to understand the heterolytic bonding mechanism behind the intrinsic (i.e., in the absence of solvent) alkali metal cation affinities (AMCA) and how this compares with and differs from those of the proton affinity (PA) and methyl cation affinity (MCA). Our analyses are based on Kohn-Sham molecular orbital (KS-MO) theory in combination with a quantitative energy decomposition analysis (EDA) that pinpoints the importance of the different features in the bonding mechanism. Orbital overlap appears to play an important role in determining the trend in cation affinities.

  10. Proton Affinities of Anionic Bases:  Trends Across the Periodic Table, Structural Effects, and DFT Validation.

    Science.gov (United States)

    Swart, Marcel; Bickelhaupt, F Matthias

    2006-03-01

    We have carried out an extensive exploration of the gas-phase basicity of archetypal anionic bases across the periodic system using the generalized gradient approximation of density functional theory (DFT) at BP86/QZ4P//BP86/TZ2P. First, we validate DFT as a reliable tool for computing proton affinities and related thermochemical quantities:  BP86/QZ4P//BP86/TZ2P is shown to yield a mean absolute deviation of 1.6 kcal/mol for the proton affinity at 0 K with respect to high-level ab initio benchmark data. The main purpose of this work is to provide the proton affinities (and corresponding entropies) at 298 K of the anionic conjugate bases of all main-group-element hydrides of groups 14-17 and periods 2-6. We have also studied the effect of stepwise methylation of the protophilic center of the second- and third-period bases.

  11. Migratory Insertion of Hydrogen Isocyanide in the Pentacyano(methyl)cobaltate(III) Anion

    DEFF Research Database (Denmark)

    Kofod, Pauli; Harris, Pernille Hanne; Larsen, Sine

    2003-01-01

    The preparation of the pentacyano(iminiumacetyl)cobaltate(III) anion and its N-methyl and N,N-dimethyl derivatives is reported. The iminiumacetyl group is formed by migratory insertion of cis hydrogen isocyanide in the pentacyano(methyl)cobaltate(III) anion. The new compounds have been spectrosco......The preparation of the pentacyano(iminiumacetyl)cobaltate(III) anion and its N-methyl and N,N-dimethyl derivatives is reported. The iminiumacetyl group is formed by migratory insertion of cis hydrogen isocyanide in the pentacyano(methyl)cobaltate(III) anion. The new compounds have been...

  12. Alkali Metal Cation Affinities of Anionic Main Group-Element Hydrides Across the Periodic Table

    NARCIS (Netherlands)

    Boughlala, Zakaria; Fonseca Guerra, Célia; Bickelhaupt, F. Matthias

    2017-01-01

    We have carried out an extensive exploration of gas-phase alkali metal cation affinities (AMCA) of archetypal anionic bases across the periodic system using relativistic density functional theory at ZORA-BP86/QZ4P//ZORA-BP86/TZ2P. AMCA values of all bases were computed for the lithium, sodium,

  13. Alkali Metal Cation Affinities of Anionic Main Group-Element Hydrides Across the Periodic Table.

    Science.gov (United States)

    Boughlala, Zakaria; Fonseca Guerra, Célia; Bickelhaupt, F Matthias

    2017-10-05

    We have carried out an extensive exploration of gas-phase alkali metal cation affinities (AMCA) of archetypal anionic bases across the periodic system using relativistic density functional theory at ZORA-BP86/QZ4P//ZORA-BP86/TZ2P. AMCA values of all bases were computed for the lithium, sodium, potassium, rubidium and cesium cations and compared with the corresponding proton affinities (PA). One purpose of this work is to provide an intrinsically consistent set of values of the 298 K AMCAs of all anionic (XH n-1 - ) constituted by main group-element hydrides of groups 14-17 along the periods 2-6. In particular, we wish to establish the trend in affinity for a cation as the latter varies from proton to, and along, the alkali cations. Our main purpose is to understand these trends in terms of the underlying bonding mechanism using Kohn-Sham molecular orbital theory together with a quantitative bond energy decomposition analyses (EDA). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Rapid anion exchange separation of fermium with mineral acid-methyl alcohol mixed media

    International Nuclear Information System (INIS)

    Usuda, S.; Shinohara, N.; Ichikawa, S.; Suzuki, T.

    1987-01-01

    Anion exchange separation of 250 Fm (30 m) synthesized by the 12 C+ 242 Pu and 16 O+ 238 U reactions was investigated with mineral acid-methyl alcohol mixed media at elevated temperature. Fermium was chromatographically separated from the other transplutonium elements, the target materials and an Al catcher foil by anion exchange with mixtures of nitric acid and methyl alcohol. By use of the mixed media of hydrochloric acid and methyl alcohol, Fm together with Cf was separated from Al, Am, Cm, Pu, U and from major fission products. The separation systems are suitable for rapid separation and immediate alpha-counting source preparation of Fm. (author) 22 refs.; 4 figs

  15. In search for an optimal methodology to calculate the valence electron affinities of temporary anions.

    Science.gov (United States)

    Puiatti, Marcelo; Vera, D Mariano A; Pierini, Adriana B

    2009-10-28

    Recently, we have proposed an approach for finding the valence anion ground state, based on the stabilization exerted by a polar solvent; the methodology used standard DFT methods and relatively inexpensive basis sets and yielded correct electron affinity (EA) values by gradually decreasing the dielectric constant of the medium. In order to address the overall performance of the new methodology, to find the best conditions for stabilizing the valence state and to evaluate its scope and limitations, we gathered a pool of 60 molecules, 25 of them bearing the conventional valence state as the ground anion and 35 for which the lowest anion state found holds the extra electron in a diffuse orbital around the molecule (non valence state). The results obtained by testing this representative set suggest a very good performance for most species having an experimental EA less negative than -3.0 eV; the correlation at the B3LYP/6-311+G(2df,p) level being y = 1.01x + 0.06, with a correlation index of 0.985. As an alternative, the time dependent DFT (TD-DFT) approach was also tested with both B3LYP and PBE0 functionals. The methodology we proposed shows a comparable or better accuracy with respect to TD-DFT, although the TD-DFT approach with the PBE0 functional is suggested as a suitable estimate for species with the most negative EAs (ca.-2.5 to -3.5 eV), for which stabilization strategies can hardly reach the valence state. As an application, a pool of 8 compounds of key biological interest with EAs which remain unknown or unclear were predicted using the new methodology.

  16. Proton affinities in water of maingroup-element Hydrides - Effects of hydration and methyl substitution

    NARCIS (Netherlands)

    Swart, M.; Rosler, E.; Bickelhaupt, F.M.

    2007-01-01

    We have computed the proton affinities in water of archetypal anionic and neutral bases across the periodic table using the generalized gradient approximation (GGA) of density functional theory (DFT) at BP86/QZ4P//BP86/TZ2P. The main purpose of this work is to provide an intrinsically consistent set

  17. Alkali Metal Cation versus Proton and Methyl Cation Affinities: Structure and Bonding Mechanism

    NARCIS (Netherlands)

    Boughlala, Z.; Guerra, C.F.; Bickelhaupt, F.M.

    2016-01-01

    We have analyzed the structure and bonding of gas-phase Cl X and [HCl X](+) complexes for X+ = H+, CH3+, Li+, and Na+, using relativistic density functional theory (DFT). We wish to establish a quantitative trend in affinities of the anionic and neutral Lewis bases Cl- and HCl for the various

  18. Enzymatic methylation of band 3 anion transporter in intact human erythrocytes

    International Nuclear Information System (INIS)

    Lou, L.L.; Clarke, S.

    1987-01-01

    Band 3, the anion transport protein of erythrocyte membranes, is a major methyl-accepting substrate of the intracellular erythrocyte protein carboxyl methyltransferase (S-adenosyl-L-methionine: protein-D-aspartate O-methyltransferase; EC 2.1.1.77). The localization of methylation sites in intact cells by analysis of proteolytic fragments indicated that sites were present in the cytoplasmic N-terminal domain as well as the membranous C-terminal portion of the polypeptide. The amino acid residues that serve as carboxyl methylation sites of the erythrocyte anion transporter were also investigated. 3 H-Methylated band 3 was purified from intact erythrocytes incubated with L-[methyl- 3 H]methionine and from trypsinized and lysed erythrocytes incubated with S-adenosyl-L-[methyl- 3 H]methionine. After proteolytic digestion with carboxypeptidase Y, D-aspartic acid beta-[ 3 H]methyl ester was isolated in low yields (9% and 1%, respectively) from each preparation. The bulk of the radioactivity was recovered as [ 3 H]methanol, and the amino acid residue(s) originally associated with these methyl groups could not be determined. No L-aspartic acid beta-[ 3 H]methyl ester or glutamyl gamma-[ 3 H]methyl ester was detected. The formation of D-aspartic acid beta-[ 3 H]methyl esters in this protein in intact cells resulted from protein carboxyl methyltransferase activity since it was inhibited by adenosine and homocysteine thiolactone, which increases the intracellular concentration of the potent product inhibitor S-adenosylhomocysteine, and cycloleucine, which prevents the formation of the substrate S-adenosyl-L-[methyl- 3 H]methionine

  19. A multiplex microplatform for the detection of multiple DNA methylation events using gold-DNA affinity.

    Science.gov (United States)

    Sina, Abu Ali Ibn; Foster, Matthew Thomas; Korbie, Darren; Carrascosa, Laura G; Shiddiky, Muhammad J A; Gao, Jing; Dey, Shuvashis; Trau, Matt

    2017-10-07

    We report a new multiplexed strategy for the electrochemical detection of regional DNA methylation across multiple regions. Using the sequence dependent affinity of bisulfite treated DNA towards gold surfaces, the method integrates the high sensitivity of a micro-fabricated multiplex device comprising a microarray of gold electrodes, with the powerful multiplexing capability of multiplex-PCR. The synergy of this combination enables the monitoring of the methylation changes across several genomic regions simultaneously from as low as 500 pg μl -1 of DNA with no sequencing requirement.

  20. Alkali Metal Cation versus Proton and Methyl Cation Affinities: Structure and Bonding Mechanism

    OpenAIRE

    Boughlala, Z.; Guerra, C.F.; Bickelhaupt, F.M.

    2016-01-01

    Abstract We have analyzed the structure and bonding of gas?phase Cl?X and [HCl?X]+ complexes for X+=?H+, CH3 +, Li+, and Na+, using relativistic density functional theory (DFT). We wish to establish a quantitative trend in affinities of the anionic and neutral Lewis bases Cl? and HCl for the various cations. The Cl?X bond becomes longer and weaker along X+?=?H+, CH3 +, Li+, and Na+. Our main purpose is to understand the heterolytic bonding mechanism behind the intrinsic (i.e., in the absence ...

  1. Proton affinities of anionic bases: Trends across the periodic table, structural effects, and DFT validation

    NARCIS (Netherlands)

    Swart, M.; Bickelhaupt, F.M.

    2006-01-01

    We have carried out an extensive exploration of the gas-phase basicity of archetypal anionic bases across the periodic system using the generalized gradient approximation of density functional theory (DFT) at BP86/QZ4P//BP86/TZ2P. First, we validate DFT as a reliable tool for computing proton

  2. eMethylsorb: electrochemical quantification of DNA methylation at CpG resolution using DNA-gold affinity interactions.

    Science.gov (United States)

    Sina, Abu Ali Ibn; Howell, Sidney; Carrascosa, Laura G; Rauf, Sakandar; Shiddiky, Muhammad J A; Trau, Matt

    2014-11-07

    We report a simple electrochemical method referred to as "eMethylsorb" for the detection of DNA methylation. The method relies on the base dependent affinity interaction of DNA with gold. The methylation status of DNA is quantified by monitoring the electrochemical current as a function of the relative adsorption level of bisulphite treated DNA samples onto a bare gold electrode. This method can successfully distinguish methylated and unmethylated epigenotypes at single CpG resolution.

  3. Tissue-specific and cation/anion-specific DNA methylation variations occurred in C. virgata in response to salinity stress.

    Directory of Open Access Journals (Sweden)

    Xiang Gao

    Full Text Available Salinity is a widespread environmental problem limiting productivity and growth of plants. Halophytes which can adapt and resist certain salt stress have various mechanisms to defend the higher salinity and alkalinity, and epigenetic mechanisms especially DNA methylation may play important roles in plant adaptability and plasticity. In this study, we aimed to investigate the different influences of various single salts (NaCl, Na2SO4, NaHCO3, Na2CO3 and their mixed salts on halophyte Chloris. virgata from the DNA methylation prospective, and discover the underlying relationships between specific DNA methylation variations and specific cations/anions through the methylation-sensitive amplification polymorphism analysis. The results showed that the effects on DNA methylation variations of single salts were ranked as follows: Na2CO3> NaHCO3> Na2SO4> NaCl, and their mixed salts exerted tissue-specific effects on C. virgata seedlings. Eight types of DNA methylation variations were detected and defined in C. virgata according to the specific cations/anions existed in stressful solutions; in addition, mix-specific and higher pH-specific bands were the main type in leaves and roots independently. These findings suggested that mixed salts were not the simple combination of single salts. Furthermore, not only single salts but also mixed salts showed tissue-specific and cations/anions-specific DNA methylation variations.

  4. Tissue-specific and cation/anion-specific DNA methylation variations occurred in C. virgata in response to salinity stress.

    Science.gov (United States)

    Gao, Xiang; Cao, Donghui; Liu, Jie; Wang, Xiaoping; Geng, Shujuan; Liu, Bao; Shi, Decheng

    2013-01-01

    Salinity is a widespread environmental problem limiting productivity and growth of plants. Halophytes which can adapt and resist certain salt stress have various mechanisms to defend the higher salinity and alkalinity, and epigenetic mechanisms especially DNA methylation may play important roles in plant adaptability and plasticity. In this study, we aimed to investigate the different influences of various single salts (NaCl, Na2SO4, NaHCO3, Na2CO3) and their mixed salts on halophyte Chloris. virgata from the DNA methylation prospective, and discover the underlying relationships between specific DNA methylation variations and specific cations/anions through the methylation-sensitive amplification polymorphism analysis. The results showed that the effects on DNA methylation variations of single salts were ranked as follows: Na2CO3> NaHCO3> Na2SO4> NaCl, and their mixed salts exerted tissue-specific effects on C. virgata seedlings. Eight types of DNA methylation variations were detected and defined in C. virgata according to the specific cations/anions existed in stressful solutions; in addition, mix-specific and higher pH-specific bands were the main type in leaves and roots independently. These findings suggested that mixed salts were not the simple combination of single salts. Furthermore, not only single salts but also mixed salts showed tissue-specific and cations/anions-specific DNA methylation variations.

  5. Design and Application of Synthetic Receptors for Recognition of Methylated Lysine and Supramolecular Affinity Labeling

    Science.gov (United States)

    Gober, Isaiah Nathaniel

    This dissertation involves the design and synthesis of new synthetic receptors and their application in the molecular recognition of methylated lysine and their use as tools for chemical biology. The dissertation is divided into four parts. The first section focuses on the development of a novel labeling method that is based on ligand-directed affinity labeling principles. In this labeling method, a synthetic receptor that binds to trimethyl lysine (Kme3) is attached through a linker to an electrophilic tag group that can react with a nucleophilic amine in a histone peptide. This affinity labeling probe, which we called CX4-ONBD, is equipped with an electrophilic tag that allows for turn-on fluorescence labeling of Kme3 histone peitdes. We show that the probe gives a pronounced turn-on fluorescence response when it is incubated with a histone peptide that contains Kme3 and a nearby reactive lysine. This probe also displays >5-fold selectivity in covalent labeling over an unmethylated lysine peptide. This represents the first time a synthetic receptor has been used for affinity labeling purposes, and it also expands on the chemical toolkit that is available for sensing PTMs like lysine methylation. In the second section, the supramolecular affinity labeling method that was optimized using CX4-ONBD was applied to the development of a real-time assay for measuring enzymatic activity. More specifically, the probe was used to create a turn-on fluorescence assay for histone deacetylase (HDAC) activity and for inhibitor screening and IC50 determination. Most commercial kits for HDAC activity have limited substrate scope, and other common methods used for characterizing enzymatic activity often require chromatographic separation and are therefore not high-throughput. This small molecule receptor-mediated affinity labeling strategy allowed for facile readout of HDAC activity and inhibition. Overall, this application of supramolecular affinity labeling expands on the

  6. Photoinduced electron transfer between anionic fluorophores and methyl viologen in homogeneous and microheterogeneous media

    Energy Technology Data Exchange (ETDEWEB)

    Burai, Tarak Nath; Panda, Debashis; Iyer, E Siva Subramaniam [Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400 076 (India); Datta, Anindya, E-mail: anindya@chem.iitb.ac.in [Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400 076 (India)

    2012-11-15

    The rate and extent of photoinduced electron transfer change significantly as a result of confinement in nanovolumes. Study of such processes is an active area of research in physical chemistry. The effect is most interesting when the molecules that participate in PET are charged. In the present article, the modulation of PET has been studied for two anionic fluorophores: Lucifer Yellow CH and chlorin p{sub 6} with Methylviologen dication. PET, manifested in the quenching of fluorescence of the fluorophores, has been modulated by incorporating the molecules in organized assemblies like micelles, reverse micelles and supramolecular hosts. The dynamics of the process has been monitored in the femtosecond to nanosecond timescale. The modulation of the electron transfer has been found to be occurring mainly due to the disruption of contact ion pairs formed between the fluorophores and the quencher. - Highlights: Black-Right-Pointing-Pointer Modulation of PET of biologically active fluorophores and Methyl viologen. Black-Right-Pointing-Pointer Static and Dynamic Quenching present. Black-Right-Pointing-Pointer PET enhanced upon encapsulation, studied through Fluorescence upconversion experiments. Black-Right-Pointing-Pointer Rotational anisotropy has significant contribution in quenching.

  7. Photoinduced electron transfer between anionic fluorophores and methyl viologen in homogeneous and microheterogeneous media

    International Nuclear Information System (INIS)

    Burai, Tarak Nath; Panda, Debashis; Iyer, E Siva Subramaniam; Datta, Anindya

    2012-01-01

    The rate and extent of photoinduced electron transfer change significantly as a result of confinement in nanovolumes. Study of such processes is an active area of research in physical chemistry. The effect is most interesting when the molecules that participate in PET are charged. In the present article, the modulation of PET has been studied for two anionic fluorophores: Lucifer Yellow CH and chlorin p 6 with Methylviologen dication. PET, manifested in the quenching of fluorescence of the fluorophores, has been modulated by incorporating the molecules in organized assemblies like micelles, reverse micelles and supramolecular hosts. The dynamics of the process has been monitored in the femtosecond to nanosecond timescale. The modulation of the electron transfer has been found to be occurring mainly due to the disruption of contact ion pairs formed between the fluorophores and the quencher. - Highlights: ► Modulation of PET of biologically active fluorophores and Methyl viologen. ► Static and Dynamic Quenching present. ► PET enhanced upon encapsulation, studied through Fluorescence upconversion experiments. ► Rotational anisotropy has significant contribution in quenching.

  8. Anion exchange separation of the light lanthanoids with nitric acid-methyl alcohol mixed media at elevated temperature

    International Nuclear Information System (INIS)

    Usuda, S.; Magara, M.

    1987-01-01

    Anion exchange chromatography with nitric acid-methyl alcohol mixed media at elevated temperature was applied to mutual separation of the light lanthanoids, La, Ce, Pr, Nd and Pm. The individual elements could be effectively separated from each other, main fission products and actinoids with 0.01M HNO 3 -90% CH 3 OH or 0.5M HNO 3 -80% CH 3 OH eluent at 90 deg C. (author) 14 refs.; 3 tables

  9. SYNTHESIS OF CHIRAL BINAPHTHYL CROWN ETHERS AND THEIR USE IN ANIONIC POLYMERIZATION OF METHYL METHACRYLATE AS INITIATOR LIGANDS

    Institute of Scientific and Technical Information of China (English)

    Hong-wei Liu; Chuan-fu Chen; Fu Xi

    2004-01-01

    Some chiral binaphthyl crown ethers were synthesized. The anionic polymerization of methyl methacrylate (MMA) was carried out in the presence of t-BuOK, Ph2CHK or Ph2CHNa (RM), and RM coordination initiator by using chiral binaphthyl crown ethers as ligands, respectively. The results showed that in the former case the PMMA obtained has mainly isotactic structure but without optical activity, while in the later case the PMMA produced predominately has syndiotactic suucture also without optical activity.

  10. Argonaute pull-down and RISC analysis using 2'-O-methylated oligonucleotides affinity matrices.

    Science.gov (United States)

    Jannot, Guillaume; Vasquez-Rifo, Alejandro; Simard, Martin J

    2011-01-01

    During the last decade, several novel small non-coding RNA pathways have been unveiled, which reach out to many biological processes. Common to all these pathways is the binding of a small RNA molecule to a protein member of the Argonaute family, which forms a minimal core complex called the RNA-induced silencing complex or RISC. The RISC targets mRNAs in a sequence-specific manner, either to induce mRNA cleavage through the intrinsic activity of the Argonaute protein or to abrogate protein synthesis by a mechanism that is still under investigation. We describe here, in details, a method for the affinity chromatography of the let-7 RISC starting from extracts of the nematode Caenorhabditis elegans. Our method exploits the sequence specificity of the RISC and makes use of biotinylated and 2'-O-methylated oligonucleotides to trap and pull-down small RNAs and their associated proteins. Importantly, this technique may easily be adapted to target other small RNAs expressed in different cell types or model organisms. This method provides a useful strategy to identify the proteins associated with the RISC, and hence gain insight in the functions of small RNAs.

  11. Importance of sulfate radical anion formation and chemistry in heterogeneous OH oxidation of sodium methyl sulfate, the smallest organosulfate

    Directory of Open Access Journals (Sweden)

    K. C. Kwong

    2018-02-01

    Full Text Available Organosulfates are important organosulfur compounds present in atmospheric particles. While the abundance, composition, and formation mechanisms of organosulfates have been extensively investigated, it remains unclear how they transform and evolve throughout their atmospheric lifetime. To acquire a fundamental understanding of how organosulfates chemically transform in the atmosphere, this work investigates the heterogeneous OH radical-initiated oxidation of sodium methyl sulfate (CH3SO4Na droplets, the smallest organosulfate detected in atmospheric particles, using an aerosol flow tube reactor at a high relative humidity (RH of 85 %. Aerosol mass spectra measured by a soft atmospheric pressure ionization source (direct analysis in real time, DART coupled with a high-resolution mass spectrometer showed that neither functionalization nor fragmentation products are detected. Instead, the ion signal intensity of the bisulfate ion (HSO4− has been found to increase significantly after OH oxidation. We postulate that sodium methyl sulfate tends to fragment into a formaldehyde (CH2O and a sulfate radical anion (SO4 ⋅ − upon OH oxidation. The formaldehyde is likely partitioned back to the gas phase due to its high volatility. The sulfate radical anion, similar to OH radical, can abstract a hydrogen atom from neighboring sodium methyl sulfate to form the bisulfate ion, contributing to the secondary chemistry. Kinetic measurements show that the heterogeneous OH reaction rate constant, k, is (3.79 ± 0.19  ×  10−13 cm3 molecule−1 s−1 with an effective OH uptake coefficient, γeff, of 0.17 ± 0.03. While about 40 % of sodium methyl sulfate is being oxidized at the maximum OH exposure (1.27  ×  1012 molecule cm−3 s, only a 3 % decrease in particle diameter is observed. This can be attributed to a small fraction of particle mass lost via the formation and volatilization of formaldehyde. Overall, we

  12. Importance of sulfate radical anion formation and chemistry in heterogeneous OH oxidation of sodium methyl sulfate, the smallest organosulfate

    Science.gov (United States)

    Chung Kwong, Kai; Chim, Man Mei; Davies, James F.; Wilson, Kevin R.; Nin Chan, Man

    2018-02-01

    Organosulfates are important organosulfur compounds present in atmospheric particles. While the abundance, composition, and formation mechanisms of organosulfates have been extensively investigated, it remains unclear how they transform and evolve throughout their atmospheric lifetime. To acquire a fundamental understanding of how organosulfates chemically transform in the atmosphere, this work investigates the heterogeneous OH radical-initiated oxidation of sodium methyl sulfate (CH3SO4Na) droplets, the smallest organosulfate detected in atmospheric particles, using an aerosol flow tube reactor at a high relative humidity (RH) of 85 %. Aerosol mass spectra measured by a soft atmospheric pressure ionization source (direct analysis in real time, DART) coupled with a high-resolution mass spectrometer showed that neither functionalization nor fragmentation products are detected. Instead, the ion signal intensity of the bisulfate ion (HSO4-) has been found to increase significantly after OH oxidation. We postulate that sodium methyl sulfate tends to fragment into a formaldehyde (CH2O) and a sulfate radical anion (SO4 ṡ -) upon OH oxidation. The formaldehyde is likely partitioned back to the gas phase due to its high volatility. The sulfate radical anion, similar to OH radical, can abstract a hydrogen atom from neighboring sodium methyl sulfate to form the bisulfate ion, contributing to the secondary chemistry. Kinetic measurements show that the heterogeneous OH reaction rate constant, k, is (3.79 ± 0.19) × 10-13 cm3 molecule-1 s-1 with an effective OH uptake coefficient, γeff, of 0.17 ± 0.03. While about 40 % of sodium methyl sulfate is being oxidized at the maximum OH exposure (1.27 × 1012 molecule cm-3 s), only a 3 % decrease in particle diameter is observed. This can be attributed to a small fraction of particle mass lost via the formation and volatilization of formaldehyde. Overall, we firstly demonstrate that the heterogeneous OH oxidation of an

  13. Contributions of pocket depth and electrostatic interactions to affinity and selectivity of receptors for methylated lysine in water.

    Science.gov (United States)

    Beaver, Joshua E; Peacor, Brendan C; Bain, Julianne V; James, Lindsey I; Waters, Marcey L

    2015-03-21

    Dynamic combinatorial chemistry was used to generate a set of receptors for peptides containing methylated lysine (KMen, n = 0-3) and study the contribution of electrostatic effects and pocket depth to binding affinity and selectivity. We found that changing the location of a carboxylate resulted in an increase in preference for KMe2, presumably based on ability to form a salt bridge with KMe2. The number of charged groups on either the receptor or peptide guest systematically varied the binding affinities to all guests by approximately 1-1.5 kcal mol(-1), with little influence on selectivity. Lastly, formation of a deeper pocket led to both increased affinity and selectivity for KMe3 over the lower methylation states. From these studies, we identified that the tightest binder was a receptor with greater net charge, with a Kd of 0.2 μM, and the receptor with the highest selectivity was the one with the deepest pocket, providing 14-fold selectivity between KMe3 and KMe2 and a Kd for KMe3 of 0.3 μM. This work provides key insights into approaches to improve binding affinity and selectivity in water, while also demonstrating the versatility of dynamic combinatorial chemistry for rapidly exploring the impact of subtle changes in receptor functionality on molecular recognition in water.

  14. Proton and hydride affinities in excited states: magnitude reversals in proton and hydride affinities between the lowest singlet and triplet states of annulenyl and benzannulenyl anions and cations

    DEFF Research Database (Denmark)

    Rosenberg, Martin; Ottosson, Henrik; Kilså, Kristine

    2010-01-01

    electron counting rules for aromaticity in the two states. Using quantum chemical calculations at the G3(MP2)//(U)B3LYP/6-311+G(d,p) level we have examined the validity of this hypothesis for eight proton and eight hydride addition reactions of anions and cations, respectively, of annulenyl...

  15. Ytterbium doped silicon clusters YbSi{sub n} (n = 4–10) and their anions: Structures, thermochemistry, and electron affinities

    Energy Technology Data Exchange (ETDEWEB)

    Xie, Xiaohong [School of Chemical Engineering, Inner Mongolia University of Technology, Hohhot 010051 (China); Hao, Dongsheng [School of Chemical Engineering, Inner Mongolia University of Technology, Hohhot 010051 (China); School of Mining and Technology, Inner Mongolia University of Technology, Hohhot 010051 (China); Yang, Jucai, E-mail: yangjc@imut.edu.cn [School of Chemical Engineering, Inner Mongolia University of Technology, Hohhot 010051 (China); School of Energy and Power Engineering, Inner Mongolia University of Technology, Hohhot 010051 (China)

    2015-11-05

    Highlights: • The ground-state structure of YbSi{sub n} and its anion is substitutional structure. • The four DFT AEAs are in excellent agreement with the experimental data. • Theoretical AEA of 2.33 eV of YbSi{sub 9} is more reasonable than the experimental 2.60 eV. • Hardness analysis reveals that doping Yb to Si{sub n} raises photochemical sensitivity. • Relative stabilities of YbSi{sub n} and their anions are examined. - Abstract: The structures, electron affinities, dissociation energies, hardness, and dipole moments of YbSi{sub n} (n = 4–10) and their anions were examined using B3LYP, TPSSh, PBE and wB97X methods. The lowest-energy structures can be regarded as replacing a Si of the ground-state structure of Si{sub n+1} with a Yb atom. The theoretical adiabatic electron affinities (AEAs) of YbSi{sub n} are in excellent agreement with experimental data. The average absolute errors from experiment are by 0.08, 0.07, 0.05 and 0.08 eV at the B3LYP, the TPSSh, the PBE and the wB97X levels, respectively. Theoretical AEAs of 2.33 ± 0.05 eV for YbSi{sub 9} are more reliable than the experimental value of 2.60 ± 0.05 eV. The hardness analysis reveals that doping Yb atom to Si{sub n} (n = 4–10) clusters raises the photochemical sensitivity. The dissociation energies of Yb atom from YbSi{sub n} and their anions were calculated to examine relative stabilities.

  16. Effect of anionic surfactants on the process of Fenton degradation of methyl orange.

    Science.gov (United States)

    Yang, C W; Wang, D

    2009-01-01

    Fenton process has been shown to be very successful to remove dyes from water. However, the influence of other constituents in dyeing industry wastewater, such as Sodium Dodecyl Sulphate (SDS) surfactants, has not been investigated. In this study, the effect of SDS surfactant on the kinetics of Methyl Orange degradation undergoing Fenton process was investigated. Results show that Methyl Orange degradation rate decreased as SDS concentration increased, which was attributed to the consumption of hydroxyl radicals (OH) by surfactants and the formation of Methyl Orange-SDS complex. No evidence was found that the Methyl Orange degradation pathway was affected by the presence of SDS. The kinetics modelling indicates the reaction was the first-order reaction to Methyl Orange.

  17. Back-biting termination in methyl methacrylate/tert-butyl acrylate anionic block copolymerization

    Czech Academy of Sciences Publication Activity Database

    Čadová, Eva; Dybal, Jiří; Kříž, Jaroslav; Vlček, Petr; Janata, Miroslav; Toman, Luděk

    2008-01-01

    Roč. 209, č. 16 (2008), s. 1657-1665 ISSN 1022-1352 Institutional research plan: CEZ:AV0Z40500505 Keywords : acrylates * anionic polymerization * spontaneous termination Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.202, year: 2008

  18. New inorganic (an)ion exchangers with a higher affinity for arsenate and a competitive removal capacity towards fluoride, bromate, bromide, selenate, selenite, arsenite and borate

    KAUST Repository

    Chubar, Natalia

    2011-12-01

    Highly selective materials and effective technologies are needed to meet the increasingly stronger drinking water standards for targeted ionic species. Inorganic ion exchangers based on individual and mixed-metal hydrous oxides (or mixed adsorbents that contain inorganic ion exchangers in their composition) are adsorptive materials that are capable of lowering the concentrations of anionic contaminants, such as H 2AsO 4 -, H 3AsO 3, F -, Br -, BrO 3 -, HSeO 4 -, HSeO 3 - and H 3BO 3, to 10 μg/L or less. To achieve a higher selectivity towards arsenate, a new ion exchanger based on Mg-Al hydrous oxides was developed by a novel, cost-effective and environmentally friendly synthesis method via a non-traditional (alkoxide-free) sol-gel approach. The exceptional adsorptive capacity of the Mg-Al hydrous oxides towards H 2AsO 4 - (up to 200 mg[As]/gdw) is due to the high affinity of this sorbent towards arsenate (steep equilibrium isotherms) and its fast adsorption kinetics. Because of the mesoporous (as determined by N 2 adsorption and SEM) and layered (as determined by XRD and FTIR) structure of the ion-exchange material as well as the abundance of anion exchange sites (as determined by XPS and potentiometric titration) on its surface the material demonstrated very competitive (or very high) removal capacity towards other targeted anions, including fluoride, bromide, bromate, selenate, selenite, and borate. © 2011 IWA Publishing.

  19. Influence of anionic surfactant on the process of electro-Fenton decolorized methyl orange.

    Science.gov (United States)

    Ren, B X

    2010-01-01

    The electro-Fenton process has been shown to be very successful to remove dyes from water. However, the influence of other constituents in dyeing industry wastewater, such as Sodium Dodecyl Sulfate (SDS) surfactants, has not been investigated. In this study, the effect of SDS surfactant on the kinetics of Methyl Orange degradation undergoing Electro-Fenton process was investigated. Results show that Methyl Orange degradation rate decreased as SDS concentration (below Critical Micelle Concentration, CMC) increased, which was attributed to the consumption of hydroxyl radicals (( )OH) by surfactants. The kinetics modeling indicates the reaction was the first-order reaction to Methyl Orange even SDS existing. The pseudo first-order rate constants decreased as SDS concentration increased.

  20. Thermophysical properties of 1-hexyl-3-methyl imidazolium based ionic liquids with tetrafluoroborate, hexafluorophosphate and bis(trifluoromethylsulfonyl)imide anions

    International Nuclear Information System (INIS)

    Muhammad, Ayyaz; Abdul Mutalib, M.I.; Wilfred, C.D.; Murugesan, T.; Shafeeq, Amir

    2008-01-01

    The thermophysical properties of 1-hexyl-3-methyl imidazolium based hydrophobic room temperature ionic liquids (RTILs); with tetrafluoroborate (BF 4 ), hexafluorophosphate (PF 6 ), and bis(trifluoromethylsulfonyl)imide (Tf 2 N) anions, namely density ρ (298.15 to 348.15) K, dynamic viscosity η (288.2 to 348.2) K, surface tension σ (298.15 to 338) K, and refractive index n D (302.95 to 332.95) K have been measured. The coefficients of thermal expansion α p values were calculated from the experimental density data using an empirical correlation. The thermal stability of all ILs is also investigated at two different heating rates (10 and 20) deg. C . min -1 ) using thermogravimetric analyzer (TGA). The experimental results presented in this study reveal that the choice of anion type shows the most significant effect on the properties of ILs. The chloride and water contents of ILs (as impurities) are also investigated and reported in the present work

  1. Searsia species with affinity to the N-methyl-d-aspartic acid (NMDA) receptor

    DEFF Research Database (Denmark)

    Jäger, Anna; Knap, D.M.; Nielsen, Birgitte

    2012-01-01

    Species of Searsia are used in traditional medicine to treat epilepsy. Previous studies on S. dentata and S. pyroides have shown that this is likely mediated via the N-methyl-d-aspartic acid (NMDA) receptor. Ethanolic extracts of leaves of six Searsia species were tested in a binding assay...

  2. Effect of the low-affinity, noncompetitive N-methyl-D-aspartate receptor antagonist dextromethorphan on visceral perception in healthy volunteers

    NARCIS (Netherlands)

    Kuiken, S. D.; Lei, A.; Tytgat, G. N. J.; Holman, R.; Boeckxstaens, G. E. E.

    2002-01-01

    Background: The use of N-methyl-d-aspartate (NMDA) receptor antagonists may hold promise for the treatment of pain of visceral origin, in particular in conditions characterized by visceral hypersensitivity. Aim: To study the effect of dextromethorphan, a low affinity, non-competitive NMDA receptor

  3. Anion exchange membranes based on terminally crosslinked methyl morpholinium-functionalized poly(arylene ether sulfone)s

    Science.gov (United States)

    Kwon, Sohyun; Rao, Anil H. N.; Kim, Tae-Hyun

    2018-01-01

    Azide-assisted terminal crosslinking of methyl morpholinium-functionalized poly(arylene ether sulfone) block copolymers yields products (xMM-PESs) suitable for use as anion exchange membranes. By combining the advantages of bulky morpholinium conductors and our unique polymer network crosslinked only at the termini of the polymer chains, we can produce AEMs that after the crosslinking show minimal loss in conductivity, yet with dramatically reduced water uptake. Terminal crosslinking also significantly increases the thermal, mechanical and chemical stability levels of the membranes. A high ion conductivity of 73.4 mS cm-1 and low water uptake of 26.1% at 80 °C are obtained for the crosslinked membrane with higher amount of hydrophilic composition, denoted as xMM-PES-1.5-1. In addition, the conductivity of the crosslinked xMM-PES-1.5-1 membrane exceeds that of its non-crosslinked counterpart (denoted as MM-PES-1.5-1) above 60 °C at 95% relative humidity because of its enhanced water retention capacity caused by the terminally-crosslinked structure.

  4. Molecules for materials: germanium hydride neutrals and anions. Molecular structures, electron affinities, and thermochemistry of GeHn/GeHn- (n = 0-4) and Ge2Hn/Ge2Hn(-) (n = 0-6).

    Science.gov (United States)

    Li, Qian-Shu; Lü, Rui-Hua; Xie, Yaoming; Schaefer, Henry F

    2002-12-01

    The GeH(n) (n = 0-4) and Ge(2)H(n) (n = 0-6) systems have been studied systematically by five different density functional methods. The basis sets employed are of double-zeta plus polarization quality with additional s- and p-type diffuse functions, labeled DZP++. For each compound plausible energetically low-lying structures were optimized. The methods used have been calibrated against a comprehensive tabulation of experimental electron affinities (Chemical Reviews 102, 231, 2002). The geometries predicted in this work include yet unknown anionic species, such as Ge(2)H(-), Ge(2)H(2)(-), Ge(2)H(3)(-), Ge(2)H(4)(-), and Ge(2)H(5)(-). In general, the BHLYP method predicts the geometries closest to the few available experimental structures. A number of structures rather different from the analogous well-characterized hydrocarbon radicals and anions are predicted. For example, a vinylidene-like GeGeH(2) (-) structure is the global minimum of Ge(2)H(2) (-). For neutral Ge(2)H(4), a methylcarbene-like HGë-GeH(3) is neally degenerate with the trans-bent H(2)Ge=GeH(2) structure. For the Ge(2)H(4) (-) anion, the methylcarbene-like system is the global minimum. The three different neutral-anion energy differences reported in this research are: the adiabatic electron affinity (EA(ad)), the vertical electron affinity (EA(vert)), and the vertical detachment energy (VDE). For this family of molecules the B3LYP method appears to predict the most reliable electron affinities. The adiabatic electron affinities after the ZPVE correction are predicted to be 2.02 (Ge(2)), 2.05 (Ge(2)H), 1.25 (Ge(2)H(2)), 2.09 (Ge(2)H(3)), 1.71 (Ge(2)H(4)), 2.17 (Ge(2)H(5)), and -0.02 (Ge(2)H(6)) eV. We also reported the dissociation energies for the GeH(n) (n = 1-4) and Ge(2)H(n) (n = 1-6) systems, as well as those for their anionic counterparts. Our theoretical predictions provide strong motivation for the further experimental study of these important germanium hydrides. Copyright 2002 Wiley

  5. Solution and solid-state studies on the halide binding affinity of perfluorophenyl-armed uranyl-salophen receptors enhanced by anion-π interactions

    Energy Technology Data Exchange (ETDEWEB)

    Leoni, Luca; Mele, Andrea; Giannicchi, Ilaria; Mihan, Francesco Yafteh; Dalla Cort, Antonella [Dipartimento di Chimica and IMC-CNR, Universita di Roma La Sapienza (Italy); Puttreddy, Rakesh; Jurcek, Ondrej; Rissanen, Kari [University of Jyvaeskylae, Department of Chemistry, Nanoscience Center (Finland)

    2016-12-23

    The enhancement of the binding between halide anions and a Lewis acidic uranyl-salophen receptor has been achieved by the introduction of pendant electron-deficient arene units into the receptor skeleton. The association and the occurrence of the elusive anion-π interaction with halide anions (as tetrabutylammonium salts) have been demonstrated in solution and in the solid state, providing unambiguous evidence on the interplay of the concerted interactions responsible for the anion binding. (copyright 2016 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  6. Colorful and transparent poly(vinyl alcohol) composite films filled with layered zinc hydroxide salts, intercalated with anionic orange azo dyes (methyl orange and orange II)

    International Nuclear Information System (INIS)

    Neves da Silva, Marlon Luiz; Marangoni, Rafael; Cursino, Ana Cristina Trindade; Schreiner, Wido Herwig; Wypych, Fernando

    2012-01-01

    Highlights: ► Zinc hydroxide salts were successfully intercalated with anionic orange azo dyes. ► The anionic dye was co-intercalated with hydrated chloride anions. ► The orange materials were used as fillers for poly(vinyl alcohol). ► Transparent, homogeneous, colorful PVA films were obtained by wet casting. ► Some composites stored at lower humidity exhibited improved mechanical properties. - Abstract: Layered zinc hydroxide salts (zinc LHS) were intercalated with anionic orange azo dyes, namely methyl orange (MO) and orange II (OII), and co-intercalated with hydrated chloride anions. After characterization by X-ray diffraction (XRD), thermal analysis (TGA/DTA), Fourier transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS), the materials were used as fillers for poly(vinyl alcohol) (PVA). Colorful transparent films were obtained by wet casting, revealing good dispersion of the material into the polymer. In the case of zinc LHS/OII, PVA was intercalated between the zinc LHS layers. Evaluation of the mechanical properties of the PVA composite films revealed that the layered colorful materials were able to increase the mechanical properties of the PVA films only when the films were stored under lower relative humidity. As expected, films with higher water content displayed reduced tensile strength and modulus because of the plasticizing effect of water. As for the films stored at 43% relative humidity, more pronounced improvement of modulus was observed for 1 and 4% zinc LHS/OII, and enhanced tensile strength was achieved for 0.5 and 1% zinc LHS/OII. This effect can be attributed to better dispersion of the layered filler and its better adhesion to the PVA matrix.

  7. The intervening domain from MeCP2 enhances the DNA affinity of the methyl binding domain and provides an independent DNA interaction site.

    Science.gov (United States)

    Claveria-Gimeno, Rafael; Lanuza, Pilar M; Morales-Chueca, Ignacio; Jorge-Torres, Olga C; Vega, Sonia; Abian, Olga; Esteller, Manel; Velazquez-Campoy, Adrian

    2017-01-31

    Methyl-CpG binding protein 2 (MeCP2) preferentially interacts with methylated DNA and it is involved in epigenetic regulation and chromatin remodelling. Mutations in MeCP2 are linked to Rett syndrome, the leading cause of intellectual retardation in girls and causing mental, motor and growth impairment. Unstructured regions in MeCP2 provide the plasticity for establishing interactions with multiple binding partners. We present a biophysical characterization of the methyl binding domain (MBD) from MeCP2 reporting the contribution of flanking domains to its structural stability and dsDNA interaction. The flanking disordered intervening domain (ID) increased the structural stability of MBD, modified its dsDNA binding profile from an entropically-driven moderate-affinity binding to an overwhelmingly enthalpically-driven high-affinity binding. Additionally, ID provided an additional site for simultaneously and autonomously binding an independent dsDNA molecule, which is a key feature linked to the chromatin remodelling and looping activity of MeCP2, as well as its ability to interact with nucleosomes replacing histone H1. The dsDNA interaction is characterized by an unusually large heat capacity linked to a cluster of water molecules trapped within the binding interface. The dynamics of disordered regions together with extrinsic factors are key determinants of MeCP2 global structural properties and functional capabilities.

  8. Synthesis of Isotactic-block-Syndiotactic Poly(methyl Methacrylate via Stereospecific Living Anionic Polymerizations in Combination with Metal-Halogen Exchange, Halogenation, and Click Reactions

    Directory of Open Access Journals (Sweden)

    Naoya Usuki

    2017-12-01

    Full Text Available Isotactic (it- and syndiotactic (st- poly(methyl methacrylates (PMMAs form unique crystalline stereocomplexes, which are attractive from both fundamental and application viewpoints. This study is directed at the efficient synthesis of it- and st-stereoblock (it-b-st- PMMAs via stereospecific living anionic polymerizations in combination with metal-halogen exchange, halogenation, and click reactions. The azide-capped it-PMMA was prepared by living anionic polymerization of MMA, which was initiated with t-BuMgBr in toluene at –78 °C, and was followed by termination using CCl4 as the halogenating agent in the presence of a strong Lewis base and subsequent azidation with NaN3. The alkyne-capped st-PMMA was obtained by living anionic polymerization of MMA, which was initiated via an in situ metal-halogen exchange reaction between 1,1-diphenylhexyl lithium and an α-bromoester bearing a pendent silyl-protected alkyne group. Finally, copper-catalyzed alkyne-azide cycloaddition (CuAAC between these complimentary pairs of polymers resulted in a high yield of it-b-st-PMMAs, with controlled molecular weights and narrow molecular weight distributions. The stereocomplexation was evaluated in CH3CN and was affected by the block lengths and ratios.

  9. Electrochemical iodination of C-methyl derivatives of dodecahydro-7,8-dicarba-nido-undecaborate anion

    International Nuclear Information System (INIS)

    Rudakov, D.A.; Shirokij, V.L.; Potkin, V.I.; Dikusar, E.A.; Bragin, V.I.; Petrovskij, P.V.; Sivaev, I.B.; Bregadze, V.I.; Kisin, A.V.

    2006-01-01

    Electrochemical iodination of potassium 7-methyl-7,8-dicarba-nido-undecaborate and potassium 7,8-dimethyl-7,8-dicarba-nido-undecaborate in methanol at 50 deg C was used to prepare their monoiodide derivatives (isolated as tetramethylammonium salts). Their composition and structure are confirmed by elemental analysis, 1 H, 11 B NMR and IR spectra [ru

  10. Effect of DNA sequence, ionic strength, and cationic DNA affinity binders on the methylation of DNA by N-methyl-N-nitrosourea

    International Nuclear Information System (INIS)

    Wurdeman, R.L.; Gold, B.

    1988-01-01

    DNA alkylation by N-alkyl-N-nitrosoureas is generally accepted to be responsible for their mutagenic, carcinogenic, and antineoplastic activities. The exact nature of the ultimate alkylating intermediate is still controversial, with a variety of species having been nominated. The sequence specificity for DNA alkylation by simple N-alkyl-N-nitrosoureas has not been reported, although such information is basic in understanding the specific point mutations induced by these compounds in oncogene targets. These two points are addressed by using N-methyl-N-nitrosourea methylation of a 576 base-pair 32 P-end-labeled DNA restriction fragment and high-resolution polyacrylamide sequencing gels. This method provides information on the formation of N 7 -methylguanine, by the generation of single-strand breaks upon exposure to piperidine

  11. Anionic subsites of the acetylcholinesterase from Torpedo californica: affinity labelling with the cationic reagent N,N-dimethyl-2-phenyl-aziridinium.

    OpenAIRE

    Weise, C; Kreienkamp, H J; Raba, R; Pedak, A; Aaviksaar, A; Hucho, F

    1990-01-01

    Several peptides of acetylcholinesterase of Torpedo californica labelled with the alkylating reagent [3H]N,N-dimethyl-2-phenyl-aziridinium (DPA) were localized within the primary structure. One peptide had the sequence KPQELIDVE (positions 270-278); the incorporation of DPA into this peptide could be specifically suppressed by propidium, which suggests that it is part of the peripheral anionic site. The incorporation of DPA into two other peptides was insensitive to propidium but could be pre...

  12. Isolation and partial characterization of gypsy moth BTR-270, an anionic brush border membrane glycoconjugate that binds Bacillus thuringiensis Cry1A toxins with high affinity

    Science.gov (United States)

    Algimantas P. Valaitis; Jeremy L. Jenkins; Mi Kyong Lee; Donald H. Dean; Karen J. Garner

    2001-01-01

    BTR-270, a gypsy moth (Lymantria dispar) brush border membrane molecule that binds Bacillus thuringiensis (Bt) Cry1A toxins with high affinity, was purified by preparative gel electrophoresis. Rabbit antibodies specific for the Bt toxin-binding molecule were raised. Attempts to label BTR-270 by protein-directed techniques were...

  13. Development of a Novel Optical Biosensor for Detection of Organophoshorus Pesticides Based on Methyl Parathion Hydrolase Immobilized by Metal-Chelate Affinity

    Directory of Open Access Journals (Sweden)

    Wensheng Lan

    2012-06-01

    Full Text Available We have developed a novel optical biosensor device using recombinant methyl parathion hydrolase (MPH enzyme immobilized on agarose by metal-chelate affinity to detect organophosphorus (OP compounds with a nitrophenyl group. The biosensor principle is based on the optical measurement of the product of OP catalysis by MPH (p-nitrophenol. Briefly, MPH containing six sequential histidines (6× His tag at its N-terminal was bound to nitrilotriacetic acid (NTA agarose with Ni ions, resulting in the flexible immobilization of the bio-reaction platform. The optical biosensing system consisted of two light-emitting diodes (LEDs and one photodiode. The LED that emitted light at the wavelength of the maximum absorption for p-nitrophenol served as the signal light, while the other LED that showed no absorbance served as the reference light. The optical sensing system detected absorbance that was linearly correlated to methyl parathion (MP concentration and the detection limit was estimated to be 4 μM. Sensor hysteresis was investigated and the results showed that at lower concentration range of MP the difference got from the opposite process curves was very small. With its easy immobilization of enzymes and simple design in structure, the system has the potential for development into a practical portable detector for field applications.

  14. Development of a Novel Optical Biosensor for Detection of Organophoshorus Pesticides Based on Methyl Parathion Hydrolase Immobilized by Metal-Chelate Affinity

    Science.gov (United States)

    Lan, Wensheng; Chen, Guoping; Cui, Feng; Tan, Feng; Liu, Ran; Yushupujiang, Maolidan

    2012-01-01

    We have developed a novel optical biosensor device using recombinant methyl parathion hydrolase (MPH) enzyme immobilized on agarose by metal-chelate affinity to detect organophosphorus (OP) compounds with a nitrophenyl group. The biosensor principle is based on the optical measurement of the product of OP catalysis by MPH (p-nitrophenol). Briefly, MPH containing six sequential histidines (6× His tag) at its N-terminal was bound to nitrilotriacetic acid (NTA) agarose with Ni ions, resulting in the flexible immobilization of the bio-reaction platform. The optical biosensing system consisted of two light-emitting diodes (LEDs) and one photodiode. The LED that emitted light at the wavelength of the maximum absorption for p-nitrophenol served as the signal light, while the other LED that showed no absorbance served as the reference light. The optical sensing system detected absorbance that was linearly correlated to methyl parathion (MP) concentration and the detection limit was estimated to be 4 μM. Sensor hysteresis was investigated and the results showed that at lower concentration range of MP the difference got from the opposite process curves was very small. With its easy immobilization of enzymes and simple design in structure, the system has the potential for development into a practical portable detector for field applications. PMID:23012501

  15. Studies of the influence of different anions on extraction of neodymium with di(1-methylheptyl)methyl phosphonate

    International Nuclear Information System (INIS)

    Chun-Hui Huang; Rong-Fang Xi; Hai Guo; Guang-Xian Xu

    1988-01-01

    A study was made on extraction of Nd(NCS) 3 , Nd(ClO 4 ) 3 , Nd(NO 3 ) 3 by di-(1-methylhexyl)methyl phosphonate (P-350) in hexane. ΔG 0 (kJ/mol), ΔH 0 (kJ/mol) and ΔS 0 (kJ/mol) were calculated. They are equal to: -9.719, -29.92, -67.78 for P-350(hexane)-Nd(NCS) 3 system; 3.752, -74.31, -261.9 for P-350((hexane)-Nd(ClO 4 ) 3 system; 2.265, -22.69, -83.68 for P-350(hexane)-Nd(NO 3 ) 3 system. Structure of extracted complexes in hexane solution and corresponding solid complexes were correlated with triphenylphosphine oxide as P-350 model. Data of IR-spectroscopy show, that absorption bands of complexes in saturated organic solvents or in the solid phase are shifted to the region of lower frequencies as compared to absorption bands of corresponding salts. This testifies to similarity of complex structures in both phases

  16. Acetaminophen and aspirin inhibit superoxide anion generation and lipid peroxidation, and protect against 1-methyl-4-phenyl pyridinium-induced dopaminergic neurotoxicity in rats.

    Science.gov (United States)

    Maharaj, D S; Saravanan, K S; Maharaj, H; Mohanakumar, K P; Daya, S

    2004-04-01

    We assessed the antioxidant activity of non-narcotic analgesics, acetaminophen and aspirin in rat brain homogenates and neuroprotective effects in vivo in rats intranigrally treated with 1-methyl-4-phenyl pyridinium (MPP+). Both drugs inhibited cyanide-induced superoxide anion generation, as well as lipid peroxidation in rat brain homogenates, the combination of the agents resulting in a potentiation of this effect. Acetaminophen or aspirin when administered alone or in combination, did not alter dopamine (DA) levels in the forebrain or in the striatum. Intranigral infusion of MPP+ in rats caused severe depletion of striatal DA levels in the ipsilateral striatum in rats by the third day. Systemic post-treatment of acetaminophen afforded partial protection, whereas similar treatment of aspirin resulted in complete blockade of MPP+-induced striatal DA depletion. While these findings suggest usefulness of non-narcotic analgesics in neuroprotective therapy in neurodegenerative diseases, aspirin appears to be a potential candidate in prophylactic as well as in adjuvant therapy in Parkinson's disease.

  17. Prediction of N-Methyl-D-Aspartate Receptor GluN1-Ligand Binding Affinity by a Novel SVM-Pose/SVM-Score Combinatorial Ensemble Docking Scheme.

    Science.gov (United States)

    Leong, Max K; Syu, Ren-Guei; Ding, Yi-Lung; Weng, Ching-Feng

    2017-01-06

    The glycine-binding site of the N-methyl-D-aspartate receptor (NMDAR) subunit GluN1 is a potential pharmacological target for neurodegenerative disorders. A novel combinatorial ensemble docking scheme using ligand and protein conformation ensembles and customized support vector machine (SVM)-based models to select the docked pose and to predict the docking score was generated for predicting the NMDAR GluN1-ligand binding affinity. The predicted root mean square deviation (RMSD) values in pose by SVM-Pose models were found to be in good agreement with the observed values (n = 30, r 2  = 0.928-0.988,  = 0.894-0.954, RMSE = 0.002-0.412, s = 0.001-0.214), and the predicted pK i values by SVM-Score were found to be in good agreement with the observed values for the training samples (n = 24, r 2  = 0.967,  = 0.899, RMSE = 0.295, s = 0.170) and test samples (n = 13, q 2  = 0.894, RMSE = 0.437, s = 0.202). When subjected to various statistical validations, the developed SVM-Pose and SVM-Score models consistently met the most stringent criteria. A mock test asserted the predictivity of this novel docking scheme. Collectively, this accurate novel combinatorial ensemble docking scheme can be used to predict the NMDAR GluN1-ligand binding affinity for facilitating drug discovery.

  18. MALDI-TOF MS analysis of the self-termination products in the anionic methyl methacrylate/tert-butyl acrylate block copolymerization

    Czech Academy of Sciences Publication Activity Database

    Vlček, Petr; Čadová, Eva; Horský, Jiří; Janata, Miroslav

    2015-01-01

    Roč. 72, č. 9 (2015), s. 2227-2239 ISSN 0170-0839 Institutional support: RVO:61389013 Keywords : anionic polymerization * acrylates * block copolymer Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.371, year: 2015

  19. Anionic polymerization of acrylates. XI. Effect of composition and ageing of the Li ester enolate/tert-butoxide initiating complex on the anionic polymerization of methyl methacrylate and 2-ethylhexyl acrylate

    Czech Academy of Sciences Publication Activity Database

    Vlček, Petr; Otoupalová, Jaroslava; Kříž, Jaroslav; Schmidt, Pavel

    2000-01-01

    Roč. 161, - (2000), s. 127-134 ISSN 1022-1360. [Microsymposium: Advances in Polymerization Methods: Controlled Synthesis of Functionalized Polymers /39./. Praha, 12.07.1999-15.07.1999] R&D Projects: GA MŠk OC P1.10; GA AV ČR KSK2050602 Grant - others:CZ-US(XC) 95009 Institutional research plan: CEZ:AV0Z4050913 Keywords : anionic polymerization * acrylates * initiating system Subject RIV: CD - Macromolecular Chemistry Impact factor: 0.406, year: 2000

  20. Dissociative electron attachment to methyl chloride: A quasi-diatomic potential curve for the fragmentation of the metastable CH3Cl- anion

    International Nuclear Information System (INIS)

    Mach, P.; Urban, J.; Staemmler, V.

    2009-01-01

    Potential energy curves have been calculated for the dissociation of the neutral CH 3 Cl molecule and its negative ion into CH 3 + Cl and CH 3 +Cl - , respectively. The neutral molecule and the anion could be treated by means of standard wave function based quantum chemical ab initio methods for C-Cl distances larger than about 2.4 A, where CH 3 Cl - is a stable anion. In the present calculation MP3 and CCSD(T) were employed. At shorter C-Cl distances the CH 3 Cl - anion is only metastable and cannot be treated by such methods. We have applied a stabilization scheme, first proposed by Nestmann and Peyerimhoff, to stabilize the metastable anion by adding extra positive charges to the molecule. By this trick it was possible to generate the resonance energy E res and width Γ as functions of the C-Cl distance in the resonance regime between 1.5 and 2.5 A. The calculated values for the threshold energy E thresh and the exothermicity ΔE 0 of the DEA (dissociative electron attachment) process are in very good agreement with experiment; the vertical attachment energy (VAE) is smaller than its experimental counterpart

  1. Synthesis, in vitro validation and in vivo pharmacokinetics of [{sup 125}I]N-[2-(4-iodophenyl)ethyl]-N-methyl-2-(1-piperidinyl) ethylamine: A high-affinity ligand for imaging sigma receptor positive tumors

    Energy Technology Data Exchange (ETDEWEB)

    John, Christy S; Gulden, Mary E; Vilner, Bertold J; Bowen, Wayne D

    1996-08-01

    N-[2-(4-iodophenyl)ethyl]-N-methyl-2-(1-piperidinyl)ethylamine, IPEMP, and the corresponding bromo derivative, BrPEMP, have been synthesized and characterized. Both BrPEMP and IPEMP were evaluated for sigma-1 and sigma-2 subtype receptor affinities and found to possess very high affinities for both receptor subtypes. The precursor for radioiodination n-tributylstannylphenylethylpiperidinylethylamine was prepared from its bromo derivative by palladium-catalyzed stannylation reaction. Radioiodinated 4-[{sup 125}I]PEMP was readily prepared in high yields and high specific activity by oxidative iododestannylation reaction using chloramine-T as oxidizing agent. Sites labeled by 4-[{sup 125}I]PEMP in guinea pig brain membranes showed high affinity for BD1008, haloperidol, and (+)-pentazocine (Ki = 5.06 {+-} 0.40, 32.6 {+-} 2.75, and 48.1 {+-} 8.60 nM, respectively), which is consistent with sigma receptor pharmacology. Competition binding studies of 4-[{sup 125}I]PEMP in melanoma (A375) and MCF-7 breast cancer cells showed a high affinity, dose-dependent inhibition of binding with known sigma ligand N-[2-(3,4-dichlorophenyl)ethyl]-N-methyl-2-(1-pyrrolidinyl) ethylamine, BD1008 (Ki = 5, 11 nM, respectively), supporting the labeling of sigma sites in these cells. Haloperidol, however showed a weaker (Ki 100-200 nM) affinity for the sites labeled by 4-[{sup 125}I]PEMP in these cells. Biodistribution studies of 4-[{sup 125}I]PEMP in rats showed a fast clearance of this radiopharmaceutical from blood, liver, lung, and other organs. A co-injection of 4-IPEMP with 4-[{sup 125}I]PEMP resulted in 37%, 69%, and 35% decrease in activity in liver, kidney, and brain (organs possessing sigma receptors), respectively at 1-h postinjection. These results suggest that 4-[{sup 125}I]PEMP is a promising radiopharmaceutical for pursuing further studies in animal models with tumors.

  2. Electron affinity and excited states of methylglyoxal

    Science.gov (United States)

    Dauletyarov, Yerbolat; Dixon, Andrew R.; Wallace, Adam A.; Sanov, Andrei

    2017-07-01

    Using photoelectron imaging spectroscopy, we characterized the anion of methylglyoxal (X2A″ electronic state) and three lowest electronic states of the neutral methylglyoxal molecule: the closed-shell singlet ground state (X1A'), the lowest triplet state (a3A″), and the open-shell singlet state (A1A″). The adiabatic electron affinity (EA) of the ground state, EA(X1A') = 0.87(1) eV, spectroscopically determined for the first time, compares to 1.10(2) eV for unsubstituted glyoxal. The EAs (adiabatic attachment energies) of two excited states of methylglyoxal were also determined: EA(a3A″) = 3.27(2) eV and EA(A1A″) = 3.614(9) eV. The photodetachment of the anion to each of these two states produces the neutral species near the respective structural equilibria; hence, the a3A″ ← X2A″ and A1A″ ← X2A″ photodetachment transitions are dominated by intense peaks at their respective origins. The lowest-energy photodetachment transition, on the other hand, involves significant geometry relaxation in the X1A' state, which corresponds to a 60° internal rotation of the methyl group, compared to the anion structure. Accordingly, the X1A' ← X2A″ transition is characterized as a broad, congested band, whose vertical detachment energy, VDE = 1.20(4) eV, significantly exceeds the adiabatic EA. The experimental results are in excellent agreement with the ab initio predictions using several equation-of-motion methodologies, combined with coupled-cluster theory.

  3. Supramolecular Chemistry of Environmentally Relevant Anions

    International Nuclear Information System (INIS)

    Bowman-James, Kristin; Moyer, B.A.; Sessler, Jonathan L.

