WorldWideScience

Sample records for binds metal ions

  1. Metal ion binding with dehydroannulenes – Plausible two ...

    Indian Academy of Sciences (India)

    WINTEC

    Abstract. Theoretical investigations have been carried out at B3LYP/6-311++G** level of theory to study the binding interaction of various metal ions, Li+, Na+ and K+ with dehydroannulene systems. The present study reveals that alkali metal ions bind strongly to dehydroannulenes and the passage through the central.

  2. Metal ion binding with dehydroannulenes – Plausible two ...

    Indian Academy of Sciences (India)

    WINTEC

    has highest interaction energy of –50∙6 kcal/mol at. B3LYP/6-311++G** level and is 128∙0 kcal/mol more than 1′-K+ complex. Understandably, the binding energy of metal complexes decreases with increase in the size of the metal ion, in accordance with ear- lier results.16,21. Placement of the metal ions at the centroid of ...

  3. Metal ion binding to iron oxides

    NARCIS (Netherlands)

    Hiemstra, T.; Riemsdijk, van W.H.; Benedetti, M.F.; Ponthieu, M.

    2006-01-01

    The biogeochemistry of trace elements (TE) is largely dependent upon their interaction with heterogeneous ligands including metal oxides and hydrous oxides of iron. The modeling of TE interactions with iron oxides has been pursued using a variety of chemical models. The objective of this work is to

  4. Chirality-induced conformational preferences in peptide-metal ion binding revealed by IR spectroscopy

    NARCIS (Netherlands)

    Dunbar, R.C.; Steill, J.D.; Oomens, J.

    2011-01-01

    Chirality reversal of a residue in a peptide can change its mode of binding to a metal ion, as shown here experimentally by gas-phase IR spectroscopy of peptide−metal ion complexes. The binding conformations of Li+, Na+, and H+ with the ll and dl stereoisomers of PhePhe were compared through IR ion

  5. Chirality-Induced Conformational Preferences in Peptide-Metal Ion Binding Revealed by IR Spectroscopy

    NARCIS (Netherlands)

    Dunbar, R. C.; Steill, J. D.; Oomens, J.

    2011-01-01

    Chirality reversal of a residue in a peptide can change its mode of binding to a metal ion, as shown here experimentally by gas-phase IR spectroscopy of peptide metal ion complexes. The binding conformations of Li+, Na+, and H+ with the LL and DL stereoisomers of PhePhe were compared through IR ion

  6. Importance of diffuse metal ion binding to RNA.

    Science.gov (United States)

    Tan, Zhi-Jie; Chen, Shi-Jie

    2011-01-01

    RNAs are highly charged polyanionic molecules. RNA structure and function are strongly correlated with the ionic condition of the solution. The primary focus of this article is on the role of diffusive ions in RNA folding. Due to the long-range nature of electrostatic interactions, the diffuse ions can contribute significantly to RNA structural stability and folding kinetics. We present an overview of the experimental findings as well as the theoretical developments on the diffuse ion effects in RNA folding. This review places heavy emphasis on the effect of magnesium ions. Magnesium ions play a highly efficient role in stabilizing RNA tertiary structures and promoting tertiary structural folding. The highly efficient role goes beyond the mean-field effect such as the ionic strength. In addition to the effects of specific ion binding and ion dehydration, ion-ion correlation for the diffuse ions can contribute to the efficient role of the multivalent ions such as the magnesium ions in RNA folding.

  7. Generic NICA-Donnan model parameters for metal-ion binding by humic substances

    NARCIS (Netherlands)

    Milne, C.J.; Kinniburgh, D.G.; Riemsdijk, van W.H.; Tipping, E.

    2003-01-01

    A total of 171 datasets of literature and experimental data for metal-ion binding by fulvic and humic acids have been digitized and re-analyzed using the NICA-Donnan model. Generic parameter values have been derived that can be used for modeling in the absence of specific metal-ion binding

  8. MeRNA: a Database of Metal Ion Binding Sites in RNAStructures

    Energy Technology Data Exchange (ETDEWEB)

    Stefan, Liliana R.; Zhang, Rui; Levitan, Aaron G.; Hendrix, DonnaF.; Brenner, Steven E.; Holbrook, Stephen R.

    2005-10-05

    Metal ions are essential for the folding of RNA into stable tertiary structures and for the catalytic activity of some RNA enzymes. To aid in the study of the roles of metal ions in RNA structural biology, we have created MeRNA (Metals in RNA), a comprehensive compilation of all metal binding sites identified in RNA three-dimensional structures available from the Protein Data Bank (PDB) and Nucleic Acid Database (NDB). Currently, our database contains information relating to binding of 9764 metal ions corresponding to 23 distinct elements; in 256 RNA structures. The metal ion locations were confirmed and ligands characterized using original literature references. MeRNA includes eight manually identified metal-ion binding motifs, which are described in the literature. MeRNA is searchable by PDB identifier, metal ion, method of structure determination, resolution and R-values for X-ray structure, and distance from metal to any RNA atom or to water. New structures with their respective binding motifs will be added to the database as they become available. The MeRNA database will further our understanding of the roles of metal ions in RNA folding and catalysis and have applications in structural and functional analysis, RNA design and engineering.

  9. Calculated distortions induced by metal-ion binding to simple oligonucleotide systems: Implications for toxicity

    Energy Technology Data Exchange (ETDEWEB)

    Turner, J.E.; Hingerty, B.E.; England, M.W.; Jacobson, K.B.

    1990-01-01

    We have previously published detailed results of calculations of the binding of the metal ions, Cd{sup 2+} and Ca{sup 2+}, to the dinucleoside monophosphate GpC in water. These ions, which have the same charge and radius, differ enormously in their toxicity to man and other biological systems. Our calculations showed contrasting behavior in the binding of these two metal ions to GpC. We suggest the hypothesis that structural distortions calculated for metal ions binding to simple nucleic-acid systems might serve as a indicator of an ion's potential ability to alter molecular activity and hence to be toxic to an organism. Furthermore, the degree of distortion might be correlated with the degree of toxicity as measured by some suitable criteria. The present paper reports the results of binding calculations for a number of other metal ions, of different valence states, with several dinucleoside monophosphates in water. A general trend of distortion with the type of binding of the metal ions is found. We are seeking quantitative measures of distortion to correlate with indicators of acute toxicity that we have measured for 24 metal ions using mice, Drosophila, and CHO cells. 3 refs., 3 figs.

  10. Metal ion interaction of an oligopeptide fragment representing the regulatory metal binding site of a CueR protein

    DEFF Research Database (Denmark)

    Jancsó, Attila; Szokolai, Hajnalka; Roszahegyi, Livia

    2013-01-01

    Metalloregulatory proteins of the MerR family are transcriptional activators that sense/control the concentration of various metal ions inside bacteria.1 The Cu+ efflux regulator CueR, similarly to other MerR proteins, possesses a short multiple Cys-containing metal binding loop close to the C......-terminus. CueR has a high selectivity for Cu+, Ag+ and Au+, but exhibits no transcriptional activity for the divalent ions Hg2+ and Zn2+.2 The two Cys- residues of the metal binding loop were shown to settle M+ ions into a linear coordination environment but other factors may also play a role in the recognition...... of cognate metal ions.2 Nevertheless, it is an interesting question whether the same sequence, when removed from the protein, shows a flexibility to adopt different coordination environments and may efficiently bind metal ions having preferences for larger coordination numbers....

  11. NMR Structures and Dynamics in a Prohead RNA Loop that Binds Metal Ions.

    Science.gov (United States)

    Gu, Xiaobo; Park, Sun-Young; Tonelli, Marco; Cornilescu, Gabriel; Xia, Tianbing; Zhong, Dongping; Schroeder, Susan J

    2016-10-06

    Metal ions are critical for RNA structure and enzymatic activity. We present the structure of an asymmetric RNA loop that binds metal ions and has an essential function in a bacteriophage packaging motor. Prohead RNA is a noncoding RNA that is required for genome packaging activity in phi29-like bacteriophage. The loops in GA1 and phi29 bacteriophage share a conserved adenine that forms a base triple, although the structural context for the base triple differs. NMR relaxation studies and femtosecond time-resolved fluorescence spectroscopy reveal the dynamic behavior of the loop in the metal ion bound and unbound forms. The mechanism of metal ion binding appears to be an induced conformational change between two dynamic ensembles rather than a conformational capture mechanism. These results provide experimental benchmarks for computational models of RNA-metal ion interactions.

  12. Towards the role of metal ions in the structural variability of proteins: CdII speciation of a metal ion binding loop motif

    DEFF Research Database (Denmark)

    Jancsó, Attila; Szunyogh, Dániel; Gyurcsik, Béla

    2011-01-01

    A de novo designed dodecapeptide (HS), inspired by the metal binding loops of metal-responsive transcriptional activators, was synthesized. The aim was to create a model system for structurally promiscuous and intrinsically unstructured proteins, and explore the effect of metal ions on their stru...... the peptide is exchanging between a number of structures also in its metal ion bound state(s), as indicated by NMR and PAC data. © 2011 The Royal Society of Chemistry....

  13. A mononuclear non-heme manganese(IV)-oxo complex binding redox-inactive metal ions.

    Science.gov (United States)

    Chen, Junying; Lee, Yong-Min; Davis, Katherine M; Wu, Xiujuan; Seo, Mi Sook; Cho, Kyung-Bin; Yoon, Heejung; Park, Young Jun; Fukuzumi, Shunichi; Pushkar, Yulia N; Nam, Wonwoo

    2013-05-01

    Redox-inactive metal ions play pivotal roles in regulating the reactivities of high-valent metal-oxo species in a variety of enzymatic and chemical reactions. A mononuclear non-heme Mn(IV)-oxo complex bearing a pentadentate N5 ligand has been synthesized and used in the synthesis of a Mn(IV)-oxo complex binding scandium ions. The Mn(IV)-oxo complexes were characterized with various spectroscopic methods. The reactivities of the Mn(IV)-oxo complex are markedly influenced by binding of Sc(3+) ions in oxidation reactions, such as a ~2200-fold increase in the rate of oxidation of thioanisole (i.e., oxygen atom transfer) but a ~180-fold decrease in the rate of C-H bond activation of 1,4-cyclohexadiene (i.e., hydrogen atom transfer). The present results provide the first example of a non-heme Mn(IV)-oxo complex binding redox-inactive metal ions that shows a contrasting effect of the redox-inactive metal ions on the reactivities of metal-oxo species in the oxygen atom transfer and hydrogen atom transfer reactions.

  14. Identification of metal ion binding sites based on amino acid sequences

    Science.gov (United States)

    Cao, Xiaoyong; Zhang, Xiaojin; Gao, Sujuan; Ding, Changjiang; Feng, Yonge; Bao, Weihua

    2017-01-01

    The identification of metal ion binding sites is important for protein function annotation and the design of new drug molecules. This study presents an effective method of analyzing and identifying the binding residues of metal ions based solely on sequence information. Ten metal ions were extracted from the BioLip database: Zn2+, Cu2+, Fe2+, Fe3+, Ca2+, Mg2+, Mn2+, Na+, K+ and Co2+. The analysis showed that Zn2+, Cu2+, Fe2+, Fe3+, and Co2+ were sensitive to the conservation of amino acids at binding sites, and promising results can be achieved using the Position Weight Scoring Matrix algorithm, with an accuracy of over 79.9% and a Matthews correlation coefficient of over 0.6. The binding sites of other metals can also be accurately identified using the Support Vector Machine algorithm with multifeature parameters as input. In addition, we found that Ca2+ was insensitive to hydrophobicity and hydrophilicity information and Mn2+ was insensitive to polarization charge information. An online server was constructed based on the framework of the proposed method and is freely available at http://60.31.198.140:8081/metal/HomePage/HomePage.html. PMID:28854211

  15. A Mononuclear Non-Heme Manganese(IV)-Oxo Complex Binding Redox-Inactive Metal Ions

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Junying; Lee, Yong-Min; Davis, Katherine M.; Wu, Xiujuan; Seo, Mi Sook; Cho, Kyung-Bin; Yoon, Heejung; Park, Young Jun; Fukuzumi, Shunichi; Pushkar, Yulia N.; Nam, Wonwoo [Ewha; (Purdue); (Osaka)

    2013-05-29

    Redox-inactive metal ions play pivotal roles in regulating the reactivities of high-valent metal–oxo species in a variety of enzymatic and chemical reactions. A mononuclear non-heme Mn(IV)–oxo complex bearing a pentadentate N5 ligand has been synthesized and used in the synthesis of a Mn(IV)–oxo complex binding scandium ions. The Mn(IV)–oxo complexes were characterized with various spectroscopic methods. The reactivities of the Mn(IV)–oxo complex are markedly influenced by binding of Sc3+ ions in oxidation reactions, such as a ~2200-fold increase in the rate of oxidation of thioanisole (i.e., oxygen atom transfer) but a ~180-fold decrease in the rate of C–H bond activation of 1,4-cyclohexadiene (i.e., hydrogen atom transfer). The present results provide the first example of a non-heme Mn(IV)–oxo complex binding redox-inactive metal ions that shows a contrasting effect of the redox-inactive metal ions on the reactivities of metal–oxo species in the oxygen atom transfer and hydrogen atom transfer reactions.

  16. Micro-Capillary Coatings Based on Spiropyran Polymeric Brushes for Metal Ion Binding, Detection, and Release in Continuous Flow

    Directory of Open Access Journals (Sweden)

    Aishling Dunne

    2018-04-01

    Full Text Available Micro-capillaries, capable of light-regulated binding and qualitative detection of divalent metal ions in continuous flow, have been realised through functionalisation with spiropyran photochromic brush-type coatings. Upon irradiation with UV light, the coating switches from the passive non-binding spiropyran form to the active merocyanine form, which binds different divalent metal ions (Zn2+, Co2+, Cu2+, Ni2+, Cd2+, as they pass through the micro-capillary. Furthermore, the merocyanine visible absorbance spectrum changes upon metal ion binding, enabling the ion uptake to be detected optically. Irradiation with white light causes reversion of the merocyanine to the passive spiropyran form, with simultaneous release of the bound metal ion from the micro-capillary coating.

  17. Binding of monovalent alkali metal ions with negatively charged phospholipid membranes.

    Science.gov (United States)

    Maity, Pabitra; Saha, Baishakhi; Kumar, Gopinatha Suresh; Karmakar, Sanat

    2016-04-01

    We have systematically investigated the effect of various alkali metal ions with negatively charged phospholipid membranes. Size distributions of large unilamellar vesicles have been confirmed using dynamic light scattering. Zeta potential and effective charges per vesicle in the presence of various alkali metal ions have been estimated from the measured electrophoretic mobility. We have determined the intrinsic binding constant from the zeta potential using electrostatic double layer theory. The reasonable and consistent value of the intrinsic binding constant of Na(+), found at moderate NaCl concentration (10-100 mM), indicates that the Gouy-Chapman theory cannot be applied for very high (> 100mM) and very low (concentrations. The isothermal titration calorimetry study has revealed that the net binding heat of interaction of the negatively charged vesicles with monovalent alkali metal ions is small and comparable to those obtained from neutral phosphatidylcholine vesicles. The overall endothermic response of binding heat suggests that interaction is primarily entropy driven. The entropy gain might arise due to the release of water molecules from the hydration layer vicinity of the membranes. Therefore, the partition model which does not include the electrostatic contribution suffices to describe the interaction. The binding constant of Na(+) (2.4 ± 0.1 M(-1)), obtained from the ITC, is in agreement with that estimated from the zeta potential (-2.0 M(-1)) at moderate salt concentrations. Our results suggest that hydration dynamics may play a vital role in the membrane solution interface which strongly affects the ion-membrane interaction. Copyright © 2016 Elsevier B.V. All rights reserved

  18. Characteristics of the brown hagfish Paramyxine atami transthyretin: Metal ion-dependent thyroid hormone binding.

    Science.gov (United States)

    Suzuki, Shunsuke; Kasai, Kentaro; Nishiyama, Norihito; Ishihara, Akinori; Yamauchi, Kiyoshi

    2017-08-01

    Transthyretin (TTR) is a vertebrate-specific protein involved in thyroid hormone distribution in plasma, and its gene is thought to have emerged by gene duplication from the gene for the ancient TTR-related protein, 5-hydroxyisourate hydrolase, at some early stage of chordate evolution. We investigated the molecular and hormone-binding properties of the brown hagfish Paramyxine atami TTR. The amino acid sequence deduced from the cloned hagfish TTR cDNA shared 33-50% identities with those of other vertebrate TTRs but less than 24% identities with those of vertebrate and deuterostome invertebrate 5-hydroxyisourate hydrolases. Hagfish TTR, as well as lamprey and little skate TTRs, had an N-terminal histidine-rich segment, allowing purification by metal-affinity chromatography. The affinity of hagfish TTR for 3,3',5-triiodo-L-thyronine (T3) was 190 times higher than that for L-thyroxine, with a dissociation constant of 1.5-3.9nM at 4°C. The high-affinity binding sites were strongly sensitive to metal ions. Zn 2+ and Cu 2+ decreased the dissociation constant to one-order of magnitude, whereas a chelator, o-phenanthroline, increased it four times. The number of metal ions (mainly Zn 2+ and Cu 2+ ) was approximately 12/TTR (mol/mol). TTR was also a major T3-binding protein in adult hagfish sera and its serum concentration was approximately 8μM. These results suggest that metal ions and the acquisition of N-terminal histidine-rich segment may cooperatively contribute to the evolution toward an ancient TTR with high T3 binding activity from either 5-hydroxyisourate hydrolase after gene duplication. Copyright © 2017 Elsevier Inc. All rights reserved.