    2003-01-01

    The goal of this project is the development of highly selective extractants for anions targeting important and timely problems of critical interest to the EMSP mission. In particular, sulfate poses a special problem in cleaning up the Hanford waste tanks in that it interferes with vitrification, but available technologies for sulfate removal are limited. The basic chemical aspects of anion receptor design of functional pH independent systems as well as design of separations strategies for selective and efficient removal of targeted anions have been probed. Key findings include: (1) some of the first synthetic sulfate-selective anion-binding agents; (2) simple, structure-based methods for modifying the intrinsic anion selectivity of a given class of anion receptors; and (3) the first system capable of extracting sulfate from acidic, nitrate-containing aqueous media. Receptor design, structural influences on anion binding affinities, and findings from liquid-liquid extraction studies will be discussed

  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. Anionic polymerization of acrylates. XII. Polymerization of methyl methacrylate and tert-butyl acrylate initiated with alkyllithiums or methyl 2-lithioisobutyrate in the presence of lithium tert-butoxide

    Czech Academy of Sciences Publication Activity Database

    Vlček, Petr; Otoupalová, Jaroslava; Janata, Miroslav; Látalová, Petra; Masař, Bohumil; Toman, Luděk

    2002-01-01

    Roč. 43, č. 25 (2002), s. 7179-7184 ISSN 0032-3861 R&D Projects: GA ČR GA203/01/0513; GA MŠk OC P1.10 Institutional research plan: CEZ:AV0Z4050913 Keywords : ligated anionic polymerization * (meth)acrylates * lithium tert-butoxide Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.838, year: 2002

  6. Effect of cation-anion interactions on the structural and vibrational properties of 1-buthyl-3-methyl imidazolium nitrate ionic liquid

    Science.gov (United States)

    Kausteklis, Jonas; Aleksa, Valdemaras; Iramain, Maximiliano A.; Brandán, Silvia Antonia

    2018-07-01

    The cation-anion interactions present in the 1-butyl-3-methylimidazolium nitrate ionic liquid [BMIm][NO3] were studied by using density functional theory (DFT) calculations and the experimental FT-Raman spectrum in liquid phase and its available FT-IR spectrum. For the three most stable conformers found in the potential energy surface and their 1-butyl-3-methylimidazolium [BMIm] cation, the atomic charges, molecular electrostatic potentials, stabilization energies, bond orders and topological properties were computed by using NBO and AIM calculations and the hybrid B3LYP level of theory with the 6-31G* and 6-311++G** basis sets. The force fields, force constants and complete vibrational assignments were also reported for those species by using their internal coordinates and the scaled quantum mechanical force field (SQMFF) approach. The dimeric species of [BMIm][NO3] were also considered because their presence could probably explain the most intense bands observed at 1344 and 1042 cm-1 in both experimental FT-IR and FT-Raman spectra, respectively. The geometrical parameters suggest monodentate cation-anion coordination while the studies by charges, NBO and AIM calculations support bidentate coordinations between those two species. Additionally several quantum chemical descriptors were also calculated in order to interpret various molecular properties such as electronic structure, reactivity of those species and predict their gas phase behaviours.

  7. Effect of Anion on Behaviour of Li-S Battery Electrolyte Solutions Based on N-Methyl-N-Butyl-Pyrrolidinium Ionic Liquids

    International Nuclear Information System (INIS)

    Barghamadi, Marzieh; Best, Adam S.; Bhatt, Anand I.; Hollenkamp, Anthony F.; Mahon, Peter J.; Musameh, Mustafa; Rüther, Thomas

    2015-01-01

    The electrochemical behaviour and electrical performance are investigated for a series of lithium-sulfur (Li-S) cells in which the electrolyte solutions are organic solvent-ionic liquid mixtures that are based on the 1-butyl-1-methylpyrrolidinium (C 4 mpyr) cation with a range of anions. In each case, performance is compared with cells that are based on a standard mixed-ether organic electrolyte. The capacity of cells assembled with electrolytes containing 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl) trifluorophosphate (C 4 mpyr-FAP), 1-butyl-1-methylpyrrolidinium trifluoromethanesulfonate (C 4 mpyr-OTf), or 1-butyl-1-methylpyrrolidinium tricyanomethanide (C 4 mpyr-TCM) decline rapidly due to low conductivity, high polysulfide solubility and side reaction of electrolyte with electrodes, respectively. Our results confirm that polysulfide solubility is strongly controlled by the anion of the ionic liquid and verify that not all ionic liquids decrease polysulfide solubility. In agreement with previous reports, 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl) imide (C 4 mpyr-TFSI) shows the best compatibility in Li-S batteries and has a higher coulombic efficiency of greater than 99% over 100 cycles. Furthermore, impedance spectroscopy confirms that electrolyte composition influences the SEI layer formed on the lithium anode and its subsequent impedance.

  8. Probing structure, thermochemistry, electron affinity, and magnetic moment of thulium-doped silicon clusters TmSi n (n = 3-10) and their anions with density functional theory.

    Science.gov (United States)

    Huang, Xintao; Yang, Jucai

    2017-12-26

    The most stable structures and electronic properties of TmSi n (n = 3-10) clusters and their anions have been probed by using the ABCluster global search technique combined with the PBE, TPSSh, and B3LYP density functional methods. The results revealed that the most stable structures of neutral TmSi n and their anions can be regarded as substituting a Si atom of the ground state structure of Si n + 1 with a Tm atom. The reliable AEAs, VDEs and simulated PES of TmSi n (n = 3-10) are presented. Calculations of HOMO-LUMO gap revealed that introducing Tm atom to Si cluster can improve photochemical reactivity of the cluster. The NPA analyses indicated that the 4f electron of Tm atom in TmSi n (n = 3-10) and their anions do not participate in bonding. The total magnetic moments of TmSi n are mainly provided by the 4f electrons of Tm atom. The dissociation energy of Tm atom from the most stable structure of TmSi n and their anions has been calculated to examine relative stability.

  9. The Thermodynamics of Anion Complexation to Nonpolar Pockets.

    Science.gov (United States)

    Sullivan, Matthew R; Yao, Wei; Tang, Du; Ashbaugh, Henry S; Gibb, Bruce C

    2018-02-08

    The interactions between nonpolar surfaces and polarizable anions lie in a gray area between the hydrophobic and Hofmeister effects. To assess the affinity of these interactions, NMR and ITC were used to probe the thermodynamics of eight anions binding to four different hosts whose pockets each consist primarily of hydrocarbon. Two classes of host were examined: cavitands and cyclodextrins. For all hosts, anion affinity was found to follow the Hofmeister series, with associations ranging from 1.6-5.7 kcal mol -1 . Despite the fact that cavitand hosts 1 and 2 possess intrinsic negative electrostatic fields, it was determined that these more enveloping hosts generally bound anions more strongly. The observation that the four hosts each possess specific anion affinities that cannot be readily explained by their structures, points to the importance of counter cations and the solvation of the "empty" hosts, free guests, and host-guest complexes, in defining the affinity.

  10. Formation of interstellar anions

    Science.gov (United States)

    Senent, Maria Luisa

    2012-05-01

    Formation of interstellar anions: M.L. Senent. The recent detection of negative charged species in the ISM1 has instigated enthusiasm for anions in the astrophysical community2. Many of these species are new and entail characterization. How they are formed in astrophysical sources is a question of major relevance. The anion presence in ISM was first predicted theoretically on the basis of electron affinities and on the negative linear chain molecular stabilities. Although very early, they were considered in astrochemical models3-4, their discovery is so recent because their abundances seem to be relatively low. These have to be understood in terms of molecular stabilities, reaction probabilities and radiative and collisional excitations. Then, we present our theoretical work on even carbon chains type Cn and CnH (n=2,4,6) focused to the understanding of anion abundances. We use highly correlated ab initio methods. We performed spectroscopic studies of various isomers that can play important roles as intermediates5-8. In previous papers9-10, we compared C2H and C2H- collisional rates responsible for observed line intensities. Actually, we study hydrogen attachment (Cn +H → CnH and Cn- +H → CnH-) and associative detachment processes (Cn- +H → CnH +e-) for 2, 4 and 6 carbon atom chains11. [1] M.C.McCarthy, C.A.Gottlieb, H.Gupta, P.Thaddeus, Astrophys.J, 652, L141 (2006) [2] V.M.Bierbaum, J.Cernicharo, R.Bachiller, eds., 2011, pp 383-389. [3] A. Dalgarno, R.A. Mc Cray, Astrophys.J,, 181, 95 (1973) [4] E. Herbst E., Nature, 289, 656 (1981); [5] H.Massó, M.L.Senent, P.Rosmus, M.Hochlaf, J.Chem.Phys., 124, 234304 (2006) [6] M.L.Senent, M.Hochlaf, Astrophys. J. , 708, 1452(2010) [7] H.Massó, M.L.Senent, J.Phys.Chem.A, 113, 12404 (2009) [8] D. Hammoutene, M.Hochlaf, M.L.Senent, submitted. [9] A. Spielfiedel, N. Feautrier, F. Najar, D. ben Abdallah, F. Dayou, M.L. Senent, F. Lique, Mon.Not.R.Astron.Soc., 421, 1891 (2012) [10] F.Dumouchel, A, Spielfieldel , M

  11. Providing affinity

    DEFF Research Database (Denmark)

    Guglielmi, Michel; Johannesen, Hl

    2004-01-01

    , Essex, Hertfordshire, Norfolk and Suffolk. Research found that there was a lack of identity or sense of belonging and nothing anchoring people to the region as a whole. Common affinity is somehow forced to the people of East England and thereby we came to the conclusion that a single landmark...... and potential situations but also virtual events that calls for an undeterminated process of resolution. This process is activated by the user who co-produces the actualisation as an answer to a virtual reality that we defined at the first place. The potential situations or the possible it is a fantomatic real....... The possible is like the real. It is determinated and it only lakes existence. While the possible is already made, the virtual is like a problematic which needs to be resolved and actualized. Our installations are based on high tech interactivity where we use sensors and remote communication to offer a sense...

  12. Using remote substituents to control solution structure and anion binding in lanthanide complexes

    DEFF Research Database (Denmark)

    Tropiano, Manuel; Blackburn, Octavia A.; Tilney, James A.

    2013-01-01

    A study of the anion-binding properties of three structurally related lanthanide complexes, which all contain chemically identical anion-binding motifs, has revealed dramatic differences in their anion affinity. These arise as a consequence of changes in the substitution pattern on the periphery ...

  13. Crystal structure of an organic–inorganic supra­molecular salt based on a 4,4′-methyl­enebis(3,5-dimethyl-1H-pyrazol-2-ium) cation and a β-octa­molybdate anion

    Science.gov (United States)

    Amarante, Tatiana R.; Gonçalves, Isabel S.; Almeida Paz, Filipe A.

    2016-01-01

    The asymmetric unit of the title compound, bis­[4,4′-methyl­enebis(3,5-dimethyl-1H-pyrazol-2-ium)] β-octa­molybdate, (C11H18N4)2[Mo8O26] or (H4mbdpz)2[Mo8O26], is composed of an H4mbdpz2+ cation and half of the β-octa­molybdate anion which is completed by inversion symmetry. The organic mol­ecular units are engaged in a series of N—H⋯O hydrogen bonds with neighbouring anions, with N⋯O distances and N—H⋯O angles in the ranges 2.730 (2)–2.941 (2) Å and 122–166°, respectively. These inter­actions lead to the formation of a supra­molecular two-dimensional network parallel to the (010) plane. PMID:26958369

  14. Report: Affinity Chromatography.

    Science.gov (United States)

    Walters, Rodney R.

    1985-01-01

    Supports, affinity ligands, immobilization, elution methods, and a number of applications are among the topics considered in this discussion of affinity chromatography. An outline of the basic principles of affinity chromatography is included. (JN)

  15. Coumarin amide derivatives as fluorescence chemosensors for cyanide anions

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Qianqian [School of Material Science and Engineering, Shandong Provincial Key Laboratory of Preparation and Measurement of Building Materials, University of Jinan, Jinan 250022, Shandong (China); Liu, Zhiqiang [State Key Laboratory of Crystal Materials, Shandong University, Jinan 250100, Shandong (China); Cao, Duxia, E-mail: duxiacao@ujn.edu.cn [School of Material Science and Engineering, Shandong Provincial Key Laboratory of Preparation and Measurement of Building Materials, University of Jinan, Jinan 250022, Shandong (China); Guan, Ruifang, E-mail: mse_guanrf@ujn.edu.cn [School of Material Science and Engineering, Shandong Provincial Key Laboratory of Preparation and Measurement of Building Materials, University of Jinan, Jinan 250022, Shandong (China); Wang, Kangnan; Shan, Yanyan; Xu, Yongxiao; Ma, Lin [School of Material Science and Engineering, Shandong Provincial Key Laboratory of Preparation and Measurement of Building Materials, University of Jinan, Jinan 250022, Shandong (China)

    2015-07-01

    Four coumarin amide derivatives with 4-methyl coumarin or pyrene as terminal group have been synthesized. Their photophysical properties and recognition properties for cyanide anions have been examined. The results indicate that the compounds can recognize cyanide anions with obvious absorption and fluorescence spectra change, at the same time, obvious color and fluorescence change can be observed by naked eye. The in situ hydrogen nuclear magnetic resonance spectra and photophysical properties change confirm that Michael additions between the chemosensors and cyanide anions take place at the 4-position of coumarin. - Highlights: • Four coumarin amide derivatives with 4-methyl coumarin or pyrene as terminal group were synthesized. • The compounds can recognize cyanide anions with obvious absorption and fluorescence spectra change. • Michael additions between the chemosensors and cyanide anions take place at the 4-position of coumarin.

  16. Photoelectron spectroscopy of the 6-azauracil anion.

    Science.gov (United States)

    Chen, Jing; Buonaugurio, Angela; Dolgounitcheva, Olga; Zakrzewski, V G; Bowen, Kit H; Ortiz, J V

    2013-02-14

    We report the photoelectron spectrum of the 6-azauracil anion. The spectrum is dominated by a broad band exhibiting a maximum at an electron binding energy (EBE) of 1.2 eV. This spectral pattern is indicative of a valence anion. Our calculations were carried out using ab initio electron propagator and other many-body methods. Comparison of the anion and corresponding neutral of 6-azauracil with those of uracil shows that substituting a nitrogen atom for C-H at the C6 position of uracil gives rise to significant changes in the electronic structure of 6-azauracil versus that of uracil. The adiabatic electron affinity (AEA) of the canonical 6-azauracil tautomer is substantially larger than that of canonical uracil. Among the five tautomeric, 6-azauracil anions studied computationally, the canonical structure was found to be the most stable. The vertical detachment energies (VDE) of the canonical, valence-bound anion of 6-azauracil and its closest "very-rare" tautomer have been calculated. Electron propagator calculations on the canonical anion yield a VDE value that is in close agreement with the experimentally determined VDE value of 1.2 eV. The AEA value of 6-azauracil, assessed at the CCSD(T) level of theory to be 0.5 eV, corresponds with the EBE value of the onset of the experimental spectrum.

  17. Anion exchange membrane

    Science.gov (United States)

    Verkade, John G; Wadhwa, Kuldeep; Kong, Xueqian; Schmidt-Rohr, Klaus

    2013-05-07

    An anion exchange membrane and fuel cell incorporating the anion exchange membrane are detailed in which proazaphosphatrane and azaphosphatrane cations are covalently bonded to a sulfonated fluoropolymer support along with anionic counterions. A positive charge is dispersed in the aforementioned cations which are buried in the support to reduce the cation-anion interactions and increase the mobility of hydroxide ions, for example, across the membrane. The anion exchange membrane has the ability to operate at high temperatures and in highly alkaline environments with high conductivity and low resistance.

  18. Anions in Cometary Comae

    Science.gov (United States)

    Charnley, Steven B.

    2011-01-01

    The presence of negative ions (anions) in cometary comae is known from Giotto mass spectrometry of IP/Halley. The anions 0-, OH-, C-, CH- and CN- have been detected, as well as unidentified anions with masses 22-65 and 85-110 amu (Chaizy et al. 1991). Organic molecular anions are known to have a significant impact on the charge balance of interstellar clouds and circumstellar envelopes and have been shown to act as catalysts for the gas-phase synthesis of larger hydrocarbon molecules in the ISM, but their importance in cometary comae has not yet been explored. We present details of the first attempt to model the chemistry of anions in cometary comae. Based on the combined chemical and hydro dynamical model of Rodgers & Charnley (2002), we investigate the role of large carbon-chain anions in cometary coma chemistry. We calculate the effects of these anions on coma thermodynamics, charge balance and examine their impact on molecule formation.

  19. The correlation of cathodic peak potentials of vitamin K(3) derivatives and their calculated electron affinities. The role of hydrogen bonding and conformational changes.

    Science.gov (United States)

    Nasiri, Hamid Reza; Panisch, Robin; Madej, M Gregor; Bats, Jan W; Lancaster, C Roy D; Schwalbe, Harald

    2009-06-01

    2-methyl-1,4-naphtoquinone 1 (vitamin K(3), menadione) derivatives with different substituents at the 3-position were synthesized to tune their electrochemical properties. The thermodynamic midpoint potential (E(1/2)) of the naphthoquinone derivatives yielding a semi radical naphthoquinone anion were measured by cyclic voltammetry in the aprotic solvent dimethoxyethane (DME). Using quantum chemical methods, a clear correlation was found between the thermodynamic midpoint potentials and the calculated electron affinities (E(A)). Comparison of calculated and experimental values allowed delineation of additional factors such as the conformational dependence of quinone substituents and hydrogen bonding which can influence the electron affinities (E(A)) of the quinone. This information can be used as a model to gain insight into enzyme-cofactor interactions, particularly for enzyme quinone binding modes and the electrochemical adjustment of the quinone motif.

  20. Gas-Phase Reactivity of Microsolvated Anions

    DEFF Research Database (Denmark)

    Thomsen, Ditte Linde

    the gas-phase α-effect. The experimental studies are performed by means of the flowing after glow selected ion flow tube technique, and these are supplemented by electronic structure calculations. The α-nucleophile employed is the microsolvated hydrogen peroxide anion whose reactivity is compared......Gas-phase studies of ion-molecule reactions shed light on the intrinsic factors that govern reactivity; and even solvent effects can be examined in the gasphase environment by employing microsolvated ions. An area that has received considerable attention with regard to the interplay between...... to that of a series of microsolvated oxygen centered anions. The association of the nucleophiles with a single water or methanol molecule allows the α-effect to be observed in the SN2 reaction with methyl chloride; this effect was not apparent in the reactions of the unsolvated anions. The results suggest...

  1. Revisiting the electrochemical formation, stability and structure of radical and biradical anionic structures in dinitrobenzenes

    Energy Technology Data Exchange (ETDEWEB)

    Hernandez-Munoz, Lindsay S.; Gonzalez, Felipe J. [Departamento de Quimica, Centro de Investigacion y Estudios Avanzados, Av. I.P.N. 2508. Col. San Pedro Zacatenco, 07360, D.F. (Mexico); Gonzalez, Ignacio [Departamento de Quimica, Universidad Autonoma Metropolitana-Iztapalapa, Area de Electroquimica, Apartado Postal 55-534, 09340, D.F. (Mexico); Goulart, Marilia O.F.; Abreu, Fabiane Caxico de; Ribeiro, Adriana Santos [Instituto de Quimica e Biotecnologia, Universidade Federal de Alagoas, Tabuleiro do Martins, Maceio, AL, 57072-970 (Brazil); Ribeiro, Rogerio Tavares; Longo, Ricardo L. [Departamento de Quimica Fundamental, Universidade Federal de Pernambuco, Av. Prof. Luiz Freire, s/n, Cid. Universitaria, Recife, PE, 50740-540 (Brazil); Navarro, Marcelo, E-mail: navarro@ufpe.b [Departamento de Quimica Fundamental, Universidade Federal de Pernambuco, Av. Prof. Luiz Freire, s/n, Cid. Universitaria, Recife, PE, 50740-540 (Brazil); Frontana, Carlos, E-mail: ultrabuho@yahoo.com.m [Departamento de Quimica, Centro de Investigacion y Estudios Avanzados, Av. I.P.N. 2508. Col. San Pedro Zacatenco, 07360, D.F. (Mexico)

    2010-11-30

    The effects of the position of a second nitroaromatic group (orthovs.paravs.meta) during reduction of nitrobenzenes were analysed. Cyclic voltammetric experiments in acetonitrile solution revealed that ortho-, meta- and para-dinitrobenzenes show two reversible reduction processes. An Electrochemical-Electron Spin Resonance (E-ESR) study showed that the corresponding radical anions of the ortho and para derivatives, electrogenerated during the first electron transfer uptake, remain the same even after the second monoelectronic process, increasing their intensity due to the presence of a comproportionation process (A{sup 2-} + A {yields} 2A{center_dot}{sup -}). For the case of the meta derivative, the electrogenerated radical anion at the first reduction peak is consumed at the second reduction step, forming a secondary radical species. During the electrochemical study of methyl 3,5-dinitrobenzoate, two successive and reversible electron processes were also observed; however, in this case, a very rare biradical dianion structure was found. The use of ESR-spectroelectrochemistry shed some light on controversial aspects of nitroaromatic reduction, especially concerning the second and further waves. These results were corroborated and interpreted with quantum chemical calculations of the molecular and electronic structures, electron affinities and spin densities. As a result, electrochemical mechanisms are presented and discussed.

  2. Revisiting the electrochemical formation, stability and structure of radical and biradical anionic structures in dinitrobenzenes

    International Nuclear Information System (INIS)

    Hernandez-Munoz, Lindsay S.; Gonzalez, Felipe J.; Gonzalez, Ignacio; Goulart, Marilia O.F.; Abreu, Fabiane Caxico de; Ribeiro, Adriana Santos; Ribeiro, Rogerio Tavares; Longo, Ricardo L.; Navarro, Marcelo; Frontana, Carlos

    2010-01-01

    The effects of the position of a second nitroaromatic group (orthovs.paravs.meta) during reduction of nitrobenzenes were analysed. Cyclic voltammetric experiments in acetonitrile solution revealed that ortho-, meta- and para-dinitrobenzenes show two reversible reduction processes. An Electrochemical-Electron Spin Resonance (E-ESR) study showed that the corresponding radical anions of the ortho and para derivatives, electrogenerated during the first electron transfer uptake, remain the same even after the second monoelectronic process, increasing their intensity due to the presence of a comproportionation process (A 2- + A → 2A· - ). For the case of the meta derivative, the electrogenerated radical anion at the first reduction peak is consumed at the second reduction step, forming a secondary radical species. During the electrochemical study of methyl 3,5-dinitrobenzoate, two successive and reversible electron processes were also observed; however, in this case, a very rare biradical dianion structure was found. The use of ESR-spectroelectrochemistry shed some light on controversial aspects of nitroaromatic reduction, especially concerning the second and further waves. These results were corroborated and interpreted with quantum chemical calculations of the molecular and electronic structures, electron affinities and spin densities. As a result, electrochemical mechanisms are presented and discussed.

  3. Molecular electron affinities

    International Nuclear Information System (INIS)

    Fukuda, E.K.

    1983-01-01

    Molecular electron affinities have historically been difficult quantities to measure accurately. These difficulties arise from differences in structure between the ion and neutral as well as the existence of excited negative ion states. To circumvent these problems, relative electron affinities were determined in this dissertation by studying equilibrium electron transfer reactions using a pulsed ion cyclotron resonance (ICR) spectrometer. Direct measurement of ion and neutral concentrations for reactions of the general type, A - + B = B - + A, allow calculation of the equilibrium constant and, therefore, the free energy change. The free energy difference is related to the difference in electron affinities between A and B. A relative electron affinity scale covering a range of about 45 kcal/mol was constructed with various substituted p-benzoquinones, nitrobenzenes, anhydrides, and benzophenones. To assign absolute electron affinities, various species with accurately known electron affinities are tied to the scale via ion-cyclotron double resonance bracketing techniques. After the relative scale is anchored to these species with well-known electron affinities, the scale is then used as a check on other electron affinity values as well as generating new electron affinity values. Many discrepancies were found between the electron affinities measured using the ICR technique and previous literature determinations

  4. Continuous affine processes

    DEFF Research Database (Denmark)

    Buchardt, Kristian

    2016-01-01

    Affine processes possess the property that expectations of exponential affine transformations are given by a set of Riccati differential equations, which is the main feature of this popular class of processes. In this paper we generalise these results for expectations of more general transformati...

  5. Detection of cyanide anion by zinc porphyrin-spiropyran dyad

    International Nuclear Information System (INIS)

    Kho, Young Min; Hur, Dae Young; Shin, Eun Ju

    2016-01-01

    Versatile methods of the sensitive and selective detection for cyanide anion to monitor toxic cyanide have been developed. These include colorimetric, colorimetric, chromatographic, and electrochemical analyses. Among those methods for cyanide detection, optical methods based on absorption and fluorescence spectroscopy are relatively simple, inexpensive, and sensitive. A number of organic sensors for cyanide anion have been designed and synthesized. Absorption and/or fluorescence spectra of these sensors are changed by forming coordination complex or bonding covalently with cyanide. Compared with other anions, cyanide anion has some characteristic properties, such as its strong nucleophilicity and high binding affinity toward metal ions, and is superior and useful for the development of the sensors. Both covalent bond-based sensors and coordination complex-based sensors have been developed for cyanide detection. The results indicate that ZnP-SP plays a role as a CN"- selective, colorimetric sensor either without or with UV irradiation

  6. Detection of cyanide anion by zinc porphyrin-spiropyran dyad

    Energy Technology Data Exchange (ETDEWEB)

    Kho, Young Min; Hur, Dae Young; Shin, Eun Ju [Dept. of Chemistry, Sunchon National University, Suncheon (Korea, Republic of)

    2016-10-15

    Versatile methods of the sensitive and selective detection for cyanide anion to monitor toxic cyanide have been developed. These include colorimetric, colorimetric, chromatographic, and electrochemical analyses. Among those methods for cyanide detection, optical methods based on absorption and fluorescence spectroscopy are relatively simple, inexpensive, and sensitive. A number of organic sensors for cyanide anion have been designed and synthesized. Absorption and/or fluorescence spectra of these sensors are changed by forming coordination complex or bonding covalently with cyanide. Compared with other anions, cyanide anion has some characteristic properties, such as its strong nucleophilicity and high binding affinity toward metal ions, and is superior and useful for the development of the sensors. Both covalent bond-based sensors and coordination complex-based sensors have been developed for cyanide detection. The results indicate that ZnP-SP plays a role as a CN{sup -} selective, colorimetric sensor either without or with UV irradiation.

  7. Affinity in electrophoresis.

    Science.gov (United States)

    Heegaard, Niels H H

    2009-06-01

    The journal Electrophoresis has greatly influenced my approaches to biomolecular affinity studies. The methods that I have chosen as my main tools to study interacting biomolecules--native gel and later capillary zone electrophoresis--have been the topic of numerous articles in Electrophoresis. Below, the role of the journal in the development and dissemination of these techniques and applications reviewed. Many exhaustive reviews on affinity electrophoresis and affinity CE have been published in the last few years and are not in any way replaced by the present deliberations that are focused on papers published by the journal.

  8. Lectin affinity electrophoresis.

    Science.gov (United States)

    Kobayashi, Yuka

    2014-01-01

    An interaction or a binding event typically changes the electrophoretic properties of a molecule. Affinity electrophoresis methods detect changes in the electrophoretic pattern of molecules (mainly macromolecules) that occur as a result of biospecific interactions or complex formation. Lectin affinity electrophoresis is a very effective method for the detection and analysis of trace amounts of glycobiological substances. It is particularly useful for isolating and separating the glycoisomers of target molecules. Here, we describe a sensitive technique for the detection of glycoproteins separated by agarose gel-lectin affinity electrophoresis that uses antibody-affinity blotting. The technique is tested using α-fetoprotein with lectin (Lens culinaris agglutinin and Phaseolus vulgaris agglutinin)-agarose gels.

  9. A Generalized Affine Isoperimetric Inequality

    OpenAIRE

    Chen, Wenxiong; Howard, Ralph; Lutwak, Erwin; Yang, Deane; Zhang, Gaoyong

    2004-01-01

    A purely analytic proof is given for an inequality that has as a direct consequence the two most important affine isoperimetric inequalities of plane convex geometry: The Blaschke-Santalo inequality and the affine isoperimetric inequality of affine differential geometry.

  10. Electron affinities: theoretical

    International Nuclear Information System (INIS)

    Kaufman, J.J.

    1976-01-01

    A brief description is given of the conceptual background and formalism of the various ab-initio and semi-ab-initio quantum computational techniques for calculating atomic and molecular electron affinities: Hartree--Fock--Roothaan SCF, configuration interaction (CI), multiconfiguration SCF (MC-SCF), Bethe--Goldstone, superposition of configurations (SOC), ab-initio effective core model potentials, Xα-MS, plus other less common methods. Illustrative and comparative examples of electron affinities calculated by these various methods are presented

  11. Anion photoelectron spectroscopy of radicals and clusters

    Energy Technology Data Exchange (ETDEWEB)

    Travis, Taylor R. [Univ. of California, Berkeley, CA (United States)

    1999-12-01

    Anion photoelectron spectroscopy is used to study free radicals and clusters. The low-lying 2Σ and 2π states of C2nH (n = 1--4) have been studied. The anion photoelectron spectra yielded electron affinities, term values, and vibrational frequencies for these combustion and astrophysically relevant species. Photoelectron angular distributions allowed the author to correctly assign the electronic symmetry of the ground and first excited states and to assess the degree of vibronic coupling in C2H and C4H. Other radicals studied include NCN and I3. The author was able to observe the low-lying singlet and triplet states of NCN for the first time. Measurement of the electron affinity of I3 revealed that it has a bound ground state and attachment of an argon atom to this moiety enabled him to resolve the symmetric stretching progression.

  12. Introducing various ligands into superhalogen anions reduces their electronic stabilities

    Science.gov (United States)

    Smuczyńska, Sylwia; Skurski, Piotr

    2008-02-01

    The vertical electron detachment energies (VDE) of six NaX2- anions (where X = F, Cl, Br) were calculated at the OVGF level with the 6-311++G(3df) basis sets. In all the cases studied the VDE exceeds the electron affinity of chlorine atom and thus those species were classified as superhalogen anions. The largest vertical binding energy was found for the NaF2- system (6.644 eV). The strong VDE dependence on the ligand type, ligand-central atom distance, and the character of the highest occupied molecular orbital (HOMO) was observed and discussed.

  13. Interaction of environmental contaminants with zebrafish organic anion transporting polypeptide, Oatp1d1 (Slco1d1)

    Energy Technology Data Exchange (ETDEWEB)

    Popovic, Marta; Zaja, Roko [Laboratory for Molecular Ecotoxicology, Division for Marine and Environmental Research, Rudjer Boskovic Institute, Bijenicka 54, 10 000 Zagreb (Croatia); Fent, Karl [University of Applied Sciences Northwestern Switzerland, School of Life Sciences, Gründenstrasse 40, CH-4132 Muttenz (Switzerland); Swiss Federal Institute of Technology (ETH Zürich), Department of Environmental System Sciences, Institute of Biogeochemistry and Pollution Dynamics, CH-8092 Zürich (Switzerland); Smital, Tvrtko, E-mail: smital@irb.hr [Laboratory for Molecular Ecotoxicology, Division for Marine and Environmental Research, Rudjer Boskovic Institute, Bijenicka 54, 10 000 Zagreb (Croatia)

    2014-10-01

    Polyspecific transporters from the organic anion transporting polypeptide (OATP/Oatp) superfamily mediate the uptake of a wide range of compounds. In zebrafish, Oatp1d1 transports conjugated steroid hormones and cortisol. It is predominantly expressed in the liver, brain and testes. In this study we have characterized the transport of xenobiotics by the zebrafish Oatp1d1 transporter. We developed a novel assay for assessing Oatp1d1 interactors using the fluorescent probe Lucifer yellow and transient transfection in HEK293 cells. Our data showed that numerous environmental contaminants interact with zebrafish Oatp1d1. Oatp1d1 mediated the transport of diclofenac with very high affinity, followed by high affinity towards perfluorooctanesulfonic acid (PFOS), nonylphenol, gemfibrozil and 17α-ethinylestradiol; moderate affinity towards carbaryl, diazinon and caffeine; and low affinity towards metolachlor. Importantly, many environmental chemicals acted as strong inhibitors of Oatp1d1. A strong inhibition of Oatp1d1 transport activity was found by perfluorooctanoic acid (PFOA), chlorpyrifos-methyl, estrone (E1) and 17β-estradiol (E2), followed by moderate to low inhibition by diethyl phthalate, bisphenol A, 7-acetyl-1,1,3,4,4,6-hexamethyl-1,2,3,4 tetrahydronapthalene and clofibrate. In this study we identified Oatp1d1 as a first Solute Carrier (SLC) transporter involved in the transport of a wide range of xenobiotics in fish. Considering that Oatps in zebrafish have not been characterized before, our work on zebrafish Oatp1d1 offers important new insights on the understanding of uptake processes of environmental contaminants, and contributes to the better characterization of zebrafish as a model species. - Highlights: • We optimized a novel assay for determination of Oatp1d1 interactors • Oatp1d1 is the first SLC characterized fish xenobiotic transporter • PFOS, nonylphenol, diclofenac, EE2, caffeine are high affinity Oatp1d1substrates • PFOA, chlorpyrifos-methyl

  14. Interaction of environmental contaminants with zebrafish organic anion transporting polypeptide, Oatp1d1 (Slco1d1)

    International Nuclear Information System (INIS)

    Popovic, Marta; Zaja, Roko; Fent, Karl; Smital, Tvrtko

    2014-01-01

    Polyspecific transporters from the organic anion transporting polypeptide (OATP/Oatp) superfamily mediate the uptake of a wide range of compounds. In zebrafish, Oatp1d1 transports conjugated steroid hormones and cortisol. It is predominantly expressed in the liver, brain and testes. In this study we have characterized the transport of xenobiotics by the zebrafish Oatp1d1 transporter. We developed a novel assay for assessing Oatp1d1 interactors using the fluorescent probe Lucifer yellow and transient transfection in HEK293 cells. Our data showed that numerous environmental contaminants interact with zebrafish Oatp1d1. Oatp1d1 mediated the transport of diclofenac with very high affinity, followed by high affinity towards perfluorooctanesulfonic acid (PFOS), nonylphenol, gemfibrozil and 17α-ethinylestradiol; moderate affinity towards carbaryl, diazinon and caffeine; and low affinity towards metolachlor. Importantly, many environmental chemicals acted as strong inhibitors of Oatp1d1. A strong inhibition of Oatp1d1 transport activity was found by perfluorooctanoic acid (PFOA), chlorpyrifos-methyl, estrone (E1) and 17β-estradiol (E2), followed by moderate to low inhibition by diethyl phthalate, bisphenol A, 7-acetyl-1,1,3,4,4,6-hexamethyl-1,2,3,4 tetrahydronapthalene and clofibrate. In this study we identified Oatp1d1 as a first Solute Carrier (SLC) transporter involved in the transport of a wide range of xenobiotics in fish. Considering that Oatps in zebrafish have not been characterized before, our work on zebrafish Oatp1d1 offers important new insights on the understanding of uptake processes of environmental contaminants, and contributes to the better characterization of zebrafish as a model species. - Highlights: • We optimized a novel assay for determination of Oatp1d1 interactors • Oatp1d1 is the first SLC characterized fish xenobiotic transporter • PFOS, nonylphenol, diclofenac, EE2, caffeine are high affinity Oatp1d1substrates • PFOA, chlorpyrifos-methyl

  15. Ab initio theoretical study of dipole-bound anions of molecular complexes: (HF)3- and (HF)4- anions

    Science.gov (United States)

    Ramaekers, Riet; Smith, Dayle M. A.; Smets, Johan; Adamowicz, Ludwik

    1997-12-01

    Ab initio calculations have been performed to determine structures and vertical electron detachment energy (VDE) of the hydrogen fluoride trimer and tetramer anions, (HF)3- and (HF)4-. In these systems the excess electron is bound by the dipole field of the complex. It was determined that, unlike the neutral complexes which prefer the cyclic structures, the equilibrium geometries of the anions have "zig-zag" shapes. For both complexes the predicted VDEs are positive [210 meV and 363 meV for (HF)3- and (HF)4-, respectively], indicating that the anions are stable systems with respect to the vertical electron detachment. These results were obtained at the coupled-cluster level of theory with single, double and triple excitations [CCSD(T) method; the triple-excitation contribution in this method is calculated approximately using the perturbation approach] with the anion geometries obtained using the second-order Møller-Plesset perturbation theory (MP2) method. The same approach was also used to determine the adiabatic electron affinities (AEA) of (HF)3 and (HF)4. In addition to the electronic contribution, we also calculated the contributions (using the harmonic approximation) resulting from different zero-point vibration energies of the neutral and anionic clusters. The calculations predicted that while the AEA of (HF)3 is positive (44 meV), the AEA for (HF)4 is marginally negative (-16 meV). This suggests that the (HF)3- anion should be a stable system, while the (HF)4- is probably metastable.

  16. Solution and gas phase evidence of anion binding through the secondary bonding interactions of a bidentate bis-antimony(iii) anion receptor.

    Science.gov (United States)

    Qiu, J; Song, B; Li, X; Cozzolino, A F

    2017-12-20

    The solution and gas phase halide binding to a bis-antimony(iii) anion receptor was studied. This new class of anion receptors utilizes the strong Sb-centered secondary bonding interactions (SBIs) that are formed opposite to the polar Sb-O primary bond. 1 H NMR titration data were fitted statistically to binding models and solution-phase binding energetics were extracted, while the formation of anion-to-receptor complexes was observed using ESI-MS. Density functional theory calculations suggest that their affinity towards binding halide anions is mitigated by the strong explicit solvation effect in DMSO, which gives insights into future designs that circumvent direct solvent binding and are anticipated to yield tighter and perhaps more selectivity in anion binding.

  17. Affine stochastic mortality

    NARCIS (Netherlands)

    Schrager, D.F.

    2006-01-01

    We propose a new model for stochastic mortality. The model is based on the literature on affine term structure models. It satisfies three important requirements for application in practice: analytical tractibility, clear interpretation of the factors and compatibility with financial option pricing

  18. Affine pairings on ARM

    NARCIS (Netherlands)

    Acar, T.; Lauter, K.; Naehrig, M.; Shumow, D.

    2011-01-01

    Pairings on elliptic curves are being used in an increasing number of cryptographic applications on many different devices and platforms, but few performance numbers for cryptographic pairings have been reported on embedded and mobile devices. In this paper we give performance numbers for affine and

  19. Affine pairings on ARM

    NARCIS (Netherlands)

    Acar, T.; Lauter, K.; Naehrig, M.; Shumow, D.; Abdalla, M.; Lange, T.

    2013-01-01

    We report on relative performance numbers for affine and projective pairings on a dual-core Cortex A9 ARM processor. Using a fast inversion in the base field and doing inversion in extension fields by using the norm map to reduce to inversions in smaller fields, we find a very low ratio of

  20. An Anthracene-Based Tripodal Chemosensor for Anion Sensing

    Directory of Open Access Journals (Sweden)

    Whitney A. Quinn

    2010-05-01

    Full Text Available An anthracene-based tripodal ligand was synthesized from the condensation of tren with 9-anthraldehyde, and the subsequent reduction with sodium borohydride. The neutral ligand was protonated from the reaction with p-toluenesulfonic acid to give a triply charged chemosensor that was examined for its anion binding ability toward fluoride, chloride, bromide, sulfate and nitrate by the fluorescence spectroscopy in DMSO. The addition of an anion to the ligand resulted in an enhancement in fluorescence intensity at the excitation of 310 nm. Analysis of the spectral changes suggested that the ligand formed a 1:1 complex with each of the anions, showing strong affinity for fluoride and sulfate in DMSO. The unsubstituted tren was reacted with sulfuric acid to form a sulfate complex and the structure was determined by the X-ray crystallography. Analysis of the complex revealed that three sulfates are held between two ligands by multiple hydrogen bonding interactions with protonated amines.

  1. Cell wall bound anionic peroxidases from asparagus byproducts.

    Science.gov (United States)

    Jaramillo-Carmona, Sara; López, Sergio; Vazquez-Castilla, Sara; Jimenez-Araujo, Ana; Rodriguez-Arcos, Rocio; Guillen-Bejarano, Rafael

    2014-10-08

    Asparagus byproducts are a good source of cationic soluble peroxidases (CAP) useful for the bioremediation of phenol-contaminated wastewaters. In this study, cell wall bound peroxidases (POD) from the same byproducts have been purified and characterized. The covalent forms of POD represent >90% of the total cell wall bound POD. Isoelectric focusing showed that whereas the covalent fraction is constituted primarily by anionic isoenzymes, the ionic fraction is a mixture of anionic, neutral, and cationic isoenzymes. Covalently bound peroxidases were purified by means of ion exchange chromatography and affinity chromatography. In vitro detoxification studies showed that although CAP are more effective for the removal of 4-CP and 2,4-DCP, anionic asparagus peroxidase (AAP) is a better option for the removal of hydroxytyrosol (HT), the main phenol present in olive mill wastewaters.

  2. Synthesis and anion binding properties of porphyrins and related compounds

    KAUST Repository

    Figueira, Flávio

    2016-12-02

    Over the last two decades the preparation of pyrrole-based receptors for anion recognition has attracted considerable attention. In this regard porphyrins, phthalocyanines and expanded porphyrins have been used as strong and selective receptors while the combination of those with different techniques and materials can boost their applicability in different applications as chemosensors and extracting systems. Improvements in the field, including the synthesis of this kind of compounds, can contribute to the development of efficient, cheap, and easy-to-prepare anion receptors. Extensive efforts have been made to improve the affinity and selectivity of these compounds and the continuous expansion of related research makes this chemistry even more promising. In this review, we summarize the most recent developments in anion binding studies while outlining the strategies that may be used to synthesize and functionalize these type of macrocycles. © 2016 World Scientific Publishing Company.

  3. Anion concurrence and anion selectivity in the sorption of radionuclides by organotones

    International Nuclear Information System (INIS)

    Behnsen, Julia G.

    2007-01-01

    Some long-lived and radiologically important nuclear fission products, such as I-129 (half-life t 1/2 = 1,6 . 10 7 a), Tc-99 (t 1/2 = 2,1 . 10 5 a), and Se-79 (t 1/2 = 6,5 . 10 4 a) are anionic in aqueous environments. This study focuses on the adsorption of such anions to organoclays and the understanding of the selectivity of the process. The organoclays used in this study were prepared from a bentonite (MX-80) and a vermiculite clay, and the cationic surfactants hexadcylpyridium, hexadecyltrimethylammonium, and benzethonium. Surfactant adsorption to the bentonite exceeds the cation exchange capacity of the clay, with the surplus positive charge being balanced by the co-adsorption of chloride. The interlayer distance of the bentonites is increased sufficiently to contain bi- and pseudotrimolecular structures of the surfactants. Adsorption experiments were carried out using the batch technique. Anion adsorption of iodide, perrhenate, selenite, nitrate, and sulphate is mainly due to ion exchange with chloride. As an additional adsorption mechanism, the incorporation of inorganic ion pairs into the interlayer space of the clay is proposed as a result of experiments showing differences in the adsorption levels of sodium and potassium iodide. Anion adsorption results show a clear selectivity of the organoclays, with the affinity sequence being: ReO - 4 > I - > NO - 3 > Cl - > SO 2- 4 > SeO 2- 3 . This sequence corresponds to the sequence of increasing hydration energies of the anions, thus selectivity could be due to the process of minimization of free energy of the system. (orig.)

  4. Affine field theories

    International Nuclear Information System (INIS)

    Cadavid, A.C.

    1989-01-01

    The author constructs a non-Abelian field theory by gauging a Kac-Moody algebra, obtaining an infinite tower of interacting vector fields and associated ghosts, that obey slightly modified Feynman rules. She discusses the spontaneous symmetry breaking of such theory via the Higgs mechanism. If the Higgs particle lies in the Cartan subalgebra of the Kac-Moody algebra, the previously massless vectors acquire a mass spectrum that is linear in the Kac-Moody index and has additional fine structure depending on the associated Lie algebra. She proceeds to show that there is no obstacle in implementing the affine extension of supersymmetric Yang-Mills theories. The result is valid in four, six and ten space-time dimensions. Then the affine extension of supergravity is investigated. She discusses only the loop algebra since the affine extension of the super-Poincare algebra appears inconsistent. The construction of the affine supergravity theory is carried out by the group manifold method and leads to an action describing infinite towers of spin 2 and spin 3/2 fields that interact subject to the symmetries of the loop algebra. The equations of motion satisfy the usual consistency check. Finally, she postulates a theory in which both the vector and scalar fields lie in the loop algebra of SO(3). This theory has an expanded soliton sector, and corresponding to the original 't Hooft-Polyakov solitonic solutions she now finds an infinite family of exact, special solutions of the new equations. She also proposes a perturbation method for obtaining an arbitrary solution of those equations for each level of the affine index

  5. Preparation of Cationic MOFs with Mobile Anions by Anion Stripping to Remove 2,4-D from Water

    Directory of Open Access Journals (Sweden)

    Tao Chen

    2017-07-01

    Full Text Available A cationic porous framework with mobile anions (MIL-101(Cr-Cl was easily and successfully synthesized by utilizing the stronger affinity of F− to Al3+ than Cr3+ in the charge-balanced framework of MIL-101(Cr. The structure, morphology and porosity of MIL-101(Cr-Cl were characterized. The obtained new materials retain the high surface area, good thermostability, and structure topology of MIL-101(Cr. With the mobile Cl− anion, MIL-101(Cr-Cl can be used as an ion-exchange material for anionic organic pollutions. In this work, 2,4-dichlorophenoxyacetic acid (2,4-D was used as a model to test the absorption performance of this new material. This new material exhibited improved adsorbability compared to that of the original metal-organic frameworks (MOFs. At the same time, this material also shows high anti-interference performance with changing solution pH.

  6. Anionic surface binders

    OpenAIRE

    Aljaž-Rožič Mateja; Hočevar Nežka

    2004-01-01

    The MELAMIN Chemical Factory in Kočevje manufactures synthetic resins and binders for the paper industry. Binders based on AKD (alkyl ketene dimer) are produced which are used for binding paper and cardboard in the range of neutral and partially basic pH. Cationic and, lately, anionic binders are mostly used for the bulk binding of paper and board. The possibility of using AKD binders on paper or board surfaces is presented. In this case partially cationic AKD binders may be applied. When opt...

  7. Affine and quasi-affine frames for rational dilations

    DEFF Research Database (Denmark)

    Bownik, Marcin; Lemvig, Jakob

    2011-01-01

    In this paper we extend the investigation of quasi-affine systems, which were originally introduced by Ron and Shen [J. Funct. Anal. 148 (1997), 408-447] for integer, expansive dilations, to the class of rational, expansive dilations. We show that an affine system is a frame if, and only if......, the corresponding family of quasi-affine systems are frames with uniform frame bounds. We also prove a similar equivalence result between pairs of dual affine frames and dual quasi-affine frames. Finally, we uncover some fundamental differences between the integer and rational settings by exhibiting an example...

  8. The many ways of making anionic clays

    Indian Academy of Sciences (India)

    Together with hydrotalcite-like layered double hydroxides, bivalent and trivalent metal hydroxides and their hydroxy salts are actually anionic clays consisting of positively charged hydroxide layers with anions intercalated in the interlayer region. The anionic clays exhibit anion sorption, anion diffusion and exchange ...

  9. Antibody affinity maturation

    DEFF Research Database (Denmark)

    Skjødt, Mette Louise

    Yeast surface display is an effective tool for antibody affinity maturation because yeast can be used as an all-in-one workhorse to assemble, display and screen diversified antibody libraries. By employing the natural ability of yeast Saccharomyces cerevisiae to efficiently recombine multiple DNA...... laboratory conditions. A particular emphasis was put on using molecular techniques in conjunction with microenvironmental measurements (O2, pH, irradiance), a combination that is rarely found but provides a much more detailed understanding of “cause and effect” in complex natural systems...

  10. Monoclonal antibodies specific for the organophosphate pesticide azinphos-methyl

    NARCIS (Netherlands)

    Jones, WT; Harvey, D; Jones, SD; Ryan, GB; Wynberg, H; TenHoeve, W; Reynolds, PHS

    1995-01-01

    2-(2-Mercapto-5-methyl-1,3,2-dioxaphosphorinan-5-yl,2-sulphide) methoxyacetic acid has been synthesized and used to prepare an azinphos hapten and protein conjugates. Monoclonal antibodies of high affinity against the pesticide azinphos-methyl were prepared from mice immunized with the

  11. The solutions of affine and conformal affine Toda field theory

    International Nuclear Information System (INIS)

    Papadopoulos, G.; Spence, B.

    1994-02-01

    We give new formulations of the solutions of the field equations of the affine Toda and conformal affine Toda theories on a cylinder and two-dimensional Minkowski space-time. These solutions are parameterised in terms of initial data and the resulting covariant phase spaces are diffeomorphic to the Hamiltonian ones. We derive the fundamental Poisson brackets of the parameters of the solutions and give the general static solutions for the affine theory. (authors). 10 refs

  12. Anion sensing with a Lewis acidic BODIPY-antimony(v) derivative.

    Science.gov (United States)

    Christianson, Anna M; Gabbaï, François P

    2017-02-21

    We describe the synthesis of a BODIPY dye substituted with a Lewis acidic antimony(v) moiety. This compound, which has been fully characterized, shows a high affinity for small anions including fluoride and cyanide, the complexation of which elicits a fluorescence turn-on response.

  13. Phosphazene-promoted anionic polymerization

    KAUST Repository

    Zhao, Junpeng

    2014-01-01

    In the recent surge of metal-free polymerization techniques, phosphazene bases have shown their remarkable potential as organic promoters/catalysts for the anionic polymerization of various types of monomers. By complexation with the counterion (e.g. proton or lithium cation), phosphazene base significantly improve the nucleophilicity of the initiator/chain-end resulting in rapid and usually controlled anionic/quasi-anionic polymerization. In this review, we will introduce the general mechanism, i.e. in situ activation (of initiating sites) and polymerization, and summarize the applications of such a mechanism on macromolecular engineering toward functionalized polymers, block copolymers and complex macromolecular architectures.

  14. Specificity of anion-binding in the substrate-pocket ofbacteriorhodopsin

    Energy Technology Data Exchange (ETDEWEB)

    Facciotti, Marc T.; Cheung, Vincent S.; Lunde, Christopher S.; Rouhani, Shahab; Baliga, Nitin S.; Glaeser, Robert M.

    2003-08-30

    The structure of the D85S mutant of bacteriorhodopsin with a nitrate anion bound in the Schiff-base binding site, and the structure of the anion-free protein have been obtained in the same crystal form. Together with the previously solved structures of this anion pump, in both the anion-free state and bromide-bound state, these new structures provide insight into how this mutant of bacteriorhodopsin is able to bind a variety of different anions in the same binding pocket. The structural analysis reveals that the main structural change that accommodates different anions is the repositioning of the polar side-chain of S85. On the basis of these x-ray crystal structures, the prediction is then made that the D85S/D212N double mutant might bind similar anions and do so over a broader pH range than does the single mutant. Experimental comparison of the dissociation constants, K{sub d}, for a variety of anions confirms this prediction and demonstrates, in addition, that the binding affinity is dramatically improved by the D212N substitution.

  15. Fundamentals of affinity cell separations.

    Science.gov (United States)

    Zhang, Ye; Lyons, Veronica; Pappas, Dimitri

    2018-03-01

    Cell separations using affinity methods continue to be an enabling science for a wide variety of applications. In this review, we discuss the fundamental aspects of affinity separation, including the competing forces for cell capture and elution, cell-surface interactions, and models for cell adhesion. Factors affecting separation performance such as bond affinity, contact area, and temperature are presented. We also discuss and demonstrate the effects of nonspecific binding on separation performance. Metrics for evaluating cell separations are presented, along with methods of comparing separation techniques for cell isolation using affinity capture. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Simultaneous anionic and cationic redox

    Science.gov (United States)

    Jung, Sung-Kyun; Kang, Kisuk

    2017-12-01

    It is challenging to unlock anionic redox activity, accompanied by full utilization of available cationic redox process, to boost capacity of battery cathodes. Now, material design by tuning the metal-oxygen interaction is shown to be a promising solution.

  17. Schlenk Techniques for Anionic Polymerization

    KAUST Repository

    Ratkanthwar, Kedar; Zhao, Junpeng; Zhang, Hefeng; Hadjichristidis, Nikolaos; Mays, Jimmy

    2015-01-01

    Anionic polymerization-high vacuum techniques (HVTs) are doubtlessly the most prominent and reliable experimental tools to prepare polymer samples with well-defined and, in many cases, complex macromolecular architectures. Due to the high demands

  18. Rejuvenation processes applied to 'poisoned' anion exchangers in uranium processing

    International Nuclear Information System (INIS)

    Gilmore, A.J.

    1979-11-01

    The removal of 'poisons' from anion exchangers in uranium processing of Canadian radioactive ores is commonly called rejuvenation or regeneration. The cost of the ion exchange recovery of uranium is adversely affected by a decrease in the capacity and efficiency of the anion exchangers, due to their being 'poisoned' by silica, elemental sulphur, molybdenum and tetrathionates. These 'poisons' have a high affinity for the anion exchangers, are adsorbed in preference to the uranyl complex, and do not desorb with the reagents used normally in the uranyl desorption phase. The frequency of rejuvenation and the reagents required for rejuvenation are determined by the severity of the 'poisoning' accumulated by the exchanger in contact with the uranium leach liquor. Caustic soda (NaOH) at approximately equal to 18 cents/lb is commonly used to remove uranium anion exchangers of tetrathionate ((S 4 0 6 )/-/-) 'poisons'. A potential saving in operating cost would be of consequence if other reagents, e.g. sodium carbonate (Na 2 CO 3 ) at approximately equal to 3.6 cents/lb or calcium hydroxide (Ca(OH) 2 ) at approximately equal to 1.9 cents/lb, were effective in removing (S 4 0 6 )/-/-) from a 'poisoned' exchanger. A rejuvenation process for a test program was adopted after a perusal of the literature

  19. DNA methylation

    DEFF Research Database (Denmark)

    Williams, Kristine; Christensen, Jesper; Helin, Kristian

    2012-01-01

    DNA methylation is involved in key cellular processes, including X-chromosome inactivation, imprinting and transcriptional silencing of specific genes and repetitive elements. DNA methylation patterns are frequently perturbed in human diseases such as imprinting disorders and cancer. The recent...... discovery that the three members of the TET protein family can convert 5-methylcytosine (5mC) into 5-hydroxymethylcytosine (5hmC) has provided a potential mechanism leading to DNA demethylation. Moreover, the demonstration that TET2 is frequently mutated in haematopoietic tumours suggests that the TET...... proteins are important regulators of cellular identity. Here, we review the current knowledge regarding the function of the TET proteins, and discuss various mechanisms by which they contribute to transcriptional control. We propose that the TET proteins have an important role in regulating DNA methylation...

  20. Hemoglobin affinity in Andean rodents

    Directory of Open Access Journals (Sweden)

    HRVOJ OSTOJIC

    2002-01-01

    Full Text Available Blood hemoglobin oxygen affinity (P50 was measured in three Andean species and in the laboratory rat (control, all raised near sea level. Chinchilla lanigera (Molina, 1792 has an altitudinal habitat range from low Andean slopes up to 3000 m., while Chinchilla brevicaudata (Waterhouse, 1848 has an altitudinal range from 3000 to 5000 m. The laboratory type guinea pig, wild type guinea pig (Cavia porcellus, (Waterhouse, 1748, and laboratory rat (Rattus norvegicus were also raised at sea level. The Andean species had high hemoglobin oxygen affinities (low P50 compared with the rat. Chinchilla brevicaudata had a higher affinity than Chinchilla lanigera. The wild type guinea pig had a higher affinity than the laboratory type. As has been shown in other species, this is another example of an inverse correlation between the altitude level and the P50 values. This is the first hemoglobin oxygen affinity study in Chinchilla brevicaudata.

  1. Mapping Affinities in Academic Organizations

    Directory of Open Access Journals (Sweden)

    Dario Rodighiero

    2018-02-01

    Full Text Available Scholarly affinities are one of the most fundamental hidden dynamics that drive scientific development. Some affinities are actual, and consequently can be measured through classical academic metrics such as co-authoring. Other affinities are potential, and therefore do not leave visible traces in information systems; for instance, some peers may share interests without actually knowing it. This article illustrates the development of a map of affinities for academic collectives, designed to be relevant to three audiences: the management, the scholars themselves, and the external public. Our case study involves the School of Architecture, Civil and Environmental Engineering of EPFL, hereinafter ENAC. The school consists of around 1,000 scholars, 70 laboratories, and 3 institutes. The actual affinities are modeled using the data available from the information systems reporting publications, teaching, and advising scholars, whereas the potential affinities are addressed through text mining of the publications. The major challenge for designing such a map is to represent the multi-dimensionality and multi-scale nature of the information. The affinities are not limited to the computation of heterogeneous sources of information; they also apply at different scales. The map, thus, shows local affinities inside a given laboratory, as well as global affinities among laboratories. This article presents a graphical grammar to represent affinities. Its effectiveness is illustrated by two actualizations of the design proposal: an interactive online system in which the map can be parameterized, and a large-scale carpet of 250 square meters. In both cases, we discuss how the materiality influences the representation of data, in particular the way key questions could be appropriately addressed considering the three target audiences: the insights gained by the management and their consequences in terms of governance, the understanding of the scholars’ own

  2. A Computational Study of Structure and Reactivity of N-Substitued-4-Piperidones Curcumin Analogues and Their Radical Anions

    Directory of Open Access Journals (Sweden)

    Maximiliano Martínez-Cifuentes

    2016-12-01

    Full Text Available In this work, a computational study of a series of N-substitued-4-piperidones curcumin analogues is presented. The molecular structure of the neutral molecules and their radical anions, as well as their reactivity, are investigated. N-substituents include methyl and benzyl groups, while substituents on the aromatic rings cover electron-donor and electron-acceptor groups. Substitutions at the nitrogen atom do not significantly affect the geometry and frontier molecular orbitals (FMO energies of these molecules. On the other hand, substituents on the aromatic rings modify the distribution of FMO. In addition, they influence the capability of these molecules to attach an additional electron, which was studied through adiabatic (AEA and vertical electron affinities (VEA, as well as vertical detachment energy (VDE. To study electrophilic properties of these structures, local reactivity indices, such as Fukui (f+ and Parr (P+ functions, were calculated, and show the influence of the aromatic rings substituents on the reactivity of α,β-unsaturated ketones towards nucleophilic attack. This study has potential implications for the design of curcumin analogues based on a 4-piperidone core with desired reactivity.

  3. Bis(2-methyl-4-nitroanilinium tetrachloridomercurate(II

    Directory of Open Access Journals (Sweden)

    Andreas Lemmerer

    2008-12-01

    Full Text Available The title compound, (C7H9N2O22[HgCl4], self-assembles into cationic organic bilayers containing the 2-methyl-4-nitroanilinium cations, sandwiched between anionic inorganic layers built up by the distorted tetrahedral [HgCl4]2− groups. The organic sheets are interlinked through weak C—H...O hydrogen bonds, while they interact with the anionic part via strong charge-assisted N+—H...Cl—Hg hydrogen bonds. The [HgCl4]2− anions are bisected by a mirror plane passing through the metal and two of the chloride ions.

  4. Lp-dual affine surface area

    Science.gov (United States)

    Wei, Wang; Binwu, He

    2008-12-01

    According to the notion of Lp-affine surface area by Lutwak, in this paper, we introduce the concept of Lp-dual affine surface area. Further, we establish the affine isoperimetric inequality and the Blaschke-Santaló inequality for Lp-dual affine surface area. Besides, the dual Brunn-Minkowski inequality for Lp-dual affine surface area is presented.

  5. 2017 Guralp Affinity Digitizer Evaluation.

    Energy Technology Data Exchange (ETDEWEB)

    Merchant, Bion J.

    2018-03-01

    Sandia National Laboratories has tested and evaluated two Guralp Affinity digitizers. The Affinity digitizers are intended to record sensor output for seismic and infrasound monitoring applications. The purpose of this digitizer evaluation is to measure the performance characteristics in such areas as power consumption, input impedance, sensitivity, full scale, self- noise, dynamic range, system noise, response, passband, and timing. The Affinity digitizers are being evaluated for potential use in the International Monitoring System (IMS) of the Comprehensive Nuclear Test-Ban-Treaty Organization (CTBTO).

  6. The utility of affine variables and affine coherent states

    International Nuclear Information System (INIS)

    Klauder, John R

    2012-01-01

    Affine coherent states are generated by affine kinematical variables much like canonical coherent states are generated by canonical kinematical variables. Although all classical and quantum formalisms normally entail canonical variables, it is shown that affine variables can serve equally well for many classical and quantum studies. This general purpose analysis provides tools to discuss two major applications: (1) the completely successful quantization of a nonrenormalizable scalar quantum field theory by affine techniques, in complete contrast to canonical techniques which only offer triviality; and (2) a formulation of the kinematical portion of quantum gravity that favors affine kinematical variables over canonical kinematical variables, and which generates a framework in which a favorable analysis of the constrained dynamical issues can take place. All this is possible because of the close connection between the affine and the canonical stories, while the few distinctions can be used to advantage when appropriate. This article is part of a special issue of Journal of Physics A: Mathematical and Theoretical devoted to ‘Coherent states: mathematical and physical aspects’. (review)

  7. Separation of boron isotopes using NMG type anion exchange resin

    International Nuclear Information System (INIS)

    Itagaki, Takaharu; Kosuge, Masao; Fukuda, Junji; Fujii, Yasuhiko.

    1992-01-01

    Ion exchange separation of boron isotopes (B-10 and B-11) has been studied by using a special boron selective ion exchange resin; NMG (n-methyl glucamine)-type anion exchange resin. The resin has shown a large isotope separation coefficient of 1.02 at the experimental conditions of temperature, 80degC, and boric acid concentration, 0.2 M (mole/dm 3 ). Enriched B-10 (92%) was obtained after the migration of 1149 m by a recyclic operation of ion exchange columns in a merry-go-round method. (author)

  8. Modified peptides as potent inhibitors of the postsynaptic density-95/N-methyl-D-aspartate receptor interaction

    DEFF Research Database (Denmark)

    Bach, Anders; Chi, Celestine N.; Olsen, Thomas B.

    2008-01-01

    and unnatural amino acids, which disclosed a tripeptide with micromolar affinity and N-methylated tetrapeptides with improved affinities. Molecular modeling studies guided further N-terminal modifications and introduction of a range of N-terminal substitutions dramatically improved affinity. The best compound...

  9. Representations of affine Hecke algebras

    CERN Document Server

    Xi, Nanhua

    1994-01-01

    Kazhdan and Lusztig classified the simple modules of an affine Hecke algebra Hq (q E C*) provided that q is not a root of 1 (Invent. Math. 1987). Ginzburg had some very interesting work on affine Hecke algebras. Combining these results simple Hq-modules can be classified provided that the order of q is not too small. These Lecture Notes of N. Xi show that the classification of simple Hq-modules is essentially different from general cases when q is a root of 1 of certain orders. In addition the based rings of affine Weyl groups are shown to be of interest in understanding irreducible representations of affine Hecke algebras. Basic knowledge of abstract algebra is enough to read one third of the book. Some knowledge of K-theory, algebraic group, and Kazhdan-Lusztig cell of Cexeter group is useful for the rest

  10. Contractions of affine spherical varieties

    International Nuclear Information System (INIS)

    Arzhantsev, I V

    1999-01-01

    The language of filtrations and contractions is used to describe the class of G-varieties obtainable as the total spaces of the construction of contraction applied to affine spherical varieties, which is well-known in invariant theory. These varieties are local models for arbitrary affine G-varieties of complexity 1 with a one-dimensional categorical quotient. As examples, reductive algebraic semigroups and three-dimensional SL 2 -varieties are considered

  11. Pu Anion Exchange Process Intensification

    International Nuclear Information System (INIS)

    Taylor-Pashow, Kathryn M. L.