  19. Cellulose Nanocrystals Obtained from Rice By-Products and Their Binding Potential to Metallic Ions

    Directory of Open Access Journals (Sweden)

    Vanessa L. Albernaz

    2015-01-01

    Full Text Available The present study aimed to develop and optimize a method to obtain cellulose nanocrystals from the agricultural by-products rice husk and straw and to evaluate their electrostructural modifications in the presence of metallic ions. First, different particle formation conditions and routes were tested and analyzed by spectrophotometry, dynamic light scattering (DLS, and Zeta potential measurements. Then, electrostructural effects of ions Na(I, Cd(II, and Al(III on the optimized nanoparticles were analyzed by atomic force microscopy (AFM, scanning electron microscopy (SEM, and electrical conductivity (EC assessments. The produced cellulose nanocrystals adopted a rod-like shape. AFM height distribution and EC data indicated that the nanocrystals have more affinity in binding with Na(I > Al(III > Cd(II. These data suggest that the use of these cellulose nanocrystals in the bioremediation field is promising, both in metal sorption from wastewater and as an alternative for water desalination.

  20. Proton and metal ion binding to natural organic polyelectrolytes-I. Studies with synthetic model compounds

    Science.gov (United States)

    Marinsky, J.A.; Reddy, M.M.

    1984-01-01

    A unified physico-chemical model, based on a modified Henderson-Hasselbalch equation, for the analysis of ion complexation reactions involving charged polymeric systems is presented and verified. In this model pH = pKa+p(??Ka) + log(??/1 - ??) where Ka is the intrinsic acid dissociation constant of the ionizable functional groups on the polymer, ??Ka is the deviation of the intrinsic constant due to electrostatic interaction between the hydrogen ion and the polyanion, and alpha (??) is the polyacid degree of ionization. Using this approach pKa values for repeating acidic units of polyacrylic (PAA) and polymethacrylic (PMA) acids were found to be 4.25 ?? 0.03 and 4.8 ?? 0.1, respectively. The polyion electrostatic deviation term derived from the potentiometric titration data (i.e. p(??Ka)) is used to calculate metal ion concentration at the complexation site on the surface of the polyanion. Intrinsic cobalt-polycarboxylate binding constants (7.5 for PAA and 5.6 for PMA), obtained using this procedure, are consistent with the range of published binding constants for cobalt-monomer carboxylate complexes. In two phase systems incorporation of a Donnan membrane potential term allows determination of the intrinsic pKa of a cross-linked PMA gel, pKa = 4.83, in excellent agreement with the value obtained for the linear polyelectrolyte and the monomer. Similarly, the intrinsic stability constant for cobalt ion binding to a PMA-gel (??CoPMA+ = 11) was found to be in agreement with the linear polyelectrolyte analogue and the published data for cobalt-carboxylate monodentate complexes. ?? 1984.

  1. Neutralizing mutations of carboxylates that bind metal 2 in T5 flap endonuclease result in an enzyme that still requires two metal ions.

    Science.gov (United States)

    Tomlinson, Christopher G; Syson, Karl; Sengerová, Blanka; Atack, John M; Sayers, Jon R; Swanson, Linda; Tainer, John A; Williams, Nicholas H; Grasby, Jane A

    2011-09-02

    Flap endonucleases (FENs) are divalent metal ion-dependent phosphodiesterases. Metallonucleases are often assigned a "two-metal ion mechanism" where both metals contact the scissile phosphate diester. The spacing of the two metal ions observed in T5FEN structures appears to preclude this mechanism. However, the overall reaction catalyzed by wild type (WT) T5FEN requires three Mg(2+) ions, implying that a third ion is needed during catalysis, and so a two-metal ion mechanism remains possible. To investigate the positions of the ions required for chemistry, a mutant T5FEN was studied where metal 2 (M2) ligands are altered to eliminate this binding site. In contrast to WT T5FEN, the overall reaction catalyzed by D201I/D204S required two ions, but over the concentration range of Mg(2+) tested, maximal rate data were fitted to a single binding isotherm. Calcium ions do not support FEN catalysis and inhibit the reactions supported by viable metal cofactors. To establish participation of ions in stabilization of enzyme-substrate complexes, dissociation constants of WT and D201I/D204S-substrate complexes were studied as a function of [Ca(2+)]. At pH 9.3 (maximal rate conditions), Ca(2+) substantially stabilized both complexes. Inhibition of viable cofactor supported reactions of WT, and D201I/D204S T5FENs was biphasic with respect to Ca(2+) and ultimately dependent on 1/[Ca(2+)](2). By varying the concentration of viable metal cofactor, Ca(2+) ions were shown to inhibit competitively displacing two catalytic ions. Combined analyses imply that M2 is not involved in chemical catalysis but plays a role in substrate binding, and thus a two-metal ion mechanism is plausible.

  2. Neutralizing Mutations of Carboxylates That Bind Metal 2 in T5 Flap Endonuclease Result in an Enzyme That Still Requires Two Metal Ions*

    Science.gov (United States)

    Tomlinson, Christopher G.; Syson, Karl; Sengerová, Blanka; Atack, John M.; Sayers, Jon R.; Swanson, Linda; Tainer, John A.; Williams, Nicholas H.; Grasby, Jane A.

    2011-01-01

    Flap endonucleases (FENs) are divalent metal ion-dependent phosphodiesterases. Metallonucleases are often assigned a “two-metal ion mechanism” where both metals contact the scissile phosphate diester. The spacing of the two metal ions observed in T5FEN structures appears to preclude this mechanism. However, the overall reaction catalyzed by wild type (WT) T5FEN requires three Mg2+ ions, implying that a third ion is needed during catalysis, and so a two-metal ion mechanism remains possible. To investigate the positions of the ions required for chemistry, a mutant T5FEN was studied where metal 2 (M2) ligands are altered to eliminate this binding site. In contrast to WT T5FEN, the overall reaction catalyzed by D201I/D204S required two ions, but over the concentration range of Mg2+ tested, maximal rate data were fitted to a single binding isotherm. Calcium ions do not support FEN catalysis and inhibit the reactions supported by viable metal cofactors. To establish participation of ions in stabilization of enzyme-substrate complexes, dissociation constants of WT and D201I/D204S-substrate complexes were studied as a function of [Ca2+]. At pH 9.3 (maximal rate conditions), Ca2+ substantially stabilized both complexes. Inhibition of viable cofactor supported reactions of WT, and D201I/D204S T5FENs was biphasic with respect to Ca2+ and ultimately dependent on 1/[Ca2+]2. By varying the concentration of viable metal cofactor, Ca2+ ions were shown to inhibit competitively displacing two catalytic ions. Combined analyses imply that M2 is not involved in chemical catalysis but plays a role in substrate binding, and thus a two-metal ion mechanism is plausible. PMID:21734257

  3. Metal Ion Binding at the Catalytic Site Induces Widely Distributed Changes in a Sequence Specific Protein-DNA Complex.

    Science.gov (United States)

    Sinha, Kaustubh; Sangani, Sahil S; Kehr, Andrew D; Rule, Gordon S; Jen-Jacobson, Linda

    2016-11-08

    Metal ion cofactors can alter the energetics and specificity of sequence specific protein-DNA interactions, but it is unknown if the underlying effects on structure and dynamics are local or dispersed throughout the protein-DNA complex. This work uses EcoRV endonuclease as a model, and catalytically inactive lanthanide ions, which replace the Mg 2+ cofactor. Nuclear magnetic resonance (NMR) titrations indicate that four Lu 3+ or two La 3+ cations bind, and two new crystal structures confirm that Lu 3+ binding is confined to the active sites. NMR spectra show that the metal-free EcoRV complex with cognate (GATATC) DNA is structurally distinct from the nonspecific complex, and that metal ion binding sites are not assembled in the nonspecific complex. NMR chemical shift perturbations were determined for 1 H- 15 N amide resonances, for 1 H- 13 C Ile-δ-CH 3 resonances, and for stereospecifically assigned Leu-δ-CH 3 and Val-γ-CH 3 resonances. Many chemical shifts throughout the cognate complex are unperturbed, so metal binding does not induce major conformational changes. However, some large perturbations of amide and side chain methyl resonances occur as far as 34 Å from the metal ions. Concerted changes in specific residues imply that local effects of metal binding are propagated via a β-sheet and an α-helix. Both amide and methyl resonance perturbations indicate changes in the interface between subunits of the EcoRV homodimer. Bound metal ions also affect amide hydrogen exchange rates for distant residues, including a distant subdomain that contacts DNA phosphates and promotes DNA bending, showing that metal ions in the active sites, which relieve electrostatic repulsion between protein and DNA, cause changes in slow dynamics throughout the complex.

  4. Metal Ion Binding at the Catalytic Site Induces Widely Distributed Changes in a Sequence Specific Protein–DNA Complex

    Science.gov (United States)

    2016-01-01

    Metal ion cofactors can alter the energetics and specificity of sequence specific protein–DNA interactions, but it is unknown if the underlying effects on structure and dynamics are local or dispersed throughout the protein–DNA complex. This work uses EcoRV endonuclease as a model, and catalytically inactive lanthanide ions, which replace the Mg2+ cofactor. Nuclear magnetic resonance (NMR) titrations indicate that four Lu3+ or two La3+ cations bind, and two new crystal structures confirm that Lu3+ binding is confined to the active sites. NMR spectra show that the metal-free EcoRV complex with cognate (GATATC) DNA is structurally distinct from the nonspecific complex, and that metal ion binding sites are not assembled in the nonspecific complex. NMR chemical shift perturbations were determined for 1H–15N amide resonances, for 1H–13C Ile-δ-CH3 resonances, and for stereospecifically assigned Leu-δ-CH3 and Val-γ-CH3 resonances. Many chemical shifts throughout the cognate complex are unperturbed, so metal binding does not induce major conformational changes. However, some large perturbations of amide and side chain methyl resonances occur as far as 34 Å from the metal ions. Concerted changes in specific residues imply that local effects of metal binding are propagated via a β-sheet and an α-helix. Both amide and methyl resonance perturbations indicate changes in the interface between subunits of the EcoRV homodimer. Bound metal ions also affect amide hydrogen exchange rates for distant residues, including a distant subdomain that contacts DNA phosphates and promotes DNA bending, showing that metal ions in the active sites, which relieve electrostatic repulsion between protein and DNA, cause changes in slow dynamics throughout the complex. PMID:27786446

  5. Quantifying metal ions binding onto dissolved organic matter using log-transformed absorbance spectra.

    Science.gov (United States)

    Yan, Mingquan; Wang, Dongsheng; Korshin, Gregory V; Benedetti, Marc F

    2013-05-01

    This study introduces the concept of consistent examination of changes of log-transformed absorbance spectra of dissolved organic matter (DOM) at incrementally increasing concentrations of heavy metal cations such as copper, cadmium, and aluminum at environmentally relevant concentrations. The approach is designed to highlight contributions of low-intensity absorbance features that appear to be especially sensitive to DOM reactions. In accord with this approach, log-transformed absorbance spectra of fractions of DOM from the Suwannee River were acquired at varying pHs and concentrations of copper, cadmium, and aluminum. These log-transformed spectra were processed using the differential approach and used to examine the nature of the observed changes of DOM absorbance and correlate them with the extent of Me-DOM complexation. Two alternative parameters, namely the change of the spectral slope in the range of wavelengths 325-375 nm (DSlope325-375) and differential logarithm of DOM absorbance at 350 nm (DLnA350) were introduced to quantify Cu(II), Cd(II), and Al(III) binding onto DOMs. DLnA350 and DSlope325-375 datasets were compared with the amount of DOM-bound Cu(II), Cd(II), and Al(III) estimated based on NICA-Donnan model calculations. This examination showed that the DLnA350 and DSlope325-375 acquired at various pH values, metal ions concentrations, and DOM types were strongly and unambiguously correlated with the concentration of DOM-bound metal ions. The obtained experimental results and their interpretation indicate that the introduced DSlope325-375 and DLnA35 parameters are predictive of and can be used to quantify in situ metal ions interactions with DOMs. The presented approach can be used to gain more information about DOM-metal interactions and for further optimization of existing formal models of metal-DOM complexation. Copyright © 2013 Elsevier Ltd. All rights reserved.

  6. Effects of urea, metal ions and surfactants on the binding of baicalein with bovine serum albumin

    Directory of Open Access Journals (Sweden)

    Atanu Singha Roy

    2016-08-01

    Full Text Available The interaction of baicalein with bovine serum albumin (BSA was investigated with the help of spectroscopic and molecular docking studies. The binding affinity of baicalein towards BSA was estimated to be in order of 105 M−1 from fluorescence quenching studies. Negative ΔH° (−5.66±0.14 kJ/mol and positive (ΔS° (+79.96±0.65 J/mol K indicate the presence of electrostatic interactions along with the hydrophobic forces that result in a positive ΔS°. The hydrophobic association of baicalein with BSA diminishes in the presence of sodium dodecyl sulfate (SDS due to probable hydrophobic association of baicalein with SDS, resulting in a negative ΔS° (−40.65±0.87 J/mol K. Matrix-assisted laser desorption ionization/time of flight (MALDI--TOF experiments indicate a 1:1 complexation between baicalein and BSA. The unfolding and refolding phenomena of BSA were investigated in the absence and presence of baicalein using steady-state and fluorescence lifetime measurements. It was observed that the presence of urea ruptured the non-covalent interaction between baicalein and BSA. The presence of metal ions (Ag+, Mg2+, Ni2+, Mn2+, Co2+and Zn2+ increased the binding affinity of ligand towards BSA. The changes in conformational aspects of BSA after ligand binding were also investigated using circular dichroism (CD and Fourier transform infrared (FT-IR spectroscopic techniques. Site selectivity studies following molecular docking analyses indicated the binding of baicalein to site 1 (subdomain IIA of BSA.

  7. Metal Cation Binding to Gas-Phase Pentaalanine: Divalent Ions Restructure the Complex

    NARCIS (Netherlands)

    Dunbar, R.C.; Steill, J.D.; Polfer, N.C.; Oomens, J.

    2013-01-01

    Ion-neutral complexes of pentaalalanine with several singly- and doubly charged metal ions are examined using conformation analysis by infrared multiple photon dissociation (IRMPD) spectroscopy and density functional theory (DFT) computations. The infrared spectroscopy in the 1500-1800 cm(-1) region

  8. Benchmarking a computational design method for the incorporation of metal ion-binding sites at symmetric protein interfaces.

    Science.gov (United States)

    Hansen, William A; Khare, Sagar D

    2017-08-01

    The design of novel metal-ion binding sites along symmetric axes in protein oligomers could provide new avenues for metalloenzyme design, construction of protein-based nanomaterials and novel ion transport systems. Here, we describe a computational design method, symmetric protein recursive ion-cofactor sampling (SyPRIS), for locating constellations of backbone positions within oligomeric protein structures that are capable of supporting desired symmetrically coordinated metal ion(s) chelated by sidechains (chelant model). Using SyPRIS on a curated benchmark set of protein structures with symmetric metal binding sites, we found high recovery of native metal coordinating rotamers: in 65 of the 67 (97.0%) cases, native rotamers featured in the best scoring model while in the remaining cases native rotamers were found within the top three scoring models. In a second test, chelant models were crossmatched against protein structures with identical cyclic symmetry. In addition to recovering all native placements, 10.4% (8939/86013) of the non-native placements, had acceptable geometric compatibility scores. Discrimination between native and non-native metal site placements was further enhanced upon constrained energy minimization using the Rosetta energy function. Upon sequence design of the surrounding first-shell residues, we found further stabilization of native placements and a small but significant (1.7%) number of non-native placement-based sites with favorable Rosetta energies, indicating their designability in existing protein interfaces. The generality of the SyPRIS approach allows design of novel symmetric metal sites including with non-natural amino acid sidechains, and should enable the predictive incorporation of a variety of metal-containing cofactors at symmetric protein interfaces. © 2017 The Protein Society.

  9. Selectivity of externally facing ion-binding sites in the Na/K pump to alkali metals and organic cations.

    Science.gov (United States)

    Ratheal, Ian M; Virgin, Gail K; Yu, Haibo; Roux, Benoît; Gatto, Craig; Artigas, Pablo

    2010-10-26

    The Na/K pump is a P-type ATPase that exchanges three intracellular Na(+) ions for two extracellular K(+) ions through the plasmalemma of nearly all animal cells. The mechanisms involved in cation selection by the pump's ion-binding sites (site I and site II bind either Na(+) or K(+); site III binds only Na(+)) are poorly understood. We studied cation selectivity by outward-facing sites (high K(+) affinity) of Na/K pumps expressed in Xenopus oocytes, under voltage clamp. Guanidinium(+), methylguanidinium(+), and aminoguanidinium(+) produced two phenomena possibly reflecting actions at site III: (i) voltage-dependent inhibition (VDI) of outwardly directed pump current at saturating K(+), and (ii) induction of pump-mediated, guanidinium-derivative-carried inward current at negative potentials without Na(+) and K(+). In contrast, formamidinium(+) and acetamidinium(+) induced K(+)-like outward currents. Measurement of ouabain-sensitive ATPase activity and radiolabeled cation uptake confirmed that these cations are external K(+) congeners. Molecular dynamics simulations indicate that bound organic cations induce minor distortion of the binding sites. Among tested metals, only Li(+) induced Na(+)-like VDI, whereas all metals tested except Na(+) induced K(+)-like outward currents. Pump-mediated K(+)-like organic cation transport challenges the concept of rigid structural models in which ion specificity at site I and site II arises from a precise and unique arrangement of coordinating ligands. Furthermore, actions by guanidinium(+) derivatives suggest that Na(+) binds to site III in a hydrated form and that the inward current observed without external Na(+) and K(+) represents cation transport when normal occlusion at sites I and II is impaired. These results provide insights on external ion selectivity at the three binding sites.

  10. Dansyl-naphthalimide dyads as molecular probes: effect of spacer group on metal ion binding properties.

    Science.gov (United States)

    Shankar, Balaraman H; Ramaiah, Danaboyina

    2011-11-17

    Interaction of a few dansyl-naphthalimide conjugates 1a-e linked through polymethylene spacer groups with various metal ions was investigated through absorption, fluorescence, NMR, isothermal calorimetric (ITC), and laser flash photolysis techniques. The characteristic feature of these dyads is that they exhibit competing singlet-singlet energy transfer (SSET) and photoinduced electron transfer (PET) processes, both of which decrease with the increase in spacer length. Depending on the spacer group, these dyads interact selectively with divalent Cu(2+) and Zn(2+) ions, as compared to other mono- and divalent metal ions. Jobs plot analysis showed that these dyads form 2:3 complexes with Cu(2+) ions, while 1:1 complexes were observed with Zn(2+) ions. The association constants for the Zn(2+) and Cu(2+) complexes were determined and are found to be in the order 10(3)-10(5) M(-1). Irrespective of the length of the spacer group, these dyads interestingly act as fluorescence ratiometric molecular probes for Cu(2+) ions by altering the emission intensity of both dansyl and naphthalimide chromophores. In contrast, only the fluorescence intensity of the naphthalimide chromophore of the lower homologues (n = 1-3) was altered by Zn(2+) ions. (1)H NMR and ITC measurements confirmed the involvement of both sulfonamide and dimethylamine groups in the complexation with Cu(2+) ions, while only the latter group was involved with Zn(2+) ions. Laser excitation of the dyads 1a-e showed formation of a transient absorption which can be attributed to the radical cation of the naphthalimide chromophore, whereas only the triplet excited state of the dyads 1a-e was observed in the presence of Cu(2+) ions. Uniquely, the complexation of 1a-e with Cu(2+) ions affects both PET and SSET processes, while only the PET process was partially inhibited by Zn(2+) ions in the lower homologues (n = 1-3) and the higher homologues exhibited negligible changes in their emission properties. Our results

  11. Binding selectivity of vitamin K3 based chemosensors towards nickel(II) and copper(II) metal ions

    Science.gov (United States)

    Patil, Amit; Lande, Dipali N.; Nalkar, Archana; Gejji, Shridhar P.; Chakrovorty, Debamitra; Gonnade, Rajesh; Moniz, Tânia; Rangel, Maria; Pereira, Eulália; Salunke-Gawali, Sunita

    2017-09-01

    The vitamin K3 derivatives 2-methyl-3-[(pyridin-2-ylmethyl)-amino]-1,4-naphthoquinone (M-1), 2-methyl-3-[(pyridin-2-ylethyl)-amino]-1,4-naphthoquinone (M-2), 2-methyl-3-((2-(thiophen-2-yl)methyl)amino)naphthalene-1,4-dione (M-3) and 2-methyl-3-((2-(thiophen-2-yl)ethyl)amino)naphthalene-1,4-dione (M-4) have been synthesized, characterized and studied for their chemosensor abilities towards transition metal ions. Crystal structures of M-1 to M-4 revealed a variety of Nsbnd H⋯O, Csbnd H⋯O, Csbnd H⋯π and π⋯π interactions. Minor variations in such interactions by chemical stimuli such as metal ions, results in change in color that can be visualized by naked eyes. It has been shown that electronic structure and 1H NMR, vibrational as well as electronic spectra from the density functional theory agree well with the experiments. The metal ion binding in ethanol, ethanol-water and in mild base triethylamine brings forth recognizing ability of M-1 toward Ni2+ whereas M-2 exhibits large sensing ability for Cu2+ ion. Interestingly M-1 display varying metal ion binding specificity in different solvents with the association constant in ethanol being 11,786 M-1 for Ni2+ compared to 9462 M-1 for the Cu2+. A reversal in preferential binding of M-2 with the respective association constants being 4190 M-1 and 6370 M-1 is discernible.

  12. Water-soluble metal-binding polymers with ultrafiltration: A technology for the removal, concentration, and recovery of metal ions from aqueous streams

    International Nuclear Information System (INIS)

    Smith, B.F.; Robison, T.W.; Jarvinen, G.D.

    1997-01-01

    The use of water-soluble metal-binding polymers coupled with ultrafiltration (UF) is a technology under development to selectively concentrate and recover valuable or regulated metal-ions from dilute process or waste waters. The polymers have a sufficiently large molecular size that they can be separated and concentrated using commercially available UF technology. The polymers can then be reused by changing the solution conditions to release the metal-ions, which are recovered in a concentrated form for recycle or disposal. Pilot-scale demonstrations have been completed for a variety of waste streams containing low concentrations of metal ions including electroplating wastes (zinc and nickel) and nuclear waste streams (plutonium and americium). Many other potential commercial applications exist including remediation of contaminated solids. An overview of both the pilot-scale demonstrated applications and small scale testing of this technology are presented

  13. Water-soluble metal-binding polymers with ultrafiltration: A technology for the removal, concentration, and recovery of metal ions from aqueous streams

    Energy Technology Data Exchange (ETDEWEB)

    Smith, B.F.; Robison, T.W.; Jarvinen, G.D.

    1997-12-31

    The use of water-soluble metal-binding polymers coupled with ultrafiltration (UF) is a technology under development to selectively concentrate and recover valuable or regulated metal-ions from dilute process or waste waters. The polymers have a sufficiently large molecular size that they can be separated and concentrated using commercially available UF technology. The polymers can then be reused by changing the solution conditions to release the metal-ions, which are recovered in a concentrated form for recycle or disposal. Pilot-scale demonstrations have been completed for a variety of waste streams containing low concentrations of metal ions including electroplating wastes (zinc and nickel) and nuclear waste streams (plutonium and americium). Many other potential commercial applications exist including remediation of contaminated solids. An overview of both the pilot-scale demonstrated applications and small scale testing of this technology are presented.

  14. Competition of dipositive metal ions for Fe (III) binding sites in chelation therapy of Iron Load

    International Nuclear Information System (INIS)

    Rehmani, Fouzia S.

    2005-01-01

    Iron overload is a condition in which excessive iron deposited in the liver, kidney and spleen of human beings in the patients of beta thalassemia and sickle cell anemia. Instead of its importance iron could be toxic when in excess, it damages the tissues. For the treatment of iron overload, a drug desferrioxamine mesylate has been used. It is linear trihydroxamic acid, a natural siderophore produced by streptomyces which removes the extra iron from body. Salicylhydroxamate type siderphore. In present research salicylhydroxamate was used for the complexation with dipositive metal ions which are available in biological environments such as Mn (II), Co (II), Ni (II) and Cu (II). The aim of our work was to study the competition reactions between Fe (III) and other dipositive ions; to calculate the thermodynamic data of chelation of these metal ions complexes with hydroxamate by computer program and comparison with hydroxamate complexes. (author)

  15. Metal ions-binding T4 lysozyme as an intramolecular protein purification tag compatible with X-ray crystallography.

    Science.gov (United States)

    Boura, Evzen; Baumlova, Adriana; Chalupska, Dominika; Dubankova, Anna; Klima, Martin

    2017-06-01

    Phage T4 lysozyme is a well folded and highly soluble protein that is widely used as an insertion tag to improve solubility and crystallization properties of poorly behaved recombinant proteins. It has been used in the fusion protein strategy to facilitate crystallization of various proteins including multiple G protein-coupled receptors, lipid kinases, or sterol binding proteins. Here, we present a structural and biochemical characterization of its novel, metal ions-binding mutant (mbT4L). We demonstrate that mbT4L can be used as a purification tag in the immobilized-metal affinity chromatography and that, in many respects, it is superior to the conventional hexahistidine tag. In addition, structural characterization of mbT4L suggests that mbT4L can be used as a purification tag compatible with X-ray crystallography. © 2017 The Protein Society.

  16. Measurement of Cadmium Ion in the Presence of Metal-Binding Biopolymers in Aqueous Sample

    Directory of Open Access Journals (Sweden)

    Jian Pu

    2013-01-01

    Full Text Available In aqueous environment, water-soluble polymers are effectively used to separate free metal ions from metal-polymer complexes. The feasibilities of four different analytical techniques, cadmium ion-selective electrode, dialysis sack, chelate disk cartridge, and ultrafiltration, in distinguishing biopolymer-bound and nonbound cadmium in aqueous samples were investigated. And two different biopolymers were used, including bovine serum albumin (BSA and biopolymer solution extracted from cultivated activated sludge (ASBP. The ISE method requires relatively large amount of sample and contaminates sample during the pretreatment. After the long reaction time of dialysis, the equilibrium of cadmium in the dialysis sack would be shifted. Due to the sample nature, chelate disk cartridge could not filter within recommended time, which makes it unavailable for biopolymer use. Ultrafiltration method would not experience the difficulties mentioned above. Ultrafiltration method measuring both weakly and strongly bound cadmium was included in nominally biopolymer-cadmium complex. It had significant correlation with the Ion-selective electrode (ISE method (R2=0.989 for BSA, 0.985 for ASBP.

  17. Binding of antioxidant flavonol morin to the native state of bovine serum albumin: Effects of urea and metal ions on the binding

    Energy Technology Data Exchange (ETDEWEB)

    Singha Roy, Atanu; Dinda, Amit Kumar; Chaudhury, Susmitnarayan; Dasgupta, Swagata, E-mail: swagata@chem.iitkgp.ernet.in

    2014-01-15

    In consideration of the various medicinal aspects of the flavonoid polyphenols, the interaction of morin with bovine serum albumin (BSA) has been investigated using multi-spectroscopic approaches. The pKa{sub 1} of morin being 5.09, which is below physiological pH, binding studies provide important insights into its potential use as a biotherapeutic. The binding was performed under different pH (5, 7 and 9) conditions and in absence and presence of Cu(II) and Fe(III) ions. It is observed that the presence of metal ions affect the binding of morin towards BSA. The binding with BSA results in a motional restriction of morin in solution that causes an increase in anisotropy (r), rotational correlation time (t{sub r}) and steady-state lifetime (t{sub av}) of the ligand. Urea causes denaturation of BSA resulting in the release of morin from the protein core as determined from both the steady-state fluorescence and anisotropy (r) measurements. The possibility of non-radiative energy transfer from the donor tryptophan to the acceptor morin is detected following the Förster's theory. The site marker displacement studies along with the molecular docking results indicated that morin binds to the hydrophobic pocket of site 1 (subdomain IIA) near Trp 213 of BSA. -- Highlights: • Binding mainly occurs through the electrostatic forces with partial hydrophobic association. • Negative ΔG° indicates the spontaneity of the complexation between morin and BSA. • Morin binds near Trp 213 (site 1, subdomain IIA) of BSA only in its native state. • Lifetime of morin increases as a function of BSA. • Motional restriction of morin occurs in the presence of BSA.

  18. Effects of mutagenesis of aspartic acid residues in the putative phosphoribosyl diphosphate binding site of Escherichia coli phosphoribosyl diphosphate synthetase on metal ion specificity and ribose-5-phosphate binding

    DEFF Research Database (Denmark)

    Willemoës, Martin; Nilsson, Dan; Hove-Jensen, Bjarne

    1996-01-01

    The three conserved aspartic acid residues of the 5-phospho-d-ribosyl a-1-diphosphate binding site (213-GRDCVLVDDMIDTGGT-228) of Escherichia coli phosphoribosyl diphosphate synthetase were studied by analysis of the mutant enzymes D220E, D220F, D221A, D224A, and D224S. The mutant enzymes showed...... enzymes were dependent on the metal ion present, suggesting a function of the investigated aspartic acid residues both in the binding of ribose 5-phosphate, possibly via a divalent metal ion, and in the interaction with a divalent metal ion during catalysis....

  19. Antiviral activity and metal ion-binding properties of some 2-hydroxy-3-methoxyphenyl acylhydrazones.

    Science.gov (United States)

    Carcelli, M; Fisicaro, E; Compari, C; Contardi, L; Rogolino, D; Solinas, C; Stevaert, A; Naesens, L

    2018-02-01

    Here we report on the results obtained from an antiviral screening, including herpes simplex virus, vaccinia virus, vesicular stomatitis virus, Coxsackie B4 virus or respiratory syncytial virus, parainfluenza-3 virus, reovirus-1 and Punta Toro virus, of three 2-hydroxy-3-methoxyphenyl acylhydrazone compounds in three cell lines (i.e. human embryonic lung fibroblast cells, human cervix carcinoma cells, and African Green monkey kidney cells). Interesting antiviral EC 50 values are obtained against herpes simplex virus-1 and vaccinia virus. The biological activity of acylhydrazones is often attributed to their metal coordinating abilities, so potentiometric and microcalorimetric studies are here discussed to unravel the behavior of the three 2-hydroxy-3-methoxyphenyl compounds in solution. It is worth of note that the acylhydrazone with the higher affinity for Cu(II) ions shows the best antiviral activity against herpes simplex and vaccinia virus (EC 50  ~ 1.5 µM, minimal cytotoxic concentration = 60 µM, selectivity index = 40).

  20. Application of equilibrium binding model for analysis of conformational transitions in poly(rA)poly(rU) complexes with metal ions

    OpenAIRE

    Sorokin V. A.; Gladchenko G. O.; Usenko E. L.; Egupov S. A.; Blagoi Yu. P.

    2010-01-01

    Aim. The study is aimed at generalization of the previous experimental results on the metal ion (Mg2+, Ni2+, Cd2+) effects on conformation transitions in poly(rA)·poly(rU). The objective was to find out how the type of a metal ion-polynucleotide complex influences the phase transitions and to estimate the constants (K) of ions binding to polymers of different structures. Methods. The K values were obtained upon theoretical and experimental transition temperature fitting by the least-square me...