    2017-01-01

    This research is focused on improving the efficiency of the anion exchange process for purifying plutonium. While initially focused on plutonium, the technology could also be applied to other ion-exchange processes. Work in FY17 focused on the improvement and optimization of porous foam columns that were initially developed in FY16. These foam columns were surface functionalized with poly(4-vinylpyridine) (PVP) to provide the Pu specific anion-exchange sites. Two different polymerization methods were explored for maximizing the surface functionalization with the PVP. The open-celled polymeric foams have large open pores and large surface areas available for sorption. The fluid passes through the large open pores of this material, allowing convection to be the dominant mechanism by which mass transport takes place. These materials generally have very low densities, open-celled structures with high cell interconnectivity, small cell sizes, uniform cell size distributions, and high structural integrity. These porous foam columns provide advantages over the typical porous resin beads by eliminating the slow diffusion through resin beads, making the anion-exchange sites easily accessible on the foam surfaces. The best performing samples exceeded the Pu capacity of the commercially available resin, and also offered the advantage of sharper elution profiles, resulting in a more concentrated product, with less loss of material to the dilute heads and tails cuts. An alternate approach to improving the efficiency of this process was also explored through the development of a microchannel array system for performing the anion exchange.

  12. Ionic liquids comprising heteraromatic anions

    Energy Technology Data Exchange (ETDEWEB)

    Schneider, William F.; Brennecke, Joan F.; Maginn, Edward J.; Mindrup, Elaine; Gurkan, Burcu; Price, Erica; Goodrich, Brett

    2018-04-24

    Some embodiments described herein relate to ionic liquids comprising an anion of a heteraromatic compound such as optionally substituted pyrrolide, optionally substituted pyrazolide, optionally substituted indolide, optionally substituted phospholide, or optionally substituted imidazolide. Methods and devices for gas separation or gas absorption related to these ionic liquids are also described herein.

  13. Pu Anion Exchange Process Intensification

    Energy Technology Data Exchange (ETDEWEB)

    Taylor-Pashow, Kathryn M. L. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

    2017-10-06

    This research is focused on improving the efficiency of the anion exchange process for purifying plutonium. While initially focused on plutonium, the technology could also be applied to other ion-exchange processes. Work in FY17 focused on the improvement and optimization of porous foam columns that were initially developed in FY16. These foam columns were surface functionalized with poly(4-vinylpyridine) (PVP) to provide the Pu specific anion-exchange sites. Two different polymerization methods were explored for maximizing the surface functionalization with the PVP. The open-celled polymeric foams have large open pores and large surface areas available for sorption. The fluid passes through the large open pores of this material, allowing convection to be the dominant mechanism by which mass transport takes place. These materials generally have very low densities, open-celled structures with high cell interconnectivity, small cell sizes, uniform cell size distributions, and high structural integrity. These porous foam columns provide advantages over the typical porous resin beads by eliminating the slow diffusion through resin beads, making the anion-exchange sites easily accessible on the foam surfaces. The best performing samples exceeded the Pu capacity of the commercially available resin, and also offered the advantage of sharper elution profiles, resulting in a more concentrated product, with less loss of material to the dilute heads and tails cuts. An alternate approach to improving the efficiency of this process was also explored through the development of a microchannel array system for performing the anion exchange.

  14. IMPROVING OF ANION EXCHANGERES REGENERATION

    Directory of Open Access Journals (Sweden)

    Muzher M. Ibrahim

    2013-05-01

    Full Text Available Inthis study, Different basis [NaOH and KOH] of variable concentration are usedto reactivate Anion exchangers employing different schemes .The Laboratoryresults showed large improvement in efficiency of these exchangers ( i.eoperating time was increased from 12 to 42 hours .The results of this work showed that the environmentalload (waste water can be reduced greatly when using the proposed regenerationscheme .

  15. Quantum mechanics of toroidal anions

    International Nuclear Information System (INIS)

    Afanas'ev, G.N.

    1990-01-01

    We consider a toroidal solenoid with an electric charge attached to it. It turns out that statistical properties of the wave function describing interacting toroidal anions depend on both their relative position and orientation. The influence of the particular gauge choice on the exchange properties of the wave function is studied. 30 refs.; 6 figs

  16. Anion binding in biological systems

    Energy Technology Data Exchange (ETDEWEB)

    Feiters, Martin C [Department of Organic Chemistry, Institute for Molecules and Materials, Faculty of Science, Radboud University Nijmegen, Heyendaalseweg 135, 6525 AJ Nijmegen (Netherlands); Meyer-Klaucke, Wolfram [EMBL Hamburg Outstation at DESY, Notkestrasse 85, D-22607 Hamburg (Germany); Kostenko, Alexander V; Soldatov, Alexander V [Faculty of Physics, Southern Federal University, Sorge 5, Rostov-na-Donu, 344090 (Russian Federation); Leblanc, Catherine; Michel, Gurvan; Potin, Philippe [Centre National de la Recherche Scientifique and Universite Pierre et Marie Curie Paris-VI, Station Biologique de Roscoff, Place Georges Teissier, BP 74, F-29682 Roscoff cedex, Bretagne (France); Kuepper, Frithjof C [Scottish Association for Marine Science, Dunstaffnage Marine Laboratory, Oban, Argyll PA37 1QA, Scotland (United Kingdom); Hollenstein, Kaspar; Locher, Kaspar P [Institute of Molecular Biology and Biophysics, ETH Zuerich, Schafmattstrasse 20, Zuerich, 8093 (Switzerland); Bevers, Loes E; Hagedoorn, Peter-Leon; Hagen, Wilfred R, E-mail: m.feiters@science.ru.n [Department of Biotechnology, Delft University of Technology, Julianalaan 67, 2628 BC Delft (Netherlands)

    2009-11-15

    We compare aspects of biological X-ray absorption spectroscopy (XAS) studies of cations and anions, and report on some examples of anion binding in biological systems. Brown algae such as Laminaria digitata (oarweed) are effective accumulators of I from seawater, with tissue concentrations exceeding 50 mM, and the vanadate-containing enzyme haloperoxidase is implicated in halide accumulation. We have studied the chemical state of iodine and its biological role in Laminaria at the I K edge, and bromoperoxidase from Ascophyllum nodosum (knotted wrack) at the Br K edge. Mo is essential for many forms of life; W only for certain archaea, such as Archaeoglobus fulgidus and the hyperthermophilic archaeon Pyrococcus furiosus, and some bacteria. The metals are bound and transported as their oxo-anions, molybdate and tungstate, which are similar in size. The transport protein WtpA from P. furiosus binds tungstate more strongly than molybdate, and is related in sequence to Archaeoglobus fulgidus ModA, of which a crystal structure is known. We have measured A. fulgidus ModA with tungstate at the W L{sub 3} (2p{sub 3/2}) edge, and compared the results with the refined crystal structure. XAS studies of anion binding are feasible even if only weak interactions are present, are biologically relevant, and give new insights in the spectroscopy.

  17. Anion binding in biological systems

    International Nuclear Information System (INIS)

    Feiters, Martin C; Meyer-Klaucke, Wolfram; Kostenko, Alexander V; Soldatov, Alexander V; Leblanc, Catherine; Michel, Gurvan; Potin, Philippe; Kuepper, Frithjof C; Hollenstein, Kaspar; Locher, Kaspar P; Bevers, Loes E; Hagedoorn, Peter-Leon; Hagen, Wilfred R

    2009-01-01

    We compare aspects of biological X-ray absorption spectroscopy (XAS) studies of cations and anions, and report on some examples of anion binding in biological systems. Brown algae such as Laminaria digitata (oarweed) are effective accumulators of I from seawater, with tissue concentrations exceeding 50 mM, and the vanadate-containing enzyme haloperoxidase is implicated in halide accumulation. We have studied the chemical state of iodine and its biological role in Laminaria at the I K edge, and bromoperoxidase from Ascophyllum nodosum (knotted wrack) at the Br K edge. Mo is essential for many forms of life; W only for certain archaea, such as Archaeoglobus fulgidus and the hyperthermophilic archaeon Pyrococcus furiosus, and some bacteria. The metals are bound and transported as their oxo-anions, molybdate and tungstate, which are similar in size. The transport protein WtpA from P. furiosus binds tungstate more strongly than molybdate, and is related in sequence to Archaeoglobus fulgidus ModA, of which a crystal structure is known. We have measured A. fulgidus ModA with tungstate at the W L 3 (2p 3/2 ) edge, and compared the results with the refined crystal structure. XAS studies of anion binding are feasible even if only weak interactions are present, are biologically relevant, and give new insights in the spectroscopy.

  18. Anion binding in biological systems

    Science.gov (United States)

    Feiters, Martin C.; Meyer-Klaucke, Wolfram; Kostenko, Alexander V.; Soldatov, Alexander V.; Leblanc, Catherine; Michel, Gurvan; Potin, Philippe; Küpper, Frithjof C.; Hollenstein, Kaspar; Locher, Kaspar P.; Bevers, Loes E.; Hagedoorn, Peter-Leon; Hagen, Wilfred R.

    2009-11-01

    We compare aspects of biological X-ray absorption spectroscopy (XAS) studies of cations and anions, and report on some examples of anion binding in biological systems. Brown algae such as Laminaria digitata (oarweed) are effective accumulators of I from seawater, with tissue concentrations exceeding 50 mM, and the vanadate-containing enzyme haloperoxidase is implicated in halide accumulation. We have studied the chemical state of iodine and its biological role in Laminaria at the I K edge, and bromoperoxidase from Ascophyllum nodosum (knotted wrack) at the Br K edge. Mo is essential for many forms of life; W only for certain archaea, such as Archaeoglobus fulgidus and the hyperthermophilic archaeon Pyrococcus furiosus, and some bacteria. The metals are bound and transported as their oxo-anions, molybdate and tungstate, which are similar in size. The transport protein WtpA from P. furiosus binds tungstate more strongly than molybdate, and is related in sequence to Archaeoglobus fulgidus ModA, of which a crystal structure is known. We have measured A. fulgidus ModA with tungstate at the W L3 (2p3/2) edge, and compared the results with the refined crystal structure. XAS studies of anion binding are feasible even if only weak interactions are present, are biologically relevant, and give new insights in the spectroscopy.

  19. Communication: Remarkable electrophilicity of the oxalic acid monomer: An anion photoelectron spectroscopy and theoretical study

    International Nuclear Information System (INIS)

    Buonaugurio, Angela; Graham, Jacob; Buytendyk, Allyson; Bowen, Kit H.; Ryder, Matthew R.; Gutowski, Maciej; Keolopile, Zibo G.; Haranczyk, Maciej

    2014-01-01

    Our experimental and computational results demonstrate an unusual electrophilicity of oxalic acid, the simplest dicarboxylic acid. The monomer is characterized by an adiabatic electron affinity and electron vertical detachment energy of 0.72 and 1.08 eV (±0.05 eV), respectively. The electrophilicity results primarily from the bonding carbon-carbon interaction in the singly occupied molecular orbital of the anion, but it is further enhanced by intramolecular hydrogen bonds. The well-resolved structure in the photoelectron spectrum is reproduced theoretically, based on Franck-Condon factors for the vibronic anion → neutral transitions

  20. Heavy atom vibrational modes and low-energy vibrational autodetachment in nitromethane anions

    International Nuclear Information System (INIS)

    Thompson, Michael C.; Weber, J. Mathias; Baraban, Joshua H.; Matthews, Devin A.; Stanton, John F.

    2015-01-01

    We report infrared spectra of nitromethane anion, CH 3 NO 2 − , in the region 700–2150 cm −1 , obtained by Ar predissociation spectroscopy and electron detachment spectroscopy. The data are interpreted in the framework of second-order vibrational perturbation theory based on coupled-cluster electronic structure calculations. The modes in the spectroscopic region studied here are mainly based on vibrations involving the heavier atoms; this work complements earlier studies on nitromethane anion that focused on the CH stretching region of the spectrum. Electron detachment begins at photon energies far below the adiabatic electron affinity due to thermal population of excited vibrational states

  1. meta-PBI/methylated PBI-OO blend membranes for acid doped HT PEMFC

    DEFF Research Database (Denmark)

    Cho, Hyeongrae; Hur, Eun; Henkensmeier, Dirk

    2014-01-01

    Methylation of polybenzimidazole leads to positively charged polymer backbones, and moveable anions. Ion exchange of methylated PBI-OO in phosphoric acid (PA) shows that the resulting polymers dissolve. meta-PBI, however, absorbs about 400wt% PA while remaining a self supported membrane. We inves...

  2. How does methylation suppress the electron-induced decomposition of 1-methyl-nitroimidazoles?

    Science.gov (United States)

    Kossoski, F.; Varella, M. T. do N.

    2017-10-01

    The efficient decomposition of nitroimidazoles (NIs) by low energy electrons is believed to underlie their radiosensitizing properties. Recent dissociative electron attachment (DEA) measurements showed that methylation at the N1 site unexpectedly suppresses the electron-induced reactions in 4(5)-NI. We report theoretical results that provide a clear interpretation of that astounding finding. Around 1.5 eV, DEA reactions into several fragments are initiated by a π* resonance, not considered in previous studies. The autoionization lifetime of this anion state, which limits the predissociation dynamics, is considerably shorter in the methylated species, thereby suppressing the DEA signals. On the other hand, the lifetime of the π* resonance located around 3 eV is less affected by methylation, which explains why DEA is still observed at these energies. Our results demonstrate how even a simple methylation can significantly modify the probabilities for DEA reactions, which may be significant for NI-based cancer therapy.

  3. Tripodal receptors for cation and anion sensors

    NARCIS (Netherlands)

    Kuswandi, Bambang; Nuriman, [Unknown; Verboom, Willem; Reinhoudt, David

    2006-01-01

    This review discusses different types of artificial tripodal receptors for the selectiverecognition and sensing of cations and anions. Examples on the relationship between structure andselectivity towards cations and anions are described. Furthermore, their applications as potentiometricion sensing

  4. Isotopic enrichments via altered first and second solution electron affinities

    International Nuclear Information System (INIS)

    Stevenson, G.R.; Espe, M.P.; Reiter, R.C.

    1986-01-01

    Electron spin resonance experiments have been utilized to show that the solution electron affinity of benzene- 13 C 6 is less than that of benzene by 0.24 kcal/mol and that the solution EA of benzene-d 6 is less than that of benzene by 0.44 kcal/mol. Perdeuteration of naphthalene, anthracene, or perylene results in a very similar lowering of the solution EA of the hydrocarbon as evidenced by the fact that the equilibrium constant for the electron transfer between the hydrocarbon anion radical, X/sup .-/, and the perdeuterated hydrocarbon, Xd (X/sup .-/ + Xd = Xd/sup .-/ + X), is less than unity. Likewise the second EAs of perdeuterated perylene and anthracene are lower than those of the unsubstituted hydrocarbons (K/sub eq/ for X 2- + Xd/sup .-/ = X/sup .-/ + Xd 2- is less than unity). The free energy and enthalpy of electron transfer from the anthracene anion radical to perdeuterated anthracene is 0.41 kcal/mol and that from the anthracene dianion to the perdeuterated anion radical is 0.10 kcal/mol. The fact that these equilibrium constants are not equal to 1 enables one to use the difference in the chemical reactivity of the ions and neutral molecules to selectively isotopically enrich the hydrocarbons involved

  5. Methods and systems for measuring anions

    KAUST Repository

    Masih, Dilshad; Mohammed, Omar F.; Aly, Shawkat M.; Alarousu, Erkki

    2016-01-01

    Embodiments of the present disclosure provide for methods for detecting the presence and/or concentration of anions in a solution, systems for detecting the presence and/or concentration of anions in a solution, anion sensor systems, and the like.

  6. Methods and systems for measuring anions

    KAUST Repository

    Masih, Dilshad

    2016-08-18

    Embodiments of the present disclosure provide for methods for detecting the presence and/or concentration of anions in a solution, systems for detecting the presence and/or concentration of anions in a solution, anion sensor systems, and the like.

  7. The Structure of Affine Buildings

    CERN Document Server

    Weiss, Richard M

    2009-01-01

    In The Structure of Affine Buildings, Richard Weiss gives a detailed presentation of the complete proof of the classification of Bruhat-Tits buildings first completed by Jacques Tits in 1986. The book includes numerous results about automorphisms, completions, and residues of these buildings. It also includes tables correlating the results in the locally finite case with the results of Tits's classification of absolutely simple algebraic groups defined over a local field. A companion to Weiss's The Structure of Spherical Buildings, The Structure of Affine Buildings is organized around the clas

  8. Current trends in electrochemical sensing and biosensing of DNA methylation.

    Science.gov (United States)

    Krejcova, Ludmila; Richtera, Lukas; Hynek, David; Labuda, Jan; Adam, Vojtech

    2017-11-15

    DNA methylation plays an important role in physiological and pathological processes. Several genetic diseases and most malignancies tend to be associated with aberrant DNA methylation. Among other analytical methods, electrochemical approaches have been successfully employed for characterisation of DNA methylation patterns that are essential for the diagnosis and treatment of particular diseases. This article discusses current trends in the electrochemical sensing and biosensing of DNA methylation. Particularly, it provides an overview of applied electrode materials, electrode modifications and biorecognition elements applications with an emphasis on strategies that form the core DNA methylation detection approaches. The three main strategies as (i) bisulfite treatment, (ii) cleavage by restriction endonucleases, and (iii) immuno/affinity reaction were described in greater detail. Additionally, the availability of the reviewed platforms for early cancer diagnosis and the approval of methylation inhibitors for anticancer therapy were discussed. Copyright © 2017 Elsevier B.V. All rights reserved.

  9. N-Oxide analogs of WAY-100635 : new high affinity 5-HT (1A) receptor antagonists

    NARCIS (Netherlands)

    Oberwinkler - Marchais, Sandrine; Nowicki, B; Pike, VW; Halldin, C; Sandell, J; Chou, YH; Gulyas, B; Brennum, LT; Farde, L; Wikstrom, H V

    2005-01-01

    WAY-100635 [N-(2-(1-(4-(2-methoxyphenyl)piperazinyl)ethyl))-N-(2-pyridinyl)cyclohexanecarboxamide] 1 and its O-des-methyl derivative DWAY 2 are well-known high affinity 5-HT1A receptor antagonists. which when labeled with carbon-II (beta(+): t(1/2) 20.4min) in the carbonyl group are effective

  10. A pharmacological profile of the high-affinity GluK5 kainate receptor

    DEFF Research Database (Denmark)

    Møllerud, Stine; Kastrup, Jette Sandholm Jensen; Pickering, Darryl S

    2016-01-01

    -hydroxyisoxazol-4-yl)propionate (ATPA), dihydrokainate and (2 S,4 R)−4-methyl-glutamate (SYM2081) have higher affinity at GluK3 compared to GluK5. Since some studies have indicated that GluK5 is associated with various diseases in the central nervous system (e.g. schizophrenia, temporal lobe epilepsy, bipolar...

  11. Synthetic Receptors for the High-Affinity Recognition of O-GlcNAc Derivatives

    NARCIS (Netherlands)

    Rios, Pablo; Carter, Tom S; Mooibroek, Tiddo J; Crump, Matthew P; Lisbjerg, Micke; Pittelkow, Michael; Supekar, Nitin T; Boons, Geert-Jan|info:eu-repo/dai/nl/088245489; Davis, Anthony P

    2016-01-01

    The combination of a pyrenyl tetraamine with an isophthaloyl spacer has led to two new water-soluble carbohydrate receptors ("synthetic lectins"). Both systems show outstanding affinities for derivatives of N-acetylglucosamine (GlcNAc) in aqueous solution. One receptor binds the methyl glycoside

  12. Simultaneous anion and cation mobility in polypyrrole

    DEFF Research Database (Denmark)

    Skaarup, Steen; Bay, Lasse; Vidanapathirana, K.

    2003-01-01

    and the expulsion of anions; a broad anodic peak centered at ca. - 0.5 V representing the expulsion of cations; and a second broad peak at +0.2 to +0.5 V corresponding to anions being inserted. Although the motion of cations is the most important, as expected, there is a significant anion contribution, thereby...... complicating reproducibility when employing PPy(DBS) polymers as actuators. When the cation is doubly charged, it enters the film less readily, and anions dominate the mobility. Using a large and bulky cation switches the mechanism to apparently total anion motion. The changes in area of the three peaks...

  13. Anion capture and sensing with cationic boranes: on the synergy of Coulombic effects and onium ion-centred Lewis acidity.

    Science.gov (United States)

    Zhao, Haiyan; Leamer, Lauren A; Gabbaï, François P

    2013-06-21

    Stimulated by the growing importance and recognized toxicity of anions such as fluoride, cyanide and azides, we have, in the past few years, developed a family of Lewis acidic triarylboranes that can be used for the complexation of these anions in organic and protic solvents, including water. A central aspect of our approach lies in the decoration of the boranes with peripheral ammonium, phosphonium, sulfonium stibonium or telluronium groups. The presence of these cationic groups provides a Coulombic drive for the capture of the anion, leading to boranes that can be used in aqueous solutions where anion hydration and/or protonation are usually competitive. The anion affinity of these boranes can be markedly enhanced by narrowing the separation between the anion binding site (i.e. the boron atom) and the onium ion. In such systems, the latent Lewis acidity of the onium ion also plays a role as manifested by the formation of B-X→E (E = P, S, Sb, or Te; X = F, CN or N3) chelate motifs that provide additional stability to the resulting complexes. These effects, which are maximum in stibonium and telluronium boranes, show that the Lewis acidity of heavy onium ions can be exploited for anion coordination and capture. The significance of these advances is illustrated by the development of applications in anion sensing, fluorination chemistry and (18)F radiolabeling for positron emission tomography.

  14. Affinity biosensors: techniques and protocols

    National Research Council Canada - National Science Library

    Rogers, Kim R; Mulchandani, Ashok

    1998-01-01

    ..., and government to begin or expand their biosensors research. This volume, Methods in Biotechnology vol. 7: Affinity Biosensors: Techniques and Protocols, describes a variety of classical and emerging transduction technologies that have been interfaced to bioaffinity elements (e.g., antibodies and receptors). Some of the reas...

  15. Affinity of serum apolipoproteins for lipid monolayers

    International Nuclear Information System (INIS)

    Ibdah, J.A.

    1987-01-01

    The effects of lipid composition and packing as well as the structure of the protein on the affinities of apolipoproteins for lipid monolayers have been investigated. The adsorption of 14 C-reductively methylated human apolipoproteins A-I and A-II at saturating subphase concentrations to monolayers prepared with synthetic lipids or lipoprotein surface lipids spread at various initial surface pressures has been studied. The adsorption of apolipoproteins is monitored by following the surface radioactivity using a gas flow counter and Wilhelmy plate, respectively. The physical states of the lipid monolayers are evaluated by measurement of the surface pressure-molecular area isotherms using a Langmuir-Adam surface balance. The probable helical regions in various apolipoproteins have been predicted using a secondary structure analysis computer program. The mean residue hydrophobicity and mean residue hydrophobic moment for the predicted helical segments have been calculated. The surface properties of synthetic peptides which are amphipathic helix analogs have been investigated at the air-water and lipid-water interfaces

  16. Anion

    Directory of Open Access Journals (Sweden)

    A. Vadivel Murugan

    2003-01-01

    . Its characterization is investigated by Fourier Transform Infrared Spectroscopy (FT-IR and Scanning Electron Microscopy (SEM. The hybrid material presents predominantly high electronic conductivities of around 2.0 and 7.0 S cm-1 at 300 and 400K respectively.

  17. Selective Interaction of a Cationic Polyfluorene with Model Lipid Membranes: Anionic versus Zwitterionic Lipids

    Directory of Open Access Journals (Sweden)

    Zehra Kahveci

    2014-03-01

    Full Text Available This paper explores the interaction mechanism between the conjugated polyelectrolyte {[9,9-bis(6'-N,N,N-trimethylammoniumhexyl]fluorene-phenylene}bromide (HTMA-PFP and model lipid membranes. The study was carried out using different biophysical techniques, mainly fluorescence spectroscopy and microscopy. Results show that despite the preferential interaction of HTMA-PFP with anionic lipids, HTMA-PFP shows affinity for zwitterionic lipids; although the interaction mechanism is different as well as HTMA-PFP’s final membrane location. Whilst the polyelectrolyte is embedded within the lipid bilayer in the anionic membrane, it remains close to the surface, forming aggregates that are sensitive to the physical state of the lipid bilayer in the zwitterionic system. The different interaction mechanism is reflected in the polyelectrolyte fluorescence spectrum, since the maximum shifts to longer wavelengths in the zwitterionic system. The intrinsic fluorescence of HTMA-PFP was used to visualize the interaction between polymer and vesicles via fluorescence microscopy, thanks to its high quantum yield and photostability. This technique allows the selectivity of the polyelectrolyte and higher affinity for anionic membranes to be observed. The results confirmed the appropriateness of using HTMA-PFP as a membrane fluorescent marker and suggest that, given its different behaviour towards anionic and zwitterionic membranes, HTMA-PFP could be used for selective recognition and imaging of bacteria over mammalian cells.

  18. Anion-selective interaction and colorimeter by an optical metalloreceptor based on ruthenium(II) 2,2'-biimidazole: hydrogen bonding and proton transfer.

    Science.gov (United States)

    Cui, Ying; Mo, Hao-Jun; Chen, Jin-Can; Niu, Yan-Li; Zhong, Yong-Rui; Zheng, Kang-Cheng; Ye, Bao-Hui

    2007-08-06

    A new anion sensor [Ru(bpy)2(H2biim)](PF6)2 (1) (bpy = 2,2'-bipyridine and H2biim = 2,2'-biimidazole) has been developed, in which the Ru(II)-bpy moiety acts as a chromophore and the H2biim ligand as an anion receptor via hydrogen bonding. A systematic investigation shows that 1 is an eligible sensor for various anions. It donates protons for hydrogen bonding to Cl-, Br-, I-, NO3-, HSO4-, H2PO4-, and OAc- anions and further actualizes monoproton transfer to the OAc- anion, changing color from yellow to orange brown. The fluoride ion has a high affinity toward the N-H group of the H2biim ligand for proton transfer, rather than hydrogen bonding, because of the formation of the highly stable HF2- anion, resulting in stepwise deprotonation of the two N-H fragments. These processes are signaled by vivid color changes from yellow to orange brown and then to violet because of second-sphere donor-acceptor interactions between Ru(II)-H2biim and the anions. The significant color changes can be distinguished visually. The processes are not only determined by the basicity of anion but also by the strength of hydrogen bonding and the stability of the anion-receptor complexes. The design strategy and remarkable photophysical properties of sensor 1 help to extend the development of anion sensors.

  19. The effect of guanidinium functionalization on the structural properties and anion affinity of polyelectrolyte multilayers

    NARCIS (Netherlands)

    Cao, Zheng; Gordiichuk, Pavlo; Loos, Katja; Sudhölter, Ernst Jan Robert; Smet, Louis

    2015-01-01

    Poly(allylamine hydrochloride) (PAH) is chemically functionalized with guanidinium (Gu) moieties in water at room temperature. The resulting PAH-Gu is used to prepare polyelectrolyte multilayers (PEMs) with poly(sodium 4-styrene sulfonate) (PSS) via layer-by-layer deposition. The polyelectrolyte

  20. Affinity of hydroxyapatite by radionuclides parent/child in 188Re/188W generator for radiotherapy

    International Nuclear Information System (INIS)

    Carrera D, A. A.; Badillo A, V.; Badillo A, V. E.; Monroy G, F.

    2009-10-01

    To assess the feasibility of using apatites as matrices of 188 W/ 188 Re generator is essential to obtain the distribution coefficients as much of parent radionuclide as child radionuclide in apatite, that is to say to know their affinity for the solid. It was selected the mineral species more representative as adsorbent, the hydroxyapatite Ca 10 (PO 4 ) 6 (OH) 2 it is known for its great capacity of ions retention and by presenting a large affinity for anionic species in their surface. In this paper we use a synthetic hydroxyapatite marketed by Bio-Rad. This paper presents the preliminary results regarding the affinity of hydroxyapatite for the anionic species tungstates (WO 4 2- ) and perrhenates (ReO 4 - in EDTA, as background electrolyte expressed as distribution coefficients between two immiscible phases obtained with the help of radioactive tracers 187 W and 188 Re respectively. The retention measures of these ions, traces show that Bio-Gel hydroxyapatite presents moderate values of distribution coefficients for anionic species of W(Vi) in EDTA 0.01 mol/L that are in the range p H 5 to 6.5; the parent radionuclide of generator 188 Re/ 188 W is fixed but not enough to consider it a good absorbent. By contrast, the fixation of perrhenate ions is virtually wiped as may be easily removed from a hydroxyapatite column packed with a saline solution. The influence of this saline solution in the removal of perrhenate ions is null practically. (Author)

  1. Equilibrium and Thermodynamic Studies of Anionic Dyes Removal by an Anionic Clay-Layered Double Hydroxide

    International Nuclear Information System (INIS)

    Kantasamy, N.; Siti Mariam Sumari

    2016-01-01

    Adsorption isotherm describes the interaction of adsorbates with adsorbent in equilibrium. Equilibrium data was examined using Langmuir and Freundlich isotherm models. Thermodynamic studies were used to evaluate the thermodynamic parameters; heat of enthalpy change (ΔH degree), Gibbs free energy change (ΔG degree) and heat of entropy change (ΔSdegree) in order to gain information regarding the nature of adsorption (exothermic or endothermic). Four reactive dyes of anionic type, Acid Blue 29 (AB29), Reactive Black 5 (RB5), Reactive Orange 16 (RO16) and Reactive Red 120 (RR120) were used to obtain equilibrium isotherms at 25, 35, 45 and 55 degree Celsius. Based on Giles' classification, the isotherm produced were of L2-type, indicating strong dye affinity towards the adsorbent, and with weak competition with the solvent molecules for active adsorption sites. Equilibrium data fitted both Langmuir and Freundlich isotherm models with high correlation coefficient (R"2 > 0.91) indicating the possibility of both homogeneity and heterogeneous nature of adsorption. The negative values of ΔGdegree indicate the adsorption processes were spontaneous and feasible. The negative values of ΔHdegree lie between -20 to -75 kJ/ mol, suggesting these processes were exothermic and physical in nature. The negative values of ΔSdegree are indication of decreased disorder and randomness of spontaneous adsorption of reactive dyes on layered double hydroxide as adsorbent. (author)

  2. Cell cycle-dependent activity of the volume- and Ca2+-activated anion currents in Ehrlich lettre ascites cells

    DEFF Research Database (Denmark)

    Klausen, Thomas Kjaer; Bergdahl, Andreas; Christophersen, Palle

    2007-01-01

    Recent evidence implicates the volume-regulated anion current (VRAC) and other anion currents in control or modulation of cell cycle progression; however, the precise involvement of anion channels in this process is unclear. Here, Cl- currents in Ehrlich Lettre Ascites (ELA) cells were monitored...... during cell cycle progression, under three conditions: (i) after osmotic swelling (i.e., VRAC), (ii) after an increase in the free intracellular Ca2+ concentration (i.e., the Ca2+-activated Cl- current, CaCC), and (iii) under steady-state isotonic conditions. The maximal swelling-activated VRAC current......+ in the pipette), was unaltered from G0 to G1, but decreased in early S phase. A novel high-affinity anion channel inhibitor, the acidic di-aryl-urea NS3728, which inhibited both VRAC and CaCC, attenuated ELA cell growth, suggesting a possible mechanistic link between cell cycle progression and cell cycle...

  3. Environmental behavior of inorganic anions

    International Nuclear Information System (INIS)

    Garland, T.R.; Cataldo, D.A.; Fellows, R.J.; Wildung, R.E.

    1987-01-01

    Recent efforts have addressed two aspects of anion behavior in the soil/plant system. The first involves evaluation of the gaseous component of the terrestrial iodine cycle in soils and plants. Field analyses of 129 I in soils and vegetation adjacent to a fuels reprocessing facility, which was idle for 10 years prior to the study, indicated that there may be a significant gaseous component to the terrestrial iodine cycle. Soil substrates, including a silt-sand, organic forest soil, quartz sand, and a sterilized soil, were amended with radioiodide, and the rates and quality of the volatile components evaluated

  4. The affine quantum gravity programme

    CERN Document Server

    Klauder, J R

    2002-01-01

    The central principle of affine quantum gravity is securing and maintaining the strict positivity of the matrix left brace g-hat sub a sub b (x)right brace composed of the spatial components of the local metric operator. On spectral grounds, canonical commutation relations are incompatible with this principle, and they must be replaced by noncanonical, affine commutation relations. Due to the partial second-class nature of the quantum gravitational constraints, it is advantageous to use the recently developed projection operator method, which treats all quantum constraints on an equal footing. Using this method, enforcement of regularized versions of the gravitational operator constraints is formulated quite naturally by means of a novel and relatively well-defined functional integral involving only the same set of variables that appears in the usual classical formulation. It is anticipated that skills and insight to study this formulation can be developed by studying special, reduced-variable models that sti...

  5. Affine invariants of convex polygons.

    Science.gov (United States)

    Flusser, Jan

    2002-01-01

    In this correspondence, we prove that the affine invariants, for image registration and object recognition, proposed recently by Yang and Cohen (see ibid., vol.8, no.7, p.934-46, July 1999) are algebraically dependent. We show how to select an independent and complete set of the invariants. The use of this new set leads to a significant reduction of the computing complexity without decreasing the discrimination power.

  6. Schlenk Techniques for Anionic Polymerization

    KAUST Repository

    Ratkanthwar, Kedar

    2015-09-01

    Anionic polymerization-high vacuum techniques (HVTs) are doubtlessly the most prominent and reliable experimental tools to prepare polymer samples with well-defined and, in many cases, complex macromolecular architectures. Due to the high demands for time and skilled technical personnel, HVTs are currently used in only a few research laboratories worldwide. Instead, most researchers in this filed are attracted to more facile Schlenk techniques. The basic principle of this technique followed in all laboratories is substantially the same, i.e. the use of alternate vacuum and inert gas atmosphere in glass apparatus for the purification/charging of monomer, solvents, additives, and for the manipulation of air-sensitive compounds such as alkyl metal initiators, organometallic or organic catalysts. However, it is executed quite differently in each research group in terms of the structure of Schlenk apparatus (manifolds, connections, purification/storage flasks, reactors, etc.), the use of small supplementary devices (soft tubing, cannulas, stopcocks, etc.) and experimental procedures. The operational methods are partly purpose-oriented while also featured by a high flexibility, which makes it impossible to describe in detail each specific one. In this chapter we will briefly exemplify the application of Schlenk techniques for anionic polymerization by describing the performance of a few experiments from our own work.

  7. Rank Two Affine Manifolds in Genus 3

    OpenAIRE

    Aulicino, David; Nguyen, Duc-Manh

    2016-01-01

    We complete the classification of rank two affine manifolds in the moduli space of translation surfaces in genus three. Combined with a recent result of Mirzakhani and Wright, this completes the classification of higher rank affine manifolds in genus three.

  8. Alternative affinity tools: more attractive than antibodies?

    NARCIS (Netherlands)

    Ruigrok, V.J.B.; Levisson, M.; Eppink, M.H.M.; Smidt, H.; Oost, van der J.

    2011-01-01

    Antibodies are the most successful affinity tools used today, in both fundamental and applied research (diagnostics, purification and therapeutics). Nonetheless, antibodies do have their limitations, including high production costs and low stability. Alternative affinity tools based on nucleic acids

  9. Spectral affinity in protein networks.

    Science.gov (United States)

    Voevodski, Konstantin; Teng, Shang-Hua; Xia, Yu

    2009-11-29

    Protein-protein interaction (PPI) networks enable us to better understand the functional organization of the proteome. We can learn a lot about a particular protein by querying its neighborhood in a PPI network to find proteins with similar function. A spectral approach that considers random walks between nodes of interest is particularly useful in evaluating closeness in PPI networks. Spectral measures of closeness are more robust to noise in the data and are more precise than simpler methods based on edge density and shortest path length. We develop a novel affinity measure for pairs of proteins in PPI networks, which uses personalized PageRank, a random walk based method used in context-sensitive search on the Web. Our measure of closeness, which we call PageRank Affinity, is proportional to the number of times the smaller-degree protein is visited in a random walk that restarts at the larger-degree protein. PageRank considers paths of all lengths in a network, therefore PageRank Affinity is a precise measure that is robust to noise in the data. PageRank Affinity is also provably related to cluster co-membership, making it a meaningful measure. In our experiments on protein networks we find that our measure is better at predicting co-complex membership and finding functionally related proteins than other commonly used measures of closeness. Moreover, our experiments indicate that PageRank Affinity is very resilient to noise in the network. In addition, based on our method we build a tool that quickly finds nodes closest to a queried protein in any protein network, and easily scales to much larger biological networks. We define a meaningful way to assess the closeness of two proteins in a PPI network, and show that our closeness measure is more biologically significant than other commonly used methods. We also develop a tool, accessible at http://xialab.bu.edu/resources/pnns, that allows the user to quickly find nodes closest to a queried vertex in any protein

  10. Spectral affinity in protein networks

    Directory of Open Access Journals (Sweden)

    Teng Shang-Hua

    2009-11-01

    Full Text Available Abstract Background Protein-protein interaction (PPI networks enable us to better understand the functional organization of the proteome. We can learn a lot about a particular protein by querying its neighborhood in a PPI network to find proteins with similar function. A spectral approach that considers random walks between nodes of interest is particularly useful in evaluating closeness in PPI networks. Spectral measures of closeness are more robust to noise in the data and are more precise than simpler methods based on edge density and shortest path length. Results We develop a novel affinity measure for pairs of proteins in PPI networks, which uses personalized PageRank, a random walk based method used in context-sensitive search on the Web. Our measure of closeness, which we call PageRank Affinity, is proportional to the number of times the smaller-degree protein is visited in a random walk that restarts at the larger-degree protein. PageRank considers paths of all lengths in a network, therefore PageRank Affinity is a precise measure that is robust to noise in the data. PageRank Affinity is also provably related to cluster co-membership, making it a meaningful measure. In our experiments on protein networks we find that our measure is better at predicting co-complex membership and finding functionally related proteins than other commonly used measures of closeness. Moreover, our experiments indicate that PageRank Affinity is very resilient to noise in the network. In addition, based on our method we build a tool that quickly finds nodes closest to a queried protein in any protein network, and easily scales to much larger biological networks. Conclusion We define a meaningful way to assess the closeness of two proteins in a PPI network, and show that our closeness measure is more biologically significant than other commonly used methods. We also develop a tool, accessible at http://xialab.bu.edu/resources/pnns, that allows the user to

  11. Barrier-free proton transfer in the valence anion of 2'-deoxyadenosine-5'-monophosphate. II. A computational study

    Science.gov (United States)

    Kobyłecka, Monika; Gu, Jiande; Rak, Janusz; Leszczynski, Jerzy

    2008-01-01

    The propensity of four representative conformations of 2'-deoxyadenosine-5'-monophosphate (5'-dAMPH) to bind an excess electron has been studied at the B3LYP /6-31++G(d,p) level. While isolated canonical adenine does not support stable valence anions in the gas phase, all considered neutral conformations of 5'-dAMPH form adiabatically stable anions. The type of an anionic 5'-dAMPH state, i.e., the valence, dipole bound, or mixed (valence/dipole bound), depends on the internal hydrogen bond(s) pattern exhibited by a particular tautomer. The most stable anion results from an electron attachment to the neutral syn-south conformer. The formation of this anion is associated with a barrier-free proton transfer triggered by electron attachment and the internal rotation around the C4'-C5' bond. The adiabatic electron affinity of the a&barbelow;south-syn anion is 1.19eV, while its vertical detachment energy is 1.89eV. Our results are compared with the photoelectron spectrum (PES) of 5'-dAMPH- measured recently by Stokes et al., [J. Chem. Phys. 128, 044314 (2008)]. The computational VDE obtained for the most stable anionic structure matches well with the experimental electron binding energy region of maximum intensity. A further understanding of DNA damage might require experimental and computational studies on the systems in which purine nucleotides are engaged in hydrogen bonding.

  12. Lp-mixed affine surface area

    Science.gov (United States)

    Wang, Weidong; Leng, Gangsong

    2007-11-01

    According to the three notions of mixed affine surface area, Lp-affine surface area and Lp-mixed affine surface area proposed by Lutwak, in this article, we give the concept of ith Lp-mixed affine surface area such that the first and second notions of Lutwak are its special cases. Further, some Lutwak's results are extended associated with this concept. Besides, applying this concept, we establish an inequality for the volumes and dual quermassintegrals of a class of star bodies.

  13. Manifolds with integrable affine shape operator

    Directory of Open Access Journals (Sweden)

    Daniel A. Joaquín

    2005-05-01

    Full Text Available This work establishes the conditions for the existence of vector fields with the property that theirs covariant derivative, with respect to the affine normal connection, be the affine shape operatorS in hypersurfaces. Some results are obtained from this property and, in particular, for some kind of affine decomposable hypersurfaces we explicitely get the actual vector fields.

  14. Affinity Spaces and 21st Century Learning

    Science.gov (United States)

    Gee, James Paul

    2017-01-01

    This article discusses video games as "attractors" to "affinity spaces." It argues that affinity spaces are key sites today where people teach and learn 21st Century skills. While affinity spaces are proliferating on the Internet as interest-and-passion-driven sites devoted to a common set of endeavors, they are not new, just…

  15. Using Affinity Diagrams to Evaluate Interactive Prototypes

    DEFF Research Database (Denmark)

    Lucero, Andrés

    2015-01-01

    our particular use of affinity diagramming in prototype evaluations. We reflect on a decade’s experience using affinity diagramming across a number of projects, both in industry and academia. Our affinity diagramming process in interaction design has been tailored and consists of four stages: creating...

  16. Cancer-affine radiopharmaceuticals for the study of biochemical nature of cancer and in the early diagnosis and follow-up of cancer and its systemic therapy

    International Nuclear Information System (INIS)

    Shukla, S.K.; Cipriani, C.; Atzei, G.

    1998-01-01

    Cancer patient needs less diagnosis but an effective therapy. The systemic nature of cancer, often right from its inception, requires systemic therapy with cancer-affine radiopharmaceuticals which contain radionuclide species recognizing both the primary and secondary cancers which have generally different biochemical properties. Cancers may be classified into two groups: I. CATIONIC COMPLEX-AFFINE TUMOURS; Lung cancer, thyroid cancer, primary breast cancer, renal cell carcinoma, bone metastases from anionic complex-affine cancers, ...; II. ANIONIC COMPLEX-AFFINE TUMOURS; Primary prostate cancer, melanoma, hepatocellular carcinoma, osteosarcoma, Ewing's sarcoma, bone metastases from cationic complex-affine cancer. With cancer-affine citratogallate-67 complexes we have diagnosed and followed up, and with citratoyttrate-90 complexes we have treated advanced breast, prostate, renal cell cancer patients. The patient preparation by advising to avoid cancer risk factors and to take cancer preventing and radiopharmaceutical stabilizing diets during diagnosis and therapy have given better results. Friendliness, caring visits and telephone calls from the therapist group help to obtain better outcomes of the diagnosis, and mainly of the therapy. The complexes of these radionuclides with other chelating agents EDTA and DPTA are expected to give better images and cure of advanced cancer patients. Cancer-affine formulations of Tc-99m(V), Re-186(V) and Re-188(V)-DMSA are being studied for their future use in early diagnosis and follow-up, and for the systemic therapy of cancer which will show affinity for them. (author)

  17. Determination of thermodynamic affinities of various polar olefins as hydride, hydrogen atom, and electron acceptors in acetonitrile.

    Science.gov (United States)

    Cao, Ying; Zhang, Song-Chen; Zhang, Min; Shen, Guang-Bin; Zhu, Xiao-Qing

    2013-07-19

    A series of 69 polar olefins with various typical structures (X) were synthesized and the thermodynamic affinities (defined in terms of the molar enthalpy changes or the standard redox potentials in this work) of the polar olefins obtaining hydride anions, hydrogen atoms, and electrons, the thermodynamic affinities of the radical anions of the polar olefins (X(•-)) obtaining protons and hydrogen atoms, and the thermodynamic affinities of the hydrogen adducts of the polar olefins (XH(•)) obtaining electrons in acetonitrile were determined using titration calorimetry and electrochemical methods. The pure C═C π-bond heterolytic and homolytic dissociation energies of the polar olefins (X) in acetonitrile and the pure C═C π-bond homolytic dissociation energies of the radical anions of the polar olefins (X(•-)) in acetonitrile were estimated. The remote substituent effects on the six thermodynamic affinities of the polar olefins and their related reaction intermediates were examined using the Hammett linear free-energy relationships; the results show that the Hammett linear free-energy relationships all hold in the six chemical and electrochemical processes. The information disclosed in this work could not only supply a gap of the chemical thermodynamics of olefins as one class of very important organic unsaturated compounds but also strongly promote the fast development of the chemistry and applications of olefins.

  18. Test procedure for anion exchange chromatography

    International Nuclear Information System (INIS)

    Cooper, T.D.

    1994-01-01

    Plutonium from stored nitrate solutions will be sorbed onto anion exchange resins and converted to storable plutonium dioxide. Useful information will be simultaneously gained on the thermal stability and ion exchange capacity of four commercially available anion exchange resins over several years and under severe degradative conditions. This information will prove useful in predicting the safe and efficient lifetimes of these resins

  19. Tripodal Receptors for Cation and Anion Sensors

    Directory of Open Access Journals (Sweden)

    David N. Reinhoudt

    2006-08-01

    Full Text Available This review discusses different types of artificial tripodal receptors for the selectiverecognition and sensing of cations and anions. Examples on the relationship between structure andselectivity towards cations and anions are described. Furthermore, their applications as potentiometricion sensing are emphasised, along with their potential applications in optical sensors or optodes.

  20. Neutral anion receptors: design and application

    NARCIS (Netherlands)

    Antonisse, M.M.G.; Reinhoudt, David

    1998-01-01

    After the development of synthetic cation receptors in the late 1960s, only in the past decade has work started on the development of synthetic neutral anion receptors. Combination and preorganization of different anion binding groups, like amides, urea moieties, or Lewis acidic metal centers lead

  1. Creating molecular macrocycles for anion recognition

    Directory of Open Access Journals (Sweden)

    Amar H. Flood

    2016-03-01

    Full Text Available The creation and functionality of new classes of macrocycles that are shape persistent and can bind anions is described. The genesis of triazolophane macrocycles emerges out of activity surrounding 1,2,3-triazoles made using click chemistry; and the same triazoles are responsible for anion capture. Mistakes made and lessons learnt in anion recognition provide deeper understanding that, together with theory, now provides for computer-aided receptor design. The lessons are acted upon in the creation of two new macrocycles. First, cyanostars are larger and like to capture large anions. Second is tricarb, which also favors large anions but shows a propensity to self-assemble in an orderly and stable manner, laying a foundation for future designs of hierarchical nanostructures.

  2. Anion channels: master switches of stress responses.

    Science.gov (United States)

    Roelfsema, M Rob G; Hedrich, Rainer; Geiger, Dietmar

    2012-04-01

    During stress, plant cells activate anion channels and trigger the release of anions across the plasma membrane. Recently, two new gene families have been identified that encode major groups of anion channels. The SLAC/SLAH channels are characterized by slow voltage-dependent activation (S-type), whereas ALMT genes encode rapid-activating channels (R-type). Both S- and R-type channels are stimulated in guard cells by the stress hormone ABA, which leads to stomatal closure. Besides their role in ABA-dependent stomatal movement, anion channels are also activated by biotic stress factors such as microbe-associated molecular patterns (MAMPs). Given that anion channels occur throughout the plant kingdom, they are likely to serve a general function as master switches of stress responses. Copyright © 2012 Elsevier Ltd. All rights reserved.

  3. Dissociation dynamics of methylal

    Energy Technology Data Exchange (ETDEWEB)

    Beaud, P; Frey, H -M; Gerber, T; Mischler, B; Radi, P P; Tzannis, A -P [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

    1999-08-01

    The dissociation of methylal is investigated using mass spectrometry, combined with a pyrolytic radical source and femtosecond pump probe experiments. Based on preliminary results two reaction paths of methylal dissociation are proposed and discussed. (author) 4 fig., 3 refs.

  4. The affine quantum gravity programme

    International Nuclear Information System (INIS)

    Klauder, John R

    2002-01-01

    The central principle of affine quantum gravity is securing and maintaining the strict positivity of the matrix { g-hat ab (x)} composed of the spatial components of the local metric operator. On spectral grounds, canonical commutation relations are incompatible with this principle, and they must be replaced by noncanonical, affine commutation relations. Due to the partial second-class nature of the quantum gravitational constraints, it is advantageous to use the recently developed projection operator method, which treats all quantum constraints on an equal footing. Using this method, enforcement of regularized versions of the gravitational operator constraints is formulated quite naturally by means of a novel and relatively well-defined functional integral involving only the same set of variables that appears in the usual classical formulation. It is anticipated that skills and insight to study this formulation can be developed by studying special, reduced-variable models that still retain some basic characteristics of gravity, specifically a partial second-class constraint operator structure. Although perturbatively nonrenormalizable, gravity may possibly be understood nonperturbatively from a hard-core perspective that has proved valuable for specialized models. Finally, developing a procedure to pass to the genuine physical Hilbert space involves several interconnected steps that require careful coordination

  5. Affine-projective field laws

    International Nuclear Information System (INIS)

    Murphy, G.L.

    1975-01-01

    The general topic of geometric unified field theories is discussed in the first section. Some reasons are given for pursuing such theories, and some criticisms are considered. The second section develops the fundamental equations of a purely affine theory which is invariant under projective transformations of the affine connection. This theory is a generalization of that of Schrodinger. Possible identifications for the space-time metric are considered in Sec. III. Sections IV and V deal with the limits of pure gravitation and electrodynamics. In the symmetric limit, Einstein's vacuum equations with cosmological term are recovered. The theory also contains a generalized electrodynamic set of equations which is very similar to the Born-Infeld set. In the weak-field approximation, a finite mass must be attributed to the photon. The problem of motion for charges is discussed here, and it is argued that criticisms of unified field theories because of a supposed inability to produce the Lorentz force law are probably not justified. Three more speculative sections deal with possible explanations of nuclear forces, the spin-torsion relation, and particle structure

  6. Experimental vapor pressures (from 1 Pa to 100 kPa) of six saturated Fatty Acid Methyl Esters (FAMEs): Methyl hexanoate, methyl octanoate, methyl decanoate, methyl dodecanoate, methyl tetradecanoate and methyl hexadecanoate

    International Nuclear Information System (INIS)

    Sahraoui, Lakhdar; Khimeche, Kamel; Dahmani, Abdallah; Mokbel, Ilham; Jose, Jacques

    2016-01-01

    Highlight: • Vapor-liquid equilibria, Enthalpy of Vaporization, saturated Fatty Acid Methyl Ester. - Abstract: Vapor pressures of six saturated Fatty Acid Methyl Esters (FAMEs), methyl hexanoate (or methyl caproate), methyl octanoate (or methyl caprylate), Methyl decanoate (or methyl caprate), methyl dodecanoate (or methyl laurate), methyl tetradecanoate (or methyl myristate), and methyl hexadecanoate (or methyl palmitate) were measured from 1 Pa to 100 kPa and at temperature range between 262 and 453 K using a static apparatus. The experimental data (P-T) were compared with the available literature data.

  7. Self-assembled arene-ruthenium-based rectangles for the selective sensing of multi-carboxylate anions.

    Science.gov (United States)

    Vajpayee, Vaishali; Song, Young Ho; Lee, Min Hyung; Kim, Hyunuk; Wang, Ming; Stang, Peter J; Chi, Ki-Whan

    2011-07-04

    Novel arene-ruthenium [2+2] metalla-rectangles 4 and 5 have been synthesized by self-assembly using dipyridyl amide ligand 3 and arene-ruthenium acceptors (arene: benzoquinone (1), naphthacenedione (2)) and characterized by NMR spectroscopy and ESI-MS. The solid-state structure of 5 was determined by X-ray diffraction and shows encapsulated diethyl ether molecule in the rectangular cavity of 5. The luminescent 5 was further used for anion sensing with the amidic linkage serving as a hydrogen-bond donor site for anions and the ruthenium moiety serving as a signaling unit. A UV/Vis titration study demonstrated that although 5 interacts very weakly with common monoanions as well as with flexible dicarboxylate anions such as malonate and succinate, it displays significant binding affinity (K>10(3) in MeOH) for rigid multi-carboxylate anions such as oxalate, citrate, and tartrate, exhibiting a 1:1 stoichiometry. It has been suggested that 1:1 bidentate hydrogen bonding assisted by appropriate geometrical complementarity is mainly responsible for the increased affinity of 5 towards such anions. A fluorescence titration study revealed a large fluorescence enhancement of 5 upon binding to multi-carboxylate anions, which can be attributed to the blocking of the photoinduced electron-transfer process from the arene-Ru moiety to the amidic donor in 5 as a result of hydrogen bonding between the donor and the anion. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Anion Gap Blood Test: MedlinePlus Lab Test Information

    Science.gov (United States)

    ... https://medlineplus.gov/labtests/aniongapbloodtest.html Anion Gap Blood Test To use the sharing features on this page, please enable JavaScript. What is an Anion Gap Blood Test? An anion gap blood test is a way ...

  9. Reactions of guanine with methyl chloride and methyl bromide: O6-methylation versus charge transfer complex formation

    Science.gov (United States)

    Shukla, P. K.; Mishra, P. C.; Suhai, S.

    Density functional theory (DFT) at the B3LYP/6-31+G* and B3LYP/AUG-cc-pVDZ levels was employed to study O6-methylation of guanine due to its reactions with methyl chloride and methyl bromide and to obtain explanation as to why the methyl halides cause genotoxicity and possess mutagenic and carcinogenic properties. Geometries of the various isolated species involved in the reactions, reactant complexes (RCs), and product complexes (PCs) were optimized in gas phase. Transition states connecting the reactant complexes with the product complexes were also optimized in gas phase at the same levels of theory. The reactant complexes, product complexes, and transition states were solvated in aqueous media using the polarizable continuum model (PCM) of the self-consistent reaction field theory. Zero-point energy (ZPE) correction to total energy and the corresponding thermal energy correction to enthalpy were made in each case. The reactant complexes of the keto form of guanine with methyl chloride and methyl bromide in water are appreciably more stable than the corresponding complexes involving the enol form of guanine. The nature of binding in the product complexes was found to be of the charge transfer type (O6mG+ · X-, X dbond Cl, Br). Binding of HCl, HBr, and H2O molecules to the PCs obtained with the keto form of guanine did not alter the positions of the halide anions in the PCs, and the charge transfer character of the PCs was also not modified due to this binding. Further, the complexes obtained due to the binding of HCl, HBr, and H2O molecules to the PCs had greater stability than the isolated PCs. The reaction barriers involved in the formation of PCs were found to be quite high (?50 kcal/mol). Mechanisms of genotoxicity, mutagenesis and carcinogenesis caused by the methyl halides appear to involve charge transfer-type complex formation. Thus the mechanisms of these processes involving the methyl halides appear to be quite different from those that involve the

  10. Diffusion and retention of organic anions in Callovian-Oxfordian clay rock

    International Nuclear Information System (INIS)

    Rasamimanana, Sabrina

    2016-01-01

    The Callovo-Oxfordian mud-stone (CO_x) is studied as a possible host rock for a deep disposal of radioactive waste (Cigeo project). Indeed, besides being very weakly permeable, it presents a high content of clayey minerals, capable of retaining radionuclides under cationic form and to delay strongly their transport. Nevertheless, some waste packages may release a significant amount of organic molecules, capable of complexing these radionuclides and drastically increase their mobility. So, the objective of this work was to better understand the diffusive behavior of several organic molecules of interest in this mudstone, by investigating at first their affinity with the host rock. The retention of organic molecules under anionic form (acetate, phthalate, adipate, benzoate, and citrate) was quantified on to the dispersed CO_x mudstone using adsorption/desorption batch experiments. Experiments on de-carbonated rock and clay fraction only (≤ 2μm) were also performed to identify solid phases and chemical functions responsible for the retention. a correlation of the intensity of retention, R_d, was pointed out whit the dipole moment μ(Orga.), providing a qualitative estimate of retention capacity for polar hydrophilic organic molecules. So, phthalate, slightly polar, displays a reversible retention (R_d ≅1,6 L.kg"-"1), mainly on clayey phases. Citrate, very polar and strongly adsorbed (R_d ≅ 40 L.kg"-"1), displays a persistent desorption hysteresis and an affinity to different solid phases (clayey minerals and minor oxides). Lastly, acetate, adipate and benzoate, weakly polar, display a lower affinity with rock (R_d ≤ 0,2 L.kg"-"1). The diffusive behavior in compact rock of these organic anions was then studied. The effective diffusion coefficient and retardation factor values were quantified. The low diffusivity, [D_e/D_0](Organic Anions) ≅ 0,1 a0,25 * [D_e/D_0](Water) evidences an effect of anionic exclusion, with a same intensity as that observed for

  11. [(3)H]8-Ethyl-4-methyl-2-phenyl-(8R)-4,5,7,8-tetrahydro-1H-imidazo[2,1-i]-purin-5-one ([(3)H]PSB-11), a novel high-affinity antagonist radioligand for human A(3) adenosine receptors.

    Science.gov (United States)

    Müller, Christa E; Diekmann, Martina; Thorand, Mark; Ozola, Vita

    2002-02-11

    This study describes the preparation and binding properties of [(3)H]PSB-11, a novel, potent, and selective antagonist radioligand for human A(3) adenosine receptors (ARs). [(3)H]PSB-11 binding to membranes of Chinese hamster ovary (CHO) cells expressing the human A(3) AR was saturable and reversible. Saturation experiments showed that [(3)H]PSB-11 labeled a single class of binding sites with high affinity (K(D)=4.9 nM) and limited capacity (B(max)=3500 fmol/mg of protein). PSB-11 is highly selective versus the other adenosine receptor subtypes. The new radioligand shows an extraordinarily low degree of non-specific binding rendering it a very useful tool for studying the (patho)physiological roles of A(3 )ARs.

  12. Anion-π Catalysts with Axial Chirality.

    Science.gov (United States)

    Wang, Chao; Matile, Stefan

    2017-09-04

    The idea of anion-π catalysis is to stabilize anionic transition states by anion-π interactions on aromatic surfaces. For asymmetric anion-π catalysis, π-acidic surfaces have been surrounded with stereogenic centers. This manuscript introduces the first anion-π catalysts that operate with axial chirality. Bifunctional catalysts with tertiary amine bases next to π-acidic naphthalenediimide planes are equipped with a bulky aromatic substituent in the imide position to produce separable atropisomers. The addition of malonic acid half thioesters to enolate acceptors is used for evaluation. In the presence of a chiral axis, the selective acceleration of the disfavored but relevant enolate addition was much better than with point chirality, and enantioselectivity could be observed for the first time for this reaction with small-molecule anion-π catalysts. Enantioselectivity increased with the π acidity of the π surface, whereas the addition of stereogenic centers around the aromatic plane did not cause further improvements. These results identify axial chirality of the active aromatic plane generated by atropisomerism as an attractive strategy for asymmetric anion-π catalysis. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Antisymmetric tensor generalizations of affine vector fields.

    Science.gov (United States)

    Houri, Tsuyoshi; Morisawa, Yoshiyuki; Tomoda, Kentaro

    2016-02-01

    Tensor generalizations of affine vector fields called symmetric and antisymmetric affine tensor fields are discussed as symmetry of spacetimes. We review the properties of the symmetric ones, which have been studied in earlier works, and investigate the properties of the antisymmetric ones, which are the main theme in this paper. It is shown that antisymmetric affine tensor fields are closely related to one-lower-rank antisymmetric tensor fields which are parallelly transported along geodesics. It is also shown that the number of linear independent rank- p antisymmetric affine tensor fields in n -dimensions is bounded by ( n + 1)!/ p !( n - p )!. We also derive the integrability conditions for antisymmetric affine tensor fields. Using the integrability conditions, we discuss the existence of antisymmetric affine tensor fields on various spacetimes.

  14. Contrast-enhanced CT with a High-Affinity Cationic Contrast Agent for Imaging ex Vivo Bovine, Intact ex Vivo Rabbit, and in Vivo Rabbit Cartilage

    OpenAIRE

    Stewart, Rachel C.; Bansal, Prashant N.; Entezari, Vahid; Lusic, Hrvoje; Nazarian, Rosalynn M.; Snyder, Brian D.; Grinstaff, Mark W.

    2013-01-01

    The high affinity of a cationic iodinated contrast agent for cartilage provides better tissue visualization, easier segmentation, higher contrast-to-noise ratios, and longer usable imaging windows and requires a lower dose of injected contrast agent compared with an anionic contrast agent.

  15. Affine LIBOR Models with Multiple Curves

    DEFF Research Database (Denmark)

    Grbac, Zorana; Papapantoleon, Antonis; Schoenmakers, John

    2015-01-01

    are specified following the methodology of the affine LIBOR models and are driven by the wide and flexible class of affine processes. The affine property is preserved under forward measures, which allows us to derive Fourier pricing formulas for caps, swaptions, and basis swaptions. A model specification...... with dependent LIBOR rates is developed that allows for an efficient and accurate calibration to a system of caplet prices....

  16. Selection of imprinted nanoparticles by affinity chromatography.

    Science.gov (United States)

    Guerreiro, António R; Chianella, Iva; Piletska, Elena; Whitcombe, Michael J; Piletsky, Sergey A

    2009-04-15

    Soluble molecularly imprinted nanoparticles were synthesised via iniferter initiated polymerisation and separated by size via gel permeation chromatography. Subsequent fractionation of these particles by affinity chromatography allowed the separation of high affinity fractions from the mixture of nanoparticles. Fractions selected this way possess affinity similar to that of natural antibodies (K(d) 6.6x10(-8)) M and were also able to discriminate between related functional analogues of the template.

  17. Effects of cytosine methylation on transcription factor binding sites

    KAUST Repository

    Medvedeva, Yulia A

    2014-03-26

    Background: DNA methylation in promoters is closely linked to downstream gene repression. However, whether DNA methylation is a cause or a consequence of gene repression remains an open question. If it is a cause, then DNA methylation may affect the affinity of transcription factors (TFs) for their binding sites (TFBSs). If it is a consequence, then gene repression caused by chromatin modification may be stabilized by DNA methylation. Until now, these two possibilities have been supported only by non-systematic evidence and they have not been tested on a wide range of TFs. An average promoter methylation is usually used in studies, whereas recent results suggested that methylation of individual cytosines can also be important.Results: We found that the methylation profiles of 16.6% of cytosines and the expression profiles of neighboring transcriptional start sites (TSSs) were significantly negatively correlated. We called the CpGs corresponding to such cytosines " traffic lights" We observed a strong selection against CpG " traffic lights" within TFBSs. The negative selection was stronger for transcriptional repressors as compared with transcriptional activators or multifunctional TFs as well as for core TFBS positions as compared with flanking TFBS positions.Conclusions: Our results indicate that direct and selective methylation of certain TFBS that prevents TF binding is restricted to special cases and cannot be considered as a general regulatory mechanism of transcription. 2013 Medvedeva et al.; licensee BioMed Central Ltd.

  18. Connections between quantized affine algebras and superalgebras

    International Nuclear Information System (INIS)

    Zhang, R.B.

    1992-08-01

    Every affine superalgebra with a symmetrizable Cartan matrix is closely related to an ordinary affine algebra with the same Cartan matrix. It is shown that the quantum supergroup associated with the former is essentially isomorphic to the quantum group associated with the latter in an appropriate class of representations. At the classical level, each integrable irreducible highest weight representation of the affine superalgebra has a corresponding irreducible representation of the affine algebra, which has the same weight space decomposition. (author). 5 refs, 3 tabs

  19. A Novel Vertex Affinity for Community Detection

    Energy Technology Data Exchange (ETDEWEB)

    Yoo, Andy [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Sanders, Geoffrey [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Henson, Van [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Vassilevski, Panayot [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

    2015-10-05

    We propose a novel vertex affinity measure in this paper. The new vertex affinity quantifies the proximity between two vertices in terms of their clustering strength and is ideal for such graph analytics applications as community detection. We also developed a framework that combines simple graph searches and resistance circuit formulas to compute the vertex affinity efficiently. We study the properties of the new affinity measure empirically in comparison to those of other popular vertex proximity metrics. Our results show that the existing metrics are ill-suited for community detection due to their lack of fundamental properties that are essential for correctly capturing inter- and intra-cluster vertex proximity.

  20. Study of the surface-enhanced Raman spectroscopy of residual impurities in hydroxylamine-reduced silver colloid and the effects of anions on the colloid activity.

    Science.gov (United States)

    Dong, Xiao; Gu, Huaimin; Liu, Fangfang

    2012-03-01

    The paper investigated the residual ions in hydroxylamine-reduced silver colloid (HRSC) and the relationship between the condition of HRSC and the enhanced mechanisms of this colloid. We also detected the SERS of MB and studied the effects of anions on the Raman signal. In the case of HRSC, the bands of residual ions diminish while the bands of Ag-anions increase gradually with increasing the concentrations of Cl(-) and NO(3)(-). It means the affinity of residual ions on the silver surface is weaker than that of Cl(-) and NO(3)(-) and the residual ions are replaced gradually by the added Cl(-) or NO(3)(-). The Raman signal of residual ions can be detected by treatment with anions that do not bind strongly to the silver surface, such as SO(4)(2-). The most intense band of Ag-anions bonds can be also observed when adding weakly binding anions to the colloid. However, the anions which make up the Ag-anions bonds are residual Cl(-) and the effect of weakly binding anions is only to aggregate the silver particles. Residual Cl(-) can be replaced by I(-) which has the highest affinity. From the detection of methylene blue (MB), the effects of anions on the enhancement of Raman signal are discussed in detail, and these findings could make the conditions suitable for detecting analytes in high efficiency. This study will have a profound implication to SERS users about their interpretation of SERS spectra when obtaining these anomalous bands. Copyright © 2011 Elsevier B.V. All rights reserved.

  1. High Vacuum Techniques for Anionic Polymerization

    KAUST Repository

    Ratkanthwar, Kedar; Hadjichristidis, Nikolaos; Mays, Jimmy

    2015-01-01

    Anionic polymerization high vacuum techniques (HVTs) are the most suitable for the preparation of polymer samples with well-defined complex macromolecular architectures. Though HVTs require glassblowing skill for designing and making polymerization

  2. Effects of Anion Mobility on Electrochemical Behaviors of Lithium–Sulfur Batteries

    Energy Technology Data Exchange (ETDEWEB)

    Han, Kee Sung; Chen, Junzheng; Cao, Ruiguo; Rajput, Nav Nidhi; Murugesan, Vijayakumar; Shi, Lili; Pan, Huilin; Zhang, Jiguang; Liu, Jun; Persson, Kristin A.; Mueller, Karl T.

    2017-10-27

    The electrolyte is a crucial component of lithium-sulfur (Li-S) batteries, as it controls polysulfide dissolution, charge shuttling processes, and solid-electrolyte interphase (SEI) layer formation. Experimentally, the overall performance of Li-S batteries varies with choice of solvent system and Li-salt used in the electrolyte, and a lack of predictive understanding about the effects of individual electrolyte components inhibits the rational design of electrolytes for Li-S batteries. Here we analyze the role of the counter anions of common Li salts (such as TfO-, FSI-, TFSI-, and TDI-) when dissolved in DOL/DME (1:1 vol.) for use in Li-S batteries. The evolution of ion-ion and ion-solvent interactions due to vari-ous anions was analyzed using 17O NMR and pulsed-field gradient (PFG) NMR and then correlated with electrochemi-cal performance in Li-S cells. These data reveal that the for-mation of the passivation layer on the anode and the loss of active materials from the cathode (evidenced by polysulfide dissolution) are related to anion mobility and affinity with lithium polysulfide, respectively. For future electrolyte de-sign, anions with lower mobility and weaker interactions with lithium polysulfides may be superior candidates for increasing the long-term stability of Li-S batteries.

  3. Super-pnicogen bonding in the radical anion of the fluorophosphine dimer

    Science.gov (United States)

    Setiawan, Dani; Cremer, Dieter

    2016-10-01

    The LUMO of the pnicogen-bonded fluoro-phosphine dimer has PP bonding character. Radical anion and dianion form relatively strong pnicogen bonds with some covalent character where however the dianion turns out to be a second order transition state. The binding energy of (FPH 2)2- is 30.4 kcal/mol (CCSD(T)/aug-cc-pVTZ; CASPT2(5,8): 30.7 kcal/mol) and the bond strength order measured with the local PP bond stretching force constant increases from 0.055 for the neutral dimer to 0.187 thus revealing that the stabilization of the radical anion is to a large extend a result of one-electron six-center delocalization. Pnicogen-bonded complexes have a stabilizing electron affinity.

  4. Effect of carbonyl group on the lifetimes of pentafluoroacetophenone and pentafluorobenzaldehyde radical anions in aqueous solution: a pulse radiolysis study

    International Nuclear Information System (INIS)

    Shoute, L.C.T.

    1996-01-01

    Hydrated electrons react with pentafluoroacetophenone (PFA) to form radical anion. Evidence for the formation of the radical anion was obtained from observation of intermolecular electron transfer from PFA .- to p-benzoquinone (Q) and methyl viologen (MV 2+ ) to form Q .- and MV .+ . The radical anion lose fluoride with a rate constant of 5x10 4 s -1 . The radical anion has a pK a =7.5. Radical anion of pentafluorobenzaldehyde (PFB) was observed on reduction PFB with hydrated electron. It has a pK a =7.2. It loses fluoride with a rate constant of 1.2x10 5 s -1 . The studies show that substitution of a carbonyl group in the aromatic ring of a perfluorinated compound led to dramatic increase in the lifetime of the radical anion formed on electron addition due to decrease in the rate of fluoride elimination. This led to the possibility of observing their reactions with other solute present in the solution. (author). 6 refs., 1 tab

  5. Crystal structure of rubidium methyl-diazo-tate.

    Science.gov (United States)

    Grassl, Tobias; Korber, Nikolaus

    2017-02-01

    The title compound, Rb + ·H 3 CN 2 O - , has been crystallized in liquid ammonia as a reaction product of the reductive ammonolysis of the natural compound streptozocin. Elemental rubidium was used as reduction agent as it is soluble in liquid ammonia, forming a blue solution. Reductive bond cleavage in biogenic materials under kinetically controlled conditions offers a new approach to gain access to sustainably produced raw materials. The anion is nearly planar [dihedral angle O-N-N-C = -0.4 (2)°]. The Rb + cation has a coordination number of seven, and coordinates to five anions. One anion is bound via both its N atoms, one by both O and N, two anions are bound by only their O atoms, and the last is bound via the N atom adjacent to the methyl group. The diazo-tate anions are bridged by cations and do not exhibit any direct contacts with each other. The cations form corrugated layers that propagate in the (-101) plane.

  6. On affine non-negative matrix factorization

    DEFF Research Database (Denmark)

    Laurberg, Hans; Hansen, Lars Kai

    2007-01-01

    We generalize the non-negative matrix factorization (NMF) generative model to incorporate an explicit offset. Multiplicative estimation algorithms are provided for the resulting sparse affine NMF model. We show that the affine model has improved uniqueness properties and leads to more accurate id...

  7. Global affine differential geometry of hypersurfaces

    CERN Document Server

    Li, An-Min; Zhao, Guosong; Hu, Zejun

    2015-01-01

    This book draws a colorful and widespread picture of global affine hypersurface theory up to the most recent state. Moreover, the recent development revealed that affine differential geometry- as differential geometry in general- has an exciting intersection area with other fields of interest, like partial differential equations, global analysis, convex geometry and Riemann surfaces.

  8. Titanium Insertion into CO Bonds in Anionic Ti-CO2 Complexes.

    Science.gov (United States)

    Dodson, Leah G; Thompson, Michael C; Weber, J Mathias

    2018-03-22

    We explore the structures of [Ti(CO 2 ) y ] - cluster anions using infrared photodissociation spectroscopy and quantum chemistry calculations. The existence of spectral signatures of metal carbonyl CO stretching modes shows that insertion of titanium atoms into C-O bonds represents an important reaction during the formation of these clusters. In addition to carbonyl groups, the infrared spectra show that the titanium center is coordinated to oxalato, carbonato, and oxo ligands, which form along with the metal carbonyls. The presence of a metal oxalato ligand promotes C-O bond insertion in these systems. These results highlight the affinity of titanium for C-O bond insertion processes.

  9. Improving image segmentation by learning region affinities

    Energy Technology Data Exchange (ETDEWEB)

    Prasad, Lakshman [Los Alamos National Laboratory; Yang, Xingwei [TEMPLE UNIV.; Latecki, Longin J [TEMPLE UNIV.

    2010-11-03

    We utilize the context information of other regions in hierarchical image segmentation to learn new regions affinities. It is well known that a single choice of quantization of an image space is highly unlikely to be a common optimal quantization level for all categories. Each level of quantization has its own benefits. Therefore, we utilize the hierarchical information among different quantizations as well as spatial proximity of their regions. The proposed affinity learning takes into account higher order relations among image regions, both local and long range relations, making it robust to instabilities and errors of the original, pairwise region affinities. Once the learnt affinities are obtained, we use a standard image segmentation algorithm to get the final segmentation. Moreover, the learnt affinities can be naturally unutilized in interactive segmentation. Experimental results on Berkeley Segmentation Dataset and MSRC Object Recognition Dataset are comparable and in some aspects better than the state-of-art methods.

  10. Metallocene-catalyzed ethylene−α-olefin isomeric copolymerization: A perspective from hydrodynamic boundary layer mass transfer and design of MAO anion

    KAUST Repository

    Adamu, Sagir; Atiqullah, Muhammad; Malaibari, Zuhair O.; Al-Harthi, Mamdouh A.; Emwas, Abdul-Hamid M.; Ul-Hamid, Anwar

    2015-01-01

    -catalyzed ethylene polymerization. This approach was illustrated by conducting homo- and isomeric copolymerization of ethylene with 1-hexene and 4-methyl-1-pentene in the presence of bis(n-butylcyclopentadienyl) zirconium dichloride (nBuCp)2ZrCl2, using (i) MAO anion

  11. Whole-genome methylation caller designed for methyl- DNA ...

    African Journals Online (AJOL)

    etchie

    2013-02-20

    Feb 20, 2013 ... Our method uses a single-CpG-resolution, whole-genome methylation ... Key words: Methyl-DNA immunoprecipitation, next-generation sequencing, ...... methylation is prevalent in embryonic stem cells andmaybe mediated.

  12. Absorption of carbon dioxide in aqueous solutions of imidazolium ionic liquids with carboxylate anions

    Energy Technology Data Exchange (ETDEWEB)

    Baj, Stefan; Krawczyk, Tomasz; Dabrowska, Aleksandra; Siewniak, Agnieszka [Silesian University of Technology, Gliwice (Poland); Sobolewski, Aleksander [Institute for Chemical Processing of Coal, Zabrze (Poland)

    2015-11-15

    The solubility of carbon dioxide at atmospheric pressure in aqueous mixtures of 1,3-alkyl substituted imidazolium ionic liquids (ILs) containing carboxylic anions was studied. The ILs showed increased solubility of CO{sub 2} with decreasing water concentration. The relationship between the CO{sub 2} concentration in solution and the mole fraction of water in the ILs describes a sigmoidal curve. The regression constants of a logistic function were used to quantitatively assess the absorbent capacity and the effect of water on CO{sub 2} absorption. ILs containing the most basic anions, such as pivalate, propionate and acetate, had the best properties. It was observed that the impact of water on absorption primarily depended on the cation structure. The best absorption performance was observed for 1,3-dibutylimidazolium pivalate and 1-butyl-3-methyl imidazolium acetate.

  13. Absorption of carbon dioxide in aqueous solutions of imidazolium ionic liquids with carboxylate anions

    International Nuclear Information System (INIS)

    Baj, Stefan; Krawczyk, Tomasz; Dabrowska, Aleksandra; Siewniak, Agnieszka; Sobolewski, Aleksander

    2015-01-01

    The solubility of carbon dioxide at atmospheric pressure in aqueous mixtures of 1,3-alkyl substituted imidazolium ionic liquids (ILs) containing carboxylic anions was studied. The ILs showed increased solubility of CO 2 with decreasing water concentration. The relationship between the CO 2 concentration in solution and the mole fraction of water in the ILs describes a sigmoidal curve. The regression constants of a logistic function were used to quantitatively assess the absorbent capacity and the effect of water on CO 2 absorption. ILs containing the most basic anions, such as pivalate, propionate and acetate, had the best properties. It was observed that the impact of water on absorption primarily depended on the cation structure. The best absorption performance was observed for 1,3-dibutylimidazolium pivalate and 1-butyl-3-methyl imidazolium acetate.

  14. Supramolecular Chemistry of Selective Anion Recognition for Anions of Environmental Relevance

    International Nuclear Information System (INIS)

    Bowman-James, K.; Wilson, G.; Moyer, B. A.

    2004-01-01

    This project involves the design and synthesis of receptors for oxoanions of environmental importance, including emphasis on high level and low activity waste. Target anions have included primarily oxoanions and a study of the basic concepts behind selective binding of target anions. A primary target has been sulfate because of its deleterious influence on the vitrification of tank wastes

  15. Effect of adsorbed/intercalated anionic dyes into the mechanical properties of PVA: layered zinc hydroxide nitrate nanocomposites.

    Science.gov (United States)

    Marangoni, Rafael; Mikowski, Alexandre; Wypych, Fernando

    2010-11-15

    Zinc hydroxide nitrate (ZHN) was adsorbed with anions of blue dyes (Chicago sky blue, CSB; Evans blue, EB; and Niagara blue, NB) and intercalated with anions of orange dyes (Orange G, OG; Orange II, OII; methyl orange, MO). Transparent, homogeneous and colored nanocomposite films were obtained by casting after dispersing the pigments (dye-intercalated/adsorbed into LHSs) into commercial poly(vinyl alcohol) (PVA). The films were characterized by XRD, UV-Vis spectroscopy, and mechanical testing. The mechanical properties of the PVA compounded with the dye-intercalated/adsorbed ZHN were evaluated, and reasonable increases in Young's modulus and ultimate tensile strength were observed, depending on the amount and choice of layered filler. These results demonstrate the possibility of using a new class of layered hydroxide salts intercalated and adsorbed with anionic dyes to prepare multifunctional polymer nanocomposite materials. Copyright © 2010 Elsevier Inc. All rights reserved.

  16. Infrared spectroscopy of anionic hydrated fluorobenzenes

    International Nuclear Information System (INIS)

    Schneider, Holger; Vogelhuber, Kristen M.; Weber, J. Mathias

    2007-01-01

    We investigate the structural motifs of anionic hydrated fluorobenzenes by infrared photodissociation spectroscopy and density functional theory. Our calculations show that all fluorobenzene anions under investigation are strongly distorted from the neutral planar molecular geometries. In the anions, different F atoms are no longer equivalent, providing structurally different binding sites for water molecules and giving rise to a multitude of low-lying isomers. The absorption bands for hexa- and pentafluorobenzene show that only one isomer for the respective monohydrate complexes is populated in our experiment. For C 6 F 6 - ·H 2 O, we can assign these bands to an isomer where water forms a weak double ionic hydrogen bond with two F atoms in the ion, in accord with the results of Bowen et al. [J. Chem. Phys. 127, 014312 (2007), following paper.] The spectroscopic motif of the binary complexes changes slightly with decreasing fluorination of the aromatic anion. For dihydrated hexafluorobenzene anions, several isomers are populated in our experiments, some of which may be due to hydrogen bonding between water molecules

  17. The Cutting Edge of Affinity Electrophoresis Technology

    Science.gov (United States)

    Kinoshita, Eiji; Kinoshita-Kikuta, Emiko; Koike, Tohru

    2015-01-01

    Affinity electrophoresis is an important technique that is widely used to separate and analyze biomolecules in the fields of biology and medicine. Both quantitative and qualitative information can be gained through affinity electrophoresis. Affinity electrophoresis can be applied through a variety of strategies, such as mobility shift electrophoresis, charge shift electrophoresis or capillary affinity electrophoresis. These strategies are based on changes in the electrophoretic patterns of biological macromolecules that result from interactions or complex-formation processes that induce changes in the size or total charge of the molecules. Nucleic acid fragments can be characterized through their affinity to other molecules, for example transcriptional factor proteins. Hydrophobic membrane proteins can be identified by means of a shift in the mobility induced by a charged detergent. The various strategies have also been used in the estimation of association/disassociation constants. Some of these strategies have similarities to affinity chromatography, in that they use a probe or ligand immobilized on a supported matrix for electrophoresis. Such methods have recently contributed to profiling of major posttranslational modifications of proteins, such as glycosylation or phosphorylation. Here, we describe advances in analytical techniques involving affinity electrophoresis that have appeared during the last five years. PMID:28248262

  18. The Cutting Edge of Affinity Electrophoresis Technology.

    Science.gov (United States)

    Kinoshita, Eiji; Kinoshita-Kikuta, Emiko; Koike, Tohru

    2015-03-18

    Affinity electrophoresis is an important technique that is widely used to separate and analyze biomolecules in the fields of biology and medicine. Both quantitative and qualitative information can be gained through affinity electrophoresis. Affinity electrophoresis can be applied through a variety of strategies, such as mobility shift electrophoresis, charge shift electrophoresis or capillary affinity electrophoresis. These strategies are based on changes in the electrophoretic patterns of biological macromolecules that result from interactions or complex-formation processes that induce changes in the size or total charge of the molecules. Nucleic acid fragments can be characterized through their affinity to other molecules, for example transcriptional factor proteins. Hydrophobic membrane proteins can be identified by means of a shift in the mobility induced by a charged detergent. The various strategies have also been used in the estimation of association/disassociation constants. Some of these strategies have similarities to affinity chromatography, in that they use a probe or ligand immobilized on a supported matrix for electrophoresis. Such methods have recently contributed to profiling of major posttranslational modifications of proteins, such as glycosylation or phosphorylation. Here, we describe advances in analytical techniques involving affinity electrophoresis that have appeared during the last five years.

  19. Density Functional Study of Structures and Electron Affinities of BrO4F/BrO4F-

    Directory of Open Access Journals (Sweden)

    Wei Li

    2009-07-01

    Full Text Available The structures, electron affinities and bond dissociation energies of BrO4F/BrO4F− species have been investigated with five density functional theory (DFT methods with DZP++ basis sets. The planar F-Br…O2…O2 complexes possess 3A' electronic state for neutral molecule and 4A' state for the corresponding anion. Three types of the neutral-anion energy separations are the adiabatic electron affinity (EAad, the vertical electron affinity (EAvert, and the vertical detachment energy (VDE. The EAad value predicted by B3LYP method is 4.52 eV. The bond dissociation energies De (BrO4F → BrO4-mF + Om (m = 1-4 and De- (BrO4F- → BrO4-mF- + Om and BrO4F- → BrO4-mF + Om- are predicted. The adiabatic electron affinities (EAad were predicted to be 4.52 eV for F-Br…O2…O2 (3A'← 4A' (B3LYP method.

  20. Methylation pathways in schizophrenia

    International Nuclear Information System (INIS)

    Sargent, T.W. III.

    1982-01-01

    Research on the biochemical causes of human psychosis concentrates on investigating whether schizophremia is linked to abnormalities in the metabolism of methyl carbon groups in the body. The metabolism of C-14 labeled methyl groups in methionine is studied in animals, normal subjects and patient volunteers

  1. Mobile Technology Affinity in Renal Transplant Recipients.

    Science.gov (United States)

    Reber, S; Scheel, J; Stoessel, L; Schieber, K; Jank, S; Lüker, C; Vitinius, F; Grundmann, F; Eckardt, K-U; Prokosch, H-U; Erim, Y

    Medication nonadherence is a common problem in renal transplant recipients (RTRs). Mobile health approaches to improve medication adherence are a current trend, and several medication adherence apps are available. However, it is unknown whether RTRs use these technologies and to what extent. In the present study, the mobile technology affinity of RTRs was analyzed. We hypothesized significant age differences in mobile technology affinity and that mobile technology affinity is associated with better cognitive functioning as well as higher educational level. A total of 109 RTRs (63% male) participated in the cross-sectional study, with an overall mean age of 51.8 ± 14.2 years. The study included the Technology Experience Questionnaire (TEQ) for the assessment of mobile technology affinity, a cognitive test battery, and sociodemographic data. Overall, 57.4% of the patients used a smartphone or tablet and almost 45% used apps. The TEQ sum score was 20.9 in a possible range from 6 (no affinity to technology) to 30 (very high affinity). Younger patients had significantly higher scores in mobile technology affinity. The only significant gender difference was found in having fun with using electronic devices: Men enjoyed technology more than women did. Mobile technology affinity was positively associated with cognitive functioning and educational level. Young adult patients might profit most from mobile health approaches. Furthermore, high educational level and normal cognitive functioning promote mobile technology affinity. This should be kept in mind when designing mobile technology health (mHealth) interventions for RTRs. For beneficial mHealth interventions, further research on potential barriers and desired technologic features is necessary to adapt apps to patients' needs. Copyright © 2017 Elsevier Inc. All rights reserved.

  2. Synthesis of two S-(methyl-3H)-labelled enkephalins and S-(methyl-14C) substance P

    International Nuclear Information System (INIS)

    Naegren, K.; Laangstroem, B.; Franzen, H.M.; Ragnarsson, U.

    1988-01-01

    The synthesis of 3 H-labelled Met-enkephalin and Tyr-D-Ala-Gly-Phe-Met-NH 2 (DALA) and 14 C-labelled Substance P (SP) from previously described, fully protected intermediates is reported. The labelled peptides were prepared by methylation with ( 3 H)- or ( 14 C)methyl iodide of the sulphide anions formed on deprotection of the corresponding S-benzyl-homocysteine precursors with sodium in liquid ammonia. After purification by LC, the labelled peptides were obtained in radiochemical yields in the range of 9 to 24% with a radiochemical purity higher than 97%. The specific radioactivities of the 3 H- and 14 C- labelled products, corresponding to the labelled methyl iodides used, were 80 mCi/μmol and 60 μCi/μmol, respectively. (author)

  3. Cytotoxic mechanisms of hydrosulfide anion and cyanide anion in primary rat hepatocyte cultures

    International Nuclear Information System (INIS)

    Thompson, Rodney W.; Valentine, Holly L.; Valentine, William M.

    2003-01-01

    Hydrogen sulfide and hydrogen cyanide are known to compromise mitochondrial respiration through inhibition of cytochrome c oxidase and this is generally considered to be their primary mechanism of toxicity. Experimental studies and the efficiency of current treatment protocols suggest that H 2 S may exert adverse physiological effects through additional mechanisms. To evaluate the role of alternative mechanisms in H 2 S toxicity, the relative contributions of electron transport inhibition, uncoupling of mitochondrial respiration, and opening of the mitochondrial permeability transition pore (MPTP) to hydrosulfide and cyanide anion cytotoxicity in primary hepatocyte cultures were examined. Supplementation of hepatocytes with the glycolytic substrate, fructose, rescued hepatocytes from cyanide anion induced toxicity, whereas fructose supplementation increased hydrosulfide anion toxicity suggesting that hydrosulfide anion may compromise glycolysis in hepatocytes. Although inhibitors of the MPTP opening were protective for hydrosulfide anion, they had no effect on cyanide anion toxicity, consistent with an involvement of the permeability transition pore in hydrosulfide anion toxicity but not cyanide anion toxicity. Exposure of isolated rat liver mitochondria to hydrosulfide did not result in large amplitude swelling suggesting that if H 2 S induces the permeability transition it does so indirectly through a mechanism requiring other cellular components. Hydrosulfide anion did not appear to be an uncoupler of mitochondrial respiration in hepatocytes based upon the inability of oligomycin and fructose to protect hepatocytes from hydrosulfide anion toxicity. These findings support mechanisms additional to inhibition of cytochrome c oxidase in hydrogen sulfide toxicity. Further investigations are required to assess the role of the permeability transition in H 2 S toxicity, determine whether similar affects occur in other cell types or in vivo and evaluate whether this may

  4. Affinity Strings: Enterprise Data for Resource Recommendations

    Directory of Open Access Journals (Sweden)

    Shane Nackerud

    2008-12-01

    Full Text Available The University of Minnesota Libraries have created a MyLibrary portal, with databases and e-journals targeted to users, based on their affiliations. The University's enterprise authentication system provides an "affinity string", now used to personalize the MyLibrary portal. This affinity string automates discovery of a user's relationship to the University--describing a user's academic department and degree program or position at the University. Affinity strings also provide the Libraries with an anonymized view of resource usage, allowing data collection that respects users' privacy and lays the groundwork for automated recommendation of relevant resources based on the practices and habits of their peers.

  5. Patchy proteins, anions and the Hofmeister series

    Energy Technology Data Exchange (ETDEWEB)

    Lund, Mikael; Jungwirth, Pavel [Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, Flemingovo namesti 2, 16610 Prague 6 (Czech Republic); Center for Complex Molecular Systems and Biomolecules, Flemingovo namesti 2, 16610 Prague 6 (Czech Republic)], E-mail: mikael.lund@uochb.cas.cz

    2008-12-10

    We investigate specific anion binding to a range of patchy protein models and use our results to probe protein-protein interactions for aqueous lysozyme solutions. Our molecular simulation studies show that the ion-protein interaction mechanism and strength largely depend on the nature of the interfacial amino acid residues. Via direct ion pairing, small anions interact with charged side-chains while larger anions are attracted to non-polar residues due to several solvent assisted mechanisms. Incorporating ion and surface specificity into a mesoscopic model for protein-protein interactions we calculate the free energy of interaction between lysozyme molecules in aqueous solutions of sodium chloride and sodium iodide. In agreement with experiment, our finding is that 'salting out' follows the reverse Hofmeister series for pH below the iso-electric point and the direct series for pH above pI.

  6. New borohydride anion B6H7-

    International Nuclear Information System (INIS)

    Kuznetsov, I.Yu.; Vinitskij, D.M.; Solntsev, K.A.

    1985-01-01

    The [Ni(Bipy) 3 ] (B 6 H 7 ) 2 , (Ph 4 P)B 6 H 7 , [Ni(Phen) 3 ](B 6 H 7 ) 2 crystals (where Bipy = bipyridine, Phen = phenathroline, Ph = phenyl) are obtained via the exchange reaction with a subsequent recrystallization from aqua-acetonic and acetonic solutions. The structure is studied of a new borohydride anion B 6 H 7 - possessing a four-valence bond unique for polyhedral borohydride anions. A triangular face of boride skeleton coordinating a hydrogen atom is considerably larger than other faces, and the electron density on this hydrogen atom is evidently much higher than at the end hydride hydrogen atoms. The trend of B 6 H 7 - anion to form statistically disordered structurs testifies to a rather slight effect of the seventh hydrogen atom position on the structure pattern of the ionic crystal lattice

  7. Reaction of aryl diazonium tetrafluoro borates with allyl methacrylate in the presence of rhodanide-anion

    International Nuclear Information System (INIS)

    Grishchuk, B.D.; Baranovskij, V.S.; Simchak, R.V.; Tulajdan, G.N.; Gorbovoj, P.M.

    2006-01-01

    Reaction of aryl diazonium tetrafluoro borates (I) with allyl ester of methacrylic acid in the water-acetone (1:5) medium is studied by means of IR spectroscopy and 1 H NMR. It is established that (I) reacts with aryl methacrylate in the presence of rhodanide-anion and catalytic quantities of copper salts with the formation of allyl esters of 2-thiocyanato-2-methyl-3-aryl propionic acids with the yield of 32-56%. Allyl fragment of biunsaturated compound shows no reaction under the tested conditions [ru

  8. Methyl-Analyzer--whole genome DNA methylation profiling.

    Science.gov (United States)

    Xin, Yurong; Ge, Yongchao; Haghighi, Fatemeh G

    2011-08-15

    Methyl-Analyzer is a python package that analyzes genome-wide DNA methylation data produced by the Methyl-MAPS (methylation mapping analysis by paired-end sequencing) method. Methyl-MAPS is an enzymatic-based method that uses both methylation-sensitive and -dependent enzymes covering >80% of CpG dinucleotides within mammalian genomes. It combines enzymatic-based approaches with high-throughput next-generation sequencing technology to provide whole genome DNA methylation profiles. Methyl-Analyzer processes and integrates sequencing reads from methylated and unmethylated compartments and estimates CpG methylation probabilities at single base resolution. Methyl-Analyzer is available at http://github.com/epigenomics/methylmaps. Sample dataset is available for download at http://epigenomicspub.columbia.edu/methylanalyzer_data.html. fgh3@columbia.edu Supplementary data are available at Bioinformatics online.

  9. The absorption of plutonium by anion resins

    Energy Technology Data Exchange (ETDEWEB)

    Durham, R. W.; Mills, R.

    1961-10-15

    Equilibrium experiments have shown Pu{sup +4} to be absorbed from nitric acid onto an anion resin as a complex anion Pu(NO{sub 3}){sub 6}{sup -2}. The amount of absorption is dependent on the plutonium and nitric acid concentrations in the equilibrium solution with a maximum at 7N to 8N HNO{sub 3}. A low cross-linked resin has a higher capacity and reaches equilibrium more rapidly than the normally supplied resin. Saturation capacity of one per cent cross-linked Nalcite SBR (Dowex 1), 50 -- 100 mesh, is 385 mg Pu/gram dry resin. (author)

  10. High Vacuum Techniques for Anionic Polymerization

    KAUST Repository

    Ratkanthwar, Kedar

    2015-09-01

    Anionic polymerization high vacuum techniques (HVTs) are the most suitable for the preparation of polymer samples with well-defined complex macromolecular architectures. Though HVTs require glassblowing skill for designing and making polymerization reactor, it is the best way to avoid any termination of living polymers during the number of steps for the synthesis of polymers with complex structure. In this chapter, we describe the different polymerization reactors and HVTs for the purification of monomers, solvents, and other reagents for anionic polymerization as well as few model reactions for the synthesis of polymers with simple to complex structure.

  11. Dibromine radical anion reactions with heme enzymes

    International Nuclear Information System (INIS)

    Gebicka, L.; Gebicki, J.L.

    1996-01-01

    Reactions of Br 2 radical anion with heme enzymes, catalase horseradish peroxidase, have been studied by pulse radiolysis. It has been found that Br 2 - does not react with the heme centre of investigated enzymes. Dibromine radical anion reacts with tryptophan residues of catalase without any influence on the activity of catalase. It is suggested that in pulse radiolysis studies, where horseradish peroxidase is at about tenfold excess toward Br 2 - , the enzyme is modified rather by Br 2 , than by Br 2 - . (author). 26 refs., 3 figs

  12. Effects of arginine on multimodal anion exchange chromatography.

    Science.gov (United States)

    Hirano, Atsushi; Arakawa, Tsutomu; Kameda, Tomoshi

    2015-12-01

    The effects of arginine on binding and elution properties of a multimodal anion exchanger, Capto adhere, were examined using bovine serum albumin (BSA) and a monoclonal antibody against interleukin-8 (mAb-IL8). Negatively charged BSA was bound to the positively charged Capto adhere and was readily eluted from the column with a stepwise or gradient elution using 1M NaCl at pH 7.0. For heat-treated BSA, small oligomers and remaining monomers were also eluted using a NaCl gradient, whereas larger oligomers required arginine for effective elution. The positively charged mAb-IL8 was bound to Capto adhere at pH 7.0. Arginine was also more effective for elution of the bound mAb-IL8 than was NaCl. The results imply that arginine interacts with the positively charged Capto adhere. The mechanism underlying the interactions of arginine with Capto adhere was examined by calculating the binding free energy between an arginine molecule and a Capto adhere ligand in water through molecular dynamics simulations. The overall affinity of arginine for Capto adhere is attributed to the hydrophobic and π-π interactions between an arginine side chain and the aromatic moiety of the ligand as well as hydrogen bonding between arginine and the ligand hydroxyl group, which may account for the characteristics of protein elution using arginine. Copyright © 2015 Elsevier Inc. All rights reserved.

  13. Stability of anionic polymers in presence of multivalent cations

    International Nuclear Information System (INIS)

    Sabbagh, Imad

    1997-01-01

    This research thesis aimed at studying the stability of poly-electrolytes in saline environments, and the interactions between ions and poly-electrolytes of different charge densities. For this purpose, the author more particularly studied specific interactions between anionic poly-electrolytes and multivalent cations. After a recall of properties of neutral polymers and poly-electrolytes in solution, the author evokes interactions between poly-electrolytes and counter-ions, and briefly presents two models of stability of poly-electrolytes in saline solutions. The next part presents various experimental spectroscopic and electrochemical techniques and results of the characterization of the used products. Spectroscopic techniques allow ion-polymer interactions at the atomic scale to be studied, and electrochemical techniques allow the behaviour of small ions to be studied. The author then discusses the main differences of solubility between poly-electrolytes containing sulphonate or sulphate groups and those containing carboxylate groups. A model is then developed to generalise phase diagrams of a poly-electrolyte with respect to the chemical affinity of its functional group with ions of opposite sign. The author then addresses the behaviour of a non charged polyacrylic acid in various saline solutions, and presents a phase diagram model [fr

  14. Affinity purification of recombinant human plasminogen activator ...

    African Journals Online (AJOL)

    Affinity purification of recombinant human plasminogen activator from ... Screening antibody was performed using rhPA milk in an ELISA-elution assay. ... useful for purifying other tPA mutants or other novel recombinant milkderived proteins.

  15. PRINCIPLES OF AFFINITY-BASED BIOSENSORS

    Science.gov (United States)

    Despite the amount of resources that have been invested by national and international academic, government, and commercial sectors to develop affinity-based biosensor products, little obvious success has been realized through commercialization of these devices for specific applic...

  16. Quantum deformation of the affine transformation algebra

    International Nuclear Information System (INIS)

    Aizawa, N.; Sato, Haru-Tada

    1994-01-01

    We discuss a quantum deformation of the affine transformation algebra in one-dimensional space. It is shown that the quantum algebra has a non-cocommutative Hopf algebra structure, simple realizations and quantum tensor operators. (orig.)

  17. Dynamics of Open Systems with Affine Maps

    International Nuclear Information System (INIS)

    Zhang Da-Jian; Liu Chong-Long; Tong Dian-Min

    2015-01-01

    Many quantum systems of interest are initially correlated with their environments and the reduced dynamics of open systems are an interesting while challenging topic. Affine maps, as an extension of completely positive maps, are a useful tool to describe the reduced dynamics of open systems with initial correlations. However, it is unclear what kind of initial state shares an affine map. In this study, we give a sufficient condition of initial states, in which the reduced dynamics can always be described by an affine map. Our result shows that if the initial states of the combined system constitute a convex set, and if the correspondence between the initial states of the open system and those of the combined system, defined by taking the partial trace, is a bijection, then the reduced dynamics of the open system can be described by an affine map. (paper)

  18. On the Lp affine isoperimetric inequalities

    Indian Academy of Sciences (India)

    surface area measure on convex bodies. We also establish the reverse version of -Petty projection inequality and an affine isoperimetric inequality of − p K . Author Affiliations. Wuyang Yu1 Gangsong Leng2. Institute of Management Decision ...

  19. Making the invisible visible: improved electrospray ion formation of metalloporphyrins/-phthalocyanines by attachment of the formate anion (HCOO(-)).

    Science.gov (United States)

    Hitzenberger, Jakob Felix; Dammann, Claudia; Lang, Nina; Lungerich, Dominik; García-Iglesias, Miguel; Bottari, Giovanni; Torres, Tomás; Jux, Norbert; Drewello, Thomas

    2016-02-21

    A protocol is developed for the coordination of the formate anion (HCOO(-)) to neutral metalloporphyrins (Pors) and -phthalocyanines (Pcs) containing divalent metals as a means to improve their ion formation in electrospray ionization (ESI). This method is particularly useful when the oxidation of the neutral metallomacrocycle fails. While focusing on Zn(II)Pors and Zn(II)Pcs, we show that formate is also readily attached to Mn(II), Mg(II) and Co(II)Pcs. However, for the Co(II)Pc secondary reactions can be observed. Upon collision-induced dissociation (CID), Zn(II)Por/Pc·formate supramolecular complexes can undergo the loss of CO2 in combination with transfer of a hydride anion (H(-)) to the zinc metal center. Further dissociation leads to electron transfer and hydrogen atom loss, generating a route to the radical anion of the Zn(II)Por/Pc without the need for electrochemical reduction, although the Zn(II)Por/Pc may have a too low electron affinity to allow electron transfer directly from the formate anion. In addition to single Por molecules, multi Por arrays were successfully analyzed by this method. In this case, multiple addition of formate occurs, giving rise to multiply charged species. In these multi Por arrays, complexation of the formate anion occurs by two surrounding Por units (sandwich). Therefore, the maximum attainment of formate anions in these arrays corresponds to the number of such sandwich complexes rather than the number of porphyrin moieties. The same bonding motif leads to dimers of the composition [(Zn(II)Por/Pc)2·HCOO](-). In these, the formate anion can act as a structural probe, allowing the distinction of isomeric ions with the formate bridging two macrocycles or being attached to a dimer of directly connected macrocycles.

  20. Different endothelin receptor affinities in dog tissues

    International Nuclear Information System (INIS)

    Loeffler, B.M.L.; Loehrer, W.

    1991-01-01

    Endothelin (ET) is a long-lasting potent vasoconstrictor-peptide. Here the authors report different binding affinities of endothelin-1 (ET-1) to ET-receptors of various dog tissues. Crude microsomal fractions were prepared after homogenisation of dog tissues in 50 mM Tris/HCl, 20 mM MnCl2, 1 mM EDTA, pH 7.4 by differential centrifugation. Aliquots of microsomal fractions (70 micrograms of protein) were incubated at 25 degrees C for 180 min in the presence of 20 pM 125I-ET-1 and various concentrations of cold ET-1. Four different ET-1 receptor binding affinities were found: adrenals, cerebrum, liver, heart, skeletal muscle and stomach microsomal membranes contained high affinity binding sites (Kd 50 - 80 pM, Bmax 60 - 250 fmol/mg). In cerebellum and spleen medium affinity ET-1 receptors (Kd 350 pM, Bmax 880 and 1200 fmol/mg respectively) were present. In comparison lung and kidney microsomes contained a low affinity ET-1 receptor (Kd 800 and 880 pM, Bmax 1600 and 350 fmol/mg). Receptors of even lower affinity were present in heart, intestine and liver microsomes with Kd values of 3 - 6 nM

  1. The assessment of pellicular anion-exchange resins for the determination of anions by ion chromatography

    International Nuclear Information System (INIS)

    Pohlandt, C.

    1981-01-01

    Because pellicular anion-exchange resins suitable for the determination, by ion chromatography, of anions with alkaline eluents were unavailable in South Africa at the inception of this work, an attempt was made to prepare such resins. In this study it is shown that the pellicular resins produced are more efficient than the surface-aminated resins used previously. The simultaneous separation and determination of five common anions is demonstrated. The method was applied to the analysis of uranium leach liquors, effluent samples, and a solid sample of ferric oxide (goethite)

  2. The metric-affine gravitational theory as the gauge theory of the affine group

    International Nuclear Information System (INIS)

    Lord, E.A.

    1978-01-01

    The metric-affine gravitational theory is shown to be the gauge theory of the affine group, or equivalently, the gauge theory of the group GL(4,R) of tetrad deformations in a space-time with a locally Minkowskian metric. The identities of the metric-affine theory, and the relationship between them and those of general relativity and Sciama-Kibble theory, are derived. (Auth.)

  3. Interstellar dehydrogenated PAH anions: vibrational spectra

    Science.gov (United States)

    Buragohain, Mridusmita; Pathak, Amit; Sarre, Peter; Gour, Nand Kishor

    2018-03-01

    Interstellar polycyclic aromatic hydrocarbon (PAH) molecules exist in diverse forms depending on the local physical environment. Formation of ionized PAHs (anions and cations) is favourable in the extreme conditions of the interstellar medium (ISM). Besides in their pure form, PAHs are also likely to exist in substituted forms; for example, PAHs with functional groups, dehydrogenated PAHs etc. A dehydrogenated PAH molecule might subsequently form fullerenes in the ISM as a result of ongoing chemical processes. This work presents a density functional theory (DFT) calculation on dehydrogenated PAH anions to explore the infrared emission spectra of these molecules and discuss any possible contribution towards observed IR features in the ISM. The results suggest that dehydrogenated PAH anions might be significantly contributing to the 3.3 μm region. Spectroscopic features unique to dehydrogenated PAH anions are highlighted that may be used for their possible identification in the ISM. A comparison has also been made to see the size effect on spectra of these PAHs.

  4. Anion-conducting polymer, composition, and membrane

    Science.gov (United States)

    Pivovar, Bryan S [Los Alamos, NM; Thorn, David L [Los Alamos, NM

    2009-09-01

    Anion-conducing polymers and membranes with enhanced stability to aqueous alkali include a polymer backbone with attached sulfonium, phosphazenium, phosphazene, and guanidinium residues. Compositions also with enhanced stability to aqueous alkali include a support embedded with sulfonium, phosphazenium, and guanidinium salts.

  5. Synthesis of azaphenanthridines via anionic ring closure

    DEFF Research Database (Denmark)

    Hansen, Henriette Møller; Lysén, M.; Begtrup, M.

    2005-01-01

    A new and convergent synthesis of azaphenanthridines via an anionic ring closure is reported. Ortho-lithiation/in situ borylation of cyanopyridines produces the corresponding cyanopyridylboronic esters, which undergo a Suzuki-Miyaura cross-coupling to give the key intermediates. Addition of lithium...

  6. Full-dimensional characterization of photoelectron spectra of HOCO− and DOCO− and tunneling facilitated decay of HOCO prepared by anion photodetachment

    International Nuclear Information System (INIS)

    Wang, Jun; Li, Jun; Guo, Hua; Ma, Jianyi

    2014-01-01

    The photodetachment of both the HOCO − and DOCO − anions is investigated using full-dimensional quantum wave packets on new ab initio based global potential energy surfaces for both the neutral and anionic species. The calculated electron affinities and neutral fundamental vibrational frequencies of both isotopomers are in good agreement with available experimental data. The measured photoelectron spectra are also accurately reproduced, further validating the accuracy of the potential energy surfaces. In addition, strong mode specificity is found in the lifetimes of the HOCO vibrational features and the tunneling facilitated predissociation rates to H + CO 2 are rationalized using the recently proposed sudden vector projection model

  7. Hirota's solitons in the affine and the conformal affine Toda models

    International Nuclear Information System (INIS)

    Aratyn, H.; Constantinidis, C.P.; Ferreira, L.A.; Gomes, J.F.; Zimerman, A.H.

    1993-01-01

    We use Hirota's method formulated as a recursive scheme to construct a complete set of soliton solutions for the affine Toda field theory based on an arbitrary Lie algebra. Our solutions include a new class of solitons connected with two different types of degeneracies encountered in Hirota's perturbation approach. We also derive an universal mass formula for all Hirota's solutions to the affine Toda model valid for all underlying Lie groups. Embedding of the affine Toda model in the conformal affine Toda model plays a crucial role in this analysis. (orig.)

  8. Bidentate urea derivatives of p-tert-butyldihomooxacalix[4]arene: neutral receptors for anion complexation.

    Science.gov (United States)

    Marcos, Paula M; Teixeira, Filipa A; Segurado, Manuel A P; Ascenso, José R; Bernardino, Raul J; Michel, Sylvia; Hubscher-Bruder, Véronique

    2014-01-17

    Three new bidentate ureidodihomooxacalix[4]arene derivatives (phenyl 5a, n-propyl 5b, and tert-butyl 5c) were synthesized in four steps from the parent compound p-tert-butyldihomooxacalix[4]arene and obtained in the cone conformation, as shown by NMR studies. The binding ability of these neutral receptors toward spherical, linear, trigonal planar, and tetrahedrical anions was assessed by (1)H NMR and UV-vis titrations. The structures and complexation energies of some complexes were also studied by DFT methods. The data showed that the association constants are strongly dependent on the nature of the substituent (aryl/alkyl) at the urea moiety. In general, for all the receptors, the association constants decrease with decrease of anion basicity. Ph-urea 5a is the best anion receptor, showing the strongest complexation for F(-) (log K(assoc) = 3.10 in CDCl3) and also high binding affinity for the carboxylates AcO(-) and BzO(-). Similar results were obtained by UV-vis studies and were also corroborated by DFT calculations.

  9. Selection of anion exchangers for detoxification of dilute-acid hydrolysates from spruce.

    Science.gov (United States)

    Horváth, Ilona Sárvári; Sjöde, Anders; Nilvebrant, Nils-Olof; Zagorodni, Andrei; Jönsson, Leif J

    2004-01-01

    Six anion-exchange resins with different properties were compared with respect to detoxification of a dilute-acid hydrolysate of spruce prior to ethanolic fermentation with Saccharomyces cerevisiae. The six resins encompassed strong and weak functional groups as well as styrene-, phenol-, and acrylic-based matrices. In an analytical experimental series, fractions from columns packed with the different resins were analyzed regarding pH, glucose, furfural, hydroxymethylfurfural, phenolic compounds, levulinic acid, acetic acid, formic acid, and sulfate. An initial adsorption of glucose occurred in the strong alkaline environment and led to glucose accumulation at a later stage. Acetic and levulinic acid passed through the column before formic acid, whereas sulfate had the strongest affinity. In a preparative experimental series, one fraction from each of six columns packed with the different resins was collected for assay of the fermentability and analysis of glucose, mannose, and fermentation inhibitors. The fractions collected from strong anion-exchange resins with styrene-based matrices displayed the best fermentability: a sevenfold enhancement of ethanol productivity compared with untreated hydrolysate. Fractions from a strong anion exchanger with acrylic-based matrix and a weak exchanger with phenol-based resin displayed an intermediate improvement in fermentability, a four- to fivefold increase in ethanol productivity. The fractions from two weak exchangers with styrene- and acrylic-based matrices displayed a twofold increase in ethanol productivity. Phenolic compounds were more efficiently removed by resins with styrene- and phenol-based matrices than by resins with acrylic-based matrices.

  10. Modelling the transport of carbonic acid anions through anion-exchange membranes

    International Nuclear Information System (INIS)

    Nikonenko, V.; Lebedev, K.; Manzanares, J.A.; Pourcelly, G.

    2003-01-01

    Electrodiffusion of carbonate and bicarbonate anions through anion-exchange membranes (AEM) is described on the basis of the Nernst-Planck equations taking into account coupled hydrolysis reactions in the external diffusion boundary layers (DBLs) and internal pore solution. The model supposes local electroneutrality as well as chemical and thermodynamic equilibrium. The transport is considered in three layers being an anion exchange membrane and two adjoining diffusion layers. A mechanism of competitive transport of HCO 3 - and CO 3 2- anions through the membrane which takes into account Donnan exclusion of H + ions is proposed. It is predicted that the pH of the depleting solution decreases and that of the concentrating solution increases during electrodialysis (ED). Eventual deviations from local electroneutrality and local chemical equilibrium are discussed

  11. Regulation of organic anion transport in the liver

    NARCIS (Netherlands)

    Roelofsen, H; Jansen, PLM

    1997-01-01

    In several liver diseases the biliary transport is disturbed, resulting in, for example, jaundice and cholestasis. Many of these symptoms can be attributed to altered regulation of hepatic transporters. Organic anion transport, mediated by the canalicular multispecific organic anion transporter

  12. Changes in plasma osmolality and anion gap: potential predictors of ...

    African Journals Online (AJOL)

    Changes in plasma osmolality and anion gap: potential predictors of ... PROMOTING ACCESS TO AFRICAN RESEARCH ... Objective: To determine the relationship of mortality to plasma osmolality and anion gap inpatients on haemodialysis.

  13. Supramolecular Chemistry of Selective Anion Recognition for Anions of Environmental Relevance

    International Nuclear Information System (INIS)

    Sessler, Jonathan L.

    2007-01-01

    The major thrust of this project, led by the University of Kansas (Prof. Kristin Bowman-James), entails an exploration of the basic determinants of anion recognition and their application to the design, synthesis, and testing of novel sulfate extractants. A key scientific inspiration for the work comes from the need, codified in simple-to-appreciate terms by the Oak Ridge National Laboratory component of the team (viz. Dr. Bruce Moyer), for chemical entities that can help in the extractive removal of species that have low solubilities in borosilicate glass. Among such species, sulfate anion, has been identified as particularly insidious. Its presence interferes with the vitrification process, thus rendering the remediation of tank waste from, e.g., the Hanford site far more difficult and expensive. The availability of effective extractants, that would allow for the separation of separating sulfate from the major competing anions in the waste, especially nitrate, could allow for pre-vitrification removal of sulfate via liquid-liquid extraction. The efforts at The University of Texas, the subject of this report, have thus concentrated on the development of new sulfate receptors. These systems are designed to increase our basic understanding of anion recognition events and set the stage for the development of viable sulfate anion extractants. In conjunction with the Oak Ridge National Laboratory (ORNL) members of the research team, several of these new receptors were studied as putative extractants, with two of the systems being shown to act as promising synergists for anion exchange.

  14. On Affine Fusion and the Phase Model

    Directory of Open Access Journals (Sweden)

    Mark A. Walton

    2012-11-01

    Full Text Available A brief review is given of the integrable realization of affine fusion discovered recently by Korff and Stroppel. They showed that the affine fusion of the su(n Wess-Zumino-Novikov-Witten (WZNW conformal field theories appears in a simple integrable system known as the phase model. The Yang-Baxter equation leads to the construction of commuting operators as Schur polynomials, with noncommuting hopping operators as arguments. The algebraic Bethe ansatz diagonalizes them, revealing a connection to the modular S matrix and fusion of the su(n WZNW model. The noncommutative Schur polynomials play roles similar to those of the primary field operators in the corresponding WZNW model. In particular, their 3-point functions are the su(n fusion multiplicities. We show here how the new phase model realization of affine fusion makes obvious the existence of threshold levels, and how it accommodates higher-genus fusion.

  15. Affine coherent states and Toeplitz operators

    Science.gov (United States)

    Hutníková, Mária; Hutník, Ondrej

    2012-06-01

    We study a parameterized family of Toeplitz operators in the context of affine coherent states based on the Calderón reproducing formula (= resolution of unity on L_2( {R})) and the specific admissible wavelets (= affine coherent states in L_2( {R})) related to Laguerre functions. Symbols of such Calderón-Toeplitz operators as individual coordinates of the affine group (= upper half-plane with the hyperbolic geometry) are considered. In this case, a certain class of pseudo-differential operators, their properties and their operator algebras are investigated. As a result of this study, the Fredholm symbol algebras of the Calderón-Toeplitz operator algebras for these particular cases of symbols are described. This article is part of a special issue of Journal of Physics A: Mathematical and Theoretical devoted to ‘Coherent states: mathematical and physical aspects’.

  16. Design of Anion Exchange Membranes and Electrodialysis Studies for Water Desalination

    Directory of Open Access Journals (Sweden)

    Muhammad Imran Khan

    2016-05-01

    Full Text Available Anion exchange membranes are highly versatile and nowadays have many applications, ranging from water treatment to sensing materials. The preparation of anion exchange membranes (AEMs from brominated poly(2,6-dimethyl-1,6-phenylene oxide (BPPO and methyl(diphenylphosphine (MDPP for electrodialysis was performed. The physiochemical properties and electrochemical performance of fabricated membranes can be measured by changing MDPP contents in the membrane matrix. The influence of a quaternary phosphonium group associated with the removal of NaCl from water is discussed. The prepared membranes have ion exchange capacities (IEC 1.09–1.52 mmol/g, water uptake (WR 17.14%–21.77%, linear expansion ratio (LER 7.96%–11.86%, tensile strength (TS 16.66–23.97 MPa and elongation at break (Eb 485.57%–647.98%. The prepared anion exchange membranes were employed for the electrodialytic removal of 0.1 M NaCl aqueous solution at a constant applied voltage. It is found that the reported membranes could be the promising candidate for NaCl removal via electrodialysis.

  17. A series of poly(butylimidazolium) ionic liquid functionalized copolymers for anion exchange membranes

    Science.gov (United States)

    Ouadah, Amina; Xu, Hulin; Luo, Tianwei; Gao, Shuitao; Wang, Xing; Fang, Zhou; Jing, Chaojun; Zhu, Changjin

    2017-12-01

    A new series of ionic liquid functionalized copolymers for anion exchange membranes (AEM) is prepared. Poly(butylvinylimidazolium)(b-VIB) is copolymerized with para-methyl styrene (p-MS) by the radical polymerization formed block copolymers b-VIB/p-MS, which is crosslinked with poly(diphenylether bibenzimidazole) (DPEBI) providing the desired materials b-VIB/p-MS/DPEBI. Structures are characterized via H1NMR, FTIR spectra and elemental analysis. The b-VIB blocks offer the anion conduction function while DPEBI moieties contribute to enhancing other properties. The prepared membranes display chloride conductivity as high as 19.5 mS/cm at 25 °C and 69.2 mS/cm at 100 °C-higher than that of the commercial membrane tokuyuama A201-. Their hydroxide conductivity reaches 35.7 Scm-1 at 25 °C and 73.1 Scm-1 at 100 °C. The membranes showed a linear Arrhenius behavior in the anion conduction, low activation energies and distinguished nanophase separation of hydrophilic/hydrophobic regions by the transmission electron microscopy (TEM) studies. Thermal investigations using TGA and DSC confirm that the membranes are stable up to 250 °C. Particularly, drastically alkaline stability due to no decrease in the hydroxide conductivity after 168 h of treatment with 2M KOH.

  18. The dynamics of metric-affine gravity

    International Nuclear Information System (INIS)

    Vitagliano, Vincenzo; Sotiriou, Thomas P.; Liberati, Stefano

    2011-01-01

    Highlights: → The role and the dynamics of the connection in metric-affine theories is explored. → The most general second order action does not lead to a dynamical connection. → Including higher order invariants excites new degrees of freedom in the connection. → f(R) actions are also discussed and shown to be a non- representative class. - Abstract: Metric-affine theories of gravity provide an interesting alternative to general relativity: in such an approach, the metric and the affine (not necessarily symmetric) connection are independent quantities. Furthermore, the action should include covariant derivatives of the matter fields, with the covariant derivative naturally defined using the independent connection. As a result, in metric-affine theories a direct coupling involving matter and connection is also present. The role and the dynamics of the connection in such theories is explored. We employ power counting in order to construct the action and search for the minimal requirements it should satisfy for the connection to be dynamical. We find that for the most general action containing lower order invariants of the curvature and the torsion the independent connection does not carry any dynamics. It actually reduces to the role of an auxiliary field and can be completely eliminated algebraically in favour of the metric and the matter field, introducing extra interactions with respect to general relativity. However, we also show that including higher order terms in the action radically changes this picture and excites new degrees of freedom in the connection, making it (or parts of it) dynamical. Constructing actions that constitute exceptions to this rule requires significant fine tuned and/or extra a priori constraints on the connection. We also consider f(R) actions as a particular example in order to show that they constitute a distinct class of metric-affine theories with special properties, and as such they cannot be used as representative toy

  19. Use of inorganic materials for the uptake of anions from simulated nuclear wastes

    International Nuclear Information System (INIS)

    Usman, J.N.

    1991-01-01

    Investigations on some commercially available hydrous oxides (Ferrox, Zirox, Alumina, Oxti and Oxtain) have been carried out with a view to understanding their sorption properties for anions (such as 36 C1 - , 51 Cr 2 O 4 2- , 99 MoO 4 - and 106 Ru complexes) and to assess their suitability in specific applications in the nuclear fuel cycle. All the materials exhibited sorption for the anions with oxtain showing the lowest of sorption in various media solutions. Sorption was most effective at solution pH 2-9 following the amphotericism of these materials. The presence of competing anions had a marked effect on the sorption properties of the exchangers for all the anions investigated. TG and DTG results revealed a general weight loss presumably due to loss of moisture. The selectivity for NO 3 - and 36 C1 - was studied by plotting ion-exchange isotherms for each exchanger. All isotherms displayed large hysteresis. The fixed-bed column experiments revealed a high affinity for 36 C1 - on Ferrox, Zirox and Alumina than was observed in the K d measurements. In-vivo γ-radiation effects on the materials and their sorption properties were investigated. Prolonged chemical treatment had little or no effect on the sorption properties of the exchangers, and revealed that none of the materials withstood long term exposure to acid or alkaline conditions. The leachability of isotopically labelled exchangers contained in cement (OPC) composites was studied along deionised water, synthetic sea-water and synthetic ground water as leachants. The effect of cement additives (BFS) on the leachability of the composites was also studied. The diffusion coefficients for the leaching process were evaluated by using the Carman-Haul equation. Results clearly showed that BFS had little or no effect on the leachability of 36 C1 - . (author)

  20. Phosphopeptide enrichment by immobilized metal affinity chromatography

    DEFF Research Database (Denmark)

    Thingholm, Tine E.; Larsen, Martin R.

    2016-01-01

    Immobilized metal affinity chromatography (IMAC) has been the method of choice for phosphopeptide enrichment prior to mass spectrometric analysis for many years and it is still used extensively in many laboratories. Using the affinity of negatively charged phosphate groups towards positively...... charged metal ions such as Fe3+, Ga3+, Al3+, Zr4+, and Ti4+ has made it possible to enrich phosphorylated peptides from peptide samples. However, the selectivity of most of the metal ions is limited, when working with highly complex samples, e.g., whole-cell extracts, resulting in contamination from...

  1. Control and estimation of piecewise affine systems

    CERN Document Server

    Xu, Jun

    2014-01-01

    As a powerful tool to study nonlinear systems and hybrid systems, piecewise affine (PWA) systems have been widely applied to mechanical systems. Control and Estimation of Piecewise Affine Systems presents several research findings relating to the control and estimation of PWA systems in one unified view. Chapters in this title discuss stability results of PWA systems, using piecewise quadratic Lyapunov functions and piecewise homogeneous polynomial Lyapunov functions. Explicit necessary and sufficient conditions for the controllability and reachability of a class of PWA systems are

  2. New unitary affine-Virasoro constructions

    International Nuclear Information System (INIS)

    Halpern, M.B.; Kiritsis, E.; Obers, N.A.; Poratti, M.; Yamron, J.P.

    1990-01-01

    This paper reports on a quasi-systematic investigation of the Virasoro master equation. The space of all affine-Virasoro constructions is organized by K-conjugation into affine-Virasoro nests, and an estimate of the dimension of the space shows that most solutions await discovery. With consistent ansatze for the master equation, large classes of new unitary nests are constructed, including quadratic deformation nests with continuous conformal weights, and unitary irrational central charge nests, which may dominate unitary rational central charge on compact g

  3. Applications of Affine and Weyl geometry

    CERN Document Server

    García-Río, Eduardo; Nikcevic, Stana

    2013-01-01

    Pseudo-Riemannian geometry is, to a large extent, the study of the Levi-Civita connection, which is the unique torsion-free connection compatible with the metric structure. There are, however, other affine connections which arise in different contexts, such as conformal geometry, contact structures, Weyl structures, and almost Hermitian geometry. In this book, we reverse this point of view and instead associate an auxiliary pseudo-Riemannian structure of neutral signature to certain affine connections and use this correspondence to study both geometries. We examine Walker structures, Riemannia

  4. Radiochemical study of Re/W adsorption behavior on a strongly basic anion exchange resin

    International Nuclear Information System (INIS)

    Gott, Matthew D.; Missouri Univ., Columbia, MO; Ballard, Beau D.; Redman, Lindsay N.

    2014-01-01

    Rhenium-186g is a radionuclide with a high potential for therapeutic applications. It emits therapeutic β - particles accompanied by low energy γ-rays, which allows for in-vivo tracking of the radiolabeled compound and dosimetry estimates. The current reactor production pathway 185 Re(n,γ) 186g Re produces low specific activity 186g Re, thereby limiting its therapeutic application. Work is underway to develop an accelerator-based, charged particle induced production method for high specific activity 186g Re from targets of enriched 186 W. To optimize the chemical 186g Re recovery method, batch studies have been performed to characterize the adsorption behavior of Re and W on a strongly basic anion exchange resin. An in-depth physicochemical profile was developed for the interaction of Re with resin material, which showed the reaction to be endothermic and spontaneous. Basic (NaOH) and acidic (HNO 3 ) matrices were used to determine the equilibrium distribution coefficients for Re and W. The resin exhibits the best affinity for Re at slightly basic conditions and little affinity above moderately acidic concentrations. Tungsten has low affinity for the resin above moderately basic concentrations. A study was performed to examine the effect of W concentration on Re adsorption, which showed that even a high ionic WO 4 2- strength of up to 1.9 mol kg -1 does not significantly compromise ReO 4 - retention on the resin. (orig.)

  5. Photoelectron spectrum of valence anions of uracil and first-principles calculations of excess electron binding energies.