  1. Application of equilibrium binding model for analysis of conformational transitions in poly(rApoly(rU complexes with metal ions

    Directory of Open Access Journals (Sweden)

    Sorokin V. A.

    2010-09-01

    Full Text Available Aim. The study is aimed at generalization of the previous experimental results on the metal ion (Mg2+, Ni2+, Cd2+ effects on conformation transitions in poly(rA·poly(rU. The objective was to find out how the type of a metal ion-polynucleotide complex influences the phase transitions and to estimate the constants (K of ions binding to polymers of different structures. Methods. The K values were obtained upon theoretical and experimental transition temperature fitting by the least-square method with the root mean square deviation minimized through the procedure of the gradient descent in the multidimensional space. Results. Calcula- tions of diagrams with Mg2+ are shown to permit obtaining satisfactory results if concentration-independent, mean values of constants are used. For Ni2+ and Cd2+ the concentration dependence of K must be taken into account, especially for high ion contents at which compaction of single-stranded poly(rA emerges. It was revealed that the main factor responsible for the differences in diagrams with Ni2+ and Cd2+ is a significant distinction of their constants of binding to poly(rA and poly(rU. Conclusions. The model theory of equilibrium binding is capable to describe adequately conformation transitions in polynucleotides in the presence of metal ions.

  2. Alkali metal ion binding to glutamine and glutamine derivatives investigated by infrared action spectroscopy and theory

    NARCIS (Netherlands)

    Bush, M. F.; Oomens, J.; Saykally, R. J.; Williams, E. R.

    2008-01-01

    The gas-phase structures of alkali-metal cationized glutamine are investigated by using both infrared multiple photon dissociation (TRMPD) action spectroscopy, utilizing light generated by a free electron laser, and theory. The IRMPD spectra contain many similarities that are most consistent with

  3. Theoretical study of metal ion binding in modified and natural cytosine-cytosine base pairs

    Czech Academy of Sciences Publication Activity Database

    Šebera, Jakub; Sugiyama, K.; Ono, A.; Mulder, J.; Bickelhaupt, F. M.; Tanaka, Y.; Sychrovský, Vladimír; Guerra, C. F.

    2013-01-01

    Roč. 20, č. 1 (2013), s. 39-39 ISSN 1211-5894. [Discussions in Structural Molecular Biology. Annual Meeting of the Czech Society for Structural Biology /11./. 14.03.2013-16.03.2013, Nové Hrady] R&D Projects: GA ČR GAP205/10/0228; GA ČR(CZ) GAP304/10/1951; GA TA ČR TA01011165 Institutional support: RVO:61388963 Keywords : DFT * NMR * base pair * metal-mediated Subject RIV: CF - Physical ; Theoretical Chemistry

  4. Thermodynamic Studies of Cu(I) and Other d10 Metal Ions Binding to Proteins in the Copper Homeostasis Pathway and the Organomercurial Detoxification Pathway

    Science.gov (United States)

    Stevenson, Michael James

    Copper(I) is the predominant oxidation state of this essential metal in living cells due to reducing intracellular conditions. Because of deleterious copper-mediated Fenton chemistry, intracellular copper trafficking pathways involve strict regulation by metallochaperone proteins. Previous studies of the 68-residue metallochaperone, HAH1, have shown that it coordinates Cu(I) with two cysteines for transport from Ctr1 in the cell membrane to ATPases in the Golgi network. Using isothermal titration calorimetry (ITC), and methods to suppress oxidation and disproportionation of Cu(I), the thermodynamics of Cu(I), as well as other metal ions, binding to HAH1 have been accurately quantified. During the course of this study, the Cu(I) binding thermodynamics with the stabilizing ligand hexamethyltrien were determined in order to accurately quantify the Cu(I) binding thermodynamics with proteins, and revealed an unexpected Cu(I) coordination chemistry with this ligand. In addition, HAH1 binding the Cu(I) analogue Ag(I), the abundant cellular metal ion Zn(II), and the thiophilic toxic metal ion Hg(II), have been quantified. The binding thermodynamics of these metal ions were also determined in the presence of glutathione to more accurately model physiological conditions. HAH1 has a high affinity for Cu(I), which is both enthalpically and entropically favorable. It has a substantially lower affinity for Zn(II), which is entropically favored, suggesting that Zn(II) is not able to compete with Cu(I) for HAH1 in vivo. However, HAH1 has an exceptionally high affinity for Hg(II), with its larger thiophilicity, and it will displace Cu(I). Mercury(II) and particularly organomercurial compounds are very toxic, yet proteins from the bacterial mer operon provide resistance to this toxicity. In particular, the organomercurial lyase MerB, whose only known structural homologue is a putative copper metallochaperone, is responsible for cleavage of the carbon-mercury bond of MeHg(II) and

  5. Ion implantation in metals

    International Nuclear Information System (INIS)

    Vook, F.L.

    1977-02-01

    The application of ion beams to metals is rapidly emerging as a promising area of research and technology. This report briefly describes some of the recent advances in the modification and study of the basic properties of metals by ion implantation techniques. Most of the research discussed illustrates some of the new and exciting applications of ion beams to metals which are under active investigation at Sandia Laboratories, Albuquerque

  6. Effects of metal ions on stability and activity of hyperthermophilic pyrolysin and further stabilization of this enzyme by modification of a Ca2+-binding site.

    Science.gov (United States)

    Zeng, Jing; Gao, Xiaowei; Dai, Zheng; Tang, Bing; Tang, Xiao-Feng

    2014-05-01

    Pyrolysin is an extracellular subtilase produced by the marine hyperthermophilic archaeon Pyrococcus furiosus. This enzyme functions at high temperatures in seawater, but little is known about the effects of metal ions on the properties of pyrolysin. Here, we report that the supplementation of Na(+), Ca(2+), or Mg(2+) salts at concentrations similar to those in seawater destabilizes recombinant pyrolysin but leads to an increase in enzyme activity. The destabilizing effect of metal ions on pyrolysin appears to be related to the disturbance of surface electrostatic interactions of the enzyme. In addition, mutational analysis of two predicted high-affinity Ca(2+)-binding sites (Ca1 and Ca2) revealed that the binding of Ca(2+) is important for the stabilization of this enzyme. Interestingly, Asn substitutions at residues Asp818 and Asp820 of the Ca2 site, which is located in the C-terminal extension of pyrolysin, resulted in improvements in both enzyme thermostability and activity without affecting Ca(2+)-binding affinity. These effects were most likely due to the elimination of unfavorable electrostatic repulsion at the Ca2 site. Together, these results suggest that metal ions play important roles in modulating the stability and activity of pyrolysin.

  7. Effects of Metal Ions on Stability and Activity of Hyperthermophilic Pyrolysin and Further Stabilization of This Enzyme by Modification of a Ca2+-Binding Site

    Science.gov (United States)

    Zeng, Jing; Gao, Xiaowei; Dai, Zheng; Tang, Bing

    2014-01-01

    Pyrolysin is an extracellular subtilase produced by the marine hyperthermophilic archaeon Pyrococcus furiosus. This enzyme functions at high temperatures in seawater, but little is known about the effects of metal ions on the properties of pyrolysin. Here, we report that the supplementation of Na+, Ca2+, or Mg2+ salts at concentrations similar to those in seawater destabilizes recombinant pyrolysin but leads to an increase in enzyme activity. The destabilizing effect of metal ions on pyrolysin appears to be related to the disturbance of surface electrostatic interactions of the enzyme. In addition, mutational analysis of two predicted high-affinity Ca2+-binding sites (Ca1 and Ca2) revealed that the binding of Ca2+ is important for the stabilization of this enzyme. Interestingly, Asn substitutions at residues Asp818 and Asp820 of the Ca2 site, which is located in the C-terminal extension of pyrolysin, resulted in improvements in both enzyme thermostability and activity without affecting Ca2+-binding affinity. These effects were most likely due to the elimination of unfavorable electrostatic repulsion at the Ca2 site. Together, these results suggest that metal ions play important roles in modulating the stability and activity of pyrolysin. PMID:24561589

  8. Variation in one residue associated with the metal ion-dependent adhesion site regulates αIIbβ3 integrin ligand binding affinity.

    Directory of Open Access Journals (Sweden)

    Joel Raborn

    Full Text Available The Asp of the RGD motif of the ligand coordinates with the β I domain metal ion dependent adhesion site (MIDAS divalent cation, emphasizing the importance of the MIDAS in ligand binding. There appears to be two distinct groups of integrins that differ in their ligand binding affinity and adhesion ability. These differences may be due to a specific residue associated with the MIDAS, particularly the β3 residue Ala(252 and corresponding Ala in the β1 integrin compared to the analogous Asp residue in the β2 and β7 integrins. Interestingly, mutations in the adjacent to MIDAS (ADMIDAS of integrins α4β7 and αLβ2 increased the binding and adhesion abilities compared to the wild-type, while the same mutations in the α2β1, α5β1, αVβ3, and αIIbβ3 integrins demonstrated decreased ligand binding and adhesion. We introduced a mutation in the αIIbβ3 to convert this MIDAS associated Ala(252 to Asp. By combination of this mutant with mutations of one or two ADMIDAS residues, we studied the effects of this residue on ligand binding and adhesion. Then, we performed molecular dynamics simulations on the wild-type and mutant αIIbβ3 integrin β I domains, and investigated the dynamics of metal ion binding sites in different integrin-RGD complexes. We found that the tendency of calculated binding free energies was in excellent agreement with the experimental results, suggesting that the variation in this MIDAS associated residue accounts for the differences in ligand binding and adhesion among different integrins, and it accounts for the conflicting results of ADMIDAS mutations within different integrins. This study sheds more light on the role of the MIDAS associated residue pertaining to ligand binding and adhesion and suggests that this residue may play a pivotal role in integrin-mediated cell rolling and firm adhesion.

  9. Binding energy of protonium ions

    Science.gov (United States)

    Assad Abdel-Raouf, Mohamed

    2009-11-01

    The goal of the present work is to calculate the binding energy of the protonium ions bar PPe+ and bar PPe- using Rayleigh- Ritz variational method. It is indicated that an employment of 21 components of the trial wavefunction yields -0.08793 eV as the ground state energy of these ions. Our result agrees quite well with recently obtained results based on elaborate Monte Carlo approximations. It confirms the possible formation of these ions in laboratory.

  10. Mutational analysis of divalent metal ion binding in the active site of class II α-mannosidase from sulfolobus solfataricus

    DEFF Research Database (Denmark)

    Hansen, Dennis K.; Webb, Helen; Nielsen, Jonas Willum

    2015-01-01

    +). Some mutant enzyme forms displayed an altered preference for the metal ion compared to that of the wild type-enzyme. Furthermore, the H228Q, H533E, and H533Q enzymes were inhibited at increasing Zn2+ concentrations. The catalytic rate was reduced for all enzymes compared to that of the wild-type enzyme......Mutational analysis of Sulfolobus solfataricus class II α-mannosidase was focused on side chains that interact with the hydroxyls of the-1 mannosyl of the substrate (Asp-534) or form ligands to the active site divalent metal ion (His-228 and His-533) judged from crystal structures of homologous...... enzymes. D534A and D534N appeared to be completely inactive. When compared to the wild-type enzyme, the mutant enzymes in general showed only small changes in KM for the substrate, p-nitrophenyl-α-mannoside, but elevated activation constants, KA, for the divalent metal ion (Co2+, Zn2+, Mn2+, or Cd2...

  11. Spectroscopic capture and reactivity of a low-spin cobalt(IV)-oxo complex stabilized by binding redox-inactive metal ions.

    Science.gov (United States)

    Hong, Seungwoo; Pfaff, Florian Felix; Kwon, Eunji; Wang, Yong; Seo, Mi-Sook; Bill, Eckhard; Ray, Kallol; Nam, Wonwoo

    2014-09-22

    High-valent cobalt-oxo intermediates are proposed as reactive intermediates in a number of cobalt-complex-mediated oxidation reactions. Herein we report the spectroscopic capture of low-spin (S=1/2) Co(IV)-oxo species in the presence of redox-inactive metal ions, such as Sc(3+), Ce(3+), Y(3+), and Zn(2+), and the investigation of their reactivity in C-H bond activation and sulfoxidation reactions. Theoretical calculations predict that the binding of Lewis acidic metal ions to the cobalt-oxo core increases the electrophilicity of the oxygen atom, resulting in the redox tautomerism of a highly unstable [(TAML)Co(III)(O˙)](2-) species to a more stable [(TAML)Co(IV)(O)(M(n+))] core. The present report supports the proposed role of the redox-inactive metal ions in facilitating the formation of high-valent metal-oxo cores as a necessary step for oxygen evolution in chemistry and biology. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Inhibition by divalent metal ions of human histidine triad nucleotide binding protein1 (hHint1), a regulator of opioid analgesia and neuropathic pain.

    Science.gov (United States)

    Shah, Rachit; Chou, Tsui-Fen; Maize, Kimberly M; Strom, Alexander; Finzel, Barry C; Wagner, Carston R

    2017-09-23

    Human histidine triad nucleotide binding protein 1 (hHint1) is a purine nucleoside phosphoramidase and adenylate hydrolase that has emerged as a potential therapeutic target for the management of pain. However, the molecular mechanism of Hint1 in the signaling pathway has remained less clear. The role of metal ions in regulating postsynaptic transmission is well known, and the active site of hHint1 contains multiple histidines. Here we have investigated the effect of divalent metal ions (Cd 2+ , Cu 2+ , Mg 2+ , Mn 2+ , Ni 2+ , and Zn 2+ ) on the structural integrity and catalytic activity of hHint1. With the exception of Mg 2+ , all the divalent ions inhibited hHint1, the rank of order was found to be Cu 2+ >Zn 2+ >Cd 2+ ≥Ni 2+ >Mn 2+ based on their IC 50 and k in /K I values. A crystal structure of hHint1 with bound Cu 2+ is described to explain the competitive reversible inactivation of hHint1 by divalent cations. All the metal ions exhibited time- and concentration- dependent inhibition, with the rate of inactivation highly dependent on alterations of the C-terminus. With the exception of Cu 2+ ; restoration of inhibition was observed for all the metal ions after treatment with EDTA. Our studies reveal a loss in secondary structure and aggregation of hHint1 upon incubation with 10-fold excess of copper. Thus, hHint1 appears to be structurally sensitive to irreversible inactivation by copper, which may be of neurotoxicological and pharmacological significance. Copyright © 2017 Elsevier Inc. All rights reserved.

  13. ACE applied to the quantitative characterization of benzo-18-crown-6-ether binding with alkali metal ions in a methanol-water solvent system

    Czech Academy of Sciences Publication Activity Database

    Ehala, Sille; Makrlík, E.; Toman, Petr; Kašička, Václav

    2010-01-01

    Roč. 31, č. 4 (2010), s. 702-708 ISSN 0173-0835 R&D Projects: GA ČR(CZ) GA203/08/1428; GA ČR(CZ) GA203/09/0675; GA AV ČR 1ET400500402 Institutional research plan: CEZ:AV0Z40550506; CEZ:AV0Z40500505 Keywords : affinity capillary electrophoresis * alkali metal ions * binding constant Subject RIV: CB - Analytical Chemistry , Separation Impact factor: 3.569, year: 2010

  14. Emulsifying and metal ion binding activity of a glycoprotein exopolymer produced by Pseudoalteromonas sp. strain TG12.

    Science.gov (United States)

    Gutierrez, Tony; Shimmield, Tracy; Haidon, Cheryl; Black, Kenny; Green, David H

    2008-08-01

    In this study, we describe the isolation and characterization of a new exopolymer that exhibits high emulsifying activities against a range of oil substrates and demonstrates a differential capacity to desorb various mono-, di-, and trivalent metal species from marine sediment under nonionic and seawater ionic-strength conditions. This polymer, PE12, was produced by a new isolate, Pseudoalteromonas sp. strain TG12 (accession number EF685033), during growth in a modified Zobell's 2216 medium amended with 1% glucose. Chemical and chromatographic analysis showed it to be a high-molecular-mass (>2,000 kDa) glycoprotein composed of carbohydrate (32.3%) and protein (8.2%). PE12 was notable in that it contained xylose as the major sugar component at unusually high levels (27.7%) not previously reported for a Pseudoalteromonas exopolymer. The polymer was shown to desorb various metal species from marine sediment-a function putatively conferred by its high content of uronic acids (28.7%). Seawater ionic strength (simulated using 0.6 M NaCl), however, caused a significant reduction in PE12's ability to desorb the sediment-adsorbed metals. These results demonstrate the importance of electrolytes, a physical parameter intrinsic of seawater, in influencing the interaction of microbial exopolymers with metal ions. In summary, PE12 may represent a new class of Pseudoalteromonas exopolymer with a potential for use in biotechnological applications as an emulsifying or metal-chelating agent. In addition to the biotechnological potential of these findings, the ecological aspects of this and related bacterial exopolymers in marine environments are also discussed.