    Science.gov (United States)

    Bachorz, Rafał A; Klopper, Wim; Gutowski, Maciej; Li, Xiang; Bowen, Kit H

    2008-08-07

    The photoelectron spectrum (PES) of the uracil anion is reported and discussed from the perspective of quantum chemical calculations of the vertical detachment energies (VDEs) of the anions of various tautomers of uracil. The PES peak maximum is found at an electron binding energy of 2.4 eV, and the width of the main feature suggests that the parent anions are in a valence rather than a dipole-bound state. The canonical tautomer as well as four tautomers that result from proton transfer from an NH group to a C atom were investigated computationally. At the Hartree-Fock and second-order Moller-Plesset perturbation theory levels, the adiabatic electron affinity (AEA) and the VDE have been converged to the limit of a complete basis set to within +/-1 meV. Post-MP2 electron-correlation effects have been determined at the coupled-cluster level of theory including single, double, and noniterative triple excitations. The quantum chemical calculations suggest that the most stable valence anion of uracil is the anion of a tautomer that results from a proton transfer from N1H to C5. It is characterized by an AEA of 135 meV and a VDE of 1.38 eV. The peak maximum is as much as 1 eV larger, however, and the photoelectron intensity is only very weak at 1.38 eV. The PES does not lend support either to the valence anion of the canonical tautomer, which is the second most stable anion, and whose VDE is computed at about 0.60 eV. Agreement between the peak maximum and the computed VDE is only found for the third most stable tautomer, which shows an AEA of approximately -0.1 eV and a VDE of 2.58 eV. This tautomer results from a proton transfer from N3H to C5. The results illustrate that the characteristics of biomolecular anions are highly dependent on their tautomeric form. If indeed the third most stable anion is observed in the experiment, then it remains an open question why and how this species is formed under the given conditions.

  6. Crossing Chris: Some Markerian Affinities

    Directory of Open Access Journals (Sweden)

    Adrian Martin

    2010-01-01

    -pagination:widow-orphan; font-size:11.0pt; font-family:"Calibri","sans-serif"; mso-ascii-font-family:Calibri; mso-ascii-theme-font:minor-latin; mso-fareast-font-family:"Times New Roman"; mso-fareast-theme-font:minor-fareast; mso-hansi-font-family:Calibri; mso-hansi-theme-font:minor-latin; mso-bidi-font-family:"Times New Roman"; mso-bidi-theme-font:minor-bidi;}

    Abstract (E: This essay creatively explores a group of artists, writers, and other special individuals whose work or life story can be described as having an intriguing affinity with the protean career of Chris Marker. Avoiding the ‘usual suspects’ (such as Godard or Sebald, it discusses gossip columnist Milt Machlin, record collector Harry Smith, painter Gianfranco Baruchello, writer-filmmaker Edgardo Cozarinsky, and several others. From this constellation, a particular view of Markerian poetics emerges, touching upon the meanings of anonymity, storytelling, history and archiving.

     

    Abstract (F: Cet essai brosse de manière créative le portrait d’un groupe d'artistes, d'écrivains et d'autres personnes particulières dont le travail ou la biographie peuvent être décrits comme montrant une étrange mais certaine connivence avec la carrière protéiforme de Chris Marker. Evitant les lieux communs (comme Godard ou Sebald, cet article trace des références moins attendues :

  7. Water permeation through anion exchange membranes

    Science.gov (United States)

    Luo, Xiaoyan; Wright, Andrew; Weissbach, Thomas; Holdcroft, Steven

    2018-01-01

    An understanding of water permeation through solid polymer electrolyte (SPE) membranes is crucial to offset the unbalanced water activity within SPE fuel cells. We examine water permeation through an emerging class of anion exchange membranes, hexamethyl-p-terphenyl poly (dimethylbenzimidazolium) (HMT-PMBI), and compare it against series of membrane thickness for a commercial anion exchange membrane (AEM), Fumapem® FAA-3, and a series of proton exchange membranes, Nafion®. The HMT-PMBI membrane is found to possess higher water permeabilities than Fumapem® FAA-3 and comparable permeability than Nafion (H+). By measuring water permeation through membranes of different thicknesses, we are able to decouple, for the first time, internal and interfacial water permeation resistances through anion exchange membranes. Permeation resistances on liquid/membrane interface is found to be negligible compared to that for vapor/membrane for both series of AEMs. Correspondingly, the resistance of liquid water permeation is found to be one order of magnitude smaller compared to that of vapor water permeation. HMT-PMBI possesses larger effective internal water permeation coefficient than both Fumapem® FAA-3 and Nafion® membranes (60 and 18% larger, respectively). In contrast, the effective interfacial permeation coefficient of HMT-PMBI is found to be similar to Fumapem® (±5%) but smaller than Nafion®(H+) (by 14%).

  8. Affinity Programs and the Real Estate Brokerage Industry

    OpenAIRE

    G Stacy Sirmans; David A. Macpherson

    2001-01-01

    This study surveys active real estate brokers obtaining information on involvement in affinity programs and referral/relocation networks. Some results regarding affinity involvement are: (a) 13% of respondents reported affinity affilliations, 75% reported no affiliations, and 12% indicated plans to become involved within the next year; (b) about half having affinity affiliations were involved with 2-4 groups; (c) affinity relationships were most often with membership organizations, corporatio...

  9. Polynomials associated with equilibria of affine Toda-Sutherland systems

    International Nuclear Information System (INIS)

    Odake, S; Sasaki, R

    2004-01-01

    An affine Toda-Sutherland system is a quasi-exactly solvable multi-particle dynamics based on an affine simple root system. It is a 'cross' between two well-known integrable multi-particle dynamics, an affine Toda molecule (exponential potential, periodic nearest-neighbour interaction) and a Sutherland system (inverse sine-square interaction). Polynomials describing the equilibrium positions of affine Toda-Sutherland systems are determined for all affine simple root systems

  10. Syntheses with isotopically labelled carbon. Methyl iodide, formaldehyde and cyanide

    International Nuclear Information System (INIS)

    Finn, R.D.; Boothe, T.E.; Vora, M.M.; Hildner, J.C.; Emran, A.M.; Kothari, P.J.

    1984-01-01

    Many of the uniquely labelled synthetic precursors currently employed in the design of sophisticated radiolabelled compounds have their origins in the field of hot atom chemistry. Particularly, the development during the past few years of automated, on-line synthetic procedures which combine the nuclear reaction, hot atom and classical chemistry, and rapid purification methods has allowed the incorporation of useful radionuclides into suitable compounds of chemical and biochemical interest. The application of isotopically labelled methyl iodide, formaldehyde, and cyanide anion as synthetic intermediates in research involving human physiology and nuclear medicine, as well as their contributions to other scientific methodology, is reviewed. (author)

  11. Identification of Differentially Methylated Sites with Weak Methylation Effects

    Directory of Open Access Journals (Sweden)

    Hong Tran

    2018-02-01

    Full Text Available Deoxyribonucleic acid (DNA methylation is an epigenetic alteration crucial for regulating stress responses. Identifying large-scale DNA methylation at single nucleotide resolution is made possible by whole genome bisulfite sequencing. An essential task following the generation of bisulfite sequencing data is to detect differentially methylated cytosines (DMCs among treatments. Most statistical methods for DMC detection do not consider the dependency of methylation patterns across the genome, thus possibly inflating type I error. Furthermore, small sample sizes and weak methylation effects among different phenotype categories make it difficult for these statistical methods to accurately detect DMCs. To address these issues, the wavelet-based functional mixed model (WFMM was introduced to detect DMCs. To further examine the performance of WFMM in detecting weak differential methylation events, we used both simulated and empirical data and compare WFMM performance to a popular DMC detection tool methylKit. Analyses of simulated data that replicated the effects of the herbicide glyphosate on DNA methylation in Arabidopsis thaliana show that WFMM results in higher sensitivity and specificity in detecting DMCs compared to methylKit, especially when the methylation differences among phenotype groups are small. Moreover, the performance of WFMM is robust with respect to small sample sizes, making it particularly attractive considering the current high costs of bisulfite sequencing. Analysis of empirical Arabidopsis thaliana data under varying glyphosate dosages, and the analysis of monozygotic (MZ twins who have different pain sensitivities—both datasets have weak methylation effects of <1%—show that WFMM can identify more relevant DMCs related to the phenotype of interest than methylKit. Differentially methylated regions (DMRs are genomic regions with different DNA methylation status across biological samples. DMRs and DMCs are essentially the same

  12. Active site - a site of binding of affinity inhibitors in baker's yeast inorganic pyrophosphatase

    International Nuclear Information System (INIS)

    Svyato, I.E.; Sklyankina, V.A.; Avaeva, S.M.

    1986-01-01

    The interaction of the enzyme-substrate complex with methyl phosphate, O-phosphoethanolamine, O-phosphopropanolamine, N-acetylphosphoserine, and phosphoglyolic acid, as well as pyrophosphatase, modified by monoesters of phosphoric acid, with pyrophosphate and tripolyphosphate, was investigated. It was shown that the enzyme containing the substrate in the active site does not react with monophosphates, but modified pyrophosphatase entirely retains the ability to bind polyanions to the regulatory site. It is concluded that the inactivation of baker's yeast inorganic pyrophosphatase by monoesters of phosphoric acid, which are affinity inhibitors of it, is the result of modification of the active site of the enzyme

  13. DNA methylation in obesity

    Directory of Open Access Journals (Sweden)

    Małgorzata Pokrywka

    2014-11-01

    Full Text Available The number of overweight and obese people is increasing at an alarming rate, especially in the developed and developing countries. Obesity is a major risk factor for diabetes, cardiovascular disease, and cancer, and in consequence for premature death. The development of obesity results from the interplay of both genetic and environmental factors, which include sedentary life style and abnormal eating habits. In the past few years a number of events accompanying obesity, affecting expression of genes which are not directly connected with the DNA base sequence (e.g. epigenetic changes, have been described. Epigenetic processes include DNA methylation, histone modifications such as acetylation, methylation, phosphorylation, ubiquitination, and sumoylation, as well as non-coding micro-RNA (miRNA synthesis. In this review, the known changes in the profile of DNA methylation as a factor affecting obesity and its complications are described.

  14. Zwitterion radicals and anion radicals from electron transfer and solvent condensation with the fingerprint developing agent ninhydrin.

    Science.gov (United States)

    Schertz, T D; Reiter, R C; Stevenson, C D

    2001-11-16

    Ninhydrin (the fingerprint developing agent) spontaneously dehydrates in liquid ammonia and in hexamethylphosphoramide (HMPA) to form indantrione, which has a sufficiently large solution electron affinity to extract an electron from the solvent (HMPA) to produce the indantrione anion radical. In liquid NH(3), the presence of trace amounts of amide ion causes the spontaneous formation of an anion radical condensation product, wherein the no. 2 carbon (originally a carbonyl carbon) becomes substituted with -NH(2) and -OH groups. In HMPA, the indantrione anion radical spontaneously forms condensation products with the HMPA to produce a variety of zwitterionic radicals, wherein the no. 2 carbon becomes directly attached to a nitrogen of the HMPA. The mechanisms for the formation of the zwitterionic paramagnetic condensation products are analogous to that observed in the reaction of ninhydrin with amino acids to yield Ruhemann's Purple, the contrast product in fingerprint development. The formation of anion and zwitterionic radical condensation products from ninhydrin and nitrogen-containing solvents may represent an example of a host of analogous polyketone-solvent reactions.

  15. Effects of microsolvation on uracil and its radical anion: Uracil.(H2O)n (n=1-5)

    Science.gov (United States)

    Kim, Sunghwan; Schaefer, Henry F.

    2006-10-01

    Microsolvation effects on the stabilities of uracil and its anion have been investigated by explicitly considering the structures of complexes of uracil with up to five water molecules at the B3LYP /DZP++ level of theory. For all five systems, the global minimum of the neutral cluster has a different equilibrium geometry from that of the radical anion. Both the vertical detachment energy (VDE) and adiabatic electron affinity (AEA) of uracil are predicted to increase gradually with the number of hydrating molecules, qualitatively consistent with experimental results from a photodetachment-photoelectron spectroscopy study [J. Schiedt et al., Chem. Phys. 239, 511 (1998)]. The trend in the AEAs implies that while the conventional valence radical anion of uracil is only marginally bound in the gas phase, it will form a stable anion in aqueous solution. The gas-phase AEA of uracil (0.24eV) was higher than that of thymine by 0.04eV and this gap was not significantly affected by microsolvation. The largest AEA is that predicted for uracil•(H2O)5, namely, 0.96eV. The VDEs range from 0.76to1.78eV.

  16. Fatty acid and drug binding to a low-affinity component of human serum albumin, purified by affinity chromatography

    DEFF Research Database (Denmark)

    Vorum, H; Pedersen, A O; Honoré, B

    1992-01-01

    Binding equilibria for decanoate to a defatted, commercially available human serum albumin preparation were investigated by dialysis exchange rate determinations. The binding isotherm could not be fitted by the general binding equation. It was necessary to assume that the preparation was a mixture...... of two albumin components about 40% of the albumin having high affinity and about 60% having low affinity. By affinity chromatography we succeeded in purifying the low-affinity component from the mixture. The high-affinity component, however, could not be isolated. We further analyzed the fatty acid...... and drug binding abilities of the low-affinity component. The fatty acids decanoate, laurate, myristate and palmitate were bound with higher affinity to the mixture than to the low-affinity component. Diazepam was bound with nearly the same affinity to the low-affinity component as to the albumin mixture...

  17. Compound immobilization and drug-affinity chromatography.

    Science.gov (United States)

    Rix, Uwe; Gridling, Manuela; Superti-Furga, Giulio

    2012-01-01

    Bioactive small molecules act through modulating a yet unpredictable number of targets. It is therefore of critical importance to define the cellular target proteins of a compound as an entry point to understanding its mechanism of action. Often, this can be achieved in a direct fashion by chemical proteomics. As with any affinity chromatography, immobilization of the bait to a solid support is one of the earliest and most crucial steps in the process. Interfering with structural features that are important for identification of a target protein will be detrimental to binding affinity. Also, many molecules are sensitive to heat or to certain chemicals, such as acid or base, and might be destroyed during the process of immobilization, which therefore needs to be not only efficient, but also mild. The subsequent affinity chromatography step needs to preserve molecular and conformational integrity of both bait compound and proteins in order to result in the desired specific enrichment while ensuring a high level of compatibility with downstream analysis by mass spectrometry. Thus, the right choice of detergent, buffer, and protease inhibitors is also essential. This chapter describes a widely applicable procedure for the immobilization of small molecule drugs and for drug-affinity chromatography with subsequent protein identification by mass spectrometry.

  18. Fan Affinity Laws from a Collision Model

    Science.gov (United States)

    Bhattacharjee, Shayak

    2012-01-01

    The performance of a fan is usually estimated using hydrodynamical considerations. The calculations are long and involved and the results are expressed in terms of three affinity laws. In this paper we use kinetic theory to attack this problem. A hard sphere collision model is used, and subsequently a correction to account for the flow behaviour…

  19. It's the peptide-MHC affinity, stupid.

    Science.gov (United States)

    Kammertoens, Thomas; Blankenstein, Thomas

    2013-04-15

    Adoptively transferred T cells can reject large established tumors, but recurrence due to escape variants frequently occurs. In this issue of Cancer Cell, Engels et al. demonstrate that the affinity of the target peptide to the MHC molecule determines whether large tumors will relapse following adoptive T cell therapy. Copyright © 2013 Elsevier Inc. All rights reserved.

  20. General super Virasoro construction on affine G

    International Nuclear Information System (INIS)

    Mohammedi, N.

    1990-10-01

    We consider a bosonic current algebra and a theory of free fermions and construct a general N = 1 super Virasoro current algebra. We obtain a master-set of equations which comprises the bosonic master equation for general Virasoro construction on affine G. As an illustration we study the case of the group SU(2). (author). 13 refs

  1. Anion-induced reconstitution of a self-assembling system to express a chloride-binding Co10L15 pentagonal prism.

    Science.gov (United States)

    Riddell, Imogen A; Smulders, Maarten M J; Clegg, Jack K; Hristova, Yana R; Breiner, Boris; Thoburn, John D; Nitschke, Jonathan R

    2012-09-01

    Biochemical systems are adaptable, capable of reconstitution at all levels to achieve the functions associated with life. Synthetic chemical systems are more limited in their ability to reorganize to achieve new functions; they can reconfigure to bind an added substrate (template effect) or one binding event may modulate a receptor's affinity for a second substrate (allosteric effect). Here we describe a synthetic chemical system that is capable of structural reconstitution on receipt of one anionic signal (perchlorate) to create a tight binding pocket for another anion (chloride). The complex, barrel-like structure of the chloride receptor is templated by five perchlorate anions. This second-order templation phenomenon allows chemical networks to be envisaged that express more complex responses to chemical signals than is currently feasible.

  2. Glial and Neuronal Glutamate Transporters Differ in the Na+ Requirements for Activation of the Substrate-Independent Anion Conductance

    Directory of Open Access Journals (Sweden)

    Christopher B. Divito

    2017-05-01

    Full Text Available Excitatory amino acid transporters (EAATs are secondary active transporters of L-glutamate and L- or D-aspartate. These carriers also mediate a thermodynamically uncoupled anion conductance that is gated by Na+ and substrate binding. The activation of the anion channel by binding of Na+ alone, however, has only been demonstrated for mammalian EAAC1 (EAAT3 and EAAT4. To date, no difference has been observed for the substrate dependence of anion channel gating between the glial, EAAT1 and EAAT2, and the neuronal isoforms EAAT3, EAAT4 and EAAT5. Here we describe a difference in the Na+-dependence of anion channel gating between glial and neuronal isoforms. Chloride flux through transporters without glutamate binding has previously been described as substrate-independent or “leak” channel activity. Choline or N-methyl-D-glucamine replacement of external Na+ ions significantly reduced or abolished substrate-independent EAAT channel activity in EAAT3 and EAAT4 yet has no effect on EAAT1 or EAAT2. The interaction of Na+ with the neuronal carrier isoforms was concentration dependent, consistent with previous data. The presence of substrate and Na+-independent open states in the glial EAAT isoforms is a novel finding in the field of EAAT function. Our results reveal an important divergence in anion channel function between glial and neuronal glutamate transporters and highlight new potential roles for the EAAT-associated anion channel activity based on transporter expression and localization in the central nervous system.

  3. Hydration of a Large Anionic Charge Distribution - Naphthalene-Water Cluster Anions

    Science.gov (United States)

    Weber, J. Mathias; Adams, Christopher L.

    2010-06-01

    We report the infrared spectra of anionic clusters of naphthalene with up to three water molecules. Comparison of the experimental infrared spectra with theoretically predicted spectra from quantum chemistry calculations allow conclusions regarding the structures of the clusters under study. The first water molecule forms two hydrogen bonds with the π electron system of the naphthalene moiety. Subsequent water ligands interact with both the naphthalene and the other water ligands to form hydrogen bonded networks, similar to other hydrated anion clusters. Naphthalene-water anion clusters illustrate how water interacts with negative charge delocalized over a large π electron system. The clusters are interesting model systems that are discussed in the context of wetting of graphene surfaces and polyaromatic hydrocarbons.

  4. Binding affinities of cationic dyes in the presence of activated charcoal and anionic surfactant in the premicellar region

    Science.gov (United States)

    Ali, Farman; Ibrahim, Muhammad; Khan, Fawad; Bibi, Iram; Shah, Syed W. H.

    2018-03-01

    Binding preferences of cationic dyes malachite green and methylene blue in a mixed charcoal-sodium dodecyl sulfate system have been investigated using UV-visible absorption spectroscopy. The dye adsorption shows surfactant-dependent patterns, indicating diverse modes of interactions. At low surfactant concentration, a direct binding to charcoal is preferred. Comparatively greater quantities of surfactant lead to attachment of dye-surfactant complex to charcoal through hydrophobic interactions. A simple model was employed for determination of equilibrium constant K eq and concentration of dye-surfactant ion pair N DS for both dyes. The values of binding parameters revealed that malachite green was directly adsorbed onto charcoal, whereas methylene blue was bound through surfactant monomers. The model is valid for low surfactant concentrations in the premicellar region. These findings have significance for material and environmental sciences.

  5. Synthesis and anion binding studies of tris(3-aminopropyl)amine-based tripodal urea and thiourea receptors: Proton transfer-induced selectivity for hydrogen sulfate over sulfate.

    Science.gov (United States)

    Khansari, Maryam Emami; Johnson, Corey R; Basaran, Ismet; Nafis, Aemal; Wang, Jing; Leszczynski, Jerzy; Hossain, Md Alamgir

    2015-01-01

    Tris(3-aminopropyl)amine-based tripodal urea and thiourea receptors, tris([(4-cyanophenyl)amino]propyl)urea ( L1 ) and tris([(4-cyanophenyl)amino]propyl)thiourea ( L2 ), have been synthesized and their anion binding properties have been investigated for halides and oxoanions. As investigated by 1 H NMR titrations, each receptor binds an anion with a 1:1 stoichiometry via hydrogen-bonding interactions (NH⋯anion), showing the binding trend in the order of F - > H 2 PO 4 - > HCO 3 - > HSO 4 - > CH 3 COO - > SO 4 2- > Cl - > Br - > I in DMSO- d 6 . The interactions of the receptors were further studied by 2D NOESY, showing the loss of NOESY contacts of two NH resonances for the complexes of F - , H 2 PO 4 - , HCO 3 - , HSO 4 - or CH 3 COO - due to the strong NH⋯anion interactions. The observed higher binding affinity for HSO 4 - than SO 4 2- is attributed to the proton transfer from HSO 4 - to the central nitrogen of L1 or L2 which was also supported by the DFT calculations, leading to the secondary acid-base interactions. The thiourea receptor L2 has a general trend to show a higher affinity for an anion as compared to the urea receptor L1 for the corresponding anion in DMSO- d 6 . In addition, the compound L2 has been exploited for its extraction properties for fluoride in water using a liquid-liquid extraction technique, and the results indicate that the receptor effectively extracts fluoride from water showing ca. 99% efficiency (based on L2 ).

  6. Methylated β-Cyclodextrins

    DEFF Research Database (Denmark)

    Schönbeck, Jens Christian Sidney; Westh, Peter; Madsen, Jens Christian

    2011-01-01

    The complexation of 6 bile salts with various methylated β-cyclodextrins was studied to elucidate how the degree and pattern of substitution affects the binding. The structures of the CDs were determined by mass spectrometry and NMR techniques, and the structures of the inclusion complexes were...

  7. Nature of the C2-methylation effect on the properties of imidazolium ionic liquids.

    Science.gov (United States)

    Rodrigues, Ana S M C; Lima, Carlos F R A C; Coutinho, João A P; Santos, Luís M N B F

    2017-02-15

    Methylation at the C2 position of 1,3-disubstituted imidazolium-based ionic liquids (ILs) is one of the structural features that has gained attention due to its drastic impact on thermophysical and transport properties. Several hypotheses have been proposed to explain this effect but there is still much discrepancy. Aiming for the rationalization of the effects of these structural features on the properties of imidazolium ILs, we present a thermodynamic and computational study of two methylated ILs at the C2 position of imidazolium, [ 1 C 4 2 C 1 3 C 1 im][NTf 2 ] and [ 1 C 3 2 C 1 3 C 1 im][NTf 2 ]. The phase behaviour (glass transition and vaporization equilibrium) and computational studies of the anion rotation around the cation and ion pair interaction energies for both ILs were explored. The results have shown that C2-methylation has no impact on the enthalpy of vaporization. However, it decreases the entropy of vaporization, which is a consequence of the change in the ion pair dynamics that affects both the liquid and gas phases. In addition, the more hindered dynamics of the ion pair are also reflected in the increase in the glass transition temperature, T g . The entropic contribution of anion-around-cation rotation in the imidazolium [NTf 2 ] ILs was quantified experimentally by the comparative analysis of the entropy of vaporization, and computationally by the calculation of the entropies of hindered internal rotation. The global results exclude the existence of significant H-bonding in the C2-protonated (non-methylated) ILs and explain the C2-methylation effect in terms of reduced entropy of the ion pair in the liquid and gas phases. In light of these results, the C2-methylation effect is intrinsically entropic and originates from the more hindered anion-around-cation rotation as a consequence of the substitution of the -H with a bulkier -CH 3 group.

  8. Graphene-coated polymeric anion exchangers for ion chromatography

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Kai; Cao, Minyi; Lou, Chaoyan [Department of Chemistry, Xixi Campus, Zhejiang University, Hangzhou 310028 (China); Wu, Shuchao, E-mail: wushch2002@163.com [Zhejiang Institute of Geology and Mineral Resources, Hangzhou 310007 (China); Zhang, Peimin [Department of Chemistry, Xixi Campus, Zhejiang University, Hangzhou 310028 (China); Zhi, Mingyu [Hangzhou Vocational & Technical College, Hangzhou, 310018 (China); Zhu, Yan, E-mail: zhuyan@zju.edu.cn [Department of Chemistry, Xixi Campus, Zhejiang University, Hangzhou 310028 (China)

    2017-06-01

    Carbonaceous stationary phases have gained much attention for their peculiar selectivity and robustness. Herein we report the fabrication and application of a graphene-coated polymeric stationary phase for anion exchange chromatography. The graphene-coated particles were fabricated by a facile evaporation-reduction method. These hydrophilic particles were proven appropriate substrates for grafting of hyperbranched condensation polymers (HBCPs) to make pellicular anion exchangers. The new phase was characterized by zeta potentials, Fourier transform infrared spectroscopy, thermogravimetry and scanning electron microscope. Frontal displacement chromatography showed that the capacities of the anion exchangers were tuned by both graphene amount and HBCPs layer count. The chromatographic performance of graphene-coated anion exchangers was demonstrated with separation of inorganic anions, organic acids, carbohydrates and amino acids. Good reproducibility was obtained by consecutive injections, indicating high chemical stability of the coating. - Highlights: • Graphene-coated polymeric particles were fabricated by a facile method. • Hyperbranched condensation polymers (HBCPs) were grafted from graphene-coated particles to make anion exchangers. • Graphene amount and HBCPs layer count had significant effects on the anion exchange capacities. • Separation of diverse anionic analytes on the anion exchangers was demonstrated. • The prepared anion exchangers exhibited high stability.

  9. Study of organic radicals through anion photoelectron velocity-map imaging spectroscopy

    Science.gov (United States)

    Dixon, Andrew Robert

    We report preliminary results on the photoelectron imaging of phenylcarbene, cyanophenylcarbene, and chlorophenylcarbene anions. Triplet phenylcarbene is observed to have an EA of ≤ 0.83 eV, considerably lower than the previously indirectly-determined value. Transitions to the singlet and triplet ground state of both cyanophenylcarbene and chlorophenylcarbene are observable, though unidentified bands make full assignment difficult. Cyanophenylcarbene is found to have a triplet ground-state, with a tentative EA of 2.04 eV. Chlorophenylcarbene is found to have a singlet ground-state. The phenyl-group is found to favor the singlet state slightly. The cyanofluoromethyl radical, FC(H)CN, was estimated to have an EA of 1.53 +/- 0.08 eV, by a combination of experimental and theoretical results.. With similar methodology, we report the adiabatic electron affinity of the cyanobenzyl radical, EA(PhCHCN) = 1.90 +/- 0.01 eV, and assign an upper limit of the EA for the chlorobenzyl radical, EA(PhCHCl) ≤ 1.12 eV. These values were used to estimate the C-H bond dissociation energy (BDE)s for these substituted methanes. Fluoroacetonitrile was found to have a BDE of D H198 = 90.7 +/- 2.8 kcal mol□1. The C-H bond dissociation energies at the benzyl-alpha sites of the phenylmethanes are determined as 80.9 +/- 2.3 kcal mol-1 for benzyl nitrile and an upper limit of 84.2 kcal mol-1 for benzyl chloride. These results are discussed in terms of substituent interactions in a simple MO framework and in relation to other similar molecules, including recently reported results for chloroacetonitrile. The 532 nm photoelectron spectrum of glyoxal provides the first direct spectroscopic determination of the adiabatic electron affinity, EA = 1.10(2) eV. This assignment is supported by a Franck-Condon simulation of the experimental spectrum that successfully reproduces the observed spectral features. The vertical detachment energy (VDE) of the glyoxal radical anion is determined as VDE = 1

  10. Evidence that the low-affinity folate-binding protein in erythrocyte hemolysate is identical to hemoglobin

    International Nuclear Information System (INIS)

    Hansen, S.I.; Holm, J.; Lyngbye, J.

    1981-01-01

    Gel filtration studies on erythrocyte hemolysate demonstrated the presence of a folate binding protein, apparently of the low-affinity type, that co-elutes with hemoglobin. Further, the folate binder eluted with a low salt concentration after DEAE-Sepharose CL-6B anion-exchange chromatography of erythrocyte hemolysate at pH 6.3. The chromatographic behavior of hemoglobin labeled with [3H]folate was so similar to that of the present binder as to suggest that the folate binder in erythrocytes is in fact hemoglobin

  11. Infrared Spectroscopy of Discrete Uranyl Anion Complexes

    International Nuclear Information System (INIS)

    Groenewold, G. S.; Gianotto, Anita K.; McIIwain, Michael E.; Van Stipdonk, Michael J.; Kullman, Michael; Moore, David T.; Polfer, Nick; Oomens, Jos; Infante, Ivan A.; Visscher, Lucas; Siboulet, Bertrand; De Jong, Wibe A.

    2008-01-01

    The Free-Electron Laser for Infrared Experiments (FELIX) w 1 as used to study the wavelength-resolved multiple photon photodissociation of discrete, gas phase uranyl (UO2 2 2+) complexes containing a single anionic ligand (A), with or without ligated solvent molecules (S). The uranyl antisymmetric and symmetric stretching frequencies were measured for complexes with general formula [UO2A(S)n]+, where A was either hydroxide, methoxide, or acetate; S was water, ammonia, acetone, or acetonitrile; and n = 0-3. The values for the antisymmetric stretching frequency for uranyl ligated with only an anion ([UO2A]+) were as low or lower than measurements for [UO2]2+ ligated with as many as five strong neutral donor ligands, and are comparable to solution phase values. This result was surprising because initial DFT calculations predicted values that were 30-40 cm-1 higher, consistent with intuition but not with the data. Modification of the basis sets and use of alternative functionals improved computational accuracy for the methoxide and acetate complexes, but calculated values for the hydroxide were greater than the measurement regardless of the computational method used. Attachment of a neutral donor ligand S to [UO2A]+ produced [UO2AS]+, which produced only very modest changes to the uranyl antisymmetric stretch frequency, and did not universally shift the frequency to lower values. DFT calculations for [UO2AS]+ were in accord with trends in the data, and showed that attachment of the solvent was accommodated by weakening of the U-anion bond as well as the uranyl. When uranyl frequencies were compared for [UO2AS]+ species having different solvent neutrals, values decreased with increasing neutral nucleophilicity

  12. Protein methylation in pea chloroplasts

    International Nuclear Information System (INIS)

    Niemi, K.J.; Adler, J.; Selman, B.R.

    1990-01-01

    The methylation of chloroplast proteins has been investigated by incubating intact pea (Pisum sativum) chloroplasts with [ 3 H-methyl]-S-adenosylmethionine. Incubation in the light increases the amount of methylation in both the thylakoid and stromal fractions. Numerous thylakoid proteins serve as substrates for the methyltransfer reactions. Three of these thylakoid proteins are methylated to a significantly greater extent in the light than in the dark. The primary stromal polypeptide methylated is the large subunit of ribulose bisphosphate carboxylase/oxygenase. One other stromal polypeptide is also methylated much more in the light than in the dark. Two distinct types of protein methylation occur. One methylinkage is stable to basic conditions whereas a second type is base labile. The base-stable linkage is indicative of N-methylation of amino acid residues while base-lability is suggestive of carboxymethylation of amino acid residues. Labeling in the light increases the percentage of methylation that is base labile in the thylakoid fraction while no difference is observed in the amount of base-labile methylations in light-labeled and dark-labeled stromal proteins. Also suggestive of carboxymethylation is the detection of volatile [ 3 H]methyl radioactivity which increases during the labeling period and is greater in chloroplasts labeled in the light as opposed to being labeled in the dark; this implies in vivo turnover of the [ 3 H]methyl group

  13. Methylation of food commodities during fumigation with methyl bromide

    International Nuclear Information System (INIS)

    Starratt, A.N.; Bond, E.J.

    1990-01-01

    Sites of methylation in several commodities (wheat, oatmeal, peanuts, almonds, apples, oranges, maize, alfalfa and potatoes) during fumigation with 14 C-methyl bromide were studied. Differences were observed in levels of the major volatiles: methanol, dimethyl sulphide and methyl mercaptan, products of O- and S-methylation, resulting from treatment of the fumigated materials with 1N sodium hydroxide. In studies of maize and wheat, histidine was the amino acid which underwent the highest level of N-methylation. (author). 24 refs, 3 tabs

  14. Probes for anionic cell surface detection

    Science.gov (United States)

    Smith, Bradley D.

    2013-03-05

    Embodiments of the present invention are generally directed to compositions comprising a class of molecular probes for detecting the presence of anionic cell surfaces. Embodiments include compositions that are enriched for these compositions and preparations, particularly preparations suitable for use as laboratory/clinical reagents and diagnostic indicators, either alone or as part of a kit. An embodiment of the invention provides for a highly selective agent useful in the discernment and identification of dead or dying cells, such as apoptotic cells, in a relatively calcium-free environment. An embodiment of the invention provides a selective agent for the identification of bacteria in a mixed population of bacterial cells and nonbacterial cells.

  15. Crystal structure of 2-methyl-1H-imidazol-3-ium hydrogen oxalate dihydrate

    Directory of Open Access Journals (Sweden)

    Mouhamadou Birame Diop

    2016-08-01

    Full Text Available Single crystals of the title molecular salt, C4H7N2+·HC2O4−·2H2O, were isolated from the reaction of 2-methyl-1H-imidazole and oxalic acid in a 1:1 molar ratio in water. In the crystal, the cations and anions are positioned alternately along an infinite [010] ribbon and linked together through bifurcated N—H...(O,O hydrogen bonds. The water molecules of crystallization link the chains into (10-1 bilayers, with the methyl groups of the cations organized in an isotactic manner.

  16. Staircase Models from Affine Toda Field Theory

    CERN Document Server

    Dorey, P; Dorey, Patrick; Ravanini, Francesco

    1993-01-01

    We propose a class of purely elastic scattering theories generalising the staircase model of Al. B. Zamolodchikov, based on the affine Toda field theories for simply-laced Lie algebras g=A,D,E at suitable complex values of their coupling constants. Considering their Thermodynamic Bethe Ansatz equations, we give analytic arguments in support of a conjectured renormalisation group flow visiting the neighbourhood of each W_g minimal model in turn.

  17. Perspective: Electrospray photoelectron spectroscopy: From multiply-charged anions to ultracold anions

    International Nuclear Information System (INIS)

    Wang, Lai-Sheng

    2015-01-01

    Electrospray ionization (ESI) has become an essential tool in chemical physics and physical chemistry for the production of novel molecular ions from solution samples for a variety of spectroscopic experiments. ESI was used to produce free multiply-charged anions (MCAs) for photoelectron spectroscopy (PES) in the late 1990 s, allowing many interesting properties of this class of exotic species to be investigated. Free MCAs are characterized by strong intramolecular Coulomb repulsions, which create a repulsive Coulomb barrier (RCB) for electron emission. The RCB endows many fascinating properties to MCAs, giving rise to meta-stable anions with negative electron binding energies. Recent development in the PES of MCAs includes photoelectron imaging to examine the influence of the RCB on the electron emission dynamics, pump-probe experiments to examine electron tunneling through the RCB, and isomer-specific experiments by coupling PES with ion mobility for biological MCAs. The development of a cryogenically cooled Paul trap has led to much better resolved PE spectra for MCAs by creating vibrationally cold anions from the room temperature ESI source. Recent advances in coupling the cryogenic Paul trap with PE imaging have allowed high-resolution PE spectra to be obtained for singly charged anions produced by ESI. In particular, the observation of dipole-bound excited states has made it possible to conduct vibrational autodetachment spectroscopy and resonant PES, which yield much richer vibrational spectroscopic information for dipolar free radicals than traditional PES

  18. Zero-point energy effects in anion solvation shells.

    Science.gov (United States)

    Habershon, Scott

    2014-05-21

    By comparing classical and quantum-mechanical (path-integral-based) molecular simulations of solvated halide anions X(-) [X = F, Cl, Br and I], we identify an ion-specific quantum contribution to anion-water hydrogen-bond dynamics; this effect has not been identified in previous simulation studies. For anions such as fluoride, which strongly bind water molecules in the first solvation shell, quantum simulations exhibit hydrogen-bond dynamics nearly 40% faster than the corresponding classical results, whereas those anions which form a weakly bound solvation shell, such as iodide, exhibit a quantum effect of around 10%. This observation can be rationalized by considering the different zero-point energy (ZPE) of the water vibrational modes in the first solvation shell; for strongly binding anions, the ZPE of bound water molecules is larger, giving rise to faster dynamics in quantum simulations. These results are consistent with experimental investigations of anion-bound water vibrational and reorientational motion.

  19. Process for removing sulfate anions from waste water

    Science.gov (United States)

    Nilsen, David N.; Galvan, Gloria J.; Hundley, Gary L.; Wright, John B.

    1997-01-01

    A liquid emulsion membrane process for removing sulfate anions from waste water is disclosed. The liquid emulsion membrane process includes the steps of: (a) providing a liquid emulsion formed from an aqueous strip solution and an organic phase that contains an extractant capable of removing sulfate anions from waste water; (b) dispersing the liquid emulsion in globule form into a quantity of waste water containing sulfate anions to allow the organic phase in each globule of the emulsion to extract and absorb sulfate anions from the waste water and (c) separating the emulsion including its organic phase and absorbed sulfate anions from the waste water to provide waste water containing substantially no sulfate anions.

  20. The chemistry of molecular anions in circumstellar sources

    Energy Technology Data Exchange (ETDEWEB)

    Agúndez, Marcelino [LUTH, Observatoire de Paris-Meudon, 5 Place Jules Janssen, 92190 Meudon (France); Cernicharo, José [Departamento de Astrofísica, CAB, CSIC-INTA, Ctra. de Torrejón a Ajalvir km 4, 28850 Madrid (Spain); Guélin, Michel [Institut de Radioastronomie Millimétrique, 300 rue de la Piscine, 38406 Saint Martin d' Héres (France)

    2015-01-22

    The detection of negatively charged molecules in the interstellar and circumstellar medium in the past four years has been one of the most impacting surprises in the area of molecular astrophysics. It has motivated the interest of astronomers, physicists, and chemists on the study of the spectroscopy, chemical kinetics, and prevalence of molecular anions in the different astronomical regions. Up to six different molecular anions have been discovered in space to date, the last one being the small ion CN{sup −}, which has been observed in the envelope of the carbon star IRC +10216 and which contrary to the other larger anions is not formed by electron attachment to CN, but through reactions of large carbon anions with nitrogen atoms. Here we briefly review the current status of our knowledge of the chemistry of molecular anions in space, with particular emphasis on the circumstellar source IRC +10216, which to date is the astronomical source harboring the largest variety of anions.

  1. Calculation of protein-ligand binding affinities.

    Science.gov (United States)

    Gilson, Michael K; Zhou, Huan-Xiang

    2007-01-01

    Accurate methods of computing the affinity of a small molecule with a protein are needed to speed the discovery of new medications and biological probes. This paper reviews physics-based models of binding, beginning with a summary of the changes in potential energy, solvation energy, and configurational entropy that influence affinity, and a theoretical overview to frame the discussion of specific computational approaches. Important advances are reported in modeling protein-ligand energetics, such as the incorporation of electronic polarization and the use of quantum mechanical methods. Recent calculations suggest that changes in configurational entropy strongly oppose binding and must be included if accurate affinities are to be obtained. The linear interaction energy (LIE) and molecular mechanics Poisson-Boltzmann surface area (MM-PBSA) methods are analyzed, as are free energy pathway methods, which show promise and may be ready for more extensive testing. Ultimately, major improvements in modeling accuracy will likely require advances on multiple fronts, as well as continued validation against experiment.

  2. 2D Affine and Projective Shape Analysis.

    Science.gov (United States)

    Bryner, Darshan; Klassen, Eric; Huiling Le; Srivastava, Anuj

    2014-05-01

    Current techniques for shape analysis tend to seek invariance to similarity transformations (rotation, translation, and scale), but certain imaging situations require invariance to larger groups, such as affine or projective groups. Here we present a general Riemannian framework for shape analysis of planar objects where metrics and related quantities are invariant to affine and projective groups. Highlighting two possibilities for representing object boundaries-ordered points (or landmarks) and parameterized curves-we study different combinations of these representations (points and curves) and transformations (affine and projective). Specifically, we provide solutions to three out of four situations and develop algorithms for computing geodesics and intrinsic sample statistics, leading up to Gaussian-type statistical models, and classifying test shapes using such models learned from training data. In the case of parameterized curves, we also achieve the desired goal of invariance to re-parameterizations. The geodesics are constructed by particularizing the path-straightening algorithm to geometries of current manifolds and are used, in turn, to compute shape statistics and Gaussian-type shape models. We demonstrate these ideas using a number of examples from shape and activity recognition.

  3. Excited state electron affinity calculations for aluminum

    Science.gov (United States)

    Hussein, Adnan Yousif

    2017-08-01

    Excited states of negative aluminum ion are reviewed, and calculations of electron affinities of the states (3s^23p^2)^1D and (3s3p^3){^5}{S}° relative to the (3s^23p)^2P° and (3s3p^2)^4P respectively of the neutral aluminum atom are reported in the framework of nonrelativistic configuration interaction (CI) method. A priori selected CI (SCI) with truncation energy error (Bunge in J Chem Phys 125:014107, 2006) and CI by parts (Bunge and Carbó-Dorca in J Chem Phys 125:014108, 2006) are used to approximate the valence nonrelativistic energy. Systematic studies of convergence of electron affinity with respect to the CI excitation level are reported. The calculated value of the electron affinity for ^1D state is 78.675(3) meV. Detailed Calculations on the ^5S°c state reveals that is 1216.8166(3) meV below the ^4P state.

  4. Affinity functions for modeling glass dissolution rates

    Energy Technology Data Exchange (ETDEWEB)

    Bourcier, W.L. [Lawrence Livermore National Lab., CA (United States)

    1997-07-01

    Glass dissolution rates decrease dramatically as glass approach ''saturation'' with respect to the leachate solution. Most repository sites are chosen where water fluxes are minimal, and therefore the waste glass is most likely to dissolve under conditions close to ''saturation''. The key term in the rate expression used to predict glass dissolution rates close to ''saturation'' is the affinity term, which accounts for saturation effects on dissolution rates. Interpretations of recent experimental data on the dissolution behaviour of silicate glasses and silicate minerals indicate the following: 1) simple affinity control does not explain the observed dissolution rate for silicate minerals or glasses; 2) dissolution rates can be significantly modified by dissolved cations even under conditions far from saturation where the affinity term is near unity; 3) the effects of dissolved species such as Al and Si on the dissolution rate vary with pH, temperature, and saturation state; and 4) as temperature is increased, the effect of both pH and temperature on glass and mineral dissolution rates decrease, which strongly suggests a switch in rate control from surface reaction-based to diffusion control. Borosilicate glass dissolution models need to be upgraded to account for these recent experimental observations. (A.C.)

  5. Synthesis and anion recognition properties of shape-persistent binaphthyl-containing chiral macrocyclic amides

    Directory of Open Access Journals (Sweden)

    Marco Caricato

    2012-06-01

    Full Text Available We report on the synthesis and characterization of novel shape-persistent, optically active arylamide macrocycles, which can be obtained using a one-pot methodology. Resolved, axially chiral binol scaffolds, which incorporate either methoxy or acetoxy functionalities in the 2,2' positions and carboxylic functionalities in the external 3,3' positions, were used as the source of chirality. Two of these binaphthyls are joined through amidation reactions using rigid diaryl amines of differing shapes, to give homochiral tetraamidic macrocycles. The recognition properties of these supramolecular receptors have been analyzed, and the results indicate a modulation of binding affinities towards dicarboxylate anions, with a drastic change of binding mode depending on the steric and electronic features of the functional groups in the 2,2' positions.

  6. Carbon-14 methylation of the 2-methylbutyryl side chain of mevinolin and its analogs

    International Nuclear Information System (INIS)

    Prakash, S.R.; Ellsworth, R.L.

    1988-01-01

    A one step procedure for the preparation of three labeled mevinolin analogs possessing the 2,2-dimethylbutyryloxy side chain is described. Three lactones were converted into potassium salts of their corresponding di or trihydroxy carboxylic acids from which anionic ester enolates were generated and alkylated with [ 14 ]methyl iodide. Workup and purification by reverse phase HPLC provided the three radiochemically pure mevinolin analogs. The labeled lactones were converted into ammonium salts of their corresponding di or trihydroxy acids. (author)

  7. Diiodido[methyl 2-(quinolin-8-yloxyacetate-κN]mercury(II

    Directory of Open Access Journals (Sweden)

    Yu-Hong Wang

    2012-08-01

    Full Text Available In the title mononuclear complex, [HgI2(C12H11NO3], the HgII ion has a distorted trigonal–planar coordination sphere defined by two I− anions and the N atom of a methyl 2-(quinolin-8-yloxyacetate ligand. In the crystal, face-to-face π–π stacking interactions, with a centroid–centroid distance of 3.563 (9 Å, are observed.

  8. Engineering of bispecific affinity proteins with high affinity for ERBB2 and adaptable binding to albumin.

    Directory of Open Access Journals (Sweden)

    Johan Nilvebrant

    Full Text Available The epidermal growth factor receptor 2, ERBB2, is a well-validated target for cancer diagnostics and therapy. Recent studies suggest that the over-expression of this receptor in various cancers might also be exploited for antibody-based payload delivery, e.g. antibody drug conjugates. In such strategies, the full-length antibody format is probably not required for therapeutic effect and smaller tumor-specific affinity proteins might be an alternative. However, small proteins and peptides generally suffer from fast excretion through the kidneys, and thereby require frequent administration in order to maintain a therapeutic concentration. In an attempt aimed at combining ERBB2-targeting with antibody-like pharmacokinetic properties in a small protein format, we have engineered bispecific ERBB2-binding proteins that are based on a small albumin-binding domain. Phage display selection against ERBB2 was used for identification of a lead candidate, followed by affinity maturation using second-generation libraries. Cell surface display and flow-cytometric sorting allowed stringent selection of top candidates from pools pre-enriched by phage display. Several affinity-matured molecules were shown to bind human ERBB2 with sub-nanomolar affinity while retaining the interaction with human serum albumin. Moreover, parallel selections against ERBB2 in the presence of human serum albumin identified several amino acid substitutions that dramatically modulate the albumin affinity, which could provide a convenient means to control the pharmacokinetics. The new affinity proteins competed for ERBB2-binding with the monoclonal antibody trastuzumab and recognized the native receptor on a human cancer cell line. Hence, high affinity tumor targeting and tunable albumin binding were combined in one small adaptable protein.

  9. Inhibition of nuclear waste solutions containing multiple aggressive anions

    International Nuclear Information System (INIS)

    Congdon, J.W.

    1987-01-01

    The inhibition of localized corrosion of carbon steel in caustic, high-level radioactive waste solutions was studied using cyclic potentiodynamic polarization scans, supplemented by partially immersed coupon tests. The electrochemical tests provided a rapid and accurate means of determining the relationship between the minimum inhibitor requirements and the concentration of the aggressive anions in this system. Nitrate, sulfate, chloride, and fluoride were identified as aggressive anions, however, no synergistic effects were observed between these anions. This observation may have important theoretical implications because it tends to contradict the behavior of aggressive anions as predicted by existing theories for localized corrosion. 10 refs., 5 figs., 2 tabs

  10. Affine fractal functions as bases of continuous funtions | Navascues ...

    African Journals Online (AJOL)

    The objective of the present paper is the study of affine transformations of the plane, which provide self-affine curves as attractors. The properties of these curves depend decisively of the coefficients of the system of affinities involved. The corresponding functions are continuous on a compact interval. If the scale factors are ...

  11. Single-step affinity purification for fungal proteomics.

    Science.gov (United States)

    Liu, Hui-Lin; Osmani, Aysha H; Ukil, Leena; Son, Sunghun; Markossian, Sarine; Shen, Kuo-Fang; Govindaraghavan, Meera; Varadaraj, Archana; Hashmi, Shahr B; De Souza, Colin P; Osmani, Stephen A

    2010-05-01

    A single-step protein affinity purification protocol using Aspergillus nidulans is described. Detailed protocols for cell breakage, affinity purification, and depending on the application, methods for protein release from affinity beads are provided. Examples defining the utility of the approaches, which should be widely applicable, are included.

  12. Single-Step Affinity Purification for Fungal Proteomics ▿ †

    OpenAIRE

    Liu, Hui-Lin; Osmani, Aysha H.; Ukil, Leena; Son, Sunghun; Markossian, Sarine; Shen, Kuo-Fang; Govindaraghavan, Meera; Varadaraj, Archana; Hashmi, Shahr B.; De Souza, Colin P.; Osmani, Stephen A.

    2010-01-01

    A single-step protein affinity purification protocol using Aspergillus nidulans is described. Detailed protocols for cell breakage, affinity purification, and depending on the application, methods for protein release from affinity beads are provided. Examples defining the utility of the approaches, which should be widely applicable, are included.

  13. Efficient Separation of Lanthanides Using Poly (Styrene-Divinyl Benzene) Aminated Anion Exchanger

    International Nuclear Information System (INIS)

    Borai, E.H.; Hassan, R.S.; El- Dessouky, M.I.; Ghonem, A.

    2008-01-01

    New chromatographic method was developed for the determination and separation of lanthanides using AS4A anionic column. The behavior of the column towards lanthanides was studied through many parameters, From the data obtained it is found that, affinity of the column toward investigated ions increase by increasing eluent concentration and it decrease retention factors. With the two investigated eluent (oxalic and citric acids), elution order for lanthanide elements was obtained in their atomic number from La to Lu. Retention times and retention orders obtained at these conditions clearly show that, lanthanides in AS4A are displaced according to anion exchange mechanism. More over separation of lanthanides using AS4A was studied using isocratic and gradient elution programs. Light and the first intermediate lanthanide elements were separated successfully by applying a gradient program containing 70% oxalic acid (100 mM) and 30% water. The problem of separation for heavy and the last intermediate lanthanide elements was solved using 100 mM alpha hydroxy isobutyric acid (α-HIBA)

  14. N-methyl-D-aspartic acid receptor agonists

    DEFF Research Database (Denmark)

    Madsen, U; Frydenvang, Karla Andrea; Ebert, B

    1996-01-01

    (R,S)-2-Amino-2-(3-hydroxy-5-methyl-4-isoxazolyl)acetic acid [(R,S)-AMAA, 4] is a potent and selective agonist at the N-methyl-D-aspartic acid (NMDA) subtype of excitatory amino acid receptors. Using the Ugi "four-component condensation" method, the two diastereomers (2R)- and (2S)-2-[3-(benzyloxy......) showed peak affinity for [3H]AMPA receptor sites (IC50 = 72 +/- 13 microM) and was shown to be a more potent inhibitor of [3H]CPP binding (IC50 = 3.7 +/- 1.5 microM) than (S)-AMAA (9) (IC50 = 61 +/- 6.4 microM). Neither enantiomer of AMAA affected [3H]kainic acid receptor binding significantly...

  15. Binding affinity and decontamination of dermal decontamination gel to model chemical warfare agent simulants.

    Science.gov (United States)

    Cao, Yachao; Elmahdy, Akram; Zhu, Hanjiang; Hui, Xiaoying; Maibach, Howard

    2018-05-01

    Six chemical warfare agent simulants (trimethyl phosphate, dimethyl adipate, 2-chloroethyl methyl sulfide, diethyl adipate, chloroethyl phenyl sulfide and diethyl sebacate) were studied in in vitro human skin to explore relationship between dermal penetration/absorption and the mechanisms of simulant partitioning between stratum corneum (SC) and water as well as between dermal decontamination gel (DDGel) and water. Both binding affinity to and decontamination of simulants using DDGel were studied. Partition coefficients of six simulants between SC and water (Log P SC/w ) and between DDGel and water (Log P DDGel/w ) were determined. Results showed that DDGel has a similar or higher binding affinity to each simulant compared to SC. The relationship between Log P octanol/water and Log P SC/w as well as between Log P octanol/water and Log P DDGel/w demonstrated that partition coefficient of simulants correlated to their lipophilicity or hydrophilicity. Decontamination efficiency results with DDGel for these simulants were consistent with binding affinity results. Amounts of percentage dose of chemicals in DDGel of trimethyl phosphate, dimethyl adipate, 2-chloroethyl methyl sulfide, diethyl adipate, chloroethyl phenyl sulfide and diethyl sebacate were determined to be 61.15, 85.67, 75.91, 53.53, 89.89 and 76.58, with corresponding amounts absorbed in skin of 0.96, 0.65, 1.68, 0.72, 0.57 and 1.38, respectively. In vitro skin decontamination experiments coupled with a dermal absorption study demonstrated that DDGel can efficiently remove chemicals from skin surface, back-extract from the SC, and significantly reduced chemical penetration into skin or systemic absorption for all six simulants tested. Therefore, DDGel offers a great potential as a NextGen skin Decon platform technology for both military and civilian use. Copyright © 2018 John Wiley & Sons, Ltd.

  16. New Anion-Exchange Resins for Improved Separations of Nuclear Materials

    International Nuclear Information System (INIS)

    Bartsch, Richard A.; Barr, Mary E.

    2001-01-01

    Improved separations of nuclear materials will have a significant impact upon a broad range of DOE activities. DOE-EM Focus Areas and Crosscutting Programs have identified improved methods for the extraction and recovery of radioactive metal ions from process, waste, and environmental waters as critical needs for the coming years. We propose to develop multifunctional anion-exchange resins that facilitate anion uptake by carefully controlling the structure of the anion receptor site. Our new ion-exchange resins interface the field of ion-specific chelating ligands with robust, commercial ion-exchange technology to provide materials which exhibit superior selectivity and kinetics of sorption and desorption. The following Focus Areas and Crosscutting Programs have described needs that would be favorably impacted by the new material: Efficient Separations and Processing - radionuclide removal from aqueous phases; Plutonium - Pu, Am or total alpha removal to meet regulatory requirement s before discharge to the environment; Plumes - U and Tc in groundwater, U, Pu, Am, and Tc in soils; Mixed Waste - radionuclide partitioning; High-Level Tank Waste - actinide and Tc removal from supernatants and/or sludges. The basic scientific issues which need to be addressed are actinide complex speciation along with modeling of metal complex/functional site interactions in order to determine optimal binding-site characteristics. Synthesis of multifunctionalized extractants and ion-exchange materials that implement key features of the optimized binding site, and testing of these materials, will provide feedback to the modeling and design activities. Resin materials which actively facilitate the uptake of actinide complexes from solution should display both improved selectivity and kinetic properties. The long-range implications of this research, however, go far beyond the nuclear complex. This new methodology of ''facilitated uptake'' could revolutionize ion-exchange technology

  17. Adsorptive removal of Methylene blue and Methyl orange from aqueous media by carboxylated diaminoethane sporopollenin: On the usability of an aminocarboxilic acid functionality-bearing solid-stationary phase in column techniques

    International Nuclear Information System (INIS)

    Ayar, Ahmet; Gezici, Orhan; Kuecuekosmanoglu, Muhittin

    2007-01-01

    The adsorption phenomena of Methylene blue (MB) and Methyl orange (MO) on a carboxylated diaminoethane sporopollenin (CDAE-S) solid phase were investigated in a column arrangement by using breakthrough technique. The adsorption phenomena were evaluated using some common adsorption isotherm models and Scatchard plot analysis, and obtained results were interpreted for evaluating the usability of CDAE-S for removal, recovery and preconcentration of the studied dyes both at the laboratory and industrial scales. On the basis of Scatchard plot analysis, the interaction types between the CDAE-S and the studied dyes were criticized in terms of affinity phenomena. Thus, the usability of a biomacromolecule-derived material, CDAE-S, as a cheap, environmentally-friendly and effective solid-stationary phase exhibiting both cation-exchange and anion-exchange characteristics at the same time, is discussed through the present study. Besides, from the obtained results, the protonated CDAE-S, which functionally resembles an amino acid structure, are presented as a two-in-one solid-stationary phase, and its adaptability to common processes performed under column conditions is also drawn in detail

  18. Methylation in hepatocellular carcinoma

    Directory of Open Access Journals (Sweden)

    Regina M. Santella

    2007-02-01

    Full Text Available

    The development of HCC is a complex, multistep, multistage process. The molecular pathogenesis of HCC appears to involve multiple genetic aberrations in the molecular control of hepatocyte proliferation, differentiation and death and the maintenance of genomic integrity. This process is influenced by the cumulative activation and inactivation of oncogenes, tumor suppressor genes and other genes. p53, a tumor suppressor gene, is the most frequently mutated gene in human cancers. There is also a striking sequence specific binding and induction of mutations by AFB1 at codon 249 of p53 in HCC.

    Epigenetic alterations are also involved in cancer development and progression. Methylation of promoter CpG islands is associated with inhibition of transcriptional initiation and permanent silencing of downstream genes.

    It is now known that most important tumor suppressor genes are inactivated, not only by mutations and deletions but also by promoter methylation. Several studies indicated that p16, p15, RASSF1A, MGMT, and GSTP1 promoter hypermethylation are prevalent in HCC. In addition, geographic variation in the methylation status of tumor DNA indicates that environmental factors may influence the frequent and concordant degree of hypermethylation in multiple genes in HCC and that epigeneticenvironmental interactions may be involved in hepatocarcinogenesis. We have found significant relationships between promoter methylation and AFB1-DNA adducts confirming the impact of environmental exposures on gene methylation.

    DNA isolated from serum or plasma of cancer patients frequently contains the same genetic and

  19. Fluorescence anisotropy of tyrosinate anion using one-, two- and three-photon excitation: tyrosinate anion fluorescence.

    Science.gov (United States)

    Kierdaszuk, Borys

    2013-03-01

    We examined the emission spectra and steady-state anisotropy of tyrosinate anion fluorescence with one-photon (250-310 nm), two-photon (570-620 nm) and three-photon (750-930 nm) excitation. Similar emission spectra of the neutral (pH 7.2) and anionic (pH 13) forms of N-acetyl-L-tyrosinamide (NATyrA) (pKa 10.6) were observed for all modes of excitation, with the maxima at 302 and 352 nm, respectively. Two-photon excitation (2PE) and three-photon excitation (3PE) spectra of the anionic form were the same as that for one-photon excitation (1PE). In contrast, 2PE spectrum from the neutral form showed ~30-nm shift to shorter wavelengths relative to 1PE spectrum (λmax 275 nm) at two-photon energy (550 nm), the latter being overlapped with 3PE spectrum, both at two-photon energy (550 nm). Two-photon cross-sections for NATyrA anion at 565-580 nm were 10 % of that for N-acetyl-L-tryptophanamide (NATrpA), and increased to 90 % at 610 nm, while for the neutral form of NATyrA decreased from 2 % of that for NATrpA at 570 nm to near zero at 585 nm. Surprisingly, the fundamental anisotropy of NATyrA anion in vitrified solution at -60 °C was ~0.05 for 2PE at 610 nm as compared to near 0.3 for 1PE at 305 nm, and wavelength-dependence appears to be a basic feature of its anisotropy. In contrast, the 3PE anisotropy at 900 nm was about 0.5, and 3PE and 1PE anisotropy values appear to be related by the cos(6) θ to cos(2) θ photoselection factor (approx. 10/6) independently of excitation wavelength. Attention is drawn to the possible effect of tyrosinate anions in proteins on their multi-photon induced fluorescence emission and excitation spectra as well as excitation anisotropy spectra.

  20. Removal efficiency of radioactive methyl iodide on TEDA-impregnated activated carbons

    International Nuclear Information System (INIS)

    Gonzalez-Garcia, C.M.; Gonzalez, J.F.; Roman, S.

    2011-01-01

    Activated carbons were prepared by different series of carbon dioxide and steam activation from walnut shells for their optimal use as radioactive methyl iodide adsorbents in Nuclear Plants. The knowledge of the most favourable textural characteristics of the activated carbons was possible by the previous study of the commercial activated carbon currently used for this purpose. In order to increase their methyl iodide affinity, the effect of triethylenediamine impregnation was studied at 5 and 10 wt.%. The results obtained indicated that in both cases the adsorption efficiency is markedly improved by the addition of impregnant, which allows the adsorbate uptake to occur not only by physical adsorption, via non-specific interactions (as in non-impregnated carbons) but also by the specific interaction of triethylenediamine with radioactive methyl iodide. Methyl iodide retention efficiencies up to 98.1% were achieved. (author)

  1. 1,1′,2,2′,3,3′,4,4′-Octa­methyl­ferro­cenium 2,5-dibromo-4-hy­droxy-3,6-dioxocyclo­hexa-1,4-dien-1-olate

    Science.gov (United States)

    Mochida, Tomoyuki

    2011-01-01

    In the title salt, octa­methyl­ferrocenium bromanilate, [Fe(C9H13)2](C6HBr2O4), the Fe atom and the bromanilate anion lie on a mirror plane. The octa­methyl­ferrocenium cation adopts an eclipsed conformation. An intra­molecular O—H⋯O hydrogen bond is present in the bromanilate anion. In the crystal, the cations and anions are stacked alternately, forming a one-dimensional columnar structure along [010]. PMID:22090810

  2. Once upon Anion: A Tale of Photodetachment

    Science.gov (United States)

    Lineberger, W. Carl

    2013-04-01

    This contribution is very much a personal history of a journey through the wonderful world of anion chemistry, and a tale of how advances in laser technologies, theoretical methods, and computational capabilities continuously enabled advances in our understanding. It is a story of the excitement and joy that come from the opportunity to add to the fabric of science, and to do so by working as a group of excited explorers with common goals. The participants in this journey include me, my students and postdoctoral associates, my collaborators, and our many generous colleagues. It all happened, in the words of the Beatles, “with a little help from my friends.” Actually, it was so much more than a little help!

  3. Adsorption of an anionic dispersant on lignite

    Energy Technology Data Exchange (ETDEWEB)

    Yavuz, R.; Kucukbayrak, S. [Istanbul Technical University, Istanbul (Turkey). Dept. of Chemical Engineering, Chemical & Metallurgical Engineering Faculty

    2001-12-01

    Since coal is not a homogeneous substance but a mixture of carbonaceous materials and mineral matter, it has a variety of surface properties. Therefore, it is not easy to control the properties of coal suspensions by simply adjusting variables, such as pH and/or electrolyte. A chemical agent needs to be added to control the properties of the coal suspensions. The adsorption behavior of an anionic dispersant in the presence of a wetting agent using some Turkish lignite samples was investigated. The effects of dispersant concentration, temperature and pH on the dispersant adsorption were studied systematically, and the experimental results are presented. Pellupur B69 as a dispersant, commercial mixture of formaldehyde condensate sodium salt of naphthalene sulphonic acid, and Texapon N{sub 2}5 as a wetting agent, a sodium lauryl ether sulfate, have been used.

  4. Structures and properties of anionic clay minerals

    International Nuclear Information System (INIS)

    Koch, Chr. Bender

    1998-01-01

    The Moessbauer spectra of pyroaurite-sjoegrenite-type compounds (PTC) (layered anion exchangers) are discussed with reference to the crystal structure, cation order, and crystallite morphology. It is shown that cation-ordered layers are produced in the synthesis of carbonate and sulphate types of green rust. In contrast, synthetic and natural pyroaurite only occurs as disordered types. The redox chemistry of Fe(III) within the metal hydroxide layer is illustrated with examples of electrochemical oxidation and reversible reduction by boiling glycerol. The chemistry of iron in the interlayer is exemplified by the intercalation of Fe-cyanide complexes in hydrotalcite. This reaction may be used as a probe for the charge distribution in the interlayer

  5. Advanced polymer chemistry of organometallic anions

    International Nuclear Information System (INIS)

    Chamberlin, R.M.; Abney, K.D.; Balaich, G.J.; Fino, S.A.

    1997-01-01

    This is the final report of a one-year, Laboratory Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). The objective of the project was to prepare and characterize new polymers incorporating cobalt dicarbollide. Specific goals were to prepare polymerizable cobalt dicarbollide monomers using the nucleophilic substitution route discovered in laboratories and to establish the reaction conditions required to form polymers from these complexes. This one-year project resulted in two publications (in press), and provided the foundation for further investigations into polymer synthesis and characterization using cobalt dicarbollide and other metallocarboranes. Interest in synthesizing organometallic polymers containing the cobalt bis(dicarbollide) anion is motivated by their possible application as cation exchange materials for the remediation of cesium-137 and strontium-90 from nuclear wastes

  6. Affine Fullerene C60 in a GS-Quasigroup

    Directory of Open Access Journals (Sweden)

    Vladimir Volenec

    2014-01-01

    Full Text Available It will be shown that the affine fullerene C60, which is defined as an affine image of buckminsterfullerene C60, can be obtained only by means of the golden section. The concept of the affine fullerene C60 will be constructed in a general GS-quasigroup using the statements about the relationships between affine regular pentagons and affine regular hexagons. The geometrical interpretation of all discovered relations in a general GS-quasigroup will be given in the GS-quasigroup C(1/2(1+5.

  7. On the structure of self-affine convex bodies

    Energy Technology Data Exchange (ETDEWEB)

    Voynov, A S [M. V. Lomonosov Moscow State University, Faculty of Mechanics and Mathematics, Moscow (Russian Federation)

    2013-08-31

    We study the structure of convex bodies in R{sup d} that can be represented as a union of their affine images with no common interior points. Such bodies are called self-affine. Vallet's conjecture on the structure of self-affine bodies was proved for d = 2 by Richter in 2011. In the present paper we disprove the conjecture for all d≥3 and derive a detailed description of self-affine bodies in R{sup 3}. Also we consider the relation between properties of self-affine bodies and functional equations with a contraction of an argument. Bibliography: 10 titles.

  8. ANIONIC POLYMERIZATION OF ALKYL METHACRYLATES INITIATED BY nBuCu(NCy2)Li

    Institute of Scientific and Technical Information of China (English)

    Bing-yong Han; Jian-guo Liang; Jian-min Lu; Feng An; Wan-tai Yang

    2009-01-01

    Anionic polymerization of methyl methacrylate (MMA), n-butyl methacrylate (nBMA) and glycidyl methacrylate (GMA) initiated by nBuCu(NCy2)Li (1) in tetrahydrofuran (THF) at -50℃ to -10℃ was investigated. It was found that the polymerization of MMA and nBMA initiated by 1 proceeded quantitatively in THF to afford PMMA and PBMA with polydispersity index 1.15-1.30 and nearly 100% initiator efficiencies at -10℃. The molecular weights increased linearly with the ratio of [monomer]/[1]. However, a post-polymerization experiment carried out on this system revealed a double polymer peak by GPC when fresh monomer was added after an interval of 10 rain. Polymerization of styrene could be initiated by 1, but the initiator efficiency was low.

  9. Synthesis and binding affinity of an iodinated juvenile hormone

    Energy Technology Data Exchange (ETDEWEB)

    Prestwich, G.D.; Eng, W.S.; Robles, S.; Vogt, R.G.; Wisniewski, J.R.; Wawrzenczyk, C.

    1988-01-25

    The synthesis of the first iodinated juvenile hormone (JH) in enantiomerically enriched form is reported. This chiral compound, 12-iodo-JH I, has an iodine atom replacing a methyl group of the natural insect juvenile hormone, JH I, which is important in regulating morphogenesis and reproduction in the Lepidoptera. The unlabeled compound shows approximately 10% of the relative binding affinity for the larval hemolymph JH binding protein (JHBP) of Manduca sexta, which specifically binds natural /sup 3/H-10R,11S-JH I (labeled at 58 Ci/mmol) with a KD of 8 X 10(-8) M. It is also approximately one-tenth as biologically active as JH I in the black Manduca and epidermal commitment assays. The 12-hydroxy and 12-oxo compounds are poor competitors and are also biologically inactive. The radioiodinated (/sup 125/I)12-iodo-JH I can be prepared in low yield at greater than 2500 Ci/mmol by nucleophilic displacement using no-carrier-added /sup 125/I-labeled sodium iodide in acetone; however, synthesis using sodium iodide carrier to give the approximately 50 Ci/mmol radioiodinated ligand proceeds in higher radiochemical yield with fewer by-products and provides a radioligand which is more readily handled in binding assays. The KD of (/sup 125/I)12-iodo-JH I was determined for hemolymph JHBP of three insects: M. sexta, 795 nM; Galleria mellonella, 47 nM; Locusta migratoria, 77 nM. The selectivity of 12-iodo-JH I for the 32-kDa JHBP of M. sexta was demonstrated by direct autoradiography of a native polyacrylamide gel electrophoresis gel of larval hemolymph incubated with the radioiodinated ligand. Thus, the in vitro and in vivo activity of 12-iodo-JH I indicate that it can serve as an important new gamma-emitting probe in the search for JH receptor proteins in target tissues.

  10. F+ and F⁻ affinities of simple N(x)F(y) and O(x)F(y) compounds.

    Science.gov (United States)

    Grant, Daniel J; Wang, Tsang-Hsiu; Vasiliu, Monica; Dixon, David A; Christe, Karl O

    2011-03-07

    Atomization energies at 0 K and heats of formation at 0 and 298 K are predicted for the neutral and ionic N(x)F(y) and O(x)F(y) systems using coupled cluster theory with single and double excitations and including a perturbative triples correction (CCSD(T)) method with correlation consistent basis sets extrapolated to the complete basis set (CBS) limit. To achieve near chemical accuracy (±1 kcal/mol), three corrections to the electronic energy were added to the frozen core CCSD(T)/CBS binding energies: corrections for core-valence, scalar relativistic, and first order atomic spin-orbit effects. Vibrational zero point energies were computed at the CCSD(T) level of theory where possible. The calculated heats of formation are in good agreement with the available experimental values, except for FOOF because of the neglect of higher order correlation corrections. The F(+) affinity in the N(x)F(y) series increases from N(2) to N(2)F(4) by 63 kcal/mol, while that in the O(2)F(y) series decreases by 18 kcal/mol from O(2) to O(2)F(2). Neither N(2) nor N(2)F(4) is predicted to bind F(-), and N(2)F(2) is a very weak Lewis acid with an F(-) affinity of about 10 kcal/mol for either the cis or trans isomer. The low F(-) affinities of the nitrogen fluorides explain why, in spite of the fact that many stable nitrogen fluoride cations are known, no nitrogen fluoride anions have been isolated so far. For example, the F(-) affinity of NF is predicted to be only 12.5 kcal/mol which explains the numerous experimental failures to prepare NF(2)(-) salts from the well-known strong acid HNF(2). The F(-) affinity of O(2) is predicted to have a small positive value and increases for O(2)F(2) by 23 kcal/mol, indicating that the O(2)F(3)(-) anion might be marginally stable at subambient temperatures. The calculated adiabatic ionization potentials and electron affinities are in good agreement with experiment considering that many of the experimental values are for vertical processes. © 2011

  11. Competition of organic anions for furosemide and p-aminohippurate secretion in the rabbit

    International Nuclear Information System (INIS)

    Bidiville, J.; Roch-Ramel, F.

    1986-01-01

    The excretion of [ 14 C]- or [ 35 S]furosemide and [ 3 H]-p-aminohippurate (PAH) injected within 4 min into the left renal artery of rabbits was measured under brisk mannitol diuresis. The estimated rate of furosemide secretion during the first pass through the left kidney was lower than that of PAH when neither of the two transport processes were saturated: 7.9 and 12.9% of the total amounts injected were secreted per minute, respectively. Different competitive inhibitors were injected i.v. Probenecid (50 mg/kg) inhibited furosemide and PAH secretion by 95 and 80%, respectively. Pyrazinoate at plasma concentrations of 3 to 5 mM had no effect on either anion. Indomethacin (10 mg/kg) depressed furosemide secretion by 24% but had no effect on PAH secretion. PAH at a concentration of 9 to 17 mM in plasma depressed furosemide secretion by only 44 to 66%. Furosemide did not inhibit PAH secretion when infused into the left renal artery at a rate 5000 times higher than PAH. It was concluded that furosemide is secreted partly by the transport system secreting PAH, for which it had only a low affinity, and partly by a transport system for which indomethacin had some affinity. This latter transport system, in turn, differs from that secreting pyrazinoate. The furosemide-induced natriuresis, in both kidneys, was proportional to the urinary excretion rate of furosemide until the fractional excretion of Na+ reached an apparent maximum of 20 to 30%

  12. Anions mediate ligand binding in Adineta vaga glutamate receptor ion channels.

    Science.gov (United States)

    Lomash, Suvendu; Chittori, Sagar; Brown, Patrick; Mayer, Mark L

    2013-03-05

    AvGluR1, a glutamate receptor ion channel from the primitive eukaryote Adineta vaga, is activated by alanine, cysteine, methionine, and phenylalanine, which produce lectin-sensitive desensitizing responses like those to glutamate, aspartate, and serine. AvGluR1 LBD crystal structures reveal an unusual scheme for binding dissimilar ligands that may be utilized by distantly related odorant/chemosensory receptors. Arginine residues in domain 2 coordinate the γ-carboxyl group of glutamate, whereas in the alanine, methionine, and serine complexes a chloride ion acts as a surrogate ligand, replacing the γ-carboxyl group. Removal of Cl(-) lowers affinity for these ligands but not for glutamate or aspartate nor for phenylalanine, which occludes the anion binding site and binds with low affinity. AvGluR1 LBD crystal structures and sedimentation analysis also provide insights into the evolutionary link between prokaryotic and eukaryotic iGluRs and reveal features unique to both classes, emphasizing the need for additional structure-based studies on iGluR-ligand interactions. Copyright © 2013 Elsevier Ltd. All rights reserved.

  13. Anion binding by biotin[6]uril in water

    DEFF Research Database (Denmark)

    Lisbjerg, Micke; Nielsen, Bjarne Enrico; Milhøj, Birgitte Olai

    2015-01-01

    In this contribution we show that the newly discovered 6 + 6 biotin-formaldehyde macrocycle Biotin[6]uril binds a variety of anionic guest molecules in water. We discuss how and why the anions are bound based on data obtained using NMR spectroscopy, mass spectrometry, isothermal titration...

  14. A colorimetric tetrathiafulvalene-calix 4 pyrrole anion sensor

    DEFF Research Database (Denmark)

    Nielsen, K. A.

    2012-01-01

    The interaction and colorimetric sensing properties of a tetrathiafulvalene substituted calix[4]pyrrole sensor with anions were investigated using H-1 NMR and absorption spectroscopic techniques. Visual color changes were observed upon addition of different anions (Cl-, Br-, CN-, and Ac......O-) to a solution of the sensor. (C) 2012 Elsevier Ltd. All rights reserved....

  15. Diffuse neutron scattering from anion-excess strontium chloride

    DEFF Research Database (Denmark)

    Goff, J.P.; Clausen, K.N.; Fåk, B.

    1992-01-01

    The defect structure and diffusional processes have been studied in the anion-excess fluorite (Sr, Y)Cl2.03 by diffuse neutron scattering techniques. Static cuboctahedral clusters found at ambient temperature break up at temperatures below 1050 K, where the anion disorder is highly dynamic. The a...

  16. Protonation Reaction of Benzonitrile Radical Anion and Absorption of Product

    DEFF Research Database (Denmark)

    Holcman, Jerzy; Sehested, Knud

    1975-01-01

    The rate constant for the protonation of benzonitrile radical anions formed in pulse radiolysis of aqueous benzonitrile solutions is (3.5 ± 0.5)× 1010 dm3 mol–1 s–1. A new 270 nm absorption band is attributed to the protonated benzonitrile anion. The pK of the protonation reaction is determined t...

  17. Anion binding in the C3v-symmetric cavity of a protonated tripodal amine receptor: potentiometric and single crystal X-ray studies.

    Science.gov (United States)

    Bose, Purnandhu; Ravikumar, I; Ghosh, Pradyut

    2011-11-07

    Tris(2-aminoethyl)amine (tren) based pentafluorophenyl-substituted tripodal L, tris[[(2,3,4,5,6-pentafluorobenzyl)amino]ethyl]amine receptor is synthesized in good yield and characterized by single crystal X-ray diffraction analysis. Detailed structural aspects of binding of different anionic guests toward L in its triprotonated form are examined thoroughly. Crystallographic results show binding of fluoride in the C(3v)-symmetric cavity of [H(3)L](3+) where spherical anion fluoride is in tricoordinated geometry via (N-H)(+)···F interaction in the complex [H(3)L(F)]·[F](2)·2H(2)O, (3). In the case of complexes [H(3)L(OTs)]·[OTs](2), (4) and [H(3)L(OTs)]·[NO(3)]·[OTs], (5), tetrahedral p-toluenesulphonate ion is engulfed in the cavity of [H(3)L](3+) via (N-H)(+)···O interactions. Interestingly, complex [(H(3)L)(2)(SiF(6))]·[BF(4)](4)·CH(3)OH·H(2)O, (6) shows encapsulation of octahedral hexafluorosilicate in the dimeric capsular assembly of two [H(3)L](3+) units, via a number of (N-H)(+)···F interactions. The kinetic parameters of L upon binding with different anions are evaluated using a potentiometric study in solution state. The potentiometric titration experiments in a polar protic methanol/water (1:1 v/v) binary solvent system show high affinity of the receptor toward more basic fluoride and acetate anions, with a lesser affinity for other inorganic anions (e.g., chloride, bromide, nitrate, sulfate, dihydrogenphosphate, and p-toluenesulphonate). © 2011 American Chemical Society

  18. DNA methylation and memory formation.

    Science.gov (United States)

    Day, Jeremy J; Sweatt, J David

    2010-11-01

    Memory formation and storage require long-lasting changes in memory-related neuronal circuits. Recent evidence indicates that DNA methylation may serve as a contributing mechanism in memory formation and storage. These emerging findings suggest a role for an epigenetic mechanism in learning and long-term memory maintenance and raise apparent conundrums and questions. For example, it is unclear how DNA methylation might be reversed during the formation of a memory, how changes in DNA methylation alter neuronal function to promote memory formation, and how DNA methylation patterns differ between neuronal structures to enable both consolidation and storage of memories. Here we evaluate the existing evidence supporting a role for DNA methylation in memory, discuss how DNA methylation may affect genetic and neuronal function to contribute to behavior, propose several future directions for the emerging subfield of neuroepigenetics, and begin to address some of the broader implications of this work.

  19. Supramolecular Chemistry of Selective Anion Recognition for Anions of Environmental Relevance

    International Nuclear Information System (INIS)

    Moyer, Bruce a.; Bostick, Debra A.; Fowler, Christopher J.; Kang, Hyun-Ah; Ruas, Alexandre; Delmau, Laetitia H.; Haverlock, Tamara J.; Llinares, Jose M.; Hossain, Alamgir; Kang, S. O.; Bowman-James, Kristin; Shriver, James A.; Marquez, Manuel; Sessler, Jonathan L.

    2005-01-01

    The major thrust of this project led by the University of Kansas (Prof. Kristin Bowman-Jones) entails the exploration of the principles of recognition and separation of sulfate by the design, synthesis, and testing of novel sulfate extractants. A key science need for the cleanup of tank wastes at Hanford has been identified in developing methods to separate those bulk waste components that have low solubilities in borosilicate glass. Sulfate has been identified as a particularly difficult and expensive problem in that its concentration in the waste is relatively high, its solubility in glass is especially low, and it interferes with the performance of both vitrification equipment and the glass waste form. The new extractants will be synthesized by the University of Kansas and the University of Texas, Austin. Oak Ridge National Laboratory (ORNL) is subjecting the new extractants to experiments that will determine their properties and effectiveness in separating sulfate from the major competing anions in the waste, especially nitrate. Such experiments will entail primarily liquid-liquid extraction. Current efforts focus on exciting new systems in which the anion receptors act as synergists for anion exchange

  20. [Relation between location of elements in periodic table and affinity for the malignant tumor (author's transl)].

    Science.gov (United States)

    Ando, A; Hisada, K; Ando, I

    1977-10-01

    Affinity of many inorganic compounds for the malignant tumor was examined, using the rats which were subcutaneously transplanted with Yoshida sarcoma. And the relations between the uptake rate into the malignant tumor and in vitro binding power to the protein were investigated in these compounds. In these experiments, the bipositive ions and anions had not affinity for the tumor tissue with a few exceptions. On the other hand, Hg, Au and Bi, which have strong binding power to the protein, showed high uptake rate into the malignant tumor. As Hg++, Au+ and Bi+++ are soft acids according to classification of Lewis acids, it was thought that these elements would bind strongly to soft base (R-SH, R-S-) present in the tumor tissue. In many hard acids (according to classification of Lewis acids), the uptake rate into the tumor was shown as a function of ionic potentials (valency/ionic radii) of the metal ions. It is presumed that the chemical bond of these hard acids in the tumor tissue is ionic bond to hard base (R-COO-, R-PO3(2-), R-SO3-, R-NH2).

  1. Effect of isotopic substitution upon the gas phase and solution electron affinities of nitrobenzene

    International Nuclear Information System (INIS)

    Stevenson, G.R.; Reiter, R.C.; Espe, M.E.; Bartmess, J.E.

    1987-01-01

    Ion cyclotron resonance and electron spin resonance have been utilized to determine the equilibrium constant for the electron transfer from the nitrobenzene anion radical to 15 N labeled nitrobenzene (Ph 14 NO 2 - + Ph 15 NO 2 ↔ Ph 14 NO 2 + Ph 15 NO 2 9 . It was found that the equilibrium constant is within experimental error of unity at 305 K. Molecular orbital calculations indicate that this might be accounted for by the shortening of the C-N bond and a counterbalancing lengthening of the N-O bonds upon electron attachment to nitrobenzene. An equilibrium constant that is much larger than unity can be observed in liquid ammonia at 208 K when K + serves as the gegenion (K/sub eq/ = 2.1). However, when Na + serves as the gegenion, the solution electron affinity of Ph 14 NO 2 is greater than that of Ph 15 NO 2 (K/sub eq/ = 0.4). These results are explained in terms of ion association. When the hydrogen atoms are replaced with deuteriums, the gas phase electron affinity is decreased. A similar decrease is observed in liquid ammonia. In the gas phase this is attributed to the slight lengthening of all the C-H bonds upon electron attachment

  2. Superoxide anion production by human neutrophils activated by Trichomonas vaginalis.

    Science.gov (United States)

    Song, Hyun-Ouk; Ryu, Jae-Sook

    2013-08-01

    Neutrophils are the predominant inflammatory cells found in vaginal discharges of patients infected with Trichomonas vaginalis. In this study, we examined superoxide anion (O2 (.-)) production by neutrophils activated by T. vaginalis. Human neutrophils produced superoxide anions when stimulated with either a lysate of T. vaginalis, its membrane component (MC), or excretory-secretory product (ESP). To assess the role of trichomonad protease in production of superoxide anions by neutrophils, T. vaginalis lysate, ESP, and MC were each pretreated with a protease inhibitor cocktail before incubation with neutrophils. Superoxide anion production was significantly decreased by this treatment. Trichomonad growth was inhibited by preincubation with supernatants of neutrophils incubated for 3 hr with T. vaginalis lysate. Furthermore, myeloperoxidase (MPO) production by neutrophils was stimulated by live trichomonads. These results indicate that the production of superoxide anions and MPO by neutrophils stimulated with T. vaginalis may be a part of defense mechanisms of neutrophils in trichomoniasis.

  3. Use of Anion Exchange Resins for One-Step Processing of Algae from Harvest to Biofuel

    Directory of Open Access Journals (Sweden)

    Martin Poenie

    2012-07-01

    Full Text Available Some microalgae are particularly attractive as a renewable feedstock for biodiesel production due to their rapid growth, high content of triacylglycerols, and ability to be grown on non-arable land. Unfortunately, obtaining oil from algae is currently cost prohibitive in part due to the need to pump and process large volumes of dilute algal suspensions. In an effort to circumvent this problem, we have explored the use of anion exchange resins for simplifying the processing of algae to biofuel. Anion exchange resins can bind and accumulate the algal cells out of suspension to form a dewatered concentrate. Treatment of the resin-bound algae with sulfuric acid/methanol elutes the algae and regenerates the resin while converting algal lipids to biodiesel. Hydrophobic polymers can remove biodiesel from the sulfuric acid/methanol, allowing the transesterification reagent to be reused. We show that in situ transesterification of algal lipids can efficiently convert algal lipids to fatty acid methyl esters while allowing the resin and transesterification reagent to be recycled numerous times without loss of effectiveness.

  4. Preparation and performance evaluation of novel alkaline stable anion exchange membranes

    Science.gov (United States)

    Irfan, Muhammad; Bakangura, Erigene; Afsar, Noor Ul; Hossain, Md. Masem; Ran, Jin; Xu, Tongwen

    2017-07-01

    Novel alkaline stable anion exchange membranes are prepared from various amounts of N-methyl dipicolylamine (MDPA) and brominated poly (2,6-dimethyl-1,4-phenylene oxide) (BPPO). The dipicolylamine and MDPA are synthesized through condensation reaction and confirmed by 1H NMR spectroscopy. The morphologies of prepared membranes are investigated by atomic force microscopy (AFM), fourier transform infrared spectroscopy (FTIR), 1H NMR spectroscopy and scanning electron microscopy (SEM). The electrochemical and physical properties of AEMs are tested comprising water uptake (WU), ion exchange capacity (IEC), alkaline stability, linear expansion ratio (LER), thermal stability and mechanical stability. The obtained hydroxide conductivity of MDPA-4 is 66.5 mS/cm at 80 °C. The MDPA-4 membrane shows good alkaline stability, high hydroxide conductivity, low methanol permeability (3.43 × 10-7 cm2/s), higher selectivity (8.26 × 107 mS s/cm3), less water uptake (41.1%) and lower linear expansion (11.1%) despite of high IEC value (1.62 mmol/g). The results prove that MDPA membranes have great potential application in anion exchange membrane fuel cell.

  5. Effects of the anion salt nature on the rate constants of the aqueous proton exchange reactions.

    Science.gov (United States)

    Paredes, Jose M; Garzon, Andres; Crovetto, Luis; Orte, Angel; Lopez, Sergio G; Alvarez-Pez, Jose M

    2012-04-28

    The proton-transfer ground-state rate constants of the xanthenic dye 9-[1-(2-methyl-4-methoxyphenyl)]-6-hydroxy-3H-xanthen-3-one (TG-II), recovered by Fluorescence Lifetime Correlation Spectroscopy (FLCS), have proven to be useful to quantitatively reflect specific cation effects in aqueous solutions (J. M. Paredes, L. Crovetto, A. Orte, J. M. Alvarez-Pez and E. M. Talavera, Phys. Chem. Chem. Phys., 2011, 13, 1685-1694). Since these phenomena are more sensitive to anions than to cations, in this paper we have accounted for the influence of salts with the sodium cation in common, and the anion classified according to the empirical Hofmeister series, on the proton transfer rate constants of TG-II. We demonstrate that the presence of ions accelerates the rate of the ground-state proton-exchange reaction in the same order than ions that affect ion solvation in water. The combination of FLCS with a fluorophore undergoing proton transfer reactions in the ground state, along with the desirable feature of a pseudo-dark state when the dye is protonated, allows one unique direct determination of kinetic rate constants of the proton exchange chemical reaction. This journal is © the Owner Societies 2012

  6. Temperature and anion responsive self-assembly of ionic liquid block copolymers coating gold nanoparticles

    Science.gov (United States)

    Li, Junbo; Zhao, Jianlong; Wu, Wenlan; Liang, Ju; Guo, Jinwu; Zhou, Huiyun; Liang, Lijuan

    2016-06-01

    In this paper, double hydrophilic ionic liquid block copolymers (ILBCs), poly poly[1-methyl-3-(2-methacryloyloxy propylimidazolium bromine)]- block-(N-isopropylacrylamide) (PMMPImB- b-PNIPAAm) was first synthesized by reversible additionfragmentation chain transfer (RAFT) and then attached on the surface of gold nanoparticles (Au NPs) via a strong gold-sulfur bonding for preparing hybrid nanoparticles (PMMPImB- b-PNIPAAm-@-Au NPs). The hybrid NPs had a three layers micelle-like structure, including a gold core, thermo-responsive inner shell and anion responsive outer corona. The self-assembling behavior of thermal- and anion-response from shell and corona were respectively investigated by change of temperature and addition of (CF3SO2)2N-. The results showed the hybrid NPs retained a stable dispersion beyond the lower critical solution temperature (LCST) because of the space or electrostatic protecting by outer PMMPImB. However, with increasing concentration of (CF3SO2)2N-, the micellization of self-assembling PMMPImB- b-PNIPAAm-@-Au NPs was induced to form micellar structure containing the core with hydrophobic PMMPImB-(CF3SO2)2N- surrounded by composite shell of Au NPs-PNIPAAm via the anionresponsive properties of ILBCs. These results indicated that the block copolymers protected plasmonic nanoparticles remain self-assembling properties of block copolymers when phase transition from outer corona polymer.

  7. Systemic catechol-O-methyl transferase inhibition enables the D1 agonist radiotracer R-[11C]SKF 82957

    DEFF Research Database (Denmark)

    Palner, Mikael; McCormick, Patrick; Parkes, Jun

    2010-01-01

    R-[(11)C]-SKF 82957 is a high-affinity and potent dopamine D(1) receptor agonist radioligand, which gives rise to a brain-penetrant lipophilic metabolite. In this study, we demonstrate that systemic administration of catechol-O-methyl transferase (COMT) inhibitors blocks this metabolic pathway, f...

  8. High affinity hemoglobin and Parkinson's disease.

    Science.gov (United States)

    Graham, Jeffrey; Hobson, Douglas; Ponnampalam, Arjuna

    2014-12-01

    Parkinson's disease (PD) is a neurodegenerative disorder characterized by the loss of dopaminergic neurons in the substantia nigra (SN) region of the midbrain. Oxidative damage in this region has been shown to play an important role in the pathogenesis of this disease. Human neurons have been discovered to contain hemoglobin, with an increased concentration seen in the neurons of the SN. High affinity hemoglobin is a clinical entity resulting from mutations that create a functional increase in the binding of hemoglobin to oxygen and an inability to efficiently unload it to tissues. This can result in a number of metabolic compensatory changes, including an elevation in circulating hemoglobin and an increase in the molecule 2,3-diphosphoglycerate (2,3-DPG). Population based studies have revealed that patients with PD have elevated hemoglobin as well as 2,3-DPG levels. Based on these observations, we hypothesize that the oxidative damage seen in PD is related to an underlying high affinity hemoglobin subtype. Copyright © 2014 Elsevier Ltd. All rights reserved.

  9. Aspects of affine Toda field theory

    International Nuclear Information System (INIS)

    Braden, H.W.; Corrigan, E.; Dorey, P.E.; Sasaki, R.

    1990-05-01

    The report is devoted to properties of the affine Toda field theory, the intention being to highlight a selection of curious properties that should be explicable in terms of the underlying group theory but for which in most cases there are no explanation. The motivation for exploring the ideas contained in this report came principally from the recent work of Zamolodchikov concerning the two dimensional Ising model at critical temperature perturbed by a magnetic field. Hollowood and Mansfield pointed out that since Toda field theory is conformal the perturbation considered by Zamolodchikov might well be best regarded as a perturbation of a Toda field theory. This work made it seem plausible that the theory sought by Zamolodchikov was actually affine E 8 Toda field theory. However, this connection required an imaginary value of the coupling constant. Investigations here concerning exact S-matrices use a perturbative approach based on real coupling and the results differ in various ways from those thought to correspond to perturbed conformal field theory. A further motivation is to explore the connection between conformal and perturbed conformal field theories in other contexts using similar ideas. (N.K.)

  10. From affine Hecke algebras to boundary symmetries

    International Nuclear Information System (INIS)

    Doikou, Anastasia

    2005-01-01

    Motivated by earlier works we employ appropriate realizations of the affine Hecke algebra and we recover previously known non-diagonal solutions of the reflection equation for the U q (gl n -bar ) case. The corresponding N site spin chain with open boundary conditions is then constructed and boundary non-local charges associated to the non-diagonal solutions of the reflection equation are derived, as coproduct realizations of the reflection algebra. With the help of linear intertwining relations involving the aforementioned solutions of the reflection equation, the symmetry of the open spin chain with the corresponding boundary conditions is exhibited, being essentially a remnant of the U q (gl n -bar ) algebra. More specifically, we show that representations of certain boundary non-local charges commute with the generators of the affine Hecke algebra and with the local Hamiltonian of the open spin chain for a particular choice of boundary conditions. Furthermore, we are able to show that the transfer matrix of the open spin chain commutes with a certain number of boundary non-local charges, depending on the choice of boundary conditions

  11. Gravitational Goldstone fields from affine gauge theory

    Science.gov (United States)

    Tresguerres, Romualdo; Mielke, Eckehard W.

    2000-08-01

    In order to facilitate the application of standard renormalization techniques, gravitation should be described, in the pure connection formalism, as a Yang-Mills theory of a certain spacetime group, say the Poincaré or the affine group. This embodies the translational as well as the linear connection. However, the coframe is not the standard Yang-Mills-type gauge field of the translations, since it lacks the inhomogeneous gradient term in the gauge transformations. By explicitly restoring this ``hidden'' piece within the framework of nonlinear realizations, the usual geometrical interpretation of the dynamical theory becomes possible, and in addition one can avoid the metric or coframe degeneracy which would otherwise interfere with the integrations within the path integral. We claim that nonlinear realizations provide the general mathematical scheme for the foundation of gauge theories of spacetime symmetries. When applied to construct the Yang-Mills theory of the affine group, tetrads become identified with nonlinear translational connections; the anholonomic metric no longer constitutes an independent gravitational potential, since its degrees of freedom reveal a correspondence to eliminateable Goldstone bosons. This may be an important advantage for quantization.

  12. Comment on: Negative ions, molecular electron affinity and orbital structure of cata-condensed polycyclic aromatic hydrocarbons by Rustem V. Khatymov, Mars V. Muftakhov and Pavel V. Shchukin.

    Science.gov (United States)

    Chen, Edward S; Chen, Edward C M

    2018-02-15

    The anion mass spectral lifetimes for several aromatic hydrocarbons reported in the subject article were related to significantly different electron affinities. The different values are rationalized using negative ion mass spectral data. Electron affinities for polycyclic aromatic hydrocarbons are reported from the temperature dependence of unpublished electron capture detector data. These are compared with published values and the largest values are assigned to the ground state. The ground state adiabatic electron affinities: (eV) pentacene, 1.41 (3); tetracene, 1.058 (5); benz(a)pyrene, 0.82 (4); benz(a) anthracene, 0.69 (2) anthracene, 0.68 (2); and pyrene, 0.59 (1) are used to assign excited state adiabatic electron affinities: (eV) tetracene: 0.88 (4); anthracene 0.53 (1); pyrene, 0.41 (1); benz(a)anthracene, 0.39 (10); chrysene, 0.32 (1); and phenanthrene, 0.12 (2) and ground state adiabatic electron affinities: (eV) dibenz(a,j)anthracene, 0.69 (3); dibenz(a,h)anthracene, 0.68 (3); benz(e)pyrene, 0.60 (3); and picene, 0.59 (3) from experimental data. The lifetime of benz(a)pyrene is predicted to be larger than 150 μs and for benzo(c)phenanthrene and picene about 40 μs, from ground state adiabatic electron affinities. The assignments of adiabatic electron affinities of aromatic hydrocarbons determined from electron capture detector and mass spectrometric data to ground and excited states are supported by constant electronegativities. A set of consistent ground state adiabatic electron affinities for 15 polycyclic aromatic hydrocarbons is related to lifetimes from the subject article. Copyright © 2017 John Wiley & Sons, Ltd.

  13. Microhydration of cytosine and its radical anion: Cytosine.(H2O)n (n=1-5)

    Science.gov (United States)

    Kim, Sunghwan; Schaefer, Henry F.

    2007-02-01

    Microhydration effects on cytosine and its radical anion have been investigated theoretically, by explicitly considering various structures of cytosine complexes with up to five water molecules. Each successive water molecule (through n =5) is bound by 7-10kcalmol-1 to the relevant cytosine complex. The hydration energies are uniformly higher for the analogous anion systems. While the predicted vertical detachment energy (VDE) of the isolated cytosine is only 0.48eV, it is predicted to increase to 1.27eV for the lowest-lying pentahydrate of cytosine. The adiabatic electron affinity (AEA) of cytosine was also found to increase from 0.03to0.61eV for the pentahydrate, implying that the cytosine anion, while questionable in the gas phase, is bound in aqueous solution. Both the VDE and AEA values for cytosine are smaller than those of uracil and thymine for a given hydration number. These results are in qualitative agreement with available experimental results from photodetachment-photoelectron spectroscopy studies of Schiedt et al. [Chem. Phys. 239, 511 (1998)].

  14. Anion Effects on Gas Solubility in Ionic Liquids

    OpenAIRE

    Anthony, Jennifer L.; Anderson, Jessica L.; Maginn, Edward J.; Brennecke, Joan F.

    2005-01-01

    This work presents the results of solubility measurements for a series of gases in 1-n-butyl-3-methyl imidazolium tetrafluoroborate and 1-n-butyl-3-methyl imidazolium bis(trifluoromethylsulfonyl) imide. The gases considered include benzene, carbon dioxide, nitrous oxide, ethylene, ethane, oxygen, and carbon monoxide. Carbon dioxide and oxygen solubilities are also reported in methyl-tributylammonium bis(trifluoromethylsulfonyl) imide, butyl-methyl pyrrolidinium bis(trifluoromethylsulfonyl) im...

  15. Interaction between Eudragit® E100 and anionic drugs: addition of anionic polyelectrolytes and their influence on drug release performance.

    Science.gov (United States)

    Quinteros, Daniela A; Manzo, Ruben H; Allemandi, Daniel A

    2011-11-01

    In this work, we report results concerning the study of solid complexes compounded by a cationic polymethacrylate (Eudragit® E100, Eu) and mesalazine (M) (Eu-M(x) complex). The influence of an anionic polyacrylic acid polymer (carbomer, C) on dissolution behavior of M from the complex was evaluated (Eu-M(x) C(y) complex). The dissolution profiles and solvent front movements of solid matrices in different media (water, buffer pH 7.4, 0.9% NaCl) were investigated and ionic interactions among Eu, M, and C were determined through Fourier transform infrared (FT-IR) spectroscopy. For Eu-M(x) complexes, the affinity between M and Eu modulated the delivery of free M in solution, with the dissolution media affecting the delivery rate mainly due to an ionic interchange process between M and anionic electrolytes (i.e., Cl(-)). FTIR spectroscopy allowed the ionic interaction between Eu and M to be verified. The addition of C (Eu-M(x) C(y) ) influenced the dissolution behavior of these matrices. As the amount of C was increased, the release mechanism changed from diffusion (Eu-M(50) ) or anomalous (Eu-M(100)) to zero order (Eu-M(x) C(50)). This variation in rate delivery was also affected by the dissolution media, as occurred with Eu-M(x) complexes. The formation of the gel layer during the dissolution process, as consequence of Eu-M(x) C(y) matrices hydration, was influenced by C amount and dissolution media. Copyright © 2011 Wiley-Liss, Inc.

  16. Radiochemical study of Re/W adsorption behavior on a strongly basic anion exchange resin

    Energy Technology Data Exchange (ETDEWEB)

    Gott, Matthew D. [Los Alamos National Laboratory, Los Alamos, NM (United States). Chemistry Div.; Missouri Univ., Columbia, MO (United States). Dept. of Chemistry; Ballard, Beau D.; Redman, Lindsay N. [Los Alamos National Laboratory, Los Alamos, NM (United States). Chemistry Div.; and others

    2014-07-01

    Rhenium-186g is a radionuclide with a high potential for therapeutic applications. It emits therapeutic β{sup -} particles accompanied by low energy γ-rays, which allows for in-vivo tracking of the radiolabeled compound and dosimetry estimates. The current reactor production pathway {sup 185}Re(n,γ){sup 186g}Re produces low specific activity {sup 186g}Re, thereby limiting its therapeutic application. Work is underway to develop an accelerator-based, charged particle induced production method for high specific activity {sup 186g}Re from targets of enriched {sup 186}W. To optimize the chemical {sup 186g}Re recovery method, batch studies have been performed to characterize the adsorption behavior of Re and W on a strongly basic anion exchange resin. An in-depth physicochemical profile was developed for the interaction of Re with resin material, which showed the reaction to be endothermic and spontaneous. Basic (NaOH) and acidic (HNO{sub 3}) matrices were used to determine the equilibrium distribution coefficients for Re and W. The resin exhibits the best affinity for Re at slightly basic conditions and little affinity above moderately acidic concentrations. Tungsten has low affinity for the resin above moderately basic concentrations. A study was performed to examine the effect of W concentration on Re adsorption, which showed that even a high ionic WO{sub 4}{sup 2-} strength of up to 1.9 mol kg{sup -1} does not significantly compromise ReO{sub 4}{sup -} retention on the resin. (orig.)

  17. (Di­methyl­phosphor­yl)methanaminium hydrogen oxalate–oxalic acid (2/1)

    OpenAIRE

    Bialek, Sebastian; Clemens, Rebecca; Reiss, Guido J.

    2014-01-01

    The reaction of (di­methyl­phosphor­yl)methanamine (dpma) with oxalic acid in ethanol yielded the title solvated salt, C3H11NOP+·C2HO4 −·0.5C2H2O4. Its asymmetric unit consists of one dpmaH+ cation, one hydrogen oxalate anion and a half-mol­ecule of oxalic acid located around a twofold rotation axis. The H atom of the hydrogen oxalate anion is statistically disordered over two positions that are trans to each other. The hydrogen oxalate monoanion is not planar (bend angle ∼16°) whereas the ox...

  18. Affinity Crystallography: A New Approach to Extracting High-Affinity Enzyme Inhibitors from Natural Extracts.

    Science.gov (United States)

    Aguda, Adeleke H; Lavallee, Vincent; Cheng, Ping; Bott, Tina M; Meimetis, Labros G; Law, Simon; Nguyen, Nham T; Williams, David E; Kaleta, Jadwiga; Villanueva, Ivan; Davies, Julian; Andersen, Raymond J; Brayer, Gary D; Brömme, Dieter

    2016-08-26

    Natural products are an important source of novel drug scaffolds. The highly variable and unpredictable timelines associated with isolating novel compounds and elucidating their structures have led to the demise of exploring natural product extract libraries in drug discovery programs. Here we introduce affinity crystallography as a new methodology that significantly shortens the time of the hit to active structure cycle in bioactive natural product discovery research. This affinity crystallography approach is illustrated by using semipure fractions of an actinomycetes culture extract to isolate and identify a cathepsin K inhibitor and to compare the outcome with the traditional assay-guided purification/structural analysis approach. The traditional approach resulted in the identification of the known inhibitor antipain (1) and its new but lower potency dehydration product 2, while the affinity crystallography approach led to the identification of a new high-affinity inhibitor named lichostatinal (3). The structure and potency of lichostatinal (3) was verified by total synthesis and kinetic characterization. To the best of our knowledge, this is the first example of isolating and characterizing a potent enzyme inhibitor from a partially purified crude natural product extract using a protein crystallographic approach.

  19. High blood oxygen affinity in the air-breathing swamp eel Monopterus albus.

    Science.gov (United States)

    Damsgaard, Christian; Findorf, Inge; Helbo, Signe; Kocagoz, Yigit; Buchanan, Rasmus; Huong, Do Thi Thanh; Weber, Roy E; Fago, Angela; Bayley, Mark; Wang, Tobias

    2014-12-01

    The Asian swamp eel (Monopterus albus, Zuiew 1793) is a facultative air-breathing fish with reduced gills. Previous studies have shown that gas exchange seems to occur across the epithelium of the buccopharyngeal cavity, the esophagus and the integument, resulting in substantial diffusion limitations that must be compensated by adaptations in others steps of the O₂ transport system to secure adequate O₂ delivery to the respiring tissues. We therefore investigated O₂ binding properties of whole blood, stripped hemoglobin (Hb), two major isoHb components and the myoglobin (Mb) from M. albus. Whole blood was sampled using indwelling catheters for blood gas analysis and determination of O₂ equilibrium curves. Hb was purified to assess the effects of endogenous allosteric effectors, and Mb was isolated from heart and skeletal muscle to determine its O₂ binding properties. The blood of M. albus has a high O₂ carrying capacity [hematocrit (Hct) of 42.4±4.5%] and binds O₂ with an unusually high affinity (P₅₀=2.8±0.4mmHg at 27°C and pH7.7), correlating with insensitivity of the Hb to the anionic allosteric effectors that normally decrease Hb-O₂ affinity. In addition, Mb is present at high concentrations in both heart and muscle (5.16±0.99 and 1.08±0.19mg ∙ g wet tissue⁻¹, respectively). We suggest that the high Hct and high blood O₂ affinity serve to overcome the low diffusion capacity in the relatively inefficient respiratory surfaces, while high Hct and Mb concentration aid in increasing the O₂ flux from the blood to the muscles. Copyright © 2014 Elsevier Inc. All rights reserved.

  20. Whole-genome methylation caller designed for methyl- DNA ...

    African Journals Online (AJOL)

    etchie

    2013-02-20

    Feb 20, 2013 ... Key words: Methyl-DNA immunoprecipitation, next-generation sequencing, Hidden ... its response to environmental cues. .... have a great potential to become the most cost-effective ... hg18 reference genome (set to 0 if not present in retrieved reads). ..... DNA methylation patterns and epigenetic memory.

  1. FCGR2A Promoter Methylation and Risks for Intravenous Immunoglobulin Treatment Responses in Kawasaki Disease

    Directory of Open Access Journals (Sweden)

    Ho-Chang Kuo

    2015-01-01

    Full Text Available Kawasaki disease (KD is characterized by pediatric systemic vasculitis of an unknown cause. The low affinity immunoglobulin gamma Fc region receptor II-a (FCGR2A gene was reported to be involved in the susceptibility of KD. DNA methylation is one of the epigenetic mechanisms that control gene expression; thus, we hypothesized that methylation status of CpG islands in FCGR2A promoter associates with the susceptibility and therapeutic outcomes of Kawasaki disease. In this study, 36 KD patients and 24 healthy subjects from out-patient clinic were recruited. Eleven potential methylation sites within the targeted promoter region of FCGR2A were selected for investigation. We marked the eleven methylation sites from A to K. Our results indicated that methylation at the CpG sites G, H, and J associated with the risk of KD. CpG sites B, C, E, F, H, J, and K were found to associate with the outcomes of IVIG treatment. In addition, CpG sites G, J, and K were predicted as transcription factors binding sites for NF-kB, Myc-Max, and SP2, respectively. Our study reported a significant association among the promoter methylation of FCGR2A, susceptibility of KD, and the therapeutic outcomes of IVIG treatment. The methylation levels of CpG sites of FCGR2A gene promoter should be an important marker for optimizing IVIG therapy.

  2. Detailed Assessment of the Kinetics of Hg-Cell Association, Hg Methylation, and Methylmercury Degradation in Several Desulfovibrio Species

    Science.gov (United States)

    Graham, Andrew M.; Bullock, Allyson L.; Maizel, Andrew C.; Elias, Dwayne A.

    2012-01-01

    The kinetics of inorganic Hg [Hg(II)i] association, methylation, and methylmercury (MeHg) demethylation were examined for a group of Desulfovibrio species with and without MeHg production capability. We employed a detailed method for assessing MeHg production in cultures, including careful control of medium chemistry, cell density, and growth phase, plus mass balance of Hg(II)i and MeHg during the assays. We tested the hypothesis that differences in Hg(II)i sorption and/or uptake rates drive observed differences in methylation rates among Desulfovibrio species. Hg(II)i associated rapidly and with high affinity to both methylating and nonmethylating species. MeHg production by Hg-methylating strains was rapid, plateauing after ∼3 h. All MeHg produced was rapidly exported. We also tested the idea that all Desulfovibrio species are capable of Hg(II)i methylation but that rapid demethylation masks its production, but we found this was not the case. Therefore, the underlying reason why MeHg production capability is not universal in the Desulfovibrio is not differences in Hg affinity for cells nor differences in the ability of strains to degrade MeHg. However, Hg methylation rates varied substantially between Hg-methylating Desulfovibrio species even in these controlled experiments and after normalization to cell density. Thus, biological differences may drive cross-species differences in Hg methylation rates. As part of this study, we identified four new Hg methylators (Desulfovibrio aespoeensis, D. alkalitolerans, D. psychrotolerans, and D. sulfodismutans) and four nonmethylating species (Desulfovibrio alcoholivorans, D. tunisiensis, D. carbinoliphilus, and D. piger) in our ongoing effort to generate a library of strains for Hg methylation genomics. PMID:22885751

  3. Synthesis of no-carrier-added alpha-[11C]methyl-L-tryptophan

    International Nuclear Information System (INIS)

    Chaly, T.; Diksic, M.

    1988-01-01

    Described here is a synthesis of no-carrier-added alpha-[ 11 C]methyl-L-tryptophan based on alkylation with 11 CH 3 I of an anion generated by reacting the Schiff base of L-tryptophan methyl ester with di-isopropylamine. The synthesis requires approximately 30 min after the end of 11 CO 2 collection and gives alpha-[ 11 C]methyl-L-tryptophan in a 20-25% radiochemical yield calculated at the end of the synthesis and without correction for radioactive decay. The specific activity of the final radiopharmaceutical, measured at the end of the synthesis, was around 2000 Ci/mmol. Data confirming the stereospecificity of the synthesis are also presented

  4. Fixing of metallic acetates on an anion-exchange resin; Fixation d'acetates metalliques dans une resine echangeuse d'anions

    Energy Technology Data Exchange (ETDEWEB)

    Brigaudeau-Vaissiere, M [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etude Nucleaires

    1966-06-01

    After giving a brief review of the theoretical principles governing the fixation of anionic complexes of metallic elements on an anion exchange resin, we consider the particular case of uranyl acetate. By plotting the partition curves we have been able to calculate the exchange constants in the resin. By studying the changes in the logarithm of the limiting partition coefficient as a function of the logarithm of the free acetate ion concentration, it has been possible to calculate the dissociation constants for the complexes in solution. The fixation of a large number of metallic acetates has been studied. All the tests have been negative except in the case of mercury. For this reason we have been able to consider the possibility of separating uranium from a certain number of elements. Some of these separations are possible even in the presence of interfering anions such as chlorides which have a greater affinity for the resin than have the acetate ions. In the case of water-ethanol and water-isopropanol mixtures, we have improved the conditions under which copper acetate and mercury acetate may be fixed. This study has enabled us to calculate the dissociation constant for the CuAc{sub 3}{sup -} complex in the mixtures water +40% (by weight) isopropanol and water +50% (by weight) isopropanol. It should also make it possible to use separation conditions which could not hitherto be applied in aqueous media. (author) [French] Apres avoir rappele les principes theoriques de la fixation des complexes anioniques des elements metalliques dans une resine echangeuse d'anions, nous avons etudie tout particulierement le cas de l'acetate d'uranyle. Le trace des courbes de partage nous a permis de calculer les constantes d'echange dans la resine. L'etude des variations du logarithme du coefficient limite de partage avec le logarithme de la concentration des ions acetate libres nous a conduits aux calculs des constantes de dissociation des complexes en solution. La fixation d

  5. Data Stream Clustering With Affinity Propagation

    KAUST Repository

    Zhang, Xiangliang; Furtlehner, Cyril; Germain-Renaud, Cecile; Sebag, Michele

    2014-01-01

    Data stream clustering provides insights into the underlying patterns of data flows. This paper focuses on selecting the best representatives from clusters of streaming data. There are two main challenges: how to cluster with the best representatives and how to handle the evolving patterns that are important characteristics of streaming data with dynamic distributions. We employ the Affinity Propagation (AP) algorithm presented in 2007 by Frey and Dueck for the first challenge, as it offers good guarantees of clustering optimality for selecting exemplars. The second challenging problem is solved by change detection. The presented StrAP algorithm combines AP with a statistical change point detection test; the clustering model is rebuilt whenever the test detects a change in the underlying data distribution. Besides the validation on two benchmark data sets, the presented algorithm is validated on a real-world application, monitoring the data flow of jobs submitted to the EGEE grid.

  6. Data Stream Clustering With Affinity Propagation

    KAUST Repository

    Zhang, Xiangliang

    2014-07-09

    Data stream clustering provides insights into the underlying patterns of data flows. This paper focuses on selecting the best representatives from clusters of streaming data. There are two main challenges: how to cluster with the best representatives and how to handle the evolving patterns that are important characteristics of streaming data with dynamic distributions. We employ the Affinity Propagation (AP) algorithm presented in 2007 by Frey and Dueck for the first challenge, as it offers good guarantees of clustering optimality for selecting exemplars. The second challenging problem is solved by change detection. The presented StrAP algorithm combines AP with a statistical change point detection test; the clustering model is rebuilt whenever the test detects a change in the underlying data distribution. Besides the validation on two benchmark data sets, the presented algorithm is validated on a real-world application, monitoring the data flow of jobs submitted to the EGEE grid.

  7. Self-affinity and nonextensivity of sunspots

    International Nuclear Information System (INIS)

    Moret, M.A.

    2014-01-01

    In this paper we study the time series of sunspots by using two different approaches, analyzing its self-affine behavior and studying its distribution. The long-range correlation exponent α has been calculated via Detrended Fluctuation Analysis and the power law vanishes to values greater than 11 years. On the other hand, the distribution of the sunspots obeys a q-exponential decay that suggests a non-extensive behavior. This observed characteristic seems to take an alternative interpretation of the sunspots dynamics. The present findings suggest us to propose a dynamic model of sunspots formation based on a nonlinear Fokker–Planck equation. Therefore its dynamic process follows the generalized thermostatistical formalism.

  8. Contrasting Effects of Dissolved Organic Matter on Mercury Methylation by Geobacter sulfurreducens PCA and Desulfovibrio desulfuricans ND132.

    Science.gov (United States)

    Zhao, Linduo; Chen, Hongmei; Lu, Xia; Lin, Hui; Christensen, Geoff A; Pierce, Eric M; Gu, Baohua

    2017-09-19

    Natural dissolved organic matter (DOM) affects mercury (Hg) redox reactions and anaerobic microbial methylation in the environment. Several studies have shown that DOM can enhance Hg methylation, especially under sulfidic conditions, whereas others show that DOM inhibits Hg methylation due to strong Hg-DOM complexation. In this study, we investigated and compared the effects of DOM on Hg methylation by an iron-reducing bacterium Geobacter sulfurreducens PCA and a sulfate-reducing bacterium Desulfovibrio desulfuricans ND132 under nonsulfidic conditions. The methylation experiment was performed with washed cells either in the absence or presence of DOM or glutathione, both of which form strong complexes with Hg via thiol-functional groups. DOM was found to greatly inhibit Hg methylation by G. Sulfurreducens PCA but enhance Hg methylation by D. desulfuricans ND132 cells with increasing DOM concentration. These strain-dependent opposing effects of DOM were also observed with glutathione, suggesting that thiols in DOM likely played an essential role in affecting microbial Hg uptake and methylation. Additionally, DOM and glutathione greatly decreased Hg sorption by G. sulfurreducens PCA but showed little effect on D. desulfuricans ND132 cells, demonstrating that ND132 has a higher affinity to sorb or take up Hg than the PCA strain. These observations indicate that DOM effects on Hg methylation are bacterial strain specific, depend on the DOM:Hg ratio or site-specific conditions, and may thus offer new insights into the role of DOM in methylmercury production in the environment.

  9. Thermal Aging of Anions in Ionic Liquids containing Lithium Salts by IC/ESI-MS

    International Nuclear Information System (INIS)

    Pyschik, Marcelina; Kraft, Vadim; Passerini, Stefano; Winter, Martin; Nowak, Sascha

    2014-01-01

    Highlights: • Thermal aging investigation of TFSI- and FSI- based ionic liquids and their mixtures with Li salts. • PYR 13 FSI shows thermal decomposition when mixed with LiPF 6 and LiClO 4 . • PYR 13 TFSI does not show any decomposition products with the electrolyte salts. • LiPF 6 dissolved in ionic liquids suffers of thermal aging as in conventional Li-ion battery electrolytes. - Abstract: The stability of 1-methyl-1-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR 13 TFSI) and 1-methyl-1-propylpyrrolidinium bis(fluorosulfonyl)imide (PYR 13 FSI) ionic liquids at elevated temperatures (60 °C) is investigated by ion chromatography. Additionally, the influence of the electrolyte salts, lithium hexafluorophosphate (LiPF 6 ), lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and lithium perchlorate (LiClO 4 ), on the decomposition of both the ionic liquids was analysed over a long term stability study. It has been found out that TFSI has a much higher thermal stability than FSI. The addition of LiTFSI did not show any effect on the aging of both ionic liquid anions. However, PYR 13 FSI degraded when mixed with the electrolyte salts LiPF 6 and LiClO 4 , while PYR 13 TFSI did not. Finally, LiPF 6 forms the same hydrolysis products in the investigated ionic liquids as in the commonly used electrolytes based on organic solvents in lithium-ion batteries

  10. Synthesis and Properties of Anion Exchangers Derived from Chloromethyl Styrene Co divinylbenzene and Their Use in Water Treatment

    International Nuclear Information System (INIS)

    Ezzeldin, H.A.; Apblett, A.; Foutch, G.L.

    2010-01-01

    Amination of vinylbenzyl chloride-divinylbenzene (VBC-DVB) copolymers is an effective method for preparation of ion-exchange resins. Conventionally, the starting polymer is produced by chloromethylation of a styrene-divinylbenzene copolymer that utilizes chloromethyl methyl ether, a known carcinogen. An alterative approach is to co polymerize vinylbenzyl chloride with divinylbenzene to generate the necessary Vb-Dvb. This method provides precise control over the density of the ion-exchange groups. The regiochemistry of the vinylbenzyl chloride methods was realized using solvent-ion exchange groups. In this investigation, an improved solvent system was found for the preparation of anion exchange resins by the vinylbenzyl chloride route. The effectiveness of amination of the intermediate VBC-DVB polymers with a variety of trimethylamine reagents was investigated, and ethanolic trimethylamine produced the highest degree of amination. These resulting ion-exchange polymers were characterized by a variety of techniques such as analytical titrations, nitrogen analysis, Fourier transform infrared spectroscopy and thermal gravimetric analysis. Testing of these copolymers for breakthrough was performed. The results indicate that these anion exchangers have a meaningful increase in thermal stability over commercial anionic exchange beads

  11. Synthesis and Properties of Anion Exchangers Derived from Chloromethyl Styrene Codivinylbenzene and Their Use in Water Treatment

    Directory of Open Access Journals (Sweden)

    Hesham A. Ezzeldin

    2010-01-01

    Full Text Available Amination of vinylbenzyl chloride-divinylbenzene (VBC-DVB copolymers is an effective method for preparation of ion-exchange resins. Conventionally, the starting polymer is produced by chloromethylation of a styrene-divinylbenzene copolymer that utilizes chloromethyl methyl ether, a known carcinogen. An alterative approach is to copolymerize vinylbenzyl chloride with divinylbenzene to generate the necessary VBC-DVB. This method provides precise control over the density of the ion-exchange groups. The regiochemistry of the vinylbenzyl chloride methods was realized using solvent-ion exchange groups. In this investigation, an improved solvent system was found for the preparation of anion exchange resins by the vinylbenzyl chloride route. The effectiveness of amination of the intermediate VBC-DVB polymers with a variety of trimethylamine reagents was investigated, and ethanolic trimethylamine produced the highest degree of amination. These resulting ion-exchange polymers were characterized by a variety of techniques such as analytical titrations, nitrogen analysis, Fourier transform infrared spectroscopy and thermal gravimetric analysis. Testing of these copolymers for breakthrough was performed. The results indicate that these anion exchangers have a meaningful increase in thermal stability over commercial anionic exchange beads.

  12. DNA methylation in metabolic disorders

    DEFF Research Database (Denmark)

    Barres, Romain; Zierath, Juleen R

    2011-01-01

    DNA methylation is a major epigenetic modification that controls gene expression in physiologic and pathologic states. Metabolic diseases such as diabetes and obesity are associated with profound alterations in gene expression that are caused by genetic and environmental factors. Recent reports...... have provided evidence that environmental factors at all ages could modify DNA methylation in somatic tissues, which suggests that DNA methylation is a more dynamic process than previously appreciated. Because of the importance of lifestyle factors in metabolic disorders, DNA methylation provides...... a mechanism by which environmental factors, including diet and exercise, can modify genetic predisposition to disease. This article considers the current evidence that defines a role for DNA methylation in metabolic disorders....

  13. Simultaneous determination of inorganic and organic anions by ion chromatography

    International Nuclear Information System (INIS)

    Park, Yang Soon; Joe, Ki Soo; Han, Sun Ho; Park, Soon Dal; Choi, Kwang Soon

    1999-06-01

    Four methods were investigated for the simultaneous determination of several inorganic and organic anions in aqueous solution by ion chromatography. The first is two columns coupled system. The second is the gradient elution system with an anion exchange column. The third is the system with a mixed-mode stationary phase. The fourth is the system with an anion exchange column and the eluant of low conductivity without ion suppressor. The advantages and disadvantages of individual systems were discussed. The suitable methods were proposed for the application to the samples of the nuclear power industry and the environment. (author)

  14. Unusual structures of MgF5- superhalogen anion

    Science.gov (United States)

    Anusiewicz, Iwona; Skurski, Piotr

    2007-05-01

    The vertical electron detachment energies (VDE) of three MgF5- anions were calculated at the outer valence Green function level with the 6-311 + G(3df) basis sets. This species was found to form unusual geometrical structures each of which corresponds to an anionic state exhibiting superhalogen nature. The global minimum structure was described as a system in which two central magnesium atoms are linked via symmetrical triangle formed by three fluorine atoms. Extremely large electron binding energies of these anions (exceeding 8.5 eV in all cases) were predicted and discussed.

  15. Detection of anion-linked polymerization of the tetrameric hemoglobin from Scapharca inaequivalvis by 35Cl NMR spectroscopy

    International Nuclear Information System (INIS)

    Chiancone, E.; Univ. 'La Sapienza', Rome; Drakenberg, T.; Forsen, S.

    1988-01-01

    Ion binding to the hemoglobin components of Scaphara inaequivalvis has been measured directly in quadrupole relaxation experiments of 23 Na and 35 Cl. The dimeric and tetrameric hemoglobins interact weakly with sodium ions, but differ in their interaction with chloride ions. The dimeric hemoglobin binds chloride ions with low affinity, whereas the tetrameric protein has high affinity chloride binding sites. Binding of chloride ions to these high affinity sites brings about an oxygen-linked polymerization which manifests itself in an unusual dependence of the 35 Cl excess linewidth on the concentration of the anion. Polymerization is more pronounced in the deoxygenated than in the oxygenated derivative: in the former, it has been observed previously in sedimentation velocity experiments. The sensitivity of the 35 Cl excess linewidth on polymer formation indicates that the residence time of the transiently bound chloride on the tetrameric hemoglobin is not shorter than the correlation time of the molecule (2 X 10 -8 s -1 ). 17 refs.; 2 figs

  16. Multiprocessor Real-Time Scheduling with Hierarchical Processor Affinities

    OpenAIRE

    Bonifaci , Vincenzo; Brandenburg , Björn; D'Angelo , Gianlorenzo; Marchetti-Spaccamela , Alberto

    2016-01-01

    International audience; Many multiprocessor real-time operating systems offer the possibility to restrict the migrations of any task to a specified subset of processors by setting affinity masks. A notion of " strong arbitrary processor affinity scheduling " (strong APA scheduling) has been proposed; this notion avoids schedulability losses due to overly simple implementations of processor affinities. Due to potential overheads, strong APA has not been implemented so far in a real-time operat...

  17. In vitro evaluation of N-methyl amide tripeptidomimetics as substrates for the human intestinal di-/tri-peptide transporter hPEPT1

    DEFF Research Database (Denmark)

    Andersen, Rikke; Nielsen, Carsten Uhd; Begtrup, Mikael

    2006-01-01

    application of N-methyl amide bioisosteres as peptide bond replacements in tripeptides in order to decrease degradation by peptidases and yet retain affinity for and transport via hPEPT1. Seven structurally diverse N-methyl amide tripeptidomimetics were selected based on a principal component analysis...... of structural properties of 6859 N-methyl amide tripeptidomimetics. In vitro extracellular degradation of the selected tripeptidomimetics as well as affinity for and transepithelial transport via hPEPT1 were investigated in Caco-2 cells. Decreased apparent degradation was observed for all tripeptidomimetics...... to be substrates for hPEPT1 than tripeptidomimetics with charged side chains. The results of the present study indicate that the N-methyl amide peptide bond replacement approach for increasing bioavailability of tripeptidomimetic drug candidates is not generally applicable to all tripeptides. Nevertheless...

  18. Hydride, hydrogen, proton, and electron affinities of imines and their reaction intermediates in acetonitrile and construction of thermodynamic characteristic graphs (TCGs) of imines as a "molecule ID card".

    Science.gov (United States)

    Zhu, Xiao-Qing; Liu, Qiao-Yun; Chen, Qiang; Mei, Lian-Rui

    2010-02-05

    A series of 61 imines with various typical structures were synthesized, and the thermodynamic affinities (defined as enthalpy changes or redox potentials in this work) of the imines to abstract hydride anions, hydrogen atoms, and electrons, the thermodynamic affinities of the radical anions of the imines to abstract hydrogen atoms and protons, and the thermodynamic affinities of the hydrogen adducts of the imines to abstract electrons in acetonitrile were determined by using titration calorimetry and electrochemical methods. The pure heterolytic and homolytic dissociation energies of the C=N pi-bond in the imines were estimated. The polarity of the C=N double bond in the imines was examined using a linear free-energy relationship. The idea of a thermodynamic characteristic graph (TCG) of imines as an efficient "Molecule ID Card" was introduced. The TCG can be used to quantitatively diagnose and predict the characteristic chemical properties of imines and their various reaction intermediates as well as the reduction mechanism of the imines. The information disclosed in this work could not only supply a gap of thermodynamics for the chemistry of imines but also strongly promote the fast development of the applications of imines.