  15. Emulsifying and Metal Ion Binding Activity of a Glycoprotein Exopolymer Produced by Pseudoalteromonas sp. Strain TG12▿

    Science.gov (United States)

    Gutierrez, Tony; Shimmield, Tracy; Haidon, Cheryl; Black, Kenny; Green, David H.

    2008-01-01

    In this study, we describe the isolation and characterization of a new exopolymer that exhibits high emulsifying activities against a range of oil substrates and demonstrates a differential capacity to desorb various mono-, di-, and trivalent metal species from marine sediment under nonionic and seawater ionic-strength conditions. This polymer, PE12, was produced by a new isolate, Pseudoalteromonas sp. strain TG12 (accession number EF685033), during growth in a modified Zobell's 2216 medium amended with 1% glucose. Chemical and chromatographic analysis showed it to be a high-molecular-mass (>2,000 kDa) glycoprotein composed of carbohydrate (32.3%) and protein (8.2%). PE12 was notable in that it contained xylose as the major sugar component at unusually high levels (27.7%) not previously reported for a Pseudoalteromonas exopolymer. The polymer was shown to desorb various metal species from marine sediment—a function putatively conferred by its high content of uronic acids (28.7%). Seawater ionic strength (simulated using 0.6 M NaCl), however, caused a significant reduction in PE12's ability to desorb the sediment-adsorbed metals. These results demonstrate the importance of electrolytes, a physical parameter intrinsic of seawater, in influencing the interaction of microbial exopolymers with metal ions. In summary, PE12 may represent a new class of Pseudoalteromonas exopolymer with a potential for use in biotechnological applications as an emulsifying or metal-chelating agent. In addition to the biotechnological potential of these findings, the ecological aspects of this and related bacterial exopolymers in marine environments are also discussed. PMID:18552188

  16. Heavy metals binding properties of esterified lemon

    International Nuclear Information System (INIS)

    Arslanoglu, Hasan; Altundogan, Hamdi Soner; Tumen, Fikret

    2009-01-01

    Sorption of Cd 2+ , Cr 3+ , Cu 2+ , Ni 2+ , Pb 2+ and Zn 2+ onto a carboxyl groups-rich material prepared from lemon was investigated in batch systems. The results revealed that the sorption is highly pH dependent. Sorption kinetic data indicated that the equilibrium was achieved in the range of 30-240 min for different metal ions and sorption kinetics followed the pseudo-second-order model for all metals studied. Relative sorption rate of various metal cations was found to be in the general order of Ni 2+ > Cd 2+ > Cu 2+ > Pb 2+ > Zn 2+ > Cr 3+ . The binding characteristics of the sorbent for heavy metal ions were analyzed under various conditions and isotherm data was accurately fitted to the Langmuir equation. The metal binding capacity order calculated from Langmuir isotherm was Pb 2+ > Cu 2+ > Ni 2+ > Cd 2+ > Zn 2+ > Cr 3+ . The mean free energy of metal sorption process calculated from Dubinin-Radushkevich parameter and the Polanyi potential was found to be in the range of 8-11 kJ mol -1 for the metals studied showing that the main mechanism governing the sorption process seems to be ion exchange. The basic thermodynamic parameters of metals ion sorption process were calculated by using the Langmuir constants obtained from equilibration study. The ΔG o and ΔH o values for metals ion sorption on the lemon sorbent showed the process to be spontaneous and exothermic in nature. Relatively low ΔH o values revealed that physical adsorption significantly contributed to the mechanism.

  17. Heavy metals binding properties of esterified lemon.

    Science.gov (United States)

    Arslanoglu, Hasan; Altundogan, Hamdi Soner; Tumen, Fikret

    2009-05-30

    Sorption of Cd(2+), Cr(3+), Cu(2+), Ni(2+), Pb(2+) and Zn(2+) onto a carboxyl groups-rich material prepared from lemon was investigated in batch systems. The results revealed that the sorption is highly pH dependent. Sorption kinetic data indicated that the equilibrium was achieved in the range of 30-240 min for different metal ions and sorption kinetics followed the pseudo-second-order model for all metals studied. Relative sorption rate of various metal cations was found to be in the general order of Ni(2+)>Cd(2+)>Cu(2+)>Pb(2+)>Zn(2+)>Cr(3+). The binding characteristics of the sorbent for heavy metal ions were analyzed under various conditions and isotherm data was accurately fitted to the Langmuir equation. The metal binding capacity order calculated from Langmuir isotherm was Pb(2+)>Cu(2+)>Ni(2+)>Cd(2+)>Zn(2+)>Cr(3+). The mean free energy of metal sorption process calculated from Dubinin-Radushkevich parameter and the Polanyi potential was found to be in the range of 8-11 kJ mol(-1) for the metals studied showing that the main mechanism governing the sorption process seems to be ion exchange. The basic thermodynamic parameters of metals ion sorption process were calculated by using the Langmuir constants obtained from equilibration study. The DeltaG degrees and DeltaH degrees values for metals ion sorption on the lemon sorbent showed the process to be spontaneous and exothermic in nature. Relatively low DeltaH degrees values revealed that physical adsorption significantly contributed to the mechanism.

  18. Heavy metals binding properties of esterified lemon

    Energy Technology Data Exchange (ETDEWEB)

    Arslanoglu, Hasan; Altundogan, Hamdi Soner [Department of Chemical Engineering, Firat University, 23279 Elazig (Turkey); Tumen, Fikret, E-mail: ftumen@firat.edu.tr [Department of Chemical Engineering, Firat University, 23279 Elazig (Turkey)

    2009-05-30

    Sorption of Cd{sup 2+}, Cr{sup 3+}, Cu{sup 2+}, Ni{sup 2+}, Pb{sup 2+} and Zn{sup 2+} onto a carboxyl groups-rich material prepared from lemon was investigated in batch systems. The results revealed that the sorption is highly pH dependent. Sorption kinetic data indicated that the equilibrium was achieved in the range of 30-240 min for different metal ions and sorption kinetics followed the pseudo-second-order model for all metals studied. Relative sorption rate of various metal cations was found to be in the general order of Ni{sup 2+} > Cd{sup 2+} > Cu{sup 2+} > Pb{sup 2+} > Zn{sup 2+} > Cr{sup 3+}. The binding characteristics of the sorbent for heavy metal ions were analyzed under various conditions and isotherm data was accurately fitted to the Langmuir equation. The metal binding capacity order calculated from Langmuir isotherm was Pb{sup 2+} > Cu{sup 2+} > Ni{sup 2+} > Cd{sup 2+} > Zn{sup 2+} > Cr{sup 3+}. The mean free energy of metal sorption process calculated from Dubinin-Radushkevich parameter and the Polanyi potential was found to be in the range of 8-11 kJ mol{sup -1} for the metals studied showing that the main mechanism governing the sorption process seems to be ion exchange. The basic thermodynamic parameters of metals ion sorption process were calculated by using the Langmuir constants obtained from equilibration study. The {Delta}G{sup o} and {Delta}H{sup o} values for metals ion sorption on the lemon sorbent showed the process to be spontaneous and exothermic in nature. Relatively low {Delta}H{sup o} values revealed that physical adsorption significantly contributed to the mechanism.

  19. Quantifying the binding strength of salicylaldoxime-uranyl complexes relative to competing salicylaldoxime-transition metal ion complexes in aqueous solution: a combined experimental and computational study.

    Science.gov (United States)

    Mehio, Nada; Ivanov, Alexander S; Williams, Neil J; Mayes, Richard T; Bryantsev, Vyacheslav S; Hancock, Robert D; Dai, Sheng

    2016-05-31

    The design of new ligands and investigation of UO2(2+) complexations are an essential aspect of reducing the cost of extracting uranium from seawater, improving the sorption efficiency for uranium and the selectivity for uranium over competing ions (such as the transition metal cations). The binding strengths of salicylaldoxime-UO2(2+) complexes were quantified for the first time and compared with the binding strengths of salicylic acid-UO2(2+) and representative amidoxime-UO2(2+) complexes. We found that the binding strengths of salicylaldoxime-UO2(2+) complexes are ∼2-4 log β2 units greater in magnitude than their corresponding salicylic acid-UO2(2+) and representative amidoxime-UO2(2+) complexes; moreover, the selectivity of salicylaldoxime towards the UO2(2+) cation over competing Cu(2+) and Fe(3+) cations is far greater than those reported for salicylic acid and glutarimidedioxime in the literature. The higher UO2(2+) selectivity can likely be attributed to the different coordination modes observed for salicylaldoxime-UO2(2+) and salicylaldoxime-transition metal complexes. Density functional theory calculations indicate that salicylaldoxime can coordinate with UO2(2+) as a dianion species formed by η(2) coordination of the aldoximate and monodentate binding of the phenolate group. In contrast, salicylaldoxime coordinates with transition metal cations as a monoanion species via a chelate formed between phenolate and the oxime N; the complexes are stabilized via hydrogen bonding interactions between the oxime OH group and phenolate. By coupling the experimentally determined thermodynamic constants and the results of theoretical computations, we are able to derive a number of ligand design principles to further improve the UO2(2+) cation affinity, and thus further increase the selectivity of salicylaldoxime derivatives.

  20. Thermodynamic and structural properties of the specific binding between Ag⁺ ion and C:C mismatched base pair in duplex DNA to form C-Ag-C metal-mediated base pair.

    Science.gov (United States)

    Torigoe, Hidetaka; Okamoto, Itaru; Dairaku, Takenori; Tanaka, Yoshiyuki; Ono, Akira; Kozasa, Tetsuo

    2012-11-01

    Metal ion-nucleic acid interactions have attracted considerable interest for their involvement in structure formation and catalytic activity of nucleic acids. Although interactions between metal ion and mismatched base pair duplex are important to understand mechanism of gene mutations related to heavy metal ions, they have not been well-characterized. We recently found that the Ag(+) ion stabilized a C:C mismatched base pair duplex DNA. A C-Ag-C metal-mediated base pair was supposed to be formed by the binding between the Ag(+) ion and the C:C mismatched base pair to stabilize the duplex. Here, we examined specificity, thermodynamics and structure of possible C-Ag-C metal-mediated base pair. UV melting indicated that only the duplex with the C:C mismatched base pair, and not of the duplexes with the perfectly matched and other mismatched base pairs, was specifically stabilized on adding the Ag(+) ion. Isothermal titration calorimetry demonstrated that the Ag(+) ion specifically bound with the C:C base pair at 1:1 molar ratio with a binding constant of 10(6) M(-1), which was significantly larger than those for nonspecific metal ion-DNA interactions. Electrospray ionization mass spectrometry also supported the specific 1:1 binding between the Ag(+) ion and the C:C base pair. Circular dichroism spectroscopy and NMR revealed that the Ag(+) ion may bind with the N3 positions of the C:C base pair without distorting the higher-order structure of the duplex. We conclude that the specific formation of C-Ag-C base pair with large binding affinity would provide a binding mode of metal ion-DNA interactions, similar to that of the previously reported T-Hg-T base pair. The C-Ag-C base pair may be useful not only for understanding of molecular mechanism of gene mutations related to heavy metal ions but also for wide variety of potential applications of metal-mediated base pairs in various fields, such as material, life and environmental sciences. Copyright © 2012 Elsevier

  1. Adsorption of peptides and small proteins with control access polymer permeation to affinity binding sites. Part I: Polymer permeation-immobilized metal ion affinity chromatography separation adsorbents with polyethylene glycol and immobilized metal ions.

    Science.gov (United States)

    González-Ortega, Omar; Porath, Jerker; Guzmán, Roberto

    2012-03-02

    Despite the many efforts to develop efficient protein purification techniques, the isolation of peptides and small proteins on a larger than analytical scale remains a significant challenge. Recovery of small biomolecules from diluted complex biological mixtures, such as human serum, employing porous adsorbents is a difficult task mainly due to the presence of concentrated large biomolecules that can add undesired effects in the system such as blocking of adsorbent pores, impairing diffusion of small molecules, or competition for adsorption sites. Adsorption and size exclusion chromatography (AdSEC) controlled access media, using polyethylene glycol (PEG) as a semi-permeable barrier on a polysaccharide matrix, have been developed and explored in this work to overcome such effects and to preferentially adsorb small molecules while rejecting large ones. In the first part of this work, adsorption studies were performed with small peptides and proteins from synthetic mixtures using controlled access polymer permeation adsorption (CAPPA) media created by effectively grafting PEG on an immobilized metal affinity chromatography (IMAC) agarose resin, where chelating agents and immobilized metal ions were used as the primary affinity binding sites. Synthetic mixtures consisted of bovine serum albumin (BSA) with small proteins, peptides, amino acids (such as histidine or Val⁴-Angiotensin III), and small molecules-spiked human serum. The synthesized hybrid adsorbent consisted of agarose beads modified with iminodiacetic (IDA) groups, loaded with immobilized Cu(II) ions, and PEG. These CAPPA media with grafted PEG on the interior and exterior surfaces of the agarose matrix were effective in rejecting high molecular weight proteins. Different PEG grafting densities and PEG of different molecular weight were tested to determine their effect in rejecting and controlling adsorbent permeation properties. Low grafting density of high molecular weight PEG was found to be as

  2. Engineering of microorganisms towards recovery of rare metal ions

    Energy Technology Data Exchange (ETDEWEB)

    Kuroda, Kouichi; Ueda, Mitsuyoshi [Kyoto Univ. (Japan). Div. of Applied Life Sciences

    2010-06-15

    The bioadsorption of metal ions using microorganisms is an attractive technology for the recovery of rare metal ions as well as removal of toxic heavy metal ions from aqueous solution. In initial attempts, microorganisms with the ability to accumulate metal ions were isolated from nature and intracellular accumulation was enhanced by the overproduction of metal-binding proteins in the cytoplasm. As an alternative, the cell surface design of microorganisms by cell surface engineering is an emerging strategy for bioadsorption and recovery of metal ions. Cell surface engineering was firstly applied to the construction of a bioadsorbent to adsorb heavy metal ions for bioremediation. Cell surface adsorption of metal ions is rapid and reversible. Therefore, adsorbed metal ions can be easily recovered without cell breakage, and the bioadsorbent can be reused or regenerated. These advantages are suitable for the recovery of rare metal ions. Actually, the cell surface display of a molybdate-binding protein on yeast led to the enhanced adsorption of molybdate, one of the rare metal ions. An additional advantage is that the cell surface display system allows high-throughput screening of protein/peptide libraries owing to the direct evaluation of the displayed protein/peptide without purification and concentration. Therefore, the creation of novel metal-binding protein/ peptide and engineering of microorganisms towards the recovery of rare metal ions could be simultaneously achieved. (orig.)

  3. Formation of Mixed-Ligand Complexes of Pd2+ with Nucleoside 5'-Monophosphates and Some Metal-Ion-Binding Nucleoside Surrogates

    Directory of Open Access Journals (Sweden)

    Oleg Golubev

    2014-10-01

    Full Text Available Formation of mixed-ligand Pd2+ complexes between canonical nucleoside 5'-monophosphates and five metal-ion-binding nucleoside analogs has been studied by 1H-NMR spectroscopy to test the ability of these nucleoside surrogates to discriminate between unmodified nucleobases by Pd2+-mediated base pairing. The nucleoside analogs studied included 2,6-bis(3,5-dimethylpyrazol-1-yl-, 2,6-bis(1-methylhydrazinyl- and 6-(3,5-dimethylpyrazol-1-yl-substituted 9-(β-d-ribofuranosylpurines 1–3, and 2,4-bis(3,5-dimethylpyrazol-1-yl- and 2,4-bis(1-methylhydrazinyl-substituted 5-(β-d-ribofuranosyl-pyrimidines 4–5. Among these, the purine derivatives 1-3 bound Pd2+ much more tightly than the pyrimidine derivatives 4, 5 despite apparently similar structures of the potential coordination sites. Compounds 1 and 2 formed markedly stable mixed-ligand Pd2+ complexes with UMP and GMP, UMP binding favored by 1 and GMP by 2. With 3, formation of mixed-ligand complexes was retarded by binding of two molecules of 3 to Pd2+.

  4. Conserved epitope on several human vitamin K-dependent proteins: location of the antigenic site and influence of metal ions on antibody binding

    International Nuclear Information System (INIS)

    Church, W.R.; Messier, T.; Howard, P.R.; Amiral, J.; Meyer, D.; Mann, K.G.

    1988-01-01

    A murine monoclonal antibody (designated H-11) produced by injecting mice with purified human protein C was found to bind several human vitamin K-dependent proteins. Using a solid-phase competitive radioimmunoassay with antibody immobilized onto microtiter plates, binding of 125 I-labeled protein C to the antibody was inhibited by increasing amounts of protein C, prothrombin, and Factors X and VII over a concentration range of 1 x 10 -8 to 1 x 10 -6 M. Chemical treatment of prothrombin with a variety of agents did not destroy the antigenic site recognized by the antibody as measured by immunoblotting of prothrombin or prothrombin derivative immobilized onto nitrocellulose. Immunoblotting of purified vitamin K-dependent polypeptides with the monoclonal antibody following sodium dodecyl sulfate-polyacrylamide gel electrophoresis and electrophoretic transfer to nitrocellulose indicated that the antigenic site was found on the light chains of protein C and Factor X. The exact location of the antigenic determinant for antibody H-11 was established using synthetic peptides. Comparison of protein sequences of bovine and human vitamin K-dependent proteins suggests that the sequence Phe-Leu-Glu-Glu-Xaa-Arg/Lys is required for antibody binding. Increasing concentrations of Ca 2+ , Mg 2+ , or Mn 2+ partially inhibited binding of 125 I-protein C to the antibody in a solid-phase assay system with half-maximal binding observed at divalent metal ion concentrations of 2, 4, and 0.6 mM, respectively. The antigenic site thus recognized by monoclonal antibody H-11 is located at the amino-terminal region in the highly conserved γ-carboxyglutamic acid-containing domains of several, but not all, vitamin K-dependent proteins

  5. Metal binding proteins, recombinant host cells and methods

    Science.gov (United States)

    Summers, Anne O.; Caguiat, Jonathan J.

    2004-06-15

    The present disclosure provides artificial heavy metal binding proteins termed chelons by the inventors. These chelons bind cadmium and/or mercuric ions with relatively high affinity. Also disclosed are coding sequences, recombinant DNA molecules and recombinant host cells comprising those recombinant DNA molecules for expression of the chelon proteins. In the recombinant host cells or transgenic plants, the chelons can be used to bind heavy metals taken up from contaminated soil, groundwater or irrigation water and to concentrate and sequester those ions. Recombinant enteric bacteria can be used within the gastrointestinal tracts of animals or humans exposed to toxic metal ions such as mercury and/or cadmium, where the chelon recombinantly expressed in chosen in accordance with the ion to be rededicated. Alternatively, the chelons can be immobilized to solid supports to bind and concentrate heavy metals from a contaminated aqueous medium including biological fluids.

  6. Metal binding by food components

    DEFF Research Database (Denmark)

    Tang, Ning

    For calcium binding: Electrochemical method (calcium ion selective electrode) combined with quantum mechanical calculations (density functional theory) were used to investigate the calcium binding affinity of the amino acids and small glycine peptides. The effects of the ionic strength and p......, synergistic effect in calcium binding was found for the small glycine peptide rather than amino acids mixtures with the enhanced driving force up to -6 kJ/mol. Such study provides useful information for the future development of calcium supplements. For zinc binding: Isothermal titration calorimetry...... titration calorimetry and quantum mechanical calculations. This is due to the zinc binding affinity of the relatively softer ligands (investigated food components) will become much stronger than citrate or phytate when they present together in aqueous solution. This mechanism indicates these food components...

  7. Evaluation of Immobilized Metal-Ion Affinity Chromatography and Electrospray Ionization Tandem Mass Spectrometry for Recovery and Identification of Copper(II)-Binding Ligands in Seawater Using the Model Ligand 8-Hydroxyquinoline

    OpenAIRE

    Nixon, Richard L.; Ross, Andrew R. S.

    2016-01-01

    Complexation by organic ligands dominates the speciation of iron (Fe), copper (Cu), and other bioactive trace metals in seawater, controlling their bioavailability and distribution in the marine environment. Several classes of high-affinity Fe-binding ligands (siderophores) have been identified in seawater but the chemical structures of marine Cu-complexing ligands remain unknown. Immobilized metal-ion affinity chromatography (IMAC) allows Cu ligands to be isolated from bulk dissolved organic...

  8. IDENTIFICATION OF CATALYTIC METAL ION LIGANDS IN RIBOZYMES

    Science.gov (United States)

    Frederiksen, John K.; Piccirilli, Joseph A.

    2012-01-01

    Site-bound metal ions participate in the catalytic mechanisms of many ribozymes. Understanding these mechanisms therefore requires knowledge of the specific ligands on both substrate and ribozyme that coordinate these catalytic metal ions. A number of different structural and biochemical strategies have been developed and refined for identifying metal ion binding sites within ribozymes, and for assessing the catalytic contributions of the metal ions bound at those sites. We review these approaches and provide examples of their application, focusing in particular on metal ion rescue experiments and their roles in the construction of the transition state models for the Tetrahymena group I and RNase P ribozymes. PMID:19651216

  9. Effects of Metal Ions on Stability and Activity of Hyperthermophilic Pyrolysin and Further Stabilization of This Enzyme by Modification of a Ca2+-Binding Site

    OpenAIRE

    Zeng, Jing; Gao, Xiaowei; Dai, Zheng; Tang, Bing; Tang, Xiao-Feng

    2014-01-01

    Pyrolysin is an extracellular subtilase produced by the marine hyperthermophilic archaeon Pyrococcus furiosus. This enzyme functions at high temperatures in seawater, but little is known about the effects of metal ions on the properties of pyrolysin. Here, we report that the supplementation of Na+, Ca2+, or Mg2+ salts at concentrations similar to those in seawater destabilizes recombinant pyrolysin but leads to an increase in enzyme activity. The destabilizing effect of metal ions on pyrolysi...

  10. Emulsifying and Metal Ion Binding Activity of a Glycoprotein Exopolymer Produced by Pseudoalteromonas sp. Strain TG12▿

    OpenAIRE

    Gutierrez, Tony; Shimmield, Tracy; Haidon, Cheryl; Black, Kenny; Green, David H.

    2008-01-01

    In this study, we describe the isolation and characterization of a new exopolymer that exhibits high emulsifying activities against a range of oil substrates and demonstrates a differential capacity to desorb various mono-, di-, and trivalent metal species from marine sediment under nonionic and seawater ionic-strength conditions. This polymer, PE12, was produced by a new isolate, Pseudoalteromonas sp. strain TG12 (accession number EF685033), during growth in a modified Zobell's 2216 medium a...

  11. High Affinity Binding of Indium and Ruthenium Ions by Gastrins.

    Directory of Open Access Journals (Sweden)

    Graham S Baldwin

    Full Text Available The peptide hormone gastrin binds two ferric ions with high affinity, and iron binding is essential for the biological activity of non-amidated forms of the hormone. Since gastrins act as growth factors in gastrointestinal cancers, and as peptides labelled with Ga and In isotopes are increasingly used for cancer diagnosis, the ability of gastrins to bind other metal ions was investigated systematically by absorption spectroscopy. The coordination structures of the complexes were characterized by extended X-ray absorption fine structure (EXAFS spectroscopy. Changes in the absorption of gastrin in the presence of increasing concentrations of Ga3+ were fitted by a 2 site model with dissociation constants (Kd of 3.3 x 10-7 and 1.1 x 10-6 M. Although the absorption of gastrin did not change upon the addition of In3+ ions, the changes in absorbance on Fe3+ ion binding in the presence of indium ions were fitted by a 2 site model with Kd values for In3+ of 6.5 x 10-15 and 1.7 x 10-7 M. Similar results were obtained with Ru3+ ions, although the Kd values for Ru3+ of 2.6 x 10-13 and 1.2 x 10-5 M were slightly larger than observed for In3+. The structures determined by EXAFS all had metal:gastrin stoichiometries of 2:1 but, while the metal ions in the Fe, Ga and In complexes were bridged by a carboxylate and an oxygen with a metal-metal separation of 3.0-3.3 Å, the Ru complex clearly demonstrated a short range Ru-Ru separation, which was significantly shorter, at 2.4 Å, indicative of a metal-metal bond. We conclude that gastrin selectively binds two In3+ or Ru3+ ions, and that the affinity of the first site for In3+ or Ru3+ ions is higher than for ferric ions. Some of the metal ion-gastrin complexes may be useful for cancer diagnosis and therapy.

  12. Metal ion sequestration: An exciting dimension for molecularly ...

    African Journals Online (AJOL)

    Metal ion sequestration: An exciting dimension for molecularly imprinted polymer technology. DMS Mosha, LL Mkayula. Abstract. The use of a tight binding macrocyclic ligand to complex a metal ion so that this serves as receptee on the Molecularly Imprinted Polymer (MIP) receptor as described here affords a sequestration ...

  13. A biosystem for removal of metal ions from water

    Energy Technology Data Exchange (ETDEWEB)

    Kilbane, J.J. II.

    1990-01-01

    The presence of heavy metal ions in ground and surface waters constitutes a potential health risk and is an environmental concern. Moreover, processes for the recovery of valuable metal ions are of interest. Bioaccumulation or biosorption is not only a factor in assessing the environmental risk posed by metal ions; it can also be used as a means of decontamination. A biological system for the removal and recovery of metal ions from contaminated water is reported here. Exopolysaccharide-producing microorganisms, including a methanotrophic culture, are demonstrated to have superior metal binding ability, compared with other microbial cultures. This paper describes a biosorption process in which dried biomass obtained from exopolysaccharide-producing microorganisms is encapsulated in porous plastic beads and is used for metal ion binding and recovery. 22 refs., 13 figs.

  14. Thermodynamics of binding interactions between extracellular polymeric substances and heavy metals by isothermal titration microcalorimetry.

    Science.gov (United States)

    Yan, Peng; Xia, Jia-Shuai; Chen, You-Peng; Liu, Zhi-Ping; Guo, Jin-Song; Shen, Yu; Zhang, Cheng-Cheng; Wang, Jing

    2017-05-01

    Extracellular polymeric substances (EPS) play a crucial role in heavy metal bio-adsorption using activated sludge, but the interaction mechanism between heavy metals and EPS remains unclear. Isothermal titration calorimetry was employed to illuminate the mechanism in this study. The results indicate that binding between heavy metals and EPS is spontaneous and driven mainly by enthalpy change. Extracellular proteins in EPS are major participants in the binding process. Environmental conditions have significant impact on the adsorption performance. Divalent and trivalent cations severely impeded the binding of heavy metal ions to EPS. Electrostatic interaction mainly attributed to competition between divalent cations and heavy metal ions; trivalent cations directly competed with heavy metal ions for EPS binding sites. Trivalent cations were more competitive than divalent cations for heavy metal ion binding because they formed complexing bonds. This study facilitates a better understanding about the interaction between heavy metals and EPS in wastewater treatment. Copyright © 2017 Elsevier Ltd. All rights reserved.

  15. Novel short-chain analogues of somatostatin as ligands for Cu(II) ions. Role of the metal ion binding on the spatial structure of the ligand.

    Science.gov (United States)

    Marciniak, Aleksandra; Cebrat, Marek; Czyżnikowska, Żaneta; Brasuń, Justyna

    2012-12-01

    In this paper we present the studies on coordination abilities of two short-chain analogues of somatostatin with free N-terminal and protected amino group towards copper (II) ions. The octreotide is the most popular analogue of the somatostatin (peptide hormone) used in medicine. Somatostatin analogues are used in diagnosis and treatment of the neuroendocrine tumors. Both analyzed analogues are characterized by the presence of two His instead of Cys residues in characteristic fragment of native peptide. We characterize coordination abilities of the ligands using potentiometric and spectroscopic methods. His-analogues of somatostatin are effective ligands for copper (II) ions. Both peptides are able to form the complexes with the cyclic structure. Copyright © 2012 Elsevier Inc. All rights reserved.

  16. Studies on the Binding of Lead and Zinc Ions by Modified Cellulosic ...

    African Journals Online (AJOL)

    substrate contact time, the metal ion concentration, the metal ion type and the substrate type. The amount of these ions absorbed varies with the cellulosic material and in the order Pb (II) > Zn (II). It is shown that the cellulosic materials could bind ...

  17. Metal ion coupled protein folding and allosteric motions

    Science.gov (United States)

    Wang, Wei

    2014-03-01

    Many proteins need the help of cofactors for their successful folding and functioning. Metal ions, i.e., Zn2+, Ca2+, and Mg2+ etc., are typical biological cofactors. Binding of metal ions can reshape the energy landscapes of proteins, thereby modifying the folding and allosteric motions. For example, such binding may make the intrinsically disordered proteins have funneled energy landscapes, consequently, ensures their spontaneous folding. In addition, the binding may activate certain biological processes by inducing related conformational changes of regulation proteins. However, how the local interactions involving the metal ion binding can induce the global conformational motions of proteins remains elusive. Investigating such question requires multiple models with different details, including quantum mechanics, atomistic models, and coarse grained models. In our recent work, we have been developing such multiscale methods which can reasonably model the metal ion binding induced charge transfer, protonation/deprotonation, and large conformational motions of proteins. With such multiscale model, we elucidated the zinc-binding induced folding mechanism of classical zinc finger and the calcium-binding induced dynamic symmetry breaking in the allosteric motions of calmodulin. In addition, we studied the coupling of folding, calcium binding and allosteric motions of calmodulin domains. In this talk, I will introduce the above progresses on the metal ion coupled protein folding and allosteric motions. We thank the finacial support from NSFC and the 973 project.

  18. Evolution of Metal(Loid) Binding Sites in Transcriptional Regulators

    Energy Technology Data Exchange (ETDEWEB)

    Ordonez, E.; Thiyagarajan, S.; Cook, J.D.; Stemmler, T.L.; Gil, J.A.; Mateos, L.M.; Rosen, B.P.

    2009-05-22

    Expression of the genes for resistance to heavy metals and metalloids is transcriptionally regulated by the toxic ions themselves. Members of the ArsR/SmtB family of small metalloregulatory proteins respond to transition metals, heavy metals, and metalloids, including As(III), Sb(III), Cd(II), Pb(II), Zn(II), Co(II), and Ni(II). These homodimeric repressors bind to DNA in the absence of inducing metal(loid) ion and dissociate from the DNA when inducer is bound. The regulatory sites are often three- or four-coordinate metal binding sites composed of cysteine thiolates. Surprisingly, in two different As(III)-responsive regulators, the metalloid binding sites were in different locations in the repressor, and the Cd(II) binding sites were in two different locations in two Cd(II)-responsive regulators. We hypothesize that ArsR/SmtB repressors have a common backbone structure, that of a winged helix DNA-binding protein, but have considerable plasticity in the location of inducer binding sites. Here we show that an As(III)-responsive member of the family, CgArsR1 from Corynebacterium glutamicum, binds As(III) to a cysteine triad composed of Cys{sup 15}, Cys{sup 16}, and Cys{sup 55}. This binding site is clearly unrelated to the binding sites of other characterized ArsR/SmtB family members. This is consistent with our hypothesis that metal(loid) binding sites in DNA binding proteins evolve convergently in response to persistent environmental pressures.

  19. Effects of copper and cadmium on ion transport and gill metal binding in the Amazonian teleost tambaqui (Colossoma macropomum) in extremely soft water.