  19. Nitrate Anion Exchange in Pu-238 Aqueous Scrap Recovery Operations

    International Nuclear Information System (INIS)

    Pansoy-Hjelvik, M.E.; Silver, G.L.; Reimus, M.A.H.; Ramsey, K.B.

    1999-01-01

    Strong base, nitrate anion exchange (IX) is crucial to the purification of 238 Pu solution feedstocks with gross levels of impurities. This paper discusses the work involved in bench scale experiments to optimize the nitrate anion exchange process. In particular, results are presented of experiments conducted to (a) demonstrate that high levels of impurities can be separated from 238 Pu solutions via nitrate anion exchange and, (b) work out chemical pretreatment methodology to adjust and maintain 238 Pu in the IV oxidation state to optimize the Pu(IV)-hexanitrato anionic complex sorption to Reillex-HPQ resin. Additional experiments performed to determine the best chemical treatment methodology to enhance recovery of sorbed Pu from the resin, and VIS-NIR absorption studies to determine the steady state equilibrium of Pu(IV), Pu(III), and Pu(VI) in nitric acid are discussed

  20. Dehydroabiethylamine acetate as metal-containing anion precipitant

    International Nuclear Information System (INIS)

    Skrylev, L.D.; Borisov, V.A.

    1979-01-01

    The precipitation is studied of vanadate, tungstate-, molybdate- and chromate-ions by dehydroabiethylamine acetate. The degree of precipitation of metal-bearing anions is a function of the anion and of pH of the treated solutions. There exists a predetermined value of pH for each anion, at which the content of metal-bearing anion in the ultra-filtrate is at a minimum. For vanadate-ions, this pH is 5.0; for tungstate-ions, 3.0; for molybdate-ions, 4.0; for chrommate-ions, 8.0. The heats of solution of methavanadate, paratungstate, paramolybdate and dehydroabiethylamine chromate, calculated in accordance with the Vant-Hoff equation, range between 3.5 and 8.3 kJ/mole; free energy varies between 45.8 and 137.5 kJ/mole; and entropy varies between 110 and 371 J/degree mole

  1. Electronic spectra of anions intercalated in layered double hydroxides

    Indian Academy of Sciences (India)

    groups of the layers and interlayer water through the termi- nal atom symmetry ... results in a reaction with the metal hydroxide layers lead- ing to the ..... List of band positions observed for potassium salts of anion and LDH samples. Salts.

  2. Two independent anion transport systems in rabbit mandibular salivary glands

    DEFF Research Database (Denmark)

    Novak, I; Young, J A

    1986-01-01

    Cholinergically stimulated Cl and HCO3 transport in perfused rabbit mandibular glands has been studied with extracellular anion substitution and administration of transport inhibitors. In glands perfused with HCO3-free solutions, replacement of Cl with other anions supported secretion in the foll......Cholinergically stimulated Cl and HCO3 transport in perfused rabbit mandibular glands has been studied with extracellular anion substitution and administration of transport inhibitors. In glands perfused with HCO3-free solutions, replacement of Cl with other anions supported secretion...... stimulated secretion by about 30%, but when infused in addition to furosemide (0.1 mmol/l), it inhibited by about 20%. Amiloride (1.0 mmol/l) caused no inhibition. The results suggest that there are at least three distinct carriers in the rabbit mandibular gland. One is a furosemide-sensitive Na-coupled Cl...

  3. Mechanism of protection of adenosine from sulphate radical anion ...

    Indian Academy of Sciences (India)

    Unknown

    Keywords. Repair by caffeic acid; repair of adenosine radicals; oxidation by sulphate radical anions. ... known that hydroxycinnamic acids are natural anti- oxidants ... acid. 2. Experimental ..... ously and independently under kinetic conditions at.

  4. New anion-exchange polymers for improved separations

    International Nuclear Information System (INIS)

    Jarvinen, G.D.; Barr, M.E.; Marsh, S.F.

    1997-01-01

    Objective is to improve the understanding of how the structure of a new class of anion-exchange polymers controls the binding of anionic actinide complexes from solution. This is needed to develop practical separation systems that will reduce the cost of actinide processing operations within the DOE complex. In addition anion exchange is widely used in industry. Several new series of bifunctional anion- exchange polymers have been designed, synthesized, and tested for removing Pu(IV), Am(III), and U(VI) from nitric acid. The polymers contain a pyridinium site derived from the host poly(4-vinylpyridine) and a second cationic site attached through a chain of 2 to 6 methylene groups. The new polymers removed Pu four to ten times more efficiently than the best commercial materials

  5. Intestinal transporters for endogenic and pharmaceutical organic anions

    DEFF Research Database (Denmark)

    Grandvuinet, Anne Sophie; Vestergaard, Henrik Tang; Rapin, Nicolas

    2012-01-01

    This review provides an overview of intestinal human transporters for organic anions and stresses the need for standardization of the various in-vitro methods presently employed in drug-drug interaction (DDI) investigations....

  6. Expanding frontiers in materials chemistry and physics with multiple anions.

    Science.gov (United States)

    Kageyama, Hiroshi; Hayashi, Katsuro; Maeda, Kazuhiko; Attfield, J Paul; Hiroi, Zenji; Rondinelli, James M; Poeppelmeier, Kenneth R

    2018-02-22

    During the last century, inorganic oxide compounds laid foundations for materials synthesis, characterization, and technology translation by adding new functions into devices previously dominated by main-group element semiconductor compounds. Today, compounds with multiple anions beyond the single-oxide ion, such as oxyhalides and oxyhydrides, offer a new materials platform from which superior functionality may arise. Here we review the recent progress, status, and future prospects and challenges facing the development and deployment of mixed-anion compounds, focusing mainly on oxide-derived materials. We devote attention to the crucial roles that multiple anions play during synthesis, characterization, and in the physical properties of these materials. We discuss the opportunities enabled by recent advances in synthetic approaches for design of both local and overall structure, state-of-the-art characterization techniques to distinguish unique structural and chemical states, and chemical/physical properties emerging from the synergy of multiple anions for catalysis, energy conversion, and electronic materials.

  7. Adsorption and desorption dynamics of citric acid anions in soil

    KAUST Repository

    Oburger, E.; Leitner, D.; Jones, D. L.; Zygalakis, K. C.; Schnepf, A.; Roose, T.

    2011-01-01

    The functional role of organic acid anions in soil has been intensively investigated, with special focus on (i) microbial respiration and soil carbon dynamics, (ii) nutrient solubilization or (iii) metal detoxification and reduction of plant metal

  8. Synthesis and anion binding properties of porphyrins and related compounds

    KAUST Repository

    Figueira, Flá vio; Rodrigues, Joã o M M; Farinha, Andreia; Cavaleiro, José A S; Tomé , Joã o P C

    2016-01-01

    promising. In this review, we summarize the most recent developments in anion binding studies while outlining the strategies that may be used to synthesize and functionalize these type of macrocycles. © 2016 World Scientific Publishing Company.

  9. Changing certain dietary cationic and anionic minerals: Impact on ...

    African Journals Online (AJOL)

    Changing certain dietary cationic and anionic minerals: Impact on blood chemistry, milk ... Increased blood pH and serum HCO3 were noticed in buffaloes fed with LC ... Serum calcium and chloride increased with decreased DCAD level while ...

  10. Ion-exchange concentration of inorganic anions from aqueous solution

    Directory of Open Access Journals (Sweden)

    L. P. Bondareva

    2016-01-01

    Full Text Available Monitoring of natural waters in the present time - consuming process, the accuracy of which is influenced by many factors: the composition of water, the presence of impurities and "interfering" components. The water sample preparation process includes the step of concentration and separation of ions determined. The most versatile, efficient, and frequently used method is the concentration of inorganic anions from aqueous solutions by ion exchanger, which can optimize the composition of water to the optimal for identification and quantitative determination of anions. The characteristics of sorption chloride, nitrate and sulfate ions of basic anion exchange resin AВ-17 and Purolite A430 were compared in the article. The constants of protolysis of ion exchangers both AB 17 and Purolite A430 are the same and equal 0.037 ± 0,002. The value of total capacity (POE Purolite A430 was 4.3 mmol/g, AB 17 – 3.4 mmol/g. The studied ion exchangers have the same type of ionic groups – quaternary ammonium, but their number and denotes differ. The number of quaternary ammonium groups is higher in Purolite A430, respectively the number of absorbed anions of these ion exchanger is higher. The values of dynamic exchange capacity (DOE of ion exchanger Purolite A430 is higher than these values of AB-17 and equal to 1.48 ± 0.03 mmol / dm3 for chloride ion, 1.50 ± 0.03 mmol / dm3 for nitrate ion, 1.62 ± 0.03 mmol / dm3 for sulfate ion. The values of the POE and DOE of anion-exchange resins Purolite A430 and AV-17 and the characteristics of the individual sorption of chloride, nitrate, sulfate ions showed an advantage of the Purolite for the concentrationing of anions. It is found that times of anions sorption from triple-anion solutions by Purolite A430 are significantly different for different anions, and these times are close for anion-exchanger AV-17. It proves the possibility of quantitative separation and concentration by anion-exchanger Purolite A430.

  11. High affinity radiopharmaceuticals based upon lansoprazole for PET imaging of aggregated tau in Alzheimer's disease and progressive supranuclear palsy: synthesis, preclinical evaluation, and lead selection.

    Science.gov (United States)

    Fawaz, Maria V; Brooks, Allen F; Rodnick, Melissa E; Carpenter, Garrett M; Shao, Xia; Desmond, Timothy J; Sherman, Phillip; Quesada, Carole A; Hockley, Brian G; Kilbourn, Michael R; Albin, Roger L; Frey, Kirk A; Scott, Peter J H

    2014-08-20

    Abnormally aggregated tau is the hallmark pathology of tauopathy neurodegenerative disorders and is a target for development of both diagnostic tools and therapeutic strategies across the tauopathy disease spectrum. Development of carbon-11- or fluorine-18-labeled radiotracers with appropriate affinity and specificity for tau would allow noninvasive quantification of tau burden using positron emission tomography (PET) imaging. We have synthesized [(18)F]lansoprazole, [(11)C]N-methyl lansoprazole, and [(18)F]N-methyl lansoprazole and identified them as high affinity radiotracers for tau with low to subnanomolar binding affinities. Herein, we report radiosyntheses and extensive preclinical evaluation with the aim of selecting a lead radiotracer for translation into human PET imaging trials. We demonstrate that [(18)F]N-methyl lansoprazole, on account of the favorable half-life of fluorine-18 and its rapid brain entry in nonhuman primates, favorable kinetics, low white matter binding, and selectivity for binding to tau over amyloid, is the lead compound for progression into clinical trials.

  12. High Affinity Radiopharmaceuticals Based Upon Lansoprazole for PET Imaging of Aggregated Tau in Alzheimer’s Disease and Progressive Supranuclear Palsy: Synthesis, Preclinical Evaluation, and Lead Selection

    Science.gov (United States)

    2014-01-01

    Abnormally aggregated tau is the hallmark pathology of tauopathy neurodegenerative disorders and is a target for development of both diagnostic tools and therapeutic strategies across the tauopathy disease spectrum. Development of carbon-11- or fluorine-18-labeled radiotracers with appropriate affinity and specificity for tau would allow noninvasive quantification of tau burden using positron emission tomography (PET) imaging. We have synthesized [18F]lansoprazole, [11C]N-methyl lansoprazole, and [18F]N-methyl lansoprazole and identified them as high affinity radiotracers for tau with low to subnanomolar binding affinities. Herein, we report radiosyntheses and extensive preclinical evaluation with the aim of selecting a lead radiotracer for translation into human PET imaging trials. We demonstrate that [18F]N-methyl lansoprazole, on account of the favorable half-life of fluorine-18 and its rapid brain entry in nonhuman primates, favorable kinetics, low white matter binding, and selectivity for binding to tau over amyloid, is the lead compound for progression into clinical trials. PMID:24896980

  13. (100) faceted anion voids in electron irradiated fluorite

    International Nuclear Information System (INIS)

    Johnson, E.

    1979-01-01

    High fluence electron irradiation of fluorite crystals in the temperature range 150 to 320 K results in formation of a simple cubic anion void superlattice. Above 320 K the damage structure changes to a random distribution of large [001] faceted anion voids. This voidage behaviour, similar to that observed in a range of irradiated metals, is discussed in terms points defect rather than conventional colour centre terminology. (Auth.)

  14. Determination of nitrate by anion exchange with ultraviolet detection

    Energy Technology Data Exchange (ETDEWEB)

    McComas, J.G.

    1976-01-01

    A weak base anion exchange resin is synthesized by surface bonding 3-aminopropyltriethoxysilane to silica gel. This silylated silica gel is used to separate nitrate from interferences. The nitrate is then determined by measuring its absorbance at 220 nm. An interference study was performed and no anions commonly found in potable water interferes. A comparison of this method was made with the brucine method on real samples and satisfactory agreement was obtained between the two methods.

  15. Gas-Grain Models for Interstellar Anion Chemistry

    Science.gov (United States)

    Cordiner, M. A.; Charnely, S. B.

    2012-01-01

    Long-chain hydrocarbon anions C(sub n) H(-) (n = 4, 6, 8) have recently been found to be abundant in a variety of interstellar clouds. In order to explain their large abundances in the denser (prestellar/protostellar) environments, new chemical models are constructed that include gas-grain interactions. Models including accretion of gas-phase species onto dust grains and cosmic-ray-induced desorption of atoms are able to reproduce the observed anion-to-neutral ratios, as well as the absolute abundances of anionic and neutral carbon chains, with a reasonable degree of accuracy. Due to their destructive effects, the depletion of oxygen atoms onto dust results in substantially greater polyyne and anion abundances in high-density gas (with n(sub H2) approx > / cubic cm). The large abundances of carbon-chain-bearing species observed in the envelopes of protostars such as L1527 can thus be explained without the need for warm carbon-chain chemistry. The C6H(-) anion-to-neutral ratio is found to be most sensitive to the atomic O and H abundances and the electron density. Therefore, as a core evolves, falling atomic abundances and rising electron densities are found to result in increasing anion-to-neutral ratios. Inclusion of cosmic-ray desorption of atoms in high-density models delays freeze-out, which results in a more temporally stable anion-to-neutral ratio, in better agreement with observations. Our models include reactions between oxygen atoms and carbon-chain anions to produce carbon-chain-oxide species C6O, C7O, HC6O, and HC7O, the abundances of which depend on the assumed branching ratios for associative electron detachment

  16. Evidence for radical anion formation during liquid secondary ion mass spectrometry analysis of oligonucleotides and synthetic oligomeric analogues: a deconvolution algorithm for molecular ion region clusters.

    Science.gov (United States)

    Laramée, J A; Arbogast, B; Deinzer, M L

    1989-10-01

    It is shown that one-electron reduction is a common process that occurs in negative ion liquid secondary ion mass spectrometry (LSIMS) of oligonucleotides and synthetic oligonucleosides and that this process is in competition with proton loss. Deconvolution of the molecular anion cluster reveals contributions from (M-2H).-, (M-H)-, M.-, and (M + H)-. A model based on these ionic species gives excellent agreement with the experimental data. A correlation between the concentration of species arising via one-electron reduction [M.- and (M + H)-] and the electron affinity of the matrix has been demonstrated. The relative intensity of M.- is mass-dependent; this is rationalized on the basis of base-stacking. Base sequence ion formation is theorized to arise from M.- radical anion among other possible pathways.

  17. Differential pulse voltammetric determination of methyl parathion based on multiwalled carbon nanotubes-poly(acrylamide) nanocomposite film modified electrode

    Energy Technology Data Exchange (ETDEWEB)

    Zeng, Yanbo [Department of Chemistry and Shanghai Key Laboratory of Green Chemistry and Chemical Process, East China Normal University, 3663 Zhongshan Road(N), Shanghai, 200062 (China); College of Biological, Chemical Sciences and Engineering, Jiaxing University, Jiaxing 314001 (China); Yu, Dajun; Yu, Yanyan [Department of Chemistry and Shanghai Key Laboratory of Green Chemistry and Chemical Process, East China Normal University, 3663 Zhongshan Road(N), Shanghai, 200062 (China); Zhou, Tianshu [Department of Environmental Science, East China Normal University, 3663 Zhongshan Road(N), Shanghai, 200062 (China); Shi, Guoyue, E-mail: gyshi@chem.ecnu.edu.cn [Department of Chemistry and Shanghai Key Laboratory of Green Chemistry and Chemical Process, East China Normal University, 3663 Zhongshan Road(N), Shanghai, 200062 (China)

    2012-05-30

    Highlights: Black-Right-Pointing-Pointer A sensitive electrochemical sensor for detecting methyl parathion in environmental samples. Black-Right-Pointing-Pointer The preparation, characterization and application of this novel MWCNTs-PAAM nanocomposite. Black-Right-Pointing-Pointer The MWCNTs-PAAM/GCE exhibited a high adsorption and strong affinity toward methyl parathion. Black-Right-Pointing-Pointer Wide linear range and low detection limit of the proposed method for detecting methyl parathion. - Abstract: A sensitive electrochemical differential pulse voltammetry method was developed for detecting methyl parathion based on multiwalled carbon nanotubes-poly(acrylamide) (MWCNTs-PAAM) nanocomposite film modified glassy carbon electrode. The novel MWCNTs-PAAM nanocomposite, containing high content of amide groups, was synthesized by PAAM polymerizing at the vinyl group functionalized MWCNTs surface using free radical polymerization. The MWCNTs-PAAM nanocomposite was characterized by Fourier transform infrared spectroscopy, thermal gravimetric analysis and scanning electron microscopy. Electrochemical behavior and interference studies of MWCNTs-PAAM/GCE for methyl parathion were investigated. The experimental results demonstrated that the MWCNTs-PAAM/GCE exhibited a high adsorption and strong affinity toward methyl parathion compared with some metal ions and nitroaromatic compounds, which exist in environmental samples. The adsorbed amount of methyl parathion on the MWCNTs-PAAM/GCE approached the equilibrium value upon 5 min adsorption time. A linear calibration curve for methyl parathion was obtained in the concentration range from 5.0 Multiplication-Sign 10{sup -9} to 1.0 Multiplication-Sign 10{sup -5} mol L{sup -1}, with a detection limit of 2.0 Multiplication-Sign 10{sup -9} mol L{sup -1}. The MWCNTs-PAAM/GCE was proved to be a suitable sensing tool for the fast, sensitive and selective determination of methyl parathion in environmental water samples.

  18. Differential pulse voltammetric determination of methyl parathion based on multiwalled carbon nanotubes–poly(acrylamide) nanocomposite film modified electrode

    International Nuclear Information System (INIS)

    Zeng, Yanbo; Yu, Dajun; Yu, Yanyan; Zhou, Tianshu; Shi, Guoyue

    2012-01-01

    Highlights: ► A sensitive electrochemical sensor for detecting methyl parathion in environmental samples. ► The preparation, characterization and application of this novel MWCNTs–PAAM nanocomposite. ► The MWCNTs–PAAM/GCE exhibited a high adsorption and strong affinity toward methyl parathion. ► Wide linear range and low detection limit of the proposed method for detecting methyl parathion. - Abstract: A sensitive electrochemical differential pulse voltammetry method was developed for detecting methyl parathion based on multiwalled carbon nanotubes–poly(acrylamide) (MWCNTs–PAAM) nanocomposite film modified glassy carbon electrode. The novel MWCNTs–PAAM nanocomposite, containing high content of amide groups, was synthesized by PAAM polymerizing at the vinyl group functionalized MWCNTs surface using free radical polymerization. The MWCNTs–PAAM nanocomposite was characterized by Fourier transform infrared spectroscopy, thermal gravimetric analysis and scanning electron microscopy. Electrochemical behavior and interference studies of MWCNTs–PAAM/GCE for methyl parathion were investigated. The experimental results demonstrated that the MWCNTs–PAAM/GCE exhibited a high adsorption and strong affinity toward methyl parathion compared with some metal ions and nitroaromatic compounds, which exist in environmental samples. The adsorbed amount of methyl parathion on the MWCNTs–PAAM/GCE approached the equilibrium value upon 5 min adsorption time. A linear calibration curve for methyl parathion was obtained in the concentration range from 5.0 × 10 −9 to 1.0 × 10 −5 mol L −1 , with a detection limit of 2.0 × 10 −9 mol L −1 . The MWCNTs–PAAM/GCE was proved to be a suitable sensing tool for the fast, sensitive and selective determination of methyl parathion in environmental water samples.

  19. The gecko visual pigment: the anion hypsochromic effect.

    Science.gov (United States)

    Crescitelli, F; Karvaly, B

    1991-01-01

    The 521-pigment in the retina of the Tokay gecko (Gekko gekko) readily responds to particular physical and chemical changes in its environment. When solubilized in chloride deficient state the addition of Class I anions (Cl-, Br-) induces a bathochromic shift of the absorption spectrum. Class II anions (NO3-, IO3-, N3-, OCN-, SCN-, SeCN-, N(CN)2-), which exhibit ambidental properties, cause an hypsochromic shift. Class III anions (F-, I-, NO2-, CN-, AsO3-, SO2(4-), S2O2(3-) have no spectral effect on the 521-pigment. Cations appear to have no influence on the pigment absorption and Class I anions prevent or reverse the hypsochromic shift caused by Class II anions. It is suggested that the spectral displacements reflect specific changes in the opsin conformation, which alter the immediate (dipolar) environment of the retinal chromophore. The protein conformation seems to promote excited-state processes most in the native 521-pigment state and least in the presence of Class II anions. This in turn suggests that the photosensitivity of the 521-pigment is controlled by the excited rather than by the ground-state properties of the pigment.

  20. Methylation-Specific PCR Unraveled

    Directory of Open Access Journals (Sweden)

    Sarah Derks

    2004-01-01

    Full Text Available Methylation‐specific PCR (MSP is a simple, quick and cost‐effective method to analyze the DNA methylation status of virtually any group of CpG sites within a CpG island. The technique comprises two parts: (1 sodium bisulfite conversion of unmethylated cytosine's to uracil under conditions whereby methylated cytosines remains unchanged and (2 detection of the bisulfite induced sequence differences by PCR using specific primer sets for both unmethylated and methylated DNA. This review discusses the critical parameters of MSP and presents an overview of the available MSP variants and the (clinical applications.

  1. Cambrian trilobites with Siberian affinities, southwestern Alaska

    Energy Technology Data Exchange (ETDEWEB)

    Palmer, A.R.; Egbert, R.M.; Sullivan, R.; Knoth, J.S.

    1985-02-01

    Cambrian trilobites occur in two levels (about 7 m apart) in the core of a large, complex anticlinal structure in the area between the Taylor Mountains and the Hoholitna River in southwestern Alaska. The lower collection contains Erbia, Macannaia (a species close to Soviet forms described as Pagetia ferox Lermontova), two species of Kootenia (including one perhaps cospecific with forms from the central Brooks range), and several species of ptychoparioid trilobites. It is clear that biogeographic affinities are with the transitional facies of the eastern Siberian platform and the south Siberian foldbelt. In Soviet terms, the age of the collection falls in a disputed interval called latest Early Cambrian (Tojonian) by some authors, and earliest Middle Cambrian (Amgan) by others. In North American terms, Macannaia is known only from early Middle Cambrian beds. The younger collection contains abundant agnostids, a variety of conocoryphids, Paradoxides, and several species of ptychoparioid trilobites. This is an assemblage of undoubted late Middle Cambrian age, comparable to faunas described from the Maya State of the Siberian platform and the Paradoxides paradoxissimus Stage of the Baltic region. Both faunas are from ocean-facing or outer shelf environments. None of the key non-agnostid or non-pagetiid elements have been seen previously in deposits of Cambrian North America.

  2. Set-Membership Proportionate Affine Projection Algorithms

    Directory of Open Access Journals (Sweden)

    Stefan Werner

    2007-01-01

    Full Text Available Proportionate adaptive filters can improve the convergence speed for the identification of sparse systems as compared to their conventional counterparts. In this paper, the idea of proportionate adaptation is combined with the framework of set-membership filtering (SMF in an attempt to derive novel computationally efficient algorithms. The resulting algorithms attain an attractive faster converge for both situations of sparse and dispersive channels while decreasing the average computational complexity due to the data discerning feature of the SMF approach. In addition, we propose a rule that allows us to automatically adjust the number of past data pairs employed in the update. This leads to a set-membership proportionate affine projection algorithm (SM-PAPA having a variable data-reuse factor allowing a significant reduction in the overall complexity when compared with a fixed data-reuse factor. Reduced-complexity implementations of the proposed algorithms are also considered that reduce the dimensions of the matrix inversions involved in the update. Simulations show good results in terms of reduced number of updates, speed of convergence, and final mean-squared error.

  3. [Separation of osteoclasts by lectin affinity chromatography].

    Science.gov (United States)

    Itokazu, M; Tan, A; Tanaka, S

    1991-09-01

    Newborn rat calvaria bone cells obtained by digestion were fractionated on columns of wheat-germ agglutinin (WGA) sepharose 6MB for osteoclast isolation. The initial nonspecific binding cells which were passed through the WGA sepharose column by a buffer acquired a high enzyme activity of alkaline phosphatase, but not that of acid phosphatase. However, elution of cells using a buffer with the addition of N-acetyl-D-glucosamine resulted in a high acid phosphatase activity but no alkaline phosphatase activity. The former WGA binding negative fraction enriched osteoblasts averaging 30 microns in size. The latter WGA binding positive fraction enriched osteoclasts ranging from 20 microns to 60 microns in size. The electron-microscope clearly demonstrated the cellular details of osteoclasts. Isolated cell counts showed a ratio of six to four. These results indicate that our method of osteoclast isolation is simple and useful in lectin affinity chromatography because all cells have sugar moieties on their surface and the binding of osteoclasts can be reversed by the addition of specific lectin-binding sugars to the eluting buffer.

  4. Affine connection form of Regge calculus

    Science.gov (United States)

    Khatsymovsky, V. M.

    2016-12-01

    Regge action is represented analogously to how the Palatini action for general relativity (GR) as some functional of the metric and a general connection as independent variables represents the Einstein-Hilbert action. The piecewise flat (or simplicial) spacetime of Regge calculus is equipped with some world coordinates and some piecewise affine metric which is completely defined by the set of edge lengths and the world coordinates of the vertices. The conjugate variables are the general nondegenerate matrices on the three-simplices which play the role of a general discrete connection. Our previous result on some representation of the Regge calculus action in terms of the local Euclidean (Minkowsky) frame vectors and orthogonal connection matrices as independent variables is somewhat modified for the considered case of the general linear group GL(4, R) of the connection matrices. As a result, we have some action invariant w.r.t. arbitrary change of coordinates of the vertices (and related GL(4, R) transformations in the four-simplices). Excluding GL(4, R) connection from this action via the equations of motion we have exactly the Regge action for the considered spacetime.

  5. Reduced DNA methylation of FKBP5 in Cushing's syndrome.

    Science.gov (United States)

    Resmini, Eugenia; Santos, Alicia; Aulinas, Anna; Webb, Susan M; Vives-Gilabert, Yolanda; Cox, Olivia; Wand, Gary; Lee, Richard S

    2016-12-01

    FKBP5 encodes a co-chaperone of HSP90 protein that regulates intracellular glucocorticoid receptor sensitivity. When it is bound to the glucocorticoid receptor complex, cortisol binds with lower affinity to glucocorticoid receptor. Cushing's syndrome is associated with memory deficits, smaller hippocampal volumes, and wide range of cognitive impairments. We aimed at evaluating blood DNA methylation of FKBP5 and its relationship with memory and hippocampal volumes in Cushing's syndrome patients. Polymorphism rs1360780 in FKBP5 has also been assessed to determine whether genetic variations can also govern CpG methylation. Thirty-two Cushing's syndrome patients and 32 matched controls underwent memory tests, 3-Tesla MRI of the brain, and DNA extraction from total leukocytes. DNA samples were bisulfite treated, PCR amplified, and pyrosequenced to assess a total of 41CpG-dinucleotides in the introns 1, 2, 5, and 7 of FKBP5. Significantly lower intronic FKBP5 DNA methylation in CS patients compared to controls was observed in ten CpG-dinucleotides. DNA methylation at these CpGs correlated with left and right HV (Intron-2-Region-2-CpG-3: LHV, r = 0.73, p = 0.02; RHV, r = 0.58, p = 0.03). Cured and active CS patients showed both lower methylation of intron 2 (92.37, 91.8, and 93.34 %, respectively, p = 0.03 for both) and of intron 7 (77.08, 73.74, and 79.71 %, respectively, p = 0.02 and p < 0.01) than controls. Twenty-two subjects had the CC genotype, 34 had the TC genotype, and eight had the TT genotype. Lower average DNA methylation in intron 7 was observed in the TT subjects compared to CC (72.5vs. 79.5 %, p = 0.02) and to TC (72.5 vs. 79.0 %, p = 0.03). Our data demonstrate, for the first time, a reduction of intronic DNA methylation of FKBP5 in CS patients.

  6. Theoretical determination of proton affinity differences in zeolites

    NARCIS (Netherlands)

    Kramer, G.J.; Santen, van R.A.

    1993-01-01

    An important factor in zeolite catalysis is the proton affinity, i.e., the energy required to remove a proton from the zeolite lattice. Differences in proton affinity are expected to influence the catalytic activity of acid sites, making the catalytically active sites inhomogeneous (within one

  7. Capillary electrophoresis-based assessment of nanobody affinity and purity

    NARCIS (Netherlands)

    Haselberg, Rob; Oliveira, Sabrina; van der Meel, Roy; Somsen, Govert W; de Jong, Gerhardus J

    2014-01-01

    Drug purity and affinity are essential attributes during development and production of therapeutic proteins. In this work, capillary electrophoresis (CE) was used to determine both the affinity and composition of the biotechnologically produced "nanobody" EGa1, the binding fragment of a

  8. Generalized Warburg impedance on realistic self-affine fractals ...

    Indian Academy of Sciences (India)

    2016-08-26

    Aug 26, 2016 ... We analyse the problem of impedance for a diffusion controlled charge transfer process across an irregular interface. These interfacial irregularities are characterized as two class of random fractals: (i) a statistically isotropic self-affine fractals and (ii) a statistically corrugated self-affine fractals.

  9. Polynomial Primal-Dual Cone Affine Scaling for Semidefinite Programming

    NARCIS (Netherlands)

    A.B. Berkelaar (Arjan); J.F. Sturm; S. Zhang (Shuzhong)

    1996-01-01

    textabstractIn this paper we generalize the primal--dual cone affine scaling algorithm of Sturm and Zhang to semidefinite programming. We show in this paper that the underlying ideas of the cone affine scaling algorithm can be naturely applied to semidefinite programming, resulting in a new

  10. Affine group formulation of the Standard Model coupled to gravity

    Energy Technology Data Exchange (ETDEWEB)

    Chou, Ching-Yi, E-mail: l2897107@mail.ncku.edu.tw [Department of Physics, National Cheng Kung University, Taiwan (China); Ita, Eyo, E-mail: ita@usna.edu [Department of Physics, US Naval Academy, Annapolis, MD (United States); Soo, Chopin, E-mail: cpsoo@mail.ncku.edu.tw [Department of Physics, National Cheng Kung University, Taiwan (China)

    2014-04-15

    In this work we apply the affine group formalism for four dimensional gravity of Lorentzian signature, which is based on Klauder’s affine algebraic program, to the formulation of the Hamiltonian constraint of the interaction of matter and all forces, including gravity with non-vanishing cosmological constant Λ, as an affine Lie algebra. We use the hermitian action of fermions coupled to gravitation and Yang–Mills theory to find the density weight one fermionic super-Hamiltonian constraint. This term, combined with the Yang–Mills and Higgs energy densities, are composed with York’s integrated time functional. The result, when combined with the imaginary part of the Chern–Simons functional Q, forms the affine commutation relation with the volume element V(x). Affine algebraic quantization of gravitation and matter on equal footing implies a fundamental uncertainty relation which is predicated upon a non-vanishing cosmological constant. -- Highlights: •Wheeler–DeWitt equation (WDW) quantized as affine algebra, realizing Klauder’s program. •WDW formulated for interaction of matter and all forces, including gravity, as affine algebra. •WDW features Hermitian generators in spite of fermionic content: Standard Model addressed. •Constructed a family of physical states for the full, coupled theory via affine coherent states. •Fundamental uncertainty relation, predicated on non-vanishing cosmological constant.

  11. Fermionic construction of vertex operators for twisted affine algebras

    International Nuclear Information System (INIS)

    Frappat, L.; Sorba, P.; Sciarrino, A.

    1988-03-01

    We construct vertex operator representations of the twisted affine algebras in terms of fermionic (or parafermionic in some cases) elementary fields. The folding method applied to the extended Dynkin diagrams of the affine algebras allows us to determine explicitly these fermionic fields as vertex operators

  12. Generalized Warburg impedance on realistic self-affine fractals

    Indian Academy of Sciences (India)

    We analyse the problem of impedance for a diffusion controlled charge transfer process across an irregular interface. These interfacial irregularities are characterized as two class of random fractals: (i) a statistically isotropic self-affine fractals and (ii) a statistically corrugated self-affine fractals. The information about the ...

  13. Pseudo-affinity chromatography of rumen microbial cellulase on ...

    African Journals Online (AJOL)

    Pseudo-affinity chromatography of rumen microbial cellulase on Sepharose- Cibacron Blue F3GA. ... African Journal of Biotechnology ... Pseudo affinity adsorption of bioproducts on Sepharose-cibacron blue F3-GA was subjected to rumen microbial enzyme evaluation through batch binding and column chromatography of ...

  14. Self-affine roughness influence on redox reaction charge admittance

    NARCIS (Netherlands)

    Palasantzas, G

    2005-01-01

    In this work we investigate the influence of self-affine electrode roughness on the admittance of redox reactions during facile charge transfer kinetics. The self-affine roughness is characterized by the rms roughness amplitude w, the correlation length xi and the roughness exponent H (0

  15. Affine Toda equations and solutions in the homogeneous grading

    Czech Academy of Sciences Publication Activity Database

    Zuevsky, Alexander

    2018-01-01

    Roč. 542, April 1 (2018), s. 149-161 ISSN 0024-3795 Institutional support: RVO:67985840 Keywords : affine Lie gebras * affine Toda modes * solitons Subject RIV: BA - General Mathematics OBOR OECD: Pure mathematics Impact factor: 0.973, year: 2016 https://www.sciencedirect.com/science/article/pii/S0024379517302100

  16. Online identification of continuous bimodal and trimodal piecewise affine systems

    NARCIS (Netherlands)

    Le, Q.T.; van den Boom, A.J.J.; Baldi, S.; Rantzer, Anders; Bagterp Jørgensen, John; Stoustrup, Jakob

    2016-01-01

    This paper investigates the identification of continuous piecewise affine systems in state space form with jointly unknown partition and subsystem matrices. The partition of the system is generated by the so-called centers. By representing continuous piecewise affine systems in the max-form and

  17. Low-energy electron-induced dissociation in gas-phase nicotine, pyridine, and methyl-pyrrolidine

    Science.gov (United States)

    Ryszka, Michal; Alizadeh, Elahe; Li, Zhou; Ptasińska, Sylwia

    2017-09-01

    Dissociative electron attachment to nicotine, pyridine, and N-methyl-pyrrolidine was studied in the gas phase in order to assess their stability with respect to low-energy electron interactions. Anion yield curves for different products at electron energies ranging from zero to 15 eV were measured, and the molecular fragmentation pathways were proposed. Nicotine does not form a stable parent anion or a dehydrogenated anion, contrary to other biological systems. However, we have observed complex dissociation pathways involving fragmentation at the pyrrolidine side accompanied by isomerization mechanisms. Combining structure optimization and enthalpy calculations, performed with the Gaussian09 package, with the comparison with a deuterium-labeled N-methyl-d3-pyrrolidine allowed for the determination of the fragmentation pathways. In contrast to nicotine and N-methylpyrrolidine, the dominant pathway in dissociative electron attachment to pyridine is the loss of hydrogen, leading to the formation of an [M—H]- anion. The presented results provide important new information about the stability of nicotine and its constituent parts and contribute to a better understanding of the fragmentation mechanisms and their effects on the biological environment.

  18. Duals of Affine Grassmann Codes and Their Relatives

    DEFF Research Database (Denmark)

    Beelen, P.; Ghorpade, S. R.; Hoholdt, T.

    2012-01-01

    Affine Grassmann codes are a variant of generalized Reed-Muller codes and are closely related to Grassmann codes. These codes were introduced in a recent work by Beelen Here, we consider, more generally, affine Grassmann codes of a given level. We explicitly determine the dual of an affine...... Grassmann code of any level and compute its minimum distance. Further, we ameliorate the results by Beelen concerning the automorphism group of affine Grassmann codes. Finally, we prove that affine Grassmann codes and their duals have the property that they are linear codes generated by their minimum......-weight codewords. This provides a clean analogue of a corresponding result for generalized Reed-Muller codes....

  19. Exploring Girls' Science Affinities Through an Informal Science Education Program

    Science.gov (United States)

    Todd, Brandy; Zvoch, Keith

    2017-10-01

    This study examines science interests, efficacy, attitudes, and identity—referred to as affinities, in the context of an informal science outreach program for girls. A mixed methods design was used to explore girls' science affinities before, during, and after participation in a cohort-based summer science camp. Multivariate analysis of survey data revealed that girls' science affinities varied as a function of the joint relationship between family background and number of years in the program, with girls from more affluent families predicted to increase affinities over time and girls from lower income families to experience initial gains in affinities that diminish over time. Qualitative examination of girls' perspectives on gender and science efficacy, attitudes toward science, and elements of science identities revealed a complex interplay of gendered stereotypes of science and girls' personal desires to prove themselves knowledgeable and competent scientists. Implications for the best practice in fostering science engagement and identities in middle school-aged girls are discussed.

  20. DAYA ANTIBAKTERI EKSTRAK ETANOL DAUN SENGGANI (Melastoma affine D. Don

    Directory of Open Access Journals (Sweden)

    Ika Trisharyanti Dian Kusumowati

    2014-08-01

    Full Text Available Melastoma affine D. Don had some activities such as anthelmintic, antibacteria, antiinfiammation, antifungal, and antitumor. The aims of this research was determine antibacteria activity of ethanolic extract of Melastoma affine D. Don. The antimicrobial activity was tested by solid dilution method to get Minimum Inhibition Concentration (MIC. The compounds in Melastoma affine D. Don was analyzed by tube test method and Thin Layer Chromatography (TLC with chloroform : methanol : formic acid (8,5:1,5:0,5 as mobile phase and silica gel GF254 as stationary phase. The result showed ethanolic extract of Melastoma affine D. Don contains alkaloid, polyphenol, fiavonoid, saponin, and essential oil. The MIC of Senggani against Staphylococcus aureus was 2% and 3% against Escherichia coli and the extract could not inhibit Staphylococcus aureus and Escherichia coli multiresistant until concentration 7% extract ethanol. Keywords: Melastoma affine D. Don, Staphylococcus aureus, Escherichia coli

  1. Vibrational Spectroscopy of Cation and Anion Channelrhodopsins

    Science.gov (United States)

    Yi, Adrian S.

    Optogenetics is a technique to control and monitor cell activity with light by expression of specific microbial rhodopsins. Cation channelrhodopsins (CCRs) and anion channelrhodopsins (ACRs) have been demonstrated to activate and silence cell activity, respectively. In this dissertation, the molecular mechanisms of two channelrhodopsins are studied: a CCR from Chlamydomonas augustae (CaChR1) and an ACR from Guillardia theta (GtACR1). The recently discovered GtACR1is especially interesting, as it achieves neural silencing with 1/1000th of the light intensity compared to previous microbial rhodopsin silencing ion pumps. Static and time-resolved resonance Raman, FTIR difference, and UV-visible spectroscopies were utilized in addition to various biochemical and genetic techniques to explore the molecular mechanisms of these channelrhodopsins. In CaChR1, Glu169 and Asp299 residues are located nearby the Schiff base (SB) similar to the homologous residues Asp85 and Asp212, which exist in an ionized state in unphotolyzed bacteriorhodopsin (BR) and play a key role in proton pumping. We observe significant changes in the protonation states of the SB, Glu169, and Asp299 of CaChR1 leading up to the open-channel P2 state, where all three groups exist in a charge neutral state. This unusual charge neutrality along with the position of these groups in the CaChR1 ion channel suggests that charge neutrality plays an important role in cation gating and selectivity in these low efficiency CCRs. Significant differences exist in the photocycle and protonation/hydrogen bonding states of key residues inGtACR1compared to BR and CaChR1. Resonance Raman studies reveal that in the unphotolyzed state of GtACR1, residues Glu68, Ser97 (BR Asp85 homolog), and Asp234 (BR Asp212 homolog) located near the SB exist in charge neutral states. Furthermore, upon K formation, these residues do not change their protonation states. At room temperature, a slow decay of the red-shifted K intermediate is

  2. Naturally occurring methyl salicylate glycosides.

    Science.gov (United States)

    Mao, Ping; Liu, Zizhen; Xie, Meng; Jiang, Rui; Liu, Weirui; Wang, Xiaohong; Meng, Shen; She, Gaimei

    2014-01-01

    As an important part of non steroids anti-inflammation drug (NSAIDs), salicylate has developed from natural substance salicylic acid to natrium salicylicum, to aspirin. Now, methyl salicylate glycoside, a new derivative of salicylic acid, is modified with a -COOH group integrated one methyl radical into formic ether, and a -OH linked with a monosaccharide, a disaccharide or a trisaccharide unit by glycosidic linkage. It has the similar pharmacological activities, anti-inflammatory, analgesic, antipyretic and antithrombotic as the previous salicylates' without resulting in serious side effects, particularly the gastrointestinal toxicity. Owing to the superiority of those significant bioactivities, methyl salicylate glycosides have became a hot research area in NSAIDs for several years. This paper compiles all 9 naturally occurring methyl salicylate glycosides, their distribution of the resource and pharmacological mechanism, which could contribute to the new drug discovery.

  3. Effect of methyl substitution on optoelectronic properties of 1,3,6,8-tetraphenyl pyrenes

    Directory of Open Access Journals (Sweden)

    LIU Yanling

    2014-06-01

    Full Text Available Geometric structures of the ground states and excited states,frontier molecular orbitals,ionization potentials,electron affinities,reorganization energies,and absorption and emission spectra of three novel methyl-substituted 1,3,6,8-tetra-phenylpyrenes were studied theoretically by quantum-chemical methods,such as density functional theory (DFT.The results show that the position of methyl substituent on benzene ring has much effect on the optoelectronic properties of methyl-substituted 1,3,6,8-tetra-phenylpyrenes.Interestingly,the geometric structures and optoelectronic properties of the designed compound 1,3,6,8-tetra-p-tolylpyrene (TPPy are similar to those of 1,3,6,8-tetrakis(3,5-dimethylphenylpyrene (TDMPPy,which is worthy of being further researched.

  4. Influence of the isomerism on the sorption of imazamethabenz-methyl by soil.

    Science.gov (United States)

    Pinna, Maria Vittoria; Pusino, Alba

    2013-04-01

    The sorption of meta and para isomers of the herbicide imazamethabenz-methyl, methyl 6-[(RS)-4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl]-m- or p-toluate, by three soils and soil organic matter, was studied. Sorption isotherms conformed to the Freundlich equation. It was found that pH was the main factor influencing the adsorption in all of the systems. The highest level of sorption was measured on soils with low pH and high organic carbon content. Moreover, at low pH value, the soil rich in smectite clays, favoured the sorption of meta rather than para isomer. The higher affinity of clay surfaces for the meta isomer of the herbicide is due to the stabilization of the meta protonated form by resonance. At all pH values, the sorption on soil organic matter did not differ between two isomers. Copyright © 2012 Elsevier Ltd. All rights reserved.

  5. Crystal structures and luminescence properties of two Cd(II) complexes based on 2-(1H-imidazol-1methyl)-6-methyl-1H-benzimidazole

    International Nuclear Information System (INIS)

    Zhang, Yuhong; Meng, Xiangru; Wen, Yu; Li, Peng; Ma, Lin; Zhang, Qiuju

    2015-01-01

    Two new complexes, {[Cd(immb)I 2 ].DMF} n (1) and {[Cd 3 (immb)(btc) 2 ]. H 2 O} n (2) (immb = 2-(1H-imidazol- 1-methyl)-6-methyl-1H-benzimidazole, btc = 1,2,3-benzenetricarboxylate, DMF = dimethyl formamide), have been synthesized and characterized. Single crystal X-ray diffraction shows that 1 exhibits a chain structure constructed by immb ligands bridging Cd(II) ions. In 2, Cd(II) ions are linked by immb ligands with bridging mode and btc3- anions with the μ 2 -η 2 :η 1 bonding pattern leading to a 2D structure. Luminescent properties have been investigated in the solid state at room temperature.

  6. Process for the production of methyl methacrylate

    NARCIS (Netherlands)

    Eastham, G.R.; Johnson, D.W.; Straathof, A.J.J.; Fraaije, Marco; Winter, Remko

    2015-01-01

    A process of producing methyl methacrylate or derivatives thereof is described. The process includes the steps of; (i) converting 2-butanone to methyl propionate using a Baeyer-Villiger monooxygenase, and (ii) treating the methyl propionate produced to obtain methyl methacrylate or derivatives

  7. 14-O-Methylmorphine: A Novel Selective Mu-Opioid Receptor Agonist with High Efficacy and Affinity.

    Science.gov (United States)

    Zádor, Ferenc; Balogh, Mihály; Váradi, András; Zádori, Zoltán S; Király, Kornél; Szűcs, Edina; Varga, Bence; Lázár, Bernadette; Hosztafi, Sándor; Riba, Pál; Benyhe, Sándor; Fürst, Susanna; Al-Khrasani, Mahmoud

    2017-11-05

    14-O-methyl (14-O-Me) group in morphine-6-O-sulfate (M6SU) or oxymorphone has been reported to be essential for enhanced affinity, potency and antinociceptive effect of these opioids. Herein we report on the pharmacological properties (potency, affinity and efficacy) of the new compound, 14-O-methylmorphine (14-O-MeM) in in vitro. Additionally, we also investigated the antinociceptive effect of the novel compound, as well as its inhibitory action on gastrointestinal transit in in vivo. The potency and efficacy of test compound were measured by [ 35 S]GTPγS binding, isolated mouse vas deferens (MVD) and rat vas deferens (RVD) assays. The affinity of 14-O-MeM for opioid receptors was assessed by radioligand binding and MVD assays. The antinociceptive and gastrointestinal effects of the novel compound were evaluated in the rat tail-flick test and charcoal meal test, respectively. Morphine, DAMGO, Ile 5,6 deltorphin II, deltorphin II and U-69593 were used as reference compounds. 14-O-MeM showed higher efficacy (E max ) and potency (EC 50 ) than morphine in MVD, RVD or [ 35 S]GTPγS binding. In addition, 14-O-MeM compared to morphine showed higher affinity for μ-opioid receptor (MOR). In vivo, in rat tail-flick test 14-O-MeM proved to be stronger antinociceptive agent than morphine after peripheral or central administration. Additionally, both compounds inhibited the gastrointestinal peristalsis. However, when the antinociceptive and antitransit doses for each test compound are compared, 14-O-MeM proved to have slightly more favorable pharmacological profile. Our results affirm that 14-O-MeM, an opioid of high efficacy and affinity for MOR can be considered as a novel analgesic agent of potential clinical value. Copyright © 2017 Elsevier B.V. All rights reserved.

  8. Electron affinities of atoms, molecules, and radicals

    International Nuclear Information System (INIS)

    Christodoulides, A.A.; McCorkle, D.L.; Christophorou, L.G.

    1982-01-01

    We review briefly but comprehensively the theoretical, semiempirical and experimental methods employed to determine electron affinities (EAs) of atoms, molecules and radicals, and summarize the EA data obtained by these methods. The detailed processes underlying the principles of the experimental methods are discussed very briefly. It is, nonetheless, instructive to recapitulate the definition of EA and those of the related quantities, namely, the vertical detachment energy, VDE, and the vertical attachment energy, VAE. The EA of an atom is defined as the difference in total energy between the ground state of the neutral atom (plus the electron at rest at infinity) and its negative ion. The EA of a molecule is defined as the difference in energy between the neutral molecule plus an electron at rest at infinity and the molecular negative ion when both, the neutral molecules and the negative ion, are in their ground electronic, vibrational and rotational states. The VDE is defined as the minimum energy required to eject the electron from the negative ion (in its ground electronic and nuclear state) without changing the internuclear separation; since the vertical transition may leave the neutral molecule in an excited vibrational/rotational state, the VDE, although the same as the EA for atoms is, in general, different (larger than), from the EA for molecules. Similarly, the VAE is defined as the difference in energy between the neutral molecule in its ground electronic, vibrational and rotational states plus an electron at rest at infinity and the molecular negative ion formed by addition of an electron to the neutral molecule without allowing a change in the intermolecular separation of the constituent nuclei; it is a quantity appropriate to those cases where the lowest negative ion state lies above the ground states of the neutral species and is less or equal to EA

  9. Convulsant bicuculline modifies CNS muscarinic receptor affinity

    Directory of Open Access Journals (Sweden)

    Rodríguez de Lores Arnaiz Georgina

    2006-04-01

    Full Text Available Abstract Background Previous work from this laboratory has shown that the administration of the convulsant drug 3-mercaptopropionic acid (MP, a GAD inhibitor, modifies not only GABA synthesis but also binding of the antagonist [3H]-quinuclidinyl benzilate ([3H]-QNB to central muscarinic receptors, an effect due to an increase in affinity without modifications in binding site number. The cholinergic system has been implicated in several experimental epilepsy models and the ability of acetylcholine to regulate neuronal excitability in the neocortex is well known. To study the potential relationship between GABAergic and cholinergic systems with seizure activity, we analyzed the muscarinic receptor after inducing seizure by bicuculline (BIC, known to antagonize the GABA-A postsynaptic receptor subtype. Results We analyzed binding of muscarinic antagonist [3H]-QNB to rat CNS membranes after i.p. administration of BIC at subconvulsant (1.0 mg/kg and convulsant (7.5 mg/kg doses. Subconvulsant BIC dose failed to develop seizures but produced binding alteration in the cerebellum and hippocampus with roughly 40% increase and 10% decrease, respectively. After convulsant BIC dose, which invariably led to generalized tonic-clonic seizures, binding increased 36% and 15% to cerebellar and striatal membranes respectively, but decreased 12% to hippocampal membranes. Kd value was accordingly modified: with the subconvulsant dose it decreased 27% in cerebellum whereas it increased 61% in hippocampus; with the convulsant dose, Kd value decreased 33% in cerebellum but increased 85% in hippocampus. No change in receptor number site was found, and Hill number was invariably close to unity. Conclusion Results indicate dissimilar central nervous system area susceptibility of muscarinic receptor to BIC. Ligand binding was modified not only by a convulsant BIC dose but also by a subconvulsant dose, indicating that changes are not attributable to the seizure process

  10. Characteristics of high affinity and low affinity adenosine binding sites in human cerebral cortex

    International Nuclear Information System (INIS)

    John, D.; Fox, I.V.

    1986-01-01

    The binding characteristics of human brain cortical membrane fractions were evaluated to test the hypothesis that there are A 1 and A 2 adenosine binding sites. The ligands used were 2-chloro(8- 3 H) adenosine and N 6 -(adenine-2, 8- 3 H) cyclohexayladenosine. Binding of chloroadenosine to human brain cortical membranes was time dependent, reversible and concentration dependent. The kinetic constant determinations from binding studies of the adenosine receptor are presented. Utilizing tritium-cyclohexyladenosine as ligand the authors observed evidence for a high affinity binding site in human brain cortical membranes with a kd of 5 nM

  11. Electron stimulated reactions of methyl iodide coadsorbed with amorphous solid water

    International Nuclear Information System (INIS)

    Perry, C. C.; Faradzhev, N. S.; Madey, T. E.; Fairbrother, D. H.

    2007-01-01

    The electron stimulated reactions of methyl iodide (MeI) adsorbed on and suspended within amorphous solid water (ice) were studied using a combination of postirradiation temperature programmed desorption and reflection absorption infrared spectroscopy. For MeI adsorbed on top of amorphous solid water (ice), electron beam irradiation is responsible for both structural and chemical transformations within the overlayer. Electron stimulated reactions of MeI result principally in the formation of methyl radicals and solvated iodide anions. The cross section for electron stimulated decomposition of MeI is comparable to the gas phase value and is only weakly dependent upon the local environment. For both adsorbed MeI and suspended MeI, reactions of methyl radicals within MeI clusters lead to the formation of ethane, ethyl iodide, and diiodomethane. In contrast, reactions between the products of methyl iodide and water dissociation are responsible for the formation of methanol and carbon dioxide. Methane, formed as a result of reactions between methyl radicals and either parent MeI molecules or hydrogen atoms, is also observed. The product distribution is found to depend on the film's initial chemical composition as well as the electron fluence. Results from this study highlight the similarities in the carbon-containing products formed when monohalomethanes coadsorbed with amorphous solid water are irradiated by either electrons or photons

  12. Use of anionic denaturing detergents to purify insoluble proteins after overexpression

    Directory of Open Access Journals (Sweden)

    Schlager Benjamin

    2012-12-01

    Full Text Available Background Many proteins form insoluble protein aggregates, called “inclusion bodies”, when overexpressed in E. coli. This is the biggest obstacle in biotechnology. Ever since the reversible denaturation of proteins by chaotropic agents such as urea or guanidinium hydrochloride had been shown, these compounds were predominantly used to dissolve inclusion bodies. Other denaturants exist but have received much less attention in protein purification. While the anionic, denaturing detergent sodiumdodecylsulphate (SDS is used extensively in analytical SDS-PAGE, it has rarely been used in preparative purification. Results Here we present a simple and versatile method to purify insoluble, hexahistidine-tagged proteins under denaturing conditions. It is based on dissolution of overexpressing bacterial cells in a buffer containing sodiumdodecylsulfate (SDS and whole-lysate denaturation of proteins. The excess of detergent is removed by cooling and centrifugation prior to affinity purification. Host- and overexpressed proteins do not co-precipitate with SDS and the residual concentration of detergent is compatible with affinity purification on Ni/NTA resin. We show that SDS can be replaced with another ionic detergent, Sarkosyl, during purification. Key advantages over denaturing purification in urea or guanidinium are speed, ease of use, low cost of denaturant and the compatibility of buffers with automated FPLC. Conclusion Ionic, denaturing detergents are useful in breaking the solubility barrier, a major obstacle in biotechnology. The method we present yields detergent-denatured protein. Methods to refold proteins from a detergent denatured state are known and therefore we propose that the procedure presented herein will be of general application in biotechnology.

  13. Molecular evidence for an involvement of organic anion transporters (OATs) in aristolochic acid nephropathy

    International Nuclear Information System (INIS)

    Bakhiya, Nadiya; Arlt, Volker M.; Bahn, Andrew; Burckhardt, Gerhard; Phillips, David H.; Glatt, Hansruedi

    2009-01-01

    Aristolochic acid (AA), present in Aristolochia species, is the major causative agent in the development of severe renal failure and urothelial cancers in patients with AA nephropathy. It may also be a cause of Balkan endemic nephropathy. Epithelial cells of the proximal tubule are the primary cellular target of AA. To study whether organic anion transporters (OATs) expressed in proximal tubule cells are involved in uptake of AA, we used human epithelial kidney (HEK293) cells stably expressing human (h) OAT1, OAT3 or OAT4. AA potently inhibited the uptake of characteristic substrates, p-aminohippurate for hOAT1 and estrone sulfate for hOAT3 and hOAT4. Aristolochic acid I (AAI), the more cytotoxic and genotoxic AA congener, exhibited high affinity for hOAT1 (K i = 0.6 μM) as well as hOAT3 (K i = 0.5 μM), and lower affinity for hOAT4 (K i = 20.6 μM). Subsequently, AAI-DNA adduct formation (investigated by 32 P-postlabelling) was used as a measure of AAI uptake. Significantly higher levels of adducts occurred in hOAT-expressing cells than in control cells: this effect was abolished in the presence of the OAT inhibitor probenecid. In Xenopus laevis oocytes hOAT-mediated efflux of p-aminohippurate was trans-stimulated by extracellular AA, providing further molecular evidence for AA translocation by hOATs. Our study indicates that OATs can mediate the uptake of AA into proximal tubule cells and thereby participate in kidney cell damage by this toxin.

  14. Alkyl chain interaction at the surface of room temperature ionic liquids: systematic variation of alkyl chain length (R = C(1)-C(4), C(8)) in both cation and anion of [RMIM][R-OSO(3)] by sum frequency generation and surface tension.

    Science.gov (United States)

    Santos, Cherry S; Baldelli, Steven

    2009-01-29

    The gas-liquid interface of halide-free 1,3-dialkylimidazolium alkyl sulfates [RMIM][R-OSO(3)] with R chain length from C(1)-C(4) and C(8) has been studied systematically using the surface-specific sum frequency generation (SFG) vibrational spectroscopy and surface tension measurements. From the SFG spectra, vibrational modes from the methyl group of both cation and anion are observed for all ionic liquid samples considered in the present study. These results suggest the presence of both ions at the gas-liquid interface, which is further supported by surface tension measurements. Surface tension data show a decreasing trend as the alkyl chain in the imidazolium cation is varied from methyl to butyl chain, with a specific anion. A similar trend is observed when the alkyl chain of the anion is modified and the cation is fixed.

  15. o-Iminobenzosemiquinonate and o-imino-p-methylbenzosemiquinonate anion radicals coupled VO2+ stabilization.

    Science.gov (United States)

    Roy, Amit Saha; Saha, Pinaki; Adhikary, Nirmal Das; Ghosh, Prasanta

    2011-03-21

    The diamagnetic VO(2+)-iminobenzosemiquinonate anion radical (L(R)(IS)(•-), R = H, Me) complexes, (L(-))(VO(2+))(L(R)(IS)(•-)): (L(1)(-))(VO(2+))(L(H)(IS)(•-))•3/2MeOH (1•3/2MeOH), (L(2)(-))(VO(2+))(L(H)(IS)(•-)) (2), and (L(2)(-))(VO(2+))(L(Me)(IS)(•-))•1/2 L(Me)(AP) (3•1/2 L(Me)(AP)), incorporating tridentate monoanionic NNO-donor ligands {L = L(1)(-) or L(2)(-), L(1)H = (2-[(phenylpyridin-2-yl-methylene)amino]phenol; L(2)H = 1-(2-pyridylazo)-2-naphthol; L(H)(IS)(•-) = o-iminobenzosemiquinonate anion radical; L(Me)(IS)(•-) = o-imino-p-methylbenzosemiquinonate anion radical; and L(Me)(AP) = o-amino-p-methylphenol} have been isolated and characterized by elemental analyses, IR, mass, NMR, and UV-vis spectra, including the single-crystal X-ray structure determinations of 1•3/2MeOH and 3•1/2 L(Me)(AP). Complexes 1•3/2MeOH, 2, and 3•1/2 L(Me)(AP) absorb strongly in the visible region because of intraligand (IL) and ligand-to-metal charge transfers (LMCT). 1•3/2MeOH is luminescent (λ(ext), 333 nm; λ(em), 522, 553 nm) in frozen dichloromethane-toluene glass at 77 K due to π(diimine→)π(diimine)* transition. The V-O(phenolato) (cis to the V═O) lengths, 1.940(2) and 1.984(2) Å, respectively, in 1•3/2MeOH and 3•1/2 L(Me)(AP) are consistent with the VO(2+) description. The V-O(iminosemiquinonate) (trans to the V═O) lengths, 2.1324(19) in 1•3/2MeOH and 2.083(2) Å in 3•1/2 L(Me)(AP), are expectedly ∼0.20 Å longer due to the trans influence of the V═O bond. Because of the stronger affinity of the paramagnetic VO(2+) ion to the L(H)(IS)(•-) or L(Me)(IS)(•-), the V-N(iminosemiquinonate) lengths, 1.908(2) and 1.921(2) Å, respectively, in 1•3/2MeOH and 3•1/2 L(Me)(AP), are unexpectedly shorter. Density functional theory (DFT) calculations using B3LYP, B3PW91, and PBE1PBE functionals on 1 and 2 have established that the closed shell singlet (CSS) solutions (VO(3+)-amidophenolato (L(R)(AP)(2-)) coordination) of these

  16. Ab initio investigation of sulfur monofluoride and its singly charged cation and anion in their ground electronic state

    International Nuclear Information System (INIS)

    Li Song; Chen Shan-Jun; Chen Yan; Chen Peng

    2016-01-01

    The SF radical and its singly charged cation and anion, SF + and SF − , have been investigated on the MRCI/aug-cc-pVXZ (X = Q, 5, 6) levels of theory with Davidson correction. Both the core–valence correlation and the relativistic effect are considered. The extrapolating to the complete basis set (CBS) limit is adopted to remove the basis set truncation error. Geometrical parameters, potential energy curves (PECs), vibrational energy levels, spectroscopic constants, ionization potentials, and electron affinities of the ground electronic state for all these species are obtained. The information with respect to molecular characteristics of the SF n (n = −1, 0, +1) systems derived in this work will help to extend our knowledge and to guide further experimental or theoretical researches. (paper)

  17. Imidazolium-Based Polymeric Materials as Alkaline Anion-Exchange Fuel Cell Membranes

    Science.gov (United States)

    Narayan, Sri R.; Yen, Shiao-Ping S.; Reddy, Prakash V.; Nair, Nanditha

    2012-01-01

    Polymer electrolyte membranes that conduct hydroxide ions have potential use in fuel cells. A variety of polystyrene-based quaternary ammonium hydroxides have been reported as anion exchange fuel cell membranes. However, the hydrolytic stability and conductivity of the commercially available membranes are not adequate to meet the requirements of fuel cell applications. When compared with commercially available membranes, polystyrene-imidazolium alkaline membrane electrolytes are more stable and more highly conducting. At the time of this reporting, this has been the first such usage for imidazolium-based polymeric materials for fuel cells. Imidazolium salts are known to be electrochemically stable over wide potential ranges. By controlling the relative ratio of imidazolium groups in polystyrene-imidazolium salts, their physiochemical properties could be modulated. Alkaline anion exchange membranes based on polystyrene-imidazolium hydroxide materials have been developed. The first step was to synthesize the poly(styrene-co-(1-((4-vinyl)methyl)-3- methylimidazolium) chloride through a free-radical polymerization. Casting of this material followed by in situ treatment of the membranes with sodium hydroxide solutions provided the corresponding hydroxide salts. Various ratios of the monomers 4-chloromoethylvinylbenzine (CMVB) and vinylbenzine (VB) provided various compositions of the polymer. The preferred material, due to the relative ease of casting the film, and its relatively low hygroscopic nature, was a 2:1 ratio of CMVB to VB. Testing confirmed that at room temperature, the new membranes outperformed commercially available membranes by a large margin. With fuel cells now in use at NASA and in transportation, and with defense potential, any improvement to fuel cell efficiency is a significant development.