    Science.gov (United States)

    Matsuo, Aline Y O; Wood, Chris M; Val, Adalberto L

    2005-09-30

    Metal toxicity in fish is expected to be most severe in soft waters because of the low availability of cations (particularly Ca(2+)) to out-compete the metal forms for binding sites on the gills. Natural waters in the Amazon basin are typically soft due to regional geochemistry, but few studies have focused on metal toxicity in fish native to the basin. We assessed the ionoregulatory effects of waterborne copper (Cu) and cadmium (Cd) on tambaqui (Colossoma macropomum) in extremely soft water (10 micromoll(-1) Ca(2+)). Tambaqui had a very high tolerance to Cu (50-400 microgl(-1)), as indicated by a complete lack of inhibition of Na(+) uptake and an ability to gradually recover over 6h from elevated diffusive Na(+) losses caused by Cu. The insensitivity of active Na(+) influx to Cu further supports the notion that Amazonian fish may have a unique Na(+) transport system. Addition of 5-10 mgCl(-1) of dissolved organic matter (DOM) did not prevent initial (0-3h) negative Na(+) balance in tambaqui exposed to Cu. Exposure to 40 mgCl(-1) DOM prevented Na(+) losses in tambaqui even at 400 microgl(-1) Cu, probably because most Cu was complexed to DOM. Tambaqui exposed to waterborne Cd (10-80 microgl(-1)) experienced an average of 42% inhibition in whole body Ca(2+) uptake relative to controls within 3h of exposure to the metal. Inhibition of Ca(2+) uptake increased over time and, at 24h, Ca(2+) uptake was suppressed by 51% and 91% in fish exposed to 10 and 80 microgl(-1) Cd, respectively. Previous acclimation of fish to either elevated [Ca(2+)] or elevated [DOM] proved to be very effective in protecting against acute short-term metal accumulation at the gills of tambaqui in soft water (in the absence of the protective agent during metal exposure), suggesting a conditioning effect on gill metal binding physiology.

  20. Binding of corroded ions to human saliva.

    Science.gov (United States)

    Mueller, H J

    1985-05-01

    Employing equilibrium dialysis, the binding abilities of Cu, Al, Co and Cr ions from corroded Cu-Al and Co-Cr dental casting alloys towards human saliva and two of its gel chromatographic fractions were determined. Results indicate that both Cu and Co bind to human saliva i.e. 0.045 and 0.027 mg/mg protein, respectively. Besides possessing the largest binding ability, Cu also possessed the largest binding capacity. The saturation of Cu binding was not reached up to the limit of 0.35 mg protein/ml employed in the tests, while Co reached full saturation at about 0.2 mg protein/ml. Chromium showed absolutely no binding to human saliva while Al ions did not pass through the dialysis membranes. Compared to the binding with solutions that were synthetically made up to contain added salivary-type proteins, it is shown that the binding to human saliva is about 1 order of magnitude larger, at least for Cu ions.

  1. Investigation of the metal binding site in methionine aminopeptidase by density functional theory

    DEFF Research Database (Denmark)

    Jørgensen, Anne Techau; Norrby, Per-Ola; Liljefors, Tommy

    2002-01-01

    All methionine aminopeptidases exhibit the same conserved metal binding site. The structure of this site with either Co2+ ions or Zn2+ ions was investigated using density functional theory. The calculations showed that the structure of the site was not influenced by the identity of the metal ions...

  2. Biosorption of Heavy Metal Ions to Brown Algae, Macrocystis pyrifera, Kjellmaniella crassiforia, and Undaria pinnatifida

    OpenAIRE

    Seki, Hideshi; Suzuki, Akira

    1998-01-01

    A fundamental study of the application of brown algae to the aqueous-phase separation of toxic heavy metals was carried out. The biosorption characteristics of cadmium and lead ions were determined with brown algae, Macrocystis pyrifera, Kjellmaniella crassiforia, and Undaria pinnatifida. A metal binding model proposed by the authors was used for the description of metal binding data. The results showed that the biosorption of bivalent metal ions to brown algae was due to bivalent binding to ...

  3. Effects of copper and cadmium on ion transport and gill metal binding in the Amazonian teleost tambaqui (Colossoma macropomum) in extremely soft water

    Energy Technology Data Exchange (ETDEWEB)

    Matsuo, Aline Y.O. [Laboratory of Ecophysiology and Molecular Evolution, National Institute for Research in the Amazon (INPA), Av. Andre Araujo, 2936 Aleixo, Manaus, Amazonas 69083-000 (Brazil)]. E-mail: matsuoaline@aol.com; Wood, Chris M. [Department of Biology, McMaster University, 1280 Main St. West, Hamilton, Ont., L8S 4K1 (Canada); Val, Adalberto L. [Laboratory of Ecophysiology and Molecular Evolution, National Institute for Research in the Amazon (INPA), Av. Andre Araujo, 2936 Aleixo, Manaus, Amazonas 69083-000 (Brazil)

    2005-09-30

    Metal toxicity in fish is expected to be most severe in soft waters because of the low availability of cations (particularly Ca{sup 2+}) to out-compete the metal forms for binding sites on the gills. Natural waters in the Amazon basin are typically soft due to regional geochemistry, but few studies have focused on metal toxicity in fish native to the basin. We assessed the ionoregulatory effects of waterborne copper (Cu) and cadmium (Cd) on tambaqui (Colossoma macropomum) in extremely soft water (10 {mu}mol l{sup -1} Ca{sup 2+}). Tambaqui had a very high tolerance to Cu (50-400 {mu}g l{sup -1}), as indicated by a complete lack of inhibition of Na{sup +} uptake and an ability to gradually recover over 6 h from elevated diffusive Na{sup +} losses caused by Cu. The insensitivity of active Na{sup +} influx to Cu further supports the notion that Amazonian fish may have a unique Na{sup +} transport system. Addition of 5-10 mg C l{sup -1} of dissolved organic matter (DOM) did not prevent initial (0-3 h) negative Na{sup +} balance in tambaqui exposed to Cu. Exposure to 40 mg C l{sup -1} DOM prevented Na{sup +} losses in tambaqui even at 400 {mu}g l{sup -1} Cu, probably because most Cu was complexed to DOM. Tambaqui exposed to waterborne Cd (10-80 {mu}g l{sup -1}) experienced an average of 42% inhibition in whole body Ca{sup 2+} uptake relative to controls within 3 h of exposure to the metal. Inhibition of Ca{sup 2+} uptake increased over time and, at 24 h, Ca{sup 2+} uptake was suppressed by 51% and 91% in fish exposed to 10 and 80 {mu}g l{sup -1} Cd, respectively. Previous acclimation of fish to either elevated [Ca{sup 2+}] or elevated [DOM] proved to be very effective in protecting against acute short-term metal accumulation at the gills of tambaqui in soft water (in the absence of the protective agent during metal exposure), suggesting a conditioning effect on gill metal binding physiology.

  4. Metals and Neuronal Metal Binding Proteins Implicated in Alzheimer's Disease

    Science.gov (United States)

    2016-01-01

    Alzheimer's disease (AD) is the most prevalent age-related dementia affecting millions of people worldwide. Its main pathological hallmark feature is the formation of insoluble protein deposits of amyloid-β and hyperphosphorylated tau protein into extracellular plaques and intracellular neurofibrillary tangles, respectively. Many of the mechanistic details of this process remain unknown, but a well-established consequence of protein aggregation is synapse dysfunction and neuronal loss in the AD brain. Different pathways including mitochondrial dysfunction, oxidative stress, inflammation, and metal metabolism have been suggested to be implicated in this process. In particular, a body of evidence suggests that neuronal metal ions such as copper, zinc, and iron play important roles in brain function in health and disease states and altered homeostasis and distribution as a common feature across different neurodegenerative diseases and aging. In this focused review, we overview neuronal proteins that are involved in AD and whose metal binding properties may underlie important biochemical and regulatory processes occurring in the brain during the AD pathophysiological process. PMID:26881049

  5. Adsorption of heavy metals ions on portulaca oleracea plants

    International Nuclear Information System (INIS)

    Naqvi, R.R.

    2005-01-01

    The aim of this study is to report the ability of portulaca oleracea (Fershi in Urdu) biomass grown in uncontaminated soils to adsorb or uptake lead, cadmium, arsenic, cobalt and copper from aqueous solutions. In order to help understand the metal binding mechanism, laboratory experiments performance to determine optimal binding, and binding capacity for each of the above mentioned metals. These experiments were carried out for the mass of crushed portulaca stems. Portulaca is a plant that grows abundantly in temperature climate in the area of Quetta Balochistan. It has reddish stem and thick succulent leaves. This plant has been found to be good adsorbent for heavy metals ions. (author)

  6. In situ NMR measurement of macromolecule-bound metal ion concentrations.

    Science.gov (United States)

    Kozlyuk, Natalia; Sengupta, Suvrajit; Lupták, Andrej; Martin, Rachel W

    2016-04-01

    Many nucleic acids and proteins require divalent metal ions such as Mg(2+) and Ca(2+) for folding and function. The lipophilic alignment media frequently used as membrane mimetics also bind these divalent metals. Here we demonstrate the use of (31)P NMR spectrum of a metal ion chelator (deoxycytidine diphosphate) to measure the bound [Mg(2+)] and [Ca(2+)] in situ for several biological model systems at relatively high divalent ion concentrations (1-10 mM). This method represents a general approach to measuring divalent metal ion binding in NMR samples where the amount and type of metal ion added to the system is known.

  7. Structural Metals in the Group I Intron: A Ribozyme with a Multiple Metal Ion Core

    Energy Technology Data Exchange (ETDEWEB)

    Stahley,M.; Adams, P.; Wang, J.; Strobel, S.

    2007-01-01

    Metal ions play key roles in the folding and function for many structured RNAs, including group I introns. We determined the X-ray crystal structure of the Azoarcus bacterial group I intron in complex with its 5' and 3' exons. In addition to 222 nucleotides of RNA, the model includes 18 Mg2+ and K+ ions. Five of the metals bind within 12 Angstroms of the scissile phosphate and coordinate the majority of the oxygen atoms biochemically implicated in conserved metal-RNA interactions. The metals are buried deep within the structure and form a multiple metal ion core that is critical to group I intron structure and function. Eight metal ions bind in other conserved regions of the intron structure, and the remaining five interact with peripheral structural elements. Each of the 18 metals mediates tertiary interactions, facilitates local bends in the sugar-phosphate backbone or binds in the major groove of helices. The group I intron has a rich history of biochemical efforts aimed to identify RNA-metal ion interactions. The structural data are correlated to the biochemical results to further understand the role of metal ions in group I intron structure and function.

  8. Metal ion adsorption characteristics of tea leaves

    OpenAIRE

    Takao, Hiromitsu; Kawahigashi, Tatsuo

    2016-01-01

    [Abstract] For effective use of tea leaves, this study experimentally evaluated metal ion adsorption by tea leaves. The experiment described herein was conducted by measuring the ionic solution at a constant density using a fluorescence X-ray device. The metallic ion concentration in the solution and the fluorescence X-ray output intensity showed good correlation. Tea leaves were put into solution adjusted with density of an already-known metallic ion. Then the decrease of the metal ion was m...

  9. Immunoglobulin classes, metal binding proteins, and trace metals in ...

    African Journals Online (AJOL)

    , IgA and IgM), metal binding proteins (Transferrin, Caeruloplasmin, Alpha-2- Macroglobulin and Haptoglobin) and nutritionally essential trace metals/heavy metals (Zn, Fe, Se, Cu, Mg, Cd and Pb) in Nigerian cassava processors using single ...

  10. The metal binding potential of a dairy isolate

    Directory of Open Access Journals (Sweden)

    K. Ramyakrishna

    2017-12-01

    Full Text Available Excess iron in water resources can lead to health hazards and problems. The ability of lactic acid bacteria to bind iron has not yet been widely studied. In the present study, sorption of iron ions from aqueous solutions onto lactic acid bacterium was determined. Elemental analyses were carried out by inductively coupled plasma optical emission spectrometry. The kinetics of Fe(III biosorption was investigated at different initial concentrations of metal ion. The highest uptake capacity was found to be 16 mg of Fe(III per gram of adsorbent with a contact time of 24 hr and at initial metal ion concentration of 34 mg/L. The uptake capacity of Fe(III ion varied from 83.2 to 46.7% across the range of initial metal ion concentrations. The equilibrium data were evaluated by Langmuir and Freundlich isotherms, and were found to fit better with the latter (R2 = 0.9999. The surface morphology of the biomass and percentage of metal was characterized by using a scanning electron microscope equipped with energy dispersive X-ray spectroscopy. The functional groups on the cell wall surface of biomass involved in biosorption of heavy metals were studied by Fourier transform infrared spectroscopy spectrum.

  11. DNA as sensors and imaging agents for metal ions.

    Science.gov (United States)

    Xiang, Yu; Lu, Yi

    2014-02-17

    Increasing interest in detecting metal ions in many chemical and biomedical fields has created demands for developing sensors and imaging agents for metal ions with high sensitivity and selectivity. This review covers recent progress in DNA-based sensors and imaging agents for metal ions. Through both combinatorial selection and rational design, a number of metal-ion-dependent DNAzymes and metal-ion-binding DNA structures that can selectively recognize specific metal ions have been obtained. By attachment of these DNA molecules with signal reporters such as fluorophores, chromophores, electrochemical tags, and Raman tags, a number of DNA-based sensors for both diamagnetic and paramagnetic metal ions have been developed for fluorescent, colorimetric, electrochemical, and surface Raman detection. These sensors are highly sensitive (with a detection limit down to 11 ppt) and selective (with selectivity up to millions-fold) toward specific metal ions. In addition, through further development to simplify the operation, such as the use of "dipstick tests", portable fluorometers, computer-readable disks, and widely available glucose meters, these sensors have been applied for on-site and real-time environmental monitoring and point-of-care medical diagnostics. The use of these sensors for in situ cellular imaging has also been reported. The generality of the combinatorial selection to obtain DNAzymes for almost any metal ion in any oxidation state and the ease of modification of the DNA with different signal reporters make DNA an emerging and promising class of molecules for metal-ion sensing and imaging in many fields of applications.

  12. Crystal structures of Dronpa complexed with quenchable metal ions provide insight into metal biosensor development.

    Science.gov (United States)

    Kim, In Jung; Kim, Sangsoo; Park, Jeahyun; Eom, Intae; Kim, Sunam; Kim, Jin-Hong; Ha, Sung Chul; Kim, Yeon Gil; Hwang, Kwang Yeon; Nam, Ki Hyun

    2016-09-01

    Many fluorescent proteins (FPs) show fluorescence quenching by specific metal ions, which can be applied towards metal biosensor development. In this study, we investigated the significant fluorescence quenching of Dronpa by Co(2+) and Cu(2+) ions. Crystal structures of Co(2+) -, Ni(2+) - and Cu(2+) -bound Dronpa revealed previously unseen, unique, metal-binding sites for fluorescence quenching. These metal ions commonly interact with surface-exposed histidine residues (His194-His210 and His210-His212), and interact indirectly with chromophores. Structural analysis of the Co(2+) - and Cu(2+) - binding sites of Dronpa provides insight into FP-based metal biosensor engineering. © 2016 Federation of European Biochemical Societies.

  13. Encapsulation of Metal Cations by the PhePhe Ligand: A Cation-pi Ion Cage

    NARCIS (Netherlands)

    Dunbar, R. C.; Steill, J. D.; Oomens, J.

    2011-01-01

    Structures and binding thermochemistry are investigated for protonated PhePhe and for complexes of PhePhe with the alkaline-earth ions Ba2+ and Ca2+, the alkali-metal ions Li+, Na+, K+, and Cs+, and the transition-metal ion Ag+. The two neighboring aromatic side chains open the possibility of a

  14. Encapsulation of metal cations by the PhePhe ligand: a cation-pi ion cage

    NARCIS (Netherlands)

    Dunbar, R.C.; Steill, J.D.; Oomens, J.

    2011-01-01

    Structures and binding thermochemistry are investigated for protonated PhePhe and for complexes of PhePhe with the alkaline-earth ions Ba2+ and Ca2+, the alkali-metal ions Li+, Na+, K+, and Cs+, and the transition-metal ion Ag+. The two neighboring aromatic side chains open the possibility of a

  15. Comparison of metal-binding strength between methionine and cysteine residues: Implications for the design of metal-binding motifs in proteins.

    Science.gov (United States)

    Krishna Deepak, R N V; Chandrakar, Brijesh; Sankararamakrishnan, Ramasubbu

    2017-05-01

    Metals play vital role in various physiological processes and are bound to biomolecules. Although cysteine sulfur is more frequently found as metal-binding ligand, methionine prefers to occur in copper-binding motifs of some proteins. To address methionine's lower preference in copper-binding sites in comparison to cysteine, we have considered copper-binding motifs (His-Cys-His-Met) from seven different high-resolution protein structures. We performed quantum chemical calculations to find out the strength of interactions between sulfur and metal ion in both Met and Cys residues. In the case of Cys, both neutral (CysH) and the deprotonated form (Cys - ) were considered. We used two different levels of theory (B3LYP and M06-2X) and the model compounds methyl propyl sulfide, ethanethiol and ethanethiolate were used to represent Met, CysH and Cys - respectively. To compare the metal-binding strength, we mutated Met in silico to CysH/Cys - and performed the calculations. We also carried out calculations with wild-type Cys present in the same metal-binding motif. On average, interactions of Met with copper ion are stronger by 13-35kcal/mol compared to CysH. However, Cys - interactions with copper is stronger than that of Met by ~250kcal/mol. We then considered the entire metal-binding motif with four residues and calculated the interaction energies with the copper ion. We also considered Met→Cys - mutation in the motif and repeated the calculations. Interaction of the wild-type motif with the copper ion is ~160kcal/mol weaker than that of mutated motif. Our studies suggest the factors that could explain why Met is not as frequently observed as Cys in the metal-binding motifs. Results of these studies will help in designing metal-binding motifs in proteins with varying interaction strengths. Copyright © 2017 Elsevier B.V. All rights reserved.

  16. Metal binding is critical for the folding and function of laminin binding protein, Lmb of Streptococcus agalactiae.

    Directory of Open Access Journals (Sweden)

    Preethi Ragunathan

    Full Text Available Lmb is a 34 kDa laminin binding surface adhesin of Streptococcus agalactiae. The structure of Lmb reported by us recently has shown that it consists of a metal binding crevice, in which a zinc ion is coordinated to three highly conserved histidines. To elucidate the structural and functional significance of the metal ion in Lmb, these histidines have been mutated to alanine and single, double and triple mutants were generated. These mutations resulted in insolubility of the protein and revealed altered secondary and tertiary structures, as evidenced by circular dichroism and fluorescence spectroscopy studies. The mutations also significantly decreased the binding affinity of Lmb to laminin, implicating the role played by the metal binding residues in maintaining the correct conformation of the protein for its binding to laminin. A highly disordered loop, proposed to be crucial for metal acquisition in homologous structures, was deleted in Lmb by mutation (ΔLmb and its crystal structure was solved at 2.6 Å. The ΔLmb structure was identical to the native Lmb structure with a bound zinc ion and exhibited laminin binding activity similar to wild type protein, suggesting that the loop might not have an important role in metal acquisition or adhesion in Lmb. Targeted mutations of histidine residues confirmed the importance of the zinc binding crevice for the structure and function of the Lmb adhesin.

  17. Controlled formation of emissive silver nanoclusters using rationally designed metal-binding proteins.

    Science.gov (United States)

    Morozov, Vasily A; Ogawa, Michael Y

    2013-08-19

    The metal-binding properties of rationally designed, synthetic proteins were used to prepare a series of emissive silver nanoclusters having predictable sizes and emission energies. Metal-binding α-helical coiled coils were designed to exist as peptide trimers, tetramers, and hexamers and found to uniquely bind 6, 8, and 12 Ag(+) ions, respectively. Subsequent treatment with a chemical reducing agent produced a series of peptide-bound Ag(0) nanoclusters that display a strong visible fluorescence whose emission energies depend on the number of bound metal ions in excellent agreement with theory.

  18. Inosylyl(3'-->5')inosine (IpI-). Acid-base and metal ion-binding properties of a dinucleoside monophosphate in aqueous solution.

    Science.gov (United States)

    Knobloch, Bernd; Okruszek, Andrzej; Sigel, Helmut

    2008-04-07

    The acidity constants of the (N7)H(+) sites of inosylyl(3'-->5')inosine (IpI(-)) were estimated and those of its (N1)H sites were measured by potentiometric pH titrations in aqueous solution (25 degrees C; I = 0.1 M, NaNO3). The same method was used for the determination of the stability constants of the 1:1 complexes formed between Mg(2+), Co(2+), Ni(2+), Zn(2+), or Cd(2+) (= M(2+)) and (IpI - H)(2-) and, in the case of Mg(2+), also of (IpI - 2H)(3-). The stability constants of the M(IpI)(+) complexes were estimated. The acidity constants of H(inosine)(+) and the stability constants of the M(Ino)(2+) and M(Ino - H)(+) complexes were taken from the literature. The comparison of these and related data allows the conclusion that, in the M(IpI - H) species, chelates are formed; most likely they are preferably of an N7/N7 type. For the metal ions Co(2+), Ni(2+), Zn(2+), or Cd(2+), the formation degrees of the chelates are on the order of 60-80%; no chelates could be detected for the Mg(IpI - H) complexes. It is noteworthy that the (N1)H deprotonation, which leads to the M(IpI - H) species, occurs in all M(IpI)(+) complexes in the physiological pH range of about 7.5 or even below.

  19. Data mining of metal ion environments present in protein structures.

    Science.gov (United States)

    Zheng, Heping; Chruszcz, Maksymilian; Lasota, Piotr; Lebioda, Lukasz; Minor, Wladek

    2008-09-01

    Analysis of metal-protein interaction distances, coordination numbers, B-factors (displacement parameters), and occupancies of metal-binding sites in protein structures determined by X-ray crystallography and deposited in the PDB shows many unusual values and unexpected correlations. By measuring the frequency of each amino acid in metal ion-binding sites, the positive or negative preferences of each residue for each type of cation were identified. Our approach may be used for fast identification of metal-binding structural motifs that cannot be identified on the basis of sequence similarity alone. The analysis compares data derived separately from high and medium-resolution structures from the PDB with those from very high-resolution small-molecule structures in the Cambridge Structural Database (CSD). For high-resolution protein structures, the distribution of metal-protein or metal-water interaction distances agrees quite well with data from CSD, but the distribution is unrealistically wide for medium (2.0-2.5A) resolution data. Our analysis of cation B-factors versus average B-factors of atoms in the cation environment reveals substantial numbers of structures contain either an incorrect metal ion assignment or an unusual coordination pattern. Correlation between data resolution and completeness of the metal coordination spheres is also found.

  20. Investigation of metal ions sorption of brown peat moss powder

    Science.gov (United States)

    Kelus, Nadezhda; Blokhina, Elena; Novikov, Dmitry; Novikova, Yaroslavna; Chuchalin, Vladimir

    2017-11-01

    For regularities research of sorptive extraction of heavy metal ions by cellulose and its derivates from aquatic solution of electrolytes it is necessary to find possible mechanism of sorption process and to choice a model describing this process. The present article investigates the regularities of aliovalent metals sorption on brown peat moss powder. The results show that sorption isotherm of Al3+ ions is described by Freundlich isotherm and sorption isotherms of Na+ i Ni2+ are described by Langmuir isotherm. To identify the mechanisms of brown peat moss powder sorption the IR-spectra of the initial brown peat moss powder samples and brown peat moss powder samples after Ni (II) sorption were studied. Metal ion binding mechanisms by brown peat moss powder points to ion exchange, physical adsorption, and complex formation with hydroxyl and carboxyl groups.

  1. Distinct effect of xenobiotics on the metal-binding properties of protein molecules.

    Science.gov (United States)

    Novikova, Natalia; Kovalchuk, Mikhail; Stepina, Nina; Gaynutdinov, Radmir; Chukhrai, Elena; Yurieva, Eleonora

    2015-07-01

    The X-ray standing-wave method was applied to study the elemental composition and molecular organization of ordered protein films of alkaline phosphatase exposed to different xenobiotics (drug compounds, lead). Binding of metal ions from triply distilled water to protein molecules has been experimentally observed. Definite differences in the arrangement of impurity metal ions in the films have been established. The considerable enhancement of protein-metal interactions is attributed to partial rearrangement of the protein native structure, induced by xenobiotics.

  2. Amorphization of metals by ion implantation and ion beam mixing

    International Nuclear Information System (INIS)

    Rauschenbach, B.; Heera, V.

    1988-01-01

    Amorphous metallic systems can be formed either by high-fluence ion implantation of glassforming species or by irradiation of layered metal systems with inert gas ions. Both techniques and experimental examples are presented. Empirical rules are discussed which predict whether a given system can be transformed into an amorphous phase. Influence of temperature, implantation dose and pre-existing crystalline metal composition on amorphization is considered. Examples are given of the implantation induced amorphous structure, recrystallization and formation of quasicrystalline structures. (author)

  3. Characterization of Mn(II) ion binding to the amyloid-β peptide in Alzheimer's disease.

    Science.gov (United States)

    Wallin, Cecilia; Kulkarni, Yashraj S; Abelein, Axel; Jarvet, Jüri; Liao, Qinghua; Strodel, Birgit; Olsson, Lisa; Luo, Jinghui; Abrahams, Jan Pieter; Sholts, Sabrina B; Roos, Per M; Kamerlin, Shina C L; Gräslund, Astrid; Wärmländer, Sebastian K T S

    2016-12-01

    Growing evidence links neurodegenerative diseases to metal exposure. Aberrant metal ion concentrations have been noted in Alzheimer's disease (AD) brains, yet the role of metals in AD pathogenesis remains unresolved. A major factor in AD pathogenesis is considered to be aggregation of and amyloid formation by amyloid-β (Aβ) peptides. Previous studies have shown that Aβ displays specific binding to Cu(II) and Zn(II) ions, and such binding has been shown to modulate Aβ aggregation. Here, we use nuclear magnetic resonance (NMR) spectroscopy to show that Mn(II) ions also bind to the N-terminal part of the Aβ(1-40) peptide, with a weak binding affinity in the milli- to micromolar range. Circular dichroism (CD) spectroscopy, solid state atomic force microscopy (AFM), fluorescence spectroscopy, and molecular modeling suggest that the weak binding of Mn(II) to Aβ may not have a large effect on the peptide's aggregation into amyloid fibrils. However, identification of an additional metal ion displaying Aβ binding reveals more complex AD metal chemistry than has been previously considered in the literature. Copyright © 2016 Elsevier GmbH. All rights reserved.

  4. Metal Ion Controlled Polymorphism of a Peptide

    DEFF Research Database (Denmark)

    Hemmingsen, Lars Bo Stegeager; Jancso, Attila; Szunyogh, Daniel

    2011-01-01

    , …) in the peptide, and the ligand and structural preferences of the metal ion (in our studies Zn2+, Cd2+, Hg2+, Cu+/2+). Simultaneously, new species such as metal ion bridged ternary complexes or even oligomers may be formed. In recent previous studies we have observed similar polymorphism of zinc finger model...

  5. Metal Ions Analysis with Capillary Zone Electrophoresis.

    Science.gov (United States)

    Malik, Ashok Kumar; Aulakh, Jatinder Singh; Kaur, Varinder

    2016-01-01

    Capillary electrophoresis has recently attracted considerable attention as a promising analytical technique for metal ion separations. Significant advances that open new application areas for capillary electrophoresis in the analysis of metal species occurred based on various auxiliary separation principles. These are mainly due to complexation, ion pairing, solvation, and micellization interactions between metal analytes and electrolyte additives, which alter the separation selectivity in a broad range. Likewise, many separation studies for metal ions have been concentrated on the use of preelectrophoresis derivatization methodology. Approaches suitable for manipulation of selectivity for different metal species including metal cations, metal complexes, metal oxoanions, and organometallic compounds, are discussed, with special attention paid to the related electrophoretic system variables using illustrative examples.

  6. Separation of metal ions from aqueous solutions

    Science.gov (United States)

    Almon, Amy C.

    1994-01-01

    A process and apparatus for quantitatively and selectively separating metal ions from mixtures thereof in aqueous solution. The apparatus includes, in combination, a horizontal electrochemical flow cell containing flow bulk electrolyte solution and an aqueous, metal ion-containing solution, the cell containing a metal mesh working electrode, a counter electrode positioned downstream from the working electrode, an independent variable power supply/potentiostat positioned outside of the flow cell and connected to the electrodes, and optionally a detector such as a chromatographic detector, positioned outside the flow cell. This apparatus and its operation has significant application where trace amounts of metal ions are to be separated.

  7. Metal binding spectrum and model structure of the Bacillus anthracis virulence determinant MntA.

    Science.gov (United States)

    Vigonsky, Elena; Fish, Inbar; Livnat-Levanon, Nurit; Ovcharenko, Elena; Ben-Tal, Nir; Lewinson, Oded

    2015-10-01

    The potentially lethal human pathogen Bacillus anthracis expresses a putative metal import system, MntBCA, which belongs to the large family of ABC transporters. MntBCA is essential for virulence of Bacillus anthracis: deletion of MntA, the system's substrate binding protein, yields a completely non-virulent strain. Here we determined the metal binding spectrum of MntA. In contrast to what can be inferred from growth complementation studies we find no evidence that MntA binds Fe(2+) or Fe(3+). Rather, MntA binds a variety of other metal ions, including Mn(2+), Zn(2+), Cd(2+), Co(2+), and Ni(2+) with affinities ranging from 10(-6) to 10(-8) M. Binding of Zn(2+) and Co(2+) have a pronounced thermo-stabilizing effect on MntA, with Mn(2+) having a milder effect. The thermodynamic stability of MntA, competition experiments, and metal binding and release experiments all suggest that Mn(2+) is the metal that is likely transported by MntBCA and is therefore the limiting factor for virulence of Bacillus anthracis. A homology-model of MntA shows a single, highly conserved metal binding site, with four residues that participate in metal coordination: two histidines, a glutamate, and an aspartate. The metals bind to this site in a mutually exclusive manner, yet surprisingly, mutational analysis shows that for proper coordination each metal requires a different subset of these four residues. ConSurf evolutionary analysis and structural comparison of MntA and its homologues suggest that substrate binding proteins (SBPs) of metal ions use a pair of highly conserved prolines to interact with their cognate ABC transporters. This proline pair is found exclusively in ABC import systems of metal ions.

  8. Electrochemical Metal Ion Sensors. Exploiting Amino Acids and Peptides as Recognition Elements

    Directory of Open Access Journals (Sweden)

    Wenrong Yang

    2001-08-01

    Full Text Available Amino acids and peptides are known to bind metal ions, in some cases very strongly. There are only a few examples of exploiting this binding in sensors. The review covers the current literature on the interaction of peptides and metals and the electrochemistry of bound metal ions. Peptides may be covalently attached to surfaces. Of particular interest is the attachment to gold via sulfur linkages. Sulfur-containing peptides (eg cysteine may be adsorbed directly, while any amino group can be covalently attached to a carboxylic acid-terminated thiol. Once at a surface, the possibility for using the attached peptide as a sensor for metal ions becomes realised. Results from the authors’ laboratory and elsewhere have shown the potential for selective monitoring of metal ions at ppt levels. Examples of the use of poly-aspartic acid and the copper binding peptide Gly-Gly-His for detecting copper ions are given.

  9. Multiheteromacrocycles that Complex Metal Ions. Sixth Progress Report, 1 May 1979-30 April 1980

    Science.gov (United States)

    Cram, D. J.

    1980-01-15

    Objective is to design synthesize, and evaluate cyclic and polycyclic host organic compounds for their abilities to complex and lipophilize guest metal ions, their complexes, and their clusters. Host organic compounds consist of strategically placed solvating, coordinating, and ion-pairing sites tied together by covalent bonds through hydrocarbon units around cavities shaped to be occupied by guest metal ions or by metal ions plus their ligands. Specificity in complexation is sought by matching the following properties of host and guest: cavity and metal ion sizes; geometric arrangements of binding sites; number of binding sites; character of binding sites; and valences. During this period, hemispherands based on an aryloxy or cyclic urea unit, spherands based on aryloxyl units only, and their complexes with alkali metals and alkaline earths were investigated. An attempt to separate {sup 6}Li and {sup 7}Li by gel permeation chromatography of lithiospherium chloride failed. (DLC)

  10. short communication binding of nickel and zinc ions with activated ...

    African Journals Online (AJOL)

    a

    Equilibrium sorption of nickel and zinc ions by the activated carbon was studied using a range of metal ion concentrations. The sorption data was observed to have an adequate fit for the. Langmuir isotherm equation. The level of metal ion uptake was found to be of the order: Ni2+ >. Zn2+. The difference in the removal ...

  11. 1H NMR study of effects of synergistic anion and metal ion binding on pH titration of the histidinyl side-chain residues of the half-molecules of ovotransferrin

    International Nuclear Information System (INIS)

    Woodworth, R.C.; Butcher, N.D.; Brown, S.A.; Brown-Mason, A.

    1987-01-01

    Separation of ovotransferrin into C-terminal (OTf/2C) and N-terminal (OTf/2N) half-molecules has made possible the resolution of all expected histidinyl C(2)H resonances by proton nuclear magnetic resonance at 250 MHz. The chemical shift of many of the resonances decreases with increasing pH