  18. Exploring rearrangements along the fragmentation pathways of diuron anion: A combined experimental and computational investigation

    Science.gov (United States)

    Kanawati, Basem; Harir, Mourad; Schmitt-Kopplin, Philippe

    2009-12-01

    Diuron (3-(3,4-dichlorophenyl)-1,1-dimethylurea), a common herbicide from phenyl urea class, was investigated by studying the formation of several negative ions [M-H]- in the gas phase and the fragmentation behaviour of the thermodynamically most probably formed isomeric anions upon linear ion acceleration/collision experiments. The collision induced dissociation experiments (CID) were carried out in a hexapole-quadrupole-hexapole hybrid system coupled to 12 T magnet with infinity ICR cell for high resolution measurements. Two distinctive main pathways were observed in the MS/MS spectrum. Sustained off-resonance irradiation (SORI) experiments inside the ICR cell reinforce the fragmentation channels obtained from linear ion acceleration experiments. The fragmentation pathways were also completely investigated by the use of B3LYP/6-311+G(2d,p)//B3LYP/6-31+G(d) level of theory. Elimination of dimethylamine takes place in a two-step process, by which two successive 1,3 proton shifts occur. The second 1,3 proton shift is concerted with the departure of dimethylamine. The driving force for the (CH3)2NH elimination is the formation of isocyanate group. The formed primary product ion can further decompose to release HCl through a new transition state. A stable new aromatic product ion is formed with 10[pi] electrons. Loss of C3H5NO neutral from another anionic isomer of the precursor ion was also observed and is characteristic for the amide terminal of the diamide functional group. A concerted mechanism is proposed, by which N-C bond breakage and cyclization of the eliminated neutral fragment C3H5NO takes place simultaneously to form 1-methyl-aziridin-2-one.

  19. Metal-Oxide Film Conversions Involving Large Anions

    International Nuclear Information System (INIS)

    Pretty, S.; Zhang, X.; Shoesmith, D.W.; Wren, J.C.

    2008-01-01

    The main objective of my research is to establish the mechanism and kinetics of metal-oxide film conversions involving large anions (I - , Br - , S 2- ). Within a given group, the anions will provide insight on the effect of anion size on the film conversion, while comparison of Group 6 and Group 7 anions will provide insight on the effect of anion charge. This research has a range of industrial applications, for example, hazardous radioiodine can be immobilized by reaction with Ag to yield AgI. From the perspective of public safety, radioiodine is one of the most important fission products from the uranium fuel because of its large fuel inventory, high volatility, and radiological hazard. Additionally, because of its mobility, the gaseous iodine concentration is a critical parameter for safety assessment and post-accident management. A full kinetic analysis using electrochemical techniques has been performed on the conversion of Ag 2 O to (1) AgI and (2) AgBr. (authors)

  20. Metal-Oxide Film Conversions Involving Large Anions

    Energy Technology Data Exchange (ETDEWEB)

    Pretty, S.; Zhang, X.; Shoesmith, D.W.; Wren, J.C. [The University of Western Ontario, Chemistry Department, 1151 Richmond St., N6A 5B7, London, Ontario (Canada)

    2008-07-01

    The main objective of my research is to establish the mechanism and kinetics of metal-oxide film conversions involving large anions (I{sup -}, Br{sup -}, S{sup 2-}). Within a given group, the anions will provide insight on the effect of anion size on the film conversion, while comparison of Group 6 and Group 7 anions will provide insight on the effect of anion charge. This research has a range of industrial applications, for example, hazardous radioiodine can be immobilized by reaction with Ag to yield AgI. From the perspective of public safety, radioiodine is one of the most important fission products from the uranium fuel because of its large fuel inventory, high volatility, and radiological hazard. Additionally, because of its mobility, the gaseous iodine concentration is a critical parameter for safety assessment and post-accident management. A full kinetic analysis using electrochemical techniques has been performed on the conversion of Ag{sub 2}O to (1) AgI and (2) AgBr. (authors)

  1. Anion analysis in uranium more concentrates by ion chromatography

    International Nuclear Information System (INIS)

    Badaut, V.

    2009-01-01

    In the present exploratory study, the applicability of anionic impurities or attributing nuclear material to a certain chemical process or origin has been investigated. Anions (e.g., nitrate, sulphate, fluoride, chloride) originate from acids or salt solutions that are used for processing of solutions containing uranium or plutonium. The study focuses on uranium ore concentrates ('yellow cakes') originating from different mines. Uranium is mined from different types of ore body and depending on the type of rock, different chemical processes for leaching, dissolving and precipitating the uranium need to be applied. Consequently, the anionic patterns observed in he products of these processes (the 'ore concentrates') are different. The concentrations of different anionic species were measured by ion chromatography using conductivity detection. The results show clear differences of anion concentrations and patterns between samples from different uranium mines. Besides this, differences between sampling campaigns n a same mine were also observed indicating that the uranium ore is not homogeneous in a mine. These within-mine variations, however, were smaller than the between-mine variations. (author)

  2. Vertical detachment energies of anionic thymidine: Microhydration effects.

    Science.gov (United States)

    Kim, Sunghwan; Schaefer, Henry F

    2010-10-14

    Density functional theory has been employed to investigate microhydration effects on the vertical detachment energy (VDE) of the thymidine anion by considering the various structures of its monohydrates. Structures were located using a random searching procedure. Among 14 distinct structures of the anionic thymidine monohydrate, the low-energy structures, in general, have the water molecule bound to the thymine base unit. The negative charge developed on the thymine moiety increases the strength of the intermolecular hydrogen bonding between the water and base units. The computed VDE values of the thymidine monohydrate anions are predicted to range from 0.67 to 1.60 eV and the lowest-energy structure has a VDE of 1.32 eV. The VDEs of the monohydrates of the thymidine anion, where the N(1)[Single Bond]H hydrogen of thymine has been replaced by a 2(')-deoxyribose ring, are greater by ∼0.30 eV, compared to those of the monohydrates of the thymine anion. The results of the present study are in excellent agreement with the accompanying experimental results of Bowen and co-workers [J. Chem. Phys. 133, 144304 (2010)].

  3. Identification of inorganic anions by gas chromatography/mass spectrometry.

    Science.gov (United States)

    Sakayanagi, Masataka; Yamada, Yaeko; Sakabe, Chikako; Watanabe, Kunio; Harigaya, Yoshihiro

    2006-03-10

    Inorganic anions were identified by using gas chromatography/mass spectrometry (GC/MS). Derivatization of the anions was achieved with pentafluorobenzyl p-toluenesulphonate (PFB-Tos) as the reaction reagent and a crown ether as a phase transfer catalyst. When PFB-Br was used as the reaction reagent, the retention time of it was close to those of the derivatized inorganic anions and interfered with the analysis. In contrast, the retention time of PFB-Tos differed greatly from the PFB derivatives of the inorganic anions and the compounds of interest could be detected without interference. Although the PFB derivatives of SO4, S2O3, CO3, ClO4, and ClO3 could not be detected, the derivatives of F, Cl, Br, I, CN, OCN, SCN, N3, NO3, and NO2 were detected using PFB-Tos as the derivatizing reagent. The inorganic anions were detectable within 30 ng approximately, which is of sufficient sensitivity for use in forensic chemistry. Accurate mass number was measured for each PFB derivative by high-resolution mass spectrometry (HRMS) within a measurement error of 2 millimass units (mmu), which allowed determination of the compositional formula from the mass number. In addition, actual analysis was performed successively by our method using trial samples of matrix.

  4. Separation of transfer ribonucleic acids on polystyrene anion exchangers

    Energy Technology Data Exchange (ETDEWEB)

    Singhal, R.P.; Griffin, G.D.; Novelli, G.D.

    1976-11-16

    The transfer RNA separation by chromatography on strong-base-polystyrene exchange materials is examined and compared with the widely used reversed-phase chromatography. Results indicate important differences in some transfer RNA (tRNA) elution patterns by the anion-exchange chromatography, as compared with the reversed-phase chromatography. Transfer RNAs containing hydrophobic groups are adsorbed more strongly. The anion exchanger has twice the number of theoretical plates. Single peaks of tRNA/sub 2//sup Glu/ and tRNA/sub 1//sup Phe/ obtained from the reversed-phase column give multiple peaks on polystyrene anion-exchange chromatography. All six leucine tRNAs (Escherichia coli) and differences in tRNA populations synthesized during early and late stages of the dividing lymphocytes from normal human blood can be characterized by the anion-exchange chromatography. Different separation profiles are obtained by two separation systems for tyrosine tRNAs from mouse liver and mouse-plasma-cell tumor. The results indicate that, in contrast to the reversed-phase chromatography, strong-base-polystyrene anion-exchange chromatography is capable of separating tRNAs with minor structural differences.

  5. REACTIVITY OF ANIONS IN INTERSTELLAR MEDIA: DETECTABILITY AND APPLICATIONS

    Energy Technology Data Exchange (ETDEWEB)

    Senent, M. L. [Departamento de Quimica y Fisica Teoricas, Instituto de Estructura de la Materia, IEM-C.S.I.C., Serrano 121, Madrid E-28006 (Spain); Hochlaf, M., E-mail: senent@iem.cfmac.csic.es, E-mail: hochlaf@univ-mlv.fr [Laboratoire de Modelisation et Simulation Multi Echelle, Universite Paris-Est, MSME UMR 8208 CNRS, 5 boulevard Descartes, F-77454 Marne-la-Vallee (France)

    2013-05-01

    We propose a general rule to distinguish between detectable and undetectable astronomical anions. We believe that only few anions live long enough in the interstellar medium and thus can be detected. Our method is based on quantum mechanical calculations capable of describing accurately the evolution of electronic states during chemical processes. The still not fully understood reactivity at low temperatures is discussed considering non-adiabatic effects. The role of excited states has usually been neglected in previous works which basically focused on the ground electronic state for interpretations of experimental observations. Here, we deal with unsaturated carbon chains (e.g., C{sub n} H{sup -}), which show a high density of electronic states close to their corresponding ground electronic states, complex molecular dynamics, and non-adiabatic phenomena. Our general rule shows that it is not sufficient that anions exist in the gas phase (in the laboratory) to be present in media such as astrophysical media, since formation and decomposition reactions of these anions may allow the population of anionic electronic states to autodetach, forming neutrals. For C{sub n} H, reactivity depends strongly on n, where long and short chains behave differently. Formation of linear chains is relevant.

  6. Accurate density functional prediction of molecular electron affinity with the scaling corrected Kohn–Sham frontier orbital energies

    Science.gov (United States)

    Zhang, DaDi; Yang, Xiaolong; Zheng, Xiao; Yang, Weitao

    2018-04-01

    Electron affinity (EA) is the energy released when an additional electron is attached to an atom or a molecule. EA is a fundamental thermochemical property, and it is closely pertinent to other important properties such as electronegativity and hardness. However, accurate prediction of EA is difficult with density functional theory methods. The somewhat large error of the calculated EAs originates mainly from the intrinsic delocalisation error associated with the approximate exchange-correlation functional. In this work, we employ a previously developed non-empirical global scaling correction approach, which explicitly imposes the Perdew-Parr-Levy-Balduz condition to the approximate functional, and achieve a substantially improved accuracy for the calculated EAs. In our approach, the EA is given by the scaling corrected Kohn-Sham lowest unoccupied molecular orbital energy of the neutral molecule, without the need to carry out the self-consistent-field calculation for the anion.

  7. ODE/IM correspondence and modified affine Toda field equations

    Energy Technology Data Exchange (ETDEWEB)

    Ito, Katsushi; Locke, Christopher

    2014-08-15

    We study the two-dimensional affine Toda field equations for affine Lie algebra g{sup ^} modified by a conformal transformation and the associated linear equations. In the conformal limit, the associated linear problem reduces to a (pseudo-)differential equation. For classical affine Lie algebra g{sup ^}, we obtain a (pseudo-)differential equation corresponding to the Bethe equations for the Langlands dual of the Lie algebra g, which were found by Dorey et al. in study of the ODE/IM correspondence.

  8. Realization of Robertson-Walker spacetimes as affine hypersurfaces

    International Nuclear Information System (INIS)

    Chen Bangyen

    2007-01-01

    Due to the growing interest in embeddings of spacetimes in higher dimensional spaces, we consider a special type of embedding. We prove that Robertson-Walker spacetimes can be embedded as centroaffine hypersurfaces and graph hypersurfaces in some affine spaces in such a way that the induced relative metrics are exactly the Lorentzian metrics on the Robertson-Walker spacetimes. Such realizations allow us to view Robertson-Walker spacetimes and their submanifolds as affine submanifolds in a natural way. Consequently, our realizations make it possible to apply the tools of affine differential geometry to study Robertson-Walker spacetimes and their submanifolds

  9. Volatility Components, Affine Restrictions and Non-Normal Innovations

    DEFF Research Database (Denmark)

    Christoffersen, Peter; Jacobs, Kris; Dorian, Christian

    Recent work by Engle and Lee (1999) shows that allowing for long-run and short-run components greatly enhances a GARCH model's ability fit daily equity return dynamics. Using the risk-neutralization in Duan (1995), we assess the option valuation performance of the Engle-Lee model and compare...... models to four conditionally non-normal versions. As in Hsieh and Ritchken (2005), we find that non-affine models dominate affine models both in terms of fitting return and in terms of option valuation. For the affine models we find strong evidence in favor of the component structure for both returns...

  10. An improved affine projection algorithm for active noise cancellation

    Science.gov (United States)

    Zhang, Congyan; Wang, Mingjiang; Han, Yufei; Sun, Yunzhuo

    2017-08-01

    Affine projection algorithm is a signal reuse algorithm, and it has a good convergence rate compared to other traditional adaptive filtering algorithm. There are two factors that affect the performance of the algorithm, which are step factor and the projection length. In the paper, we propose a new variable step size affine projection algorithm (VSS-APA). It dynamically changes the step size according to certain rules, so that it can get smaller steady-state error and faster convergence speed. Simulation results can prove that its performance is superior to the traditional affine projection algorithm and in the active noise control (ANC) applications, the new algorithm can get very good results.

  11. The topological entropy of iterated piecewise affine maps is uncomputable

    Directory of Open Access Journals (Sweden)

    Pascal Koiran

    2001-12-01

    Full Text Available We show that it is impossible to compute (or even to approximate the topological entropy of a continuous piecewise affine function in dimension four. The same result holds for saturated linear functions in unbounded dimension. We ask whether the topological entropy of a piecewise affine function is always a computable real number, and conversely whether every non-negative computable real number can be obtained as the topological entropy of a piecewise affine function. It seems that these two questions are also open for cellular automata.

  12. Combined photoelectron, collision-induced dissociation, and computational studies of parent and fragment anions of N-paranitrophenylsulfonylalanine and N-paranitrophenylalanine

    Science.gov (United States)

    Lambert, Jason; Chen, Jing; Buonaugurio, Angela; Bowen, Kit H.; Do-Thanh, Chi-Linh; Wang, Yilin; Best, Michael D.; Compton, R. N.; Sommerfeld, Thomas

    2013-12-01

    After synthesizing the compounds N-paranitrophenylsulfonylalanine (NPNPSA) and N-paranitrophenylalanine (NPNPA), the photoelectron spectrum of the valence anion of N-paranitrophenylsulfonylalanine (NPNPSA)-, was measured and the collision-induced dissociation (CID) pathways of deprotonated N-paranitrophenylsulfonylalanine (NPNPSA-H)- and deprotonated N-paranitrophenylalanine (NPNPA-H)- were determined. Pertinent calculations were conducted to analyze both sets of experimental data. From the valence anion photoelectron spectrum of (NPNPSA)-, the adiabatic electron affinity (AEA) of NPNPSA was determined to be 1.7 ± 0.1 eV, while the vertical detachment energy (VDE) of (NPNPSA)- was found to be 2.3 ± 0.1 eV. Calculations for four low lying conformers of (NPNPSA)- gave AEA values in the range of 1.6-2.1 eV and VDE values in the range of 2.0-2.4 eV. These calculations are in very good agreement with the experimental values. While the NPNPA anion (NPNPSA)- was not observed experimentally it was studied computationally. The six low lying (NPNPSA)- conformers were identified and calculated to have AEA values in the range of 0.7-1.2 eV and VDE values in the range of 0.9-1.6 eV. CID was used to study the fragmentation patterns of deprotonated NPNPA and deprotonated NPNPSA. Based on the CID data and calculations, the excess charge was located on the delocalized π-orbitals of the nitrobenzene moiety. This is made evident by the fact that the dominant fragments all contained the nitrobenzene moiety even though the parent anions used for the CID study were formed via deprotonation of the carboxylic acid. The dipole-bound anions of both molecules are studied theoretically using the results of previous studies on nitrobenzene as a reference.

  13. Capillary Electrophoresis as Analysis Technique for Battery Electrolytes: (i Monitoring Stability of Anions in Ionic Liquids and (ii Determination of Organophosphate-Based Decomposition Products in LiPF6-Based Lithium Ion Battery Electrolytes

    Directory of Open Access Journals (Sweden)

    Marcelina Pyschik

    2017-09-01

    Full Text Available In this work, a method for capillary electrophoresis (CE hyphenated to a high-resolution mass spectrometer was presented for monitoring the stability of anions in ionic liquids (ILs and in commonly used lithium ion battery (LIB electrolytes. The investigated ILs were 1-methyl-1-propylpyrrolidinium bis(trifluoromethanesulfonylimide (PYR13TFSI and 1-methyl-1-propylpyrrolidinium bis(fluorosulfonylimide (PYR13FSI. The method development was conducted by adjusting the following parameters: buffer compositions, buffer concentrations, and the pH value. Also the temperature and the voltage applied on the capillary were optimized. The ILs were aged at room temperature and at 60 °C for 16 months each. At both temperatures, no anionic decomposition products of the FSI− and TFSI− anions were detected. Accordingly, the FSI− and TFSI− anions were thermally stable at these conditions. This method was also applied for the investigation of LIB electrolyte samples, which were aged at 60 °C for one month. The LP30 (50/50 wt. % dimethyl carbonate/ethylene carbonate and 1 M lithium hexafluorophosphate electrolyte was mixed with the additive 1,3-propane sultone (PS and with one of the following organophosphates (OP: dimethyl phosphate (DMP, diethyl phosphate (DEP, and triethyl phosphate (TEP, to investigate the influence of these compounds on the formation of OPs.

  14. Copper(I) coordination compounds with closododecaborate anion

    International Nuclear Information System (INIS)

    Malinina, E.A.; Drozdova, V.V.; Mustyatsa, V.N.; Goeva, L.V.; Polyakova, I.N.; Votinova, N.A.; Zhizhin, K.Yu.; Kuznetsov, N.T.

    2006-01-01

    Cu(I) Complexes with closo-dodecaborate anion Cat[CuB 12 H 12 ], where Cat= Cs + , Ph 4 P + , Ph 4 As + , R x NH 4-x + (R=Me, Et, Pr, Bu, X=3-4) are synthesized. Synthesis of complexes was conducted in the copper(II) salt-salt of dodecaborate anion-sulfur dioxide (sodium sulfite) system. Structure of the complex [Cu 2 (NCCH 3 ) 4 B 12 H 12 ] assigned by X-ray structural analysis discloses that B 12 H 12 2- anion enters into the inner sphere of metal-complexing agent, and connection of closo-borate ligand with the metal is caused by the formation of three-centric metal-hydrogen-boron bonds [ru

  15. Reactivity of niobium cluster anions with nitrogen and carbon monoxide

    Science.gov (United States)

    Mwakapumba, Joseph; Ervin, Kent M.

    1997-02-01

    Reactions of small niobium cluster anions, Nbn-(n = 2-7), with CO and N2 are investigated using a flow tube reactor (flowing afterglow) apparatus. Carbon monoxide chemisorption on niobium cluster anions occurs with faster reaction rates than nitrogen chemisorption on corresponding cluster sizes. N2 addition to niobium cluster anions is much more size-selective than is CO addition. These general trends follow those reported in the literature for reactions of neutral and cationic niobium clusters with CO and N2. Extensive fragmentation of the clusters is observed upon chemisorption. A small fraction of the larger clusters survive and sequentially add multiple CO or N2 units without fragmentation. However, chemisorption saturation is not reached at the experimentally accessible pressure and reagent concentration ranges. The thermochemistry of the adsorption processes and the nature of the adsorbed species, molecular or dissociated, are discussed.

  16. Determination of arsenate in water by anion selective membrane electrode using polyurethane–silica gel fibrous anion exchanger composite

    Energy Technology Data Exchange (ETDEWEB)

    Khan, Asif Ali, E-mail: asifkhan42003@yahoo.com; Shaheen, Shakeeba, E-mail: shakeebashaheen@ymail.com

    2014-01-15

    Highlights: • PU–Si gel is new anion exchanger material synthesized and characterized. • This material used as anion exchange membrane is applied for electroanalytical studies. • The method for detection and determination of AsO{sub 4}{sup 3−} in traces amounts discussed. • The results are also verified from arsenic analyzer. -- Abstract: Polyurethane (PU)–silica (Si gel) based fibrous anion exchanger composites were prepared by solid–gel polymerization of polyurethane in the presence of different amounts of silica gel. The formation of PU–Si gel fibrous anion exchanger composite was characterized by Fourier transform infra-red spectroscopy (FTIR), X-ray diffraction (XRD), thermogravimetric analysis (TGA-DTA), scanning electron microscopy (SEM) and elemental analysis. The membrane having a composition of 5:3 (PU:Si gel) shows best results for water content, porosity, thickness and swelling. Our studies show that the present ion selective membrane electrode is selective for arsenic, having detection limit (1 × 10{sup −8} M to 1 × 10{sup −1} M), response time (45 s) and working pH range (5–8). The selectivity coefficient values for interfering ions indicate good selectivity for arsenate (AsO{sub 4}{sup 3−}) over interfering anions. The accuracy of the detection limit results was compared by PCA-Arsenomat.

  17. Anionic solid lipid nanoparticles supported on protamine/DNA complexes

    International Nuclear Information System (INIS)

    Ye Jiesheng; Liu Chunxi; Chen Zhijin; Zhang Na; Wang Aihua

    2008-01-01

    The objective of this study was to design novel anionic ternary nanoparticles for gene delivery. These ternary nanoparticles were equipped with protamine/DNA binary complexes (150-200 nm) as the support, and the anionic formation was achieved by absorption of anionic solid lipid nanoparticles (≤20 nm) onto the surface of the binary complexes. The small solid lipid nanoparticles (SLNs) were prepared by a modified film dispersion-ultrasonication method, and adsorption of the anionic SLNs onto the binary complexes was typically carried out in water via electrostatic interaction. The formulated ternary nanoparticles were found to be relatively uniform in size (257.7 ± 10.6 nm) with a 'bumpy' surface, and the surface charge inversion from 19.28 ± 1.14 mV to -17.16 ± 1.92 mV could be considered as evidence of the formation of the ternary nanoparticles. The fluorescence intensity measurements from three batches of the ternary nanoparticles gave a mean adsorption efficiency of 96.75 ± 1.13%. Circular dichroism spectra analysis showed that the protamine/DNA complexes had been coated by small SLNs, and that the anionic ternary nanoparticles formed did not disturb the construction of the binary complexes. SYBR Green I analysis suggested that the ternary nanoparticles could protect the DNA from nuclease degradation, and cell viability assay results showed that they exhibit lower cytotoxicity to A549 cells compared with the binary complexes and lipofectamine. The transfection efficiency of the ternary nanoparticles was better than that of naked DNA and the binary complexes, and almost equal to that of lipofectamine/DNA complexes, as revealed by inversion fluorescence microscope observation. These results indicated that the anionic ternary nanoparticles could facilitate gene transfer in cultured cells, and might alleviate the drawbacks of the conventional cationic vector/DNA complexes for gene delivery in vivo

  18. Anion effect on the retention of recoil atom of coordination crystalline compounds

    International Nuclear Information System (INIS)

    Dimotakis, P.N.; Papadopoulos, B.P.

    1980-01-01

    The anion effect of various cobaltic crystalline compounds - having the same cation and differing in anion -on the retention of neutron activated central cobalt atom has been studied. The cation was trans-dichloro(bis)ethylenediamine cobalt(III) and the anions were simple spherical anions (Cl - , Br - , I - ), planar anions (NO 3 - ), trigonal pyramidal anions (ClO 3 - , BrO 3 - ), tetrahedral anions (SO 4 2- , CrO 4 2- , MnO 4 - ) and linear anions (SCN - ). The cobalt-60 activity after reactor irradiation either in simple Co 2+ cation or in cobaltic complex cation determined the retention values. In all irradiations at ordinary temperature and at liquid nitrogen temperature the results showed an effect of the different anions, depending on the geometry, volume and charge, on the recombination of the recoil cobalt with the ligands in the coordination sphere. (author)

  19. Proton affinities of maingroup-element hydrides and noble gases: trends across the periodic table, structural effects, and DFT validation.

    Science.gov (United States)

    Swart, Marcel; Rösler, Ernst; Bickelhaupt, F Matthias

    2006-10-01

    We have carried out an extensive exploration of the gas-phase basicity of archetypal neutral bases across the periodic system using the generalized gradient approximation (GGA) of the density functional theory (DFT) at BP86/QZ4P//BP86/TZ2P. First, we validate DFT as a reliable tool for computing proton affinities and related thermochemical quantities: BP86/QZ4P//BP86/TZ2P is shown to yield a mean absolute deviation of 2.0 kcal/mol for the proton affinity at 298 K with respect to experiment, and 1.2 kcal/mol with high-level ab initio benchmark data. The main purpose of this work is to provide the proton affinities (and corresponding entropies) at 298 K of the neutral bases constituted by all maingroup-element hydrides of groups 15-17 and the noble gases, that is, group 18, and periods 1-6. We have also studied the effect of step-wise methylation of the protophilic center of the second- and third-period bases. Copyright 2006 Wiley Periodicals, Inc.

  20. Electrokinetic remediation of anionic contaminants from unsaturated soils

    International Nuclear Information System (INIS)

    Lindgren, E.R.; Kozak, M.W.; Mattson, E.D.

    1992-01-01

    Heavy-metal contamination of soil and groundwater is a widespread problem in the DOE weapons complex, and for the nation as a whole. Electrokinetic remediation is one possible technique for in situ removal of such contaminants from unsaturated soils. In previous studies at Sandia National Laboratories, the electromigration of chromate ions and anionic dye ions have been demonstrated. This paper reports on a series of experiments that were conducted to study the effect of moisture content on the electromigration rate of anionic contaminants in unsaturated soil and determine the limiting moisture content for which electromigration occurs

  1. A study of model systems in anionic exchange

    International Nuclear Information System (INIS)

    Haegele, R.; Boeyens, J.C.A.

    1977-01-01

    Preliminary experiments are reported on the preparation and characterization of anionic sulphate and chloride complexes of UO 2+ 2 and iron(III), benzyl-trimethylammonium cation being used as a model substance for the simulation of positive sites in an anionic-exchange resin. The structure of (BTMA) 4 [UO 2 CL 3 -O 2 -CL 3 UO 2 ], a binuclear uranyl-peroxocomplex that has not been reported in the literature, was elucidated by single-crystal x-ray examination, and is described and discussed [af

  2. Procedure for reducing hydrogen ion concentration in acidic anion eluate

    International Nuclear Information System (INIS)

    Parobek, P.; Baloun, S.; Plevac, S.

    1992-01-01

    A procedure is suggested for reducing the concentration of hydrogen ions in the acidic anionic eluate formed during the separation of uranium. The procedure involves anex elution, precipitation, filtration, precipitate rinsing, and anex rinsing. The procedure is included in the uranium elution process and requires at least one ion exchanger column and at least one tank in the continuous or discontinuous mode. Sparing the neutralizing agent by reducing the hydrogen ion concentration in the acidic anionic eluate is a major asset of this procedure. (Z.S.). 1 fig

  3. Derivatives of Dodecahalo-Closo-Dodecaborate Di-Anion

    OpenAIRE

    Avelar, Amy Cindy

    2009-01-01

    ABSTRACT OF THE DISSERTATIONDerivatives of the Dodecahalo-Closo-Dodecaborate Di-AnionbyAmy AvelarDoctor of Philosophy, Graduate Program in ChemistryUniversity of California, Riverside, December 2009Dr. Christopher A. Reed, ChairpersonThe di-anion, dodecahalo-closo-dodecaborate, B12X122-, where the X = Cl or Br, has been determined to be a useful weakly coordinating anion, WCA. Despite the di- negative charge, several elusive and reactive cationic species were stabilized with B12X122- as the c...

  4. Uranium extraction from sulfuric acid solution using anion exchange resin

    International Nuclear Information System (INIS)

    Sheta, M. E.; Abdel Aal, M. M.; Kandil, A. T.

    2012-12-01

    Uranium is currently recovered from sulfuric acid leach liquor using anion exchange resin as Amberlite IRA 402 (CT). This technology is based on fact that, uranium exists as anionic complexes. This takes place by controlling the pH of the solution, agitation time, temperature and resin to solution ratio (R/S). In this work, batch stirrer tank used for uranium extraction from sulfate medium and after extraction, elution process was done using 1M NaCl solution. After extraction and elution process, the resin was separated from the system and uranium was determined in the solution. (Author)

  5. Uranium isotopic effect studies on cation and anion exchange resins

    International Nuclear Information System (INIS)

    Sarpal, S.K.; Gupta, A.R.

    1975-01-01

    Uranium isotope effects in exchange reactions involving hexavalent and tetravalent uranium, on ion exchange resins, have been re-examined. The earlier work on uranium isotope effects in electron exchange reactions involving hexavalent and tetravalent uranium, has been critically reviewed. New experimental data on these systems in hydrochloric acid medium, has been obtained, using break-through technique on anion-exchange columns. The isotope effects in these break-through experiments have been reinterpreted in a way which is consistent with the anion exchange behaviour of the various uranium species in these systems. (author)

  6. Electrocoagulation-Adsorption to Remove Anionic and Cationic Dyes from Aqueous Solution by PV-Energy

    Directory of Open Access Journals (Sweden)

    J. Castañeda-Díaz

    2017-01-01

    Full Text Available The cationic dye malachite green (MG and the anionic dye Remazol yellow (RY were removed from aqueous solutions using electrocoagulation-adsorption processes. Batch and continuous electrocoagulation procedures were performed and compared. Carbonaceous materials obtained from industrial sewage sludge and commercial activated carbons were used to adsorb dyes from aqueous solutions in column systems with a 96–98% removal efficiency. The continuous electrocoagulation-adsorption system was more efficient for removing dyes than electrocoagulation alone. The thermodynamic parameters suggested the feasibility of the process and indicated that the adsorption was spontaneous and endothermic (ΔS=0.037 and −0.009 for MG and RY, resp.. The ΔG value further indicated that the adsorption process was spontaneous (−6.31 and −10.48; T=303 K. The kinetic electrocoagulation results and fixed-bed adsorption results were adequately described using a first-order model and a Bohart-Adams model, respectively. The adsorption capacities of the batch and column studies differed for each dye, and both adsorbent materials showed a high affinity for the cationic dye. Thus, the results presented in this work indicate that a continuous electrocoagulation-adsorption system can effectively remove this type of pollutant from water. The morphology and elements present in the sludge and adsorbents before and after dye adsorption were characterized using SEM-EDS and FT-IR.

  7. Structural basis of control of inward rectifier Kir2 channel gating by bulk anionic phospholipids.

    Science.gov (United States)

    Lee, Sun-Joo; Ren, Feifei; Zangerl-Plessl, Eva-Maria; Heyman, Sarah; Stary-Weinzinger, Anna; Yuan, Peng; Nichols, Colin G

    2016-09-01

    Inward rectifier potassium (Kir) channel activity is controlled by plasma membrane lipids. Phosphatidylinositol-4,5-bisphosphate (PIP2) binding to a primary site is required for opening of classic inward rectifier Kir2.1 and Kir2.2 channels, but interaction of bulk anionic phospholipid (PL(-)) with a distinct second site is required for high PIP2 sensitivity. Here we show that introduction of a lipid-partitioning tryptophan at the second site (K62W) generates high PIP2 sensitivity, even in the absence of PL(-) Furthermore, high-resolution x-ray crystal structures of Kir2.2[K62W], with or without added PIP2 (2.8- and 2.0-Å resolution, respectively), reveal tight tethering of the C-terminal domain (CTD) to the transmembrane domain (TMD) in each condition. Our results suggest a refined model for phospholipid gating in which PL(-) binding at the second site pulls the CTD toward the membrane, inducing the formation of the high-affinity primary PIP2 site and explaining the positive allostery between PL(-) binding and PIP2 sensitivity. © 2016 Lee et al.

  8. The fluoride content of an anion exchange resin in the fluoride form

    International Nuclear Information System (INIS)

    Kleijn, J.P. de; Zanten, B. van

    1977-01-01

    The fluoride content of an anion exchange resin in the F - -form depends on the material of the equipment used for the preparation. If a glass equipment is used too much fluorine is introduced. The experimental results are explained by taking into account a competition of F - and SiF 6 2- for the hydroxyl positions of the resin (OH - ). Because SiF 6 2- is bivalent and has a lower hydration energy than F - , the resin has a much larger affinity for this species than for F - . If a higher concentration of SiF 6 2- is generated by an intensive contact of the HF solution with glass, two OH-groups may be replaced by one SiF 6 2- . This results in a resin with 3 times as much fluorine as calculated from the chloride capacity. If the formation of SiF 6 2- is impossible as for example in teflon equipment, the same capacity is obtained for chloride and fluoride. (T.G.)

  9. Affinity between information retrieval system and search topic

    International Nuclear Information System (INIS)

    Ebinuma, Yukio

    1979-01-01

    Ten search profiles are tested on the INIS system at the Japan Atomic Energy Research Institute. The results are plotted on recall-precision chart ranging from 100% recall to 100% precision. The curves are not purely systems-dependent nor search-dependent, and are determined substantially by the ''affinity'' between the system and the search topic. The curves are named ''Affinity curves of search topics with information retrieval systems'', and hence retrieval affinity factors are derived. They are obtained not only for individual search topics but also for averages in the system. By such a quantitative examination, the difference of affinity among search topics in a given system, that of the same search topic among various systems, and that of systems to the same group of search topics can be compared reasonably. (author)

  10. Smooth surfaces from bilinear patches: Discrete affine minimal surfaces

    KAUST Repository

    Kä ferbö ck, Florian; Pottmann, Helmut

    2013-01-01

    Motivated by applications in freeform architecture, we study surfaces which are composed of smoothly joined bilinear patches. These surfaces turn out to be discrete versions of negatively curved affine minimal surfaces and share many properties

  11. Antibody Affinity Maturation in Fishes—Our Current Understanding

    Directory of Open Access Journals (Sweden)

    Brad G. Magor

    2015-07-01

    Full Text Available It has long been believed that fish lack antibody affinity maturation, in part because they were thought to lack germinal centers. Recent research done on sharks and bony fishes indicates that these early vertebrates are able to affinity mature their antibodies. This article reviews the functionality of the fish homologue of the immunoglobulin (Ig mutator enzyme activation-induced cytidine deaminase (AID. We also consider the protein and molecular evidence for Ig somatic hypermutation and antibody affinity maturation. In the context of recent evidence for a putative proto-germinal center in fishes we propose some possible reasons that observed affinity maturation in fishes often seems lacking and propose future work that might shed further light on this process in fishes.

  12. Congruence of genomic and ethnolinguistic affinities among five ...

    Indian Academy of Sciences (India)

    their ethnic and linguistic affinities, we analysed DNA samples of individuals drawn from five tribes with diverse, but ... arisen from admixture between the Gonds (maternal) and ..... nuclear `fossil' of the mitochondrial D-loop and the origin of.

  13. ASIFT: An Algorithm for Fully Affine Invariant Comparison

    Directory of Open Access Journals (Sweden)

    Guoshen Yu

    2011-02-01

    Full Text Available If a physical object has a smooth or piecewise smooth boundary, its images obtained by cameras in varying positions undergo smooth apparent deformations. These deformations are locally well approximated by affine transforms of the image plane. In consequence the solid object recognition problem has often been led back to the computation of affine invariant image local features. The similarity invariance (invariance to translation, rotation, and zoom is dealt with rigorously by the SIFT method The method illustrated and demonstrated in this work, Affine-SIFT (ASIFT, simulates a set of sample views of the initial images, obtainable by varying the two camera axis orientation parameters, namely the latitude and the longitude angles, which are not treated by the SIFT method. Then it applies the SIFT method itself to all images thus generated. Thus, ASIFT covers effectively all six parameters of the affine transform.

  14. Sugawara construction for affine SL(N,1)

    International Nuclear Information System (INIS)

    Henningson, M.

    1990-01-01

    We investigate the sl(N,1) superalgebras, their affine extensions and their representations. This is used to perform a Sugawara construction of the Virasoro algebra. The allowed values of the conformal anomaly and the conformal dimension are computed. (orig.)

  15. Self-affine fractal growth front of Aspergillus oryzae

    Science.gov (United States)

    Matsuura, Shu; Miyazima, Sasuke

    1992-12-01

    Aspergillus oryzae have been grown in various environmental conditions and analyzed from the viewpoint of self-affinity. The growth behavior can be described by the Eden model in favorable conditions, and by DLA in unfavorable conditions.

  16. Methods for quantifying T cell receptor binding affinities and thermodynamics

    Science.gov (United States)

    Piepenbrink, Kurt H.; Gloor, Brian E.; Armstrong, Kathryn M.; Baker, Brian M.

    2013-01-01

    αβ T cell receptors (TCRs) recognize peptide antigens bound and presented by class I or class II major histocompatibility complex (MHC) proteins. Recognition of a peptide/MHC complex is required for initiation and propagation of a cellular immune response, as well as the development and maintenance of the T cell repertoire. Here we discuss methods to quantify the affinities and thermodynamics of interactions between soluble ectodomains of TCRs and their peptide/MHC ligands, focusing on titration calorimetry, surface plasmon resonance, and fluorescence anisotropy. As TCRs typically bind ligand with weak-to-moderate affinities, we focus the discussion on means to enhance the accuracy and precision of low affinity measurements. In addition to further elucidating the biology of the T cell mediated immune response, more reliable low affinity measurements will aid with more probing studies with mutants or altered peptides that can help illuminate the physical underpinnings of how TCRs achieve their remarkable recognition properties. PMID:21609868

  17. Local uncontrollability for affine control systems with jumps

    Science.gov (United States)

    Treanţă, Savin

    2017-09-01

    This paper investigates affine control systems with jumps for which the ideal If(g1, …, gm) generated by the drift vector field f in the Lie algebra L(f, g1, …, gm) can be imbedded as a kernel of a linear first-order partial differential equation. It will lead us to uncontrollable affine control systems with jumps for which the corresponding reachable sets are included in explicitly described differentiable manifolds.

  18. On $L_p$ Affine Surface Area and Curvature Measures

    OpenAIRE

    Zhao, Yiming

    2015-01-01

    The relationship between $L_p$ affine surface area and curvature measures is investigated. As a result, a new representation of the existing notion of $L_p$ affine surface area depending only on curvature measures is derived. Direct proofs of the equivalence between this new representation and those previously known are provided. The proofs show that the new representation is, in a sense, "polar" to that of Lutwak's and "dual" to that of Sch\\"utt & Werner's.

  19. Color and Contrast Enhancement by Controlled Piecewise Affine Histogram Equalization

    Directory of Open Access Journals (Sweden)

    Jose-Luis Lisani

    2012-10-01

    Full Text Available This paper presents a simple contrast enhancement algorithm based on histogram equalization (HE. The proposed algorithm performs a piecewise affine transform of the intensity levels of a digital image such that the new cumulative distribution function will be approximately uniform (as with HE, but where the stretching of the range is locally controlled to avoid brutal noise enhancement. We call this algorithm Piecewise Affine Equalization (PAE. Several experiments show that, in general, the new algorithm improves HE results.

  20. [Relations between location of elements in periodic table and affinity for the kidneys (author's transl)].

    Science.gov (United States)

    Ando, A; Hisada, K; Ando, I

    1977-10-01

    The distribution of many inorganic compounds in rats was investigated in order to evaluate kidney affinity of inorganic compounds. In these experiments, 30%, 10-20% and 4-10% of administered dose was localized in the kidneys in 203Hg-acetate and 203 Bi-acetate, in H198AuCl4, 103PdCl2, 201TlCl, 210Pd(NO3)2 and H2(127M)TeO3, and in Na2(51)CrO4, 54MnCl2, (114m)InCl3 and 7BeCl2, respectively. Some bipositive ions and anions was hardly taken up into the kidneys. And in many hard acids according to classification of Lewis acids, the uptake rate into the kidneys was usually small. On the other hand, Hg, Au and Bi, which have strong binding power to the protein, showed high uptake rate in the kidneys. As Hg++, Au+ and Bi+++ was soft acids according to classification of Lewis acids, it was thought that these elements would bind strongly to soft base (RSH, RS-) present in the kidney.

  1. Characterization of Affinity-Purified Isoforms of Acinetobacter calcoaceticus Y1 Glutathione Transferases

    Directory of Open Access Journals (Sweden)

    Chin-Soon Chee

    2014-01-01

    Full Text Available Glutathione transferases (GST were purified from locally isolated bacteria, Acinetobacter calcoaceticus Y1, by glutathione-affinity chromatography and anion exchange, and their substrate specificities were investigated. SDS-polyacrylamide gel electrophoresis revealed that the purified GST resolved into a single band with a molecular weight (MW of 23 kDa. 2-dimensional (2-D gel electrophoresis showed the presence of two isoforms, GST1 (pI 4.5 and GST2 (pI 6.2 with identical MW. GST1 was reactive towards ethacrynic acid, hydrogen peroxide, 1-chloro-2,4-dinitrobenzene, and trans,trans-hepta-2,4-dienal while GST2 was active towards all substrates except hydrogen peroxide. This demonstrated that GST1 possessed peroxidase activity which was absent in GST2. This study also showed that only GST2 was able to conjugate GSH to isoproturon, a herbicide. GST1 and GST2 were suggested to be similar to F0KLY9 (putative glutathione S-transferase and F0KKB0 (glutathione S-transferase III of Acinetobacter calcoaceticus strain PHEA-2, respectively.

  2. Characterization of Affinity-Purified Isoforms of Acinetobacter calcoaceticus Y1 Glutathione Transferases

    Science.gov (United States)

    Chee, Chin-Soon; Tan, Irene Kit-Ping; Alias, Zazali

    2014-01-01

    Glutathione transferases (GST) were purified from locally isolated bacteria, Acinetobacter calcoaceticus Y1, by glutathione-affinity chromatography and anion exchange, and their substrate specificities were investigated. SDS-polyacrylamide gel electrophoresis revealed that the purified GST resolved into a single band with a molecular weight (MW) of 23 kDa. 2-dimensional (2-D) gel electrophoresis showed the presence of two isoforms, GST1 (pI 4.5) and GST2 (pI 6.2) with identical MW. GST1 was reactive towards ethacrynic acid, hydrogen peroxide, 1-chloro-2,4-dinitrobenzene, and trans,trans-hepta-2,4-dienal while GST2 was active towards all substrates except hydrogen peroxide. This demonstrated that GST1 possessed peroxidase activity which was absent in GST2. This study also showed that only GST2 was able to conjugate GSH to isoproturon, a herbicide. GST1 and GST2 were suggested to be similar to F0KLY9 (putative glutathione S-transferase) and F0KKB0 (glutathione S-transferase III) of Acinetobacter calcoaceticus strain PHEA-2, respectively. PMID:24892084

  3. Adsorption and wettability study of methyl ester sulphonate on precipitated asphaltene

    International Nuclear Information System (INIS)

    Okafor, H E; Gholami, R; Sukirman, Y

    2016-01-01

    Asphaltene precipitation from crude oil and its subsequent aggregation forms solid, which preferentially deposit on rock surfaces causing formation damage and wettability changes leading to loss of crude oil production. To resolve this problem, asphaltene inhibitor has been injected into the formation to prevent the precipitation of asphaltene. Asphaltene inhibitors that are usually employed are generally toxic and non-biodegradable. This paper presents a new environmentally friendly asphaltene inhibitor (methyl ester sulphonate), an anionic surfactant, which has excellent sorption on formation rock surfaces. Result from adsorption study validated by Langmuir and Freundlich models indicate a favourable adsorption. At low volumes injected, methyl ester sulphonate is capable of reverting oil-wet sandstone surface to water-wet surface. Biodegradability test profile shows that for concentrations of 100-5000ppm it is biodegradable by 65-80%. (paper)

  4. The aug-cc-pVnZ-F12 basis set family: Correlation consistent basis sets for explicitly correlated benchmark calculations on anions and noncovalent complexes.

    Science.gov (United States)

    Sylvetsky, Nitai; Kesharwani, Manoj K; Martin, Jan M L

    2017-10-07

    We have developed a new basis set family, denoted as aug-cc-pVnZ-F12 (or aVnZ-F12 for short), for explicitly correlated calculations. The sets included in this family were constructed by supplementing the corresponding cc-pVnZ-F12 sets with additional diffuse functions on the higher angular momenta (i.e., additional d-h functions on non-hydrogen atoms and p-g on hydrogen atoms), optimized for the MP2-F12 energy of the relevant atomic anions. The new basis sets have been benchmarked against electron affinities of the first- and second-row atoms, the W4-17 dataset of total atomization energies, the S66 dataset of noncovalent interactions, the Benchmark Energy and Geometry Data Base water cluster subset, and the WATER23 subset of the GMTKN24 and GMTKN30 benchmark suites. The aVnZ-F12 basis sets displayed excellent performance, not just for electron affinities but also for noncovalent interaction energies of neutral and anionic species. Appropriate CABSs (complementary auxiliary basis sets) were explored for the S66 noncovalent interaction benchmark: between similar-sized basis sets, CABSs were found to be more transferable than generally assumed.

  5. Two-parameter quantum affine algebra Ur,s(sln-circumflex), Drinfeld realization and quantum affine Lyndon basis

    International Nuclear Information System (INIS)

    Hu Naihong; Rosso, M.; Zhang Honglian

    2006-12-01

    We further find the defining structure of a two-parameter quantum affine algebra U r,s (sl n -circumflex) (n > 2) in the sense of Benkart-Witherspoon [BW1] after the work of [BGH1], [HS] and [BH], which turns out to be a Drinfeld double. Of more importance for the 'affine' cases is that we work out the compatible two-parameter version of the Drinfeld realization as a quantum affinization of U r,s (sl n ) and establish the Drinfeld isomorphism Theorem in the two-parameter setting via developing a new remarkable combinatorial approach - quantum 'affine' Lyndon basis with an explicit valid algorithm, based on the Drinfeld realization. (author)

  6. A novel CpG island set identifies tissue-specific methylation at developmental gene loci.

    Directory of Open Access Journals (Sweden)

    Robert Illingworth

    2008-01-01

    Full Text Available CpG islands (CGIs are dense clusters of CpG sequences that punctuate the CpG-deficient human genome and associate with many gene promoters. As CGIs also differ from bulk chromosomal DNA by their frequent lack of cytosine methylation, we devised a CGI enrichment method based on nonmethylated CpG affinity chromatography. The resulting library was sequenced to define a novel human blood CGI set that includes many that are not detected by current algorithms. Approximately half of CGIs were associated with annotated gene transcription start sites, the remainder being intra- or intergenic. Using an array representing over 17,000 CGIs, we established that 6%-8% of CGIs are methylated in genomic DNA of human blood, brain, muscle, and spleen. Inter- and intragenic CGIs are preferentially susceptible to methylation. CGIs showing tissue-specific methylation were overrepresented at numerous genetic loci that are essential for development, including HOX and PAX family members. The findings enable a comprehensive analysis of the roles played by CGI methylation in normal and diseased human tissues.

  7. A Protein Complex Required for Polymerase V Transcripts and RNA- Directed DNA Methylation in Arabidopsis

    KAUST Repository

    Law, Julie A.

    2010-05-01

    DNA methylation is an epigenetic modification associated with gene silencing. In Arabidopsis, DNA methylation is established by DOMAINS REARRANGED METHYLTRANSFERASE 2 (DRM2), which is targeted by small interfering RNAs through a pathway termed RNA-directed DNA methylation (RdDM) [1, 2]. Recently, RdDM was shown to require intergenic noncoding (IGN) transcripts that are dependent on the Pol V polymerase. These transcripts are proposed to function as scaffolds for the recruitment of downstream RdDM proteins, including DRM2, to loci that produce both siRNAs and IGN transcripts [3]. However, the mechanism(s) through which Pol V is targeted to specific genomic loci remains largely unknown. Through affinity purification of two known RdDM components, DEFECTIVE IN RNA-DIRECTED DNA METHYLATION 1 (DRD1) [4] and DEFECTIVE IN MERISTEM SILENCING 3 (DMS3) [5, 6], we found that they copurify with each other and with a novel protein, RNA-DIRECTED DNA METHYLATION 1 (RDM1), forming a complex we term DDR. We also found that DRD1 copurified with Pol V subunits and that RDM1, like DRD1 [3] and DMS3 [7], is required for the production of Pol V-dependent transcripts. These results suggest that the DDR complex acts in RdDM at a step upstream of the recruitment or activation of Pol V. © 2010 Elsevier Ltd. All rights reserved.

  8. A Protein Complex Required for Polymerase V Transcripts and RNA- Directed DNA Methylation in Arabidopsis

    KAUST Repository

    Law, Julie A.; Ausí n, Israel; Johnson, Lianna M.; Vashisht, Ajay  A Amar; Zhu, Jian-Kang; Wohlschlegel, James  A A.; Jacobsen, Steven E.

    2010-01-01

    DNA methylation is an epigenetic modification associated with gene silencing. In Arabidopsis, DNA methylation is established by DOMAINS REARRANGED METHYLTRANSFERASE 2 (DRM2), which is targeted by small interfering RNAs through a pathway termed RNA-directed DNA methylation (RdDM) [1, 2]. Recently, RdDM was shown to require intergenic noncoding (IGN) transcripts that are dependent on the Pol V polymerase. These transcripts are proposed to function as scaffolds for the recruitment of downstream RdDM proteins, including DRM2, to loci that produce both siRNAs and IGN transcripts [3]. However, the mechanism(s) through which Pol V is targeted to specific genomic loci remains largely unknown. Through affinity purification of two known RdDM components, DEFECTIVE IN RNA-DIRECTED DNA METHYLATION 1 (DRD1) [4] and DEFECTIVE IN MERISTEM SILENCING 3 (DMS3) [5, 6], we found that they copurify with each other and with a novel protein, RNA-DIRECTED DNA METHYLATION 1 (RDM1), forming a complex we term DDR. We also found that DRD1 copurified with Pol V subunits and that RDM1, like DRD1 [3] and DMS3 [7], is required for the production of Pol V-dependent transcripts. These results suggest that the DDR complex acts in RdDM at a step upstream of the recruitment or activation of Pol V. © 2010 Elsevier Ltd. All rights reserved.

  9. Thermochemistry and electronic structure of small boron clusters (B(n), n = 5-13) and their anions.

    Science.gov (United States)

    Truong, Ba Tai; Grant, Daniel J; Nguyen, Minh Tho; Dixon, David A

    2010-01-21

    Thermochemical parameters of a set of small-sized neutral (B(n)) and anionic (B(n)(-)) boron clusters, with n = 5-13, were determined using coupled-cluster theory CCSD(T) calculations with the aug-cc-pVnZ (n = D, T, and Q) basis sets extrapolated to the complete basis set limit (CBS) plus addition corrections and/or G3B3 calculations. Enthalpies of formation, adiabatic electron affinities (EA), vertical (VDE), and adiabatic (ADE) detachment energies were evaluated. Our calculated EAs are in good agreement with recent experiments (values in eV): B(5) (CBS, 2.29; G3B3, 2.48; exptl., 2.33 +/- 0.02), B(6) (CBS, 2.59; G3B3, 3.23; exptl., 3.01 +/- 0.04), B(7) (CBS, 2.62; G3B3, 2.67; exptl., 2.55 +/- 0.05), B(8) (CBS, 3.02; G3B3, 3.11; exptl., 3.02 +/- 0.02), B(9) (G3B3, 3.03; exptl., 3.39 +/- 0.06), B(10) (G3B3, 2.85; exptl., 2.88 +/- 0.09), B(11) (G3B4, 3.48;, exptl., 3.43 +/- 0.01), B(12) (G3B3, 2.33; exptl., 2.21 +/- 0.04), and B(13) (G3B3, 3.62; exptl., 3.78 +/- 0.02). The difference between the calculated adiabatic electron affinity and the adiabatic detachment energy for B(6) is due to the fact that the geometry of the anion is not that of the ground-state neutral. The calculated adiabatic detachment energies to the (3)A(u), C(2h) and (1)A(g), D(2h) excited states of B(6), which have geometries similar to the (1)A(g), D(2h) state of B(6)(-), are 2.93 and 3.06 eV, in excellent agreement with experiment. The VDEs were also well reproduced by the calculations. Partitioning of the electron localization functions into pi and sigma components allows probing of the partial and local delocalization in global nonaromatic systems. The larger clusters appear to exhibit multiple aromaticity. The binding energies per atom vary in a parallel manner for both neutral and anionic series and approach the experimental value for the heat of atomization of B. The resonance energies and the normalized resonance energies are convenient indices to quantify the stabilization of a cluster

  10. Anion-based approaches to tunable functionality in oxide heterostructures

    Science.gov (United States)

    May, Steven

    2014-03-01

    The ability to control the position and composition of the anion site is emerging as a promising route to tune properties in epitaxial perovskites. This talk will focus on recent and ongoing efforts aimed at developing anion-based approaches to tailor electronic and magnetic properties in oxide films. First, I will discuss how the position of the oxygen anions can be tailored to stabilize non-bulk-like bond angles and lengths, thereby altering electronic bandwidth. Recent work on La2/3Sr1/3MnO3 will be presented in which ultrathin films under the same strain state exhibit dramatically different electronic and magnetic properties when grown on substrates with different symmetries. In the second half of the talk, I will describe efforts focused on altering the composition of the anion site. In La1/3Sr2/3FeO3-δ films, a reversible change in oxygen content leads to dramatic changes in electrical, optical, and structural properties. Finally, the synthesis of oxyfluoride ferrite and nickelate perovskite films via topotactic reactions carried out following thin film deposition will be described. This work is supported by the Office of Naval Research (N00014-11-1-0664) and the U. S. Army Research Office (W911NF-12-1-0132).

  11. Anionic construction of the SLq,s(2) algebra

    International Nuclear Information System (INIS)

    Matheus-Valle, J.L.; Monteiro, M.R.

    1993-01-01

    Considering anionic oscillators in a two-dimensional lattice, the quantum semi-group sl (q,s ) (2) is realized by means of a generalized Schwinger construction. It is found that the parameter q of the algebra is connected to the statistical parameter, whereas the s parameter is related to a s-deformed oscillator introduced at each point of the lattice. (author)

  12. Effect of biocides and anionic homopolymeric inhibitors on the ...

    African Journals Online (AJOL)

    This paper describes the effect of biocides and of the anionic homopolymeric inhibitors on the precipitation behavior of calcium fluoride (CaF2).The efficiency of inhibitors in the presence and absence of biocides was calculated using the half-life (t1/2) approach, where 50% of the concentration has been precipitated.

  13. Adsorption and intercalation of anionic surfactants onto layered ...

    Indian Academy of Sciences (India)

    Unknown

    Department of Polymer Technology, Kamaraj College of Engineering and Technology, Virudhunagar 626 ... Layered double hydroxides (LDH) with brucite like structure was modified with various anionic ... Recently the application of layered double hydroxides ..... Yuan Q, Wei M, Wang Z and Duan X 2004 Clays Clay Miner.

  14. Contribution of attendant anions on cadmium toxicity to soil enzymes.

    Science.gov (United States)

    Tian, Haixia; Kong, Long; Megharaj, Mallavarapu; He, Wenxiang

    2017-11-01

    Sorption and desorption are critical processes to control the mobility and biotoxicity of cadmium (Cd) in soils. It is known that attendant anion species of heavy metals could affect metal adsorption on soils and might further alter their biotoxicity. However, for Cd, the influence of attendant anions on its sorption in soils and subsequent toxicity on soil enzymes are still unknown. In this work, four Cd compounds with different salt anions (SO 4 2- , NO 3 - , Cl - , and Ac - ) were selected to investigate their impact of on the sorption, soil dehydrogenase activity (DHA) and alkaline phosphatase activity (ALP). Thus, a series of simulated Cd pollution batch experiments including measuring adsorption-desorption behavior of Cd on soils and soil enzyme activities were carried out. Results showed that CdSO 4 exhibited highest sorption capacity among the tested soils except in Hunan soil. The Cd sorption with NO 3 - displayed a similar behavior with Cl - on all tested soils. Compared with soil properties, all four kinds of anions on Cd sorption played a more significant role affecting Cd ecological toxicity to soil DHA and ALP. Cd in acetate or nitrate form appears more sensitive towards DHA than sulphate and chloride, while the later pair is more toxic towards ALP than the former. These results have important implications for evaluation of Cd contamination using soil enzyme as bioindicator. Copyright © 2017 Elsevier Ltd. All rights reserved.

  15. Efficiency of superoxide anions in the inactivation of selected dehydrogenases

    International Nuclear Information System (INIS)

    Rodacka, Aleksandra; Serafin, Eligiusz; Puchala, Mieczyslaw

    2010-01-01

    The most ubiquitous of the primary reactive oxygen species, formed in all aerobes, is the superoxide free radical. It is believed that the superoxide anion radical shows low reactivity and in oxidative stress it is regarded mainly as an initiator of more reactive species such as · OH and ONOO - . In this paper, the effectiveness of inactivation of selected enzymes by radiation-generated superoxide radicals in comparison with the effectiveness of the other products of water radiolysis is examined. We investigate three enzymes: glyceraldehyde-3-phosphate dehydrogenase (GAPDH), alcohol dehydrogenase (ADH) and lactate dehydrogenase (LDH). We show that the direct contribution of the superoxide anion radical to GAPDH and ADH inactivation is significant. The effectiveness of the superoxide anion in the inactivation of GAPDH and ADG was only 2.4 and 2.8 times smaller, respectively, in comparison with hydroxyl radical. LDH was practically not inactivated by the superoxide anion. Despite the fact that the studied dehydrogenases belong to the same class of enzymes (oxidoreductases), all have a similar molecular weight and are tetramers, their susceptibility to free-radical damage varies. The differences in the radiosensitivity of the enzymes are not determined by the basic structural parameters analyzed. A significant role in inactivation susceptibility is played by the type of amino acid residues and their localization within enzyme molecules.

  16. Efficiency of superoxide anions in the inactivation of selected dehydrogenases

    Energy Technology Data Exchange (ETDEWEB)

    Rodacka, Aleksandra, E-mail: olakow@biol.uni.lodz.p [Department of Molecular Biophysics, University of Lodz, Banacha 12/16, 90-237 Lodz (Poland); Serafin, Eligiusz, E-mail: serafin@biol.uni.lodz.p [Laboratory of Computer and Analytical Techniques, University of Lodz, Banacha 12/16, 90-237 Lodz (Poland); Puchala, Mieczyslaw, E-mail: puchala@biol.uni.lodz.p [Department of Molecular Biophysics, University of Lodz, Banacha 12/16, 90-237 Lodz (Poland)

    2010-09-15

    The most ubiquitous of the primary reactive oxygen species, formed in all aerobes, is the superoxide free radical. It is believed that the superoxide anion radical shows low reactivity and in oxidative stress it is regarded mainly as an initiator of more reactive species such as {sup {center_dot}}OH and ONOO{sup -}. In this paper, the effectiveness of inactivation of selected enzymes by radiation-generated superoxide radicals in comparison with the effectiveness of the other products of water radiolysis is examined. We investigate three enzymes: glyceraldehyde-3-phosphate dehydrogenase (GAPDH), alcohol dehydrogenase (ADH) and lactate dehydrogenase (LDH). We show that the direct contribution of the superoxide anion radical to GAPDH and ADH inactivation is significant. The effectiveness of the superoxide anion in the inactivation of GAPDH and ADG was only 2.4 and 2.8 times smaller, respectively, in comparison with hydroxyl radical. LDH was practically not inactivated by the superoxide anion. Despite the fact that the studied dehydrogenases belong to the same class of enzymes (oxidoreductases), all have a similar molecular weight and are tetramers, their susceptibility to free-radical damage varies. The differences in the radiosensitivity of the enzymes are not determined by the basic structural parameters analyzed. A significant role in inactivation susceptibility is played by the type of amino acid residues and their localization within enzyme molecules.

  17. based anion exchange membrane for alkaline polymer electrolyte

    Indian Academy of Sciences (India)

    Administrator

    Abstract. Hydroxyl ion (OH–) conducting anion exchange membranes based on modified poly (phenylene oxide) are fabricated for their application in alkaline polymer electrolyte fuel cells (APEFCs). In the present study, chloromethylation of poly(phenylene oxide) (PPO) is performed by aryl substitution rather than benzyl.

  18. Anion-exchange membranes in electrochemical energy systems

    NARCIS (Netherlands)

    Varcoe, J.R.; Atanassov, P.; Dekel, D.R.; Herring, A.M.; Hickner, M.A.; Kohl, P.A.; Kucernak, A. R.; Mustain, W.E.; Nijmeijer, K.; Scott, Keith; Xu, Tongwen; Zhuang, Lin

    2014-01-01

    This article provides an up-to-date perspective on the use of anion-exchange membranes in fuel cells, electrolysers, redox flow batteries, reverse electrodialysis cells, and bioelectrochemical systems (e.g. microbial fuel cells). The aim is to highlight key concepts, misconceptions, the current

  19. Anion complexation by calix[4]arene–TTF conjugates

    Czech Academy of Sciences Publication Activity Database

    Flídrová, K.; Tkadlecová, M.; Lang, Kamil; Lhoták, P.

    2012-01-01

    Roč. 92, č. 1 (2012), s. 668-673 ISSN 0143-7208 R&D Projects: GA ČR GA203/09/0691 Institutional research plan: CEZ:AV0Z40320502 Keywords : calix[4]arene * tetrathiafulvalene * anion recognition * receptor * NMR titration * UV/vis spectroscopy Subject RIV: CA - Inorganic Chemistry Impact factor: 3.532, year: 2012

  20. Novel Biscalix[4]arene-based Anion Receptors

    Czech Academy of Sciences Publication Activity Database

    Šťastný, V.; Lhoták, P.; Michlová, V.; Stibor, I.; Sýkora, Jan

    2002-01-01

    Roč. 58, č. 36 (2002), s. 7207-7211 ISSN 0040-4020 R&D Projects: GA ČR GA104/00/1722; GA ČR GA203/00/1011 Keywords : calixarenes * anion receptors * NMR titration Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 2.420, year: 2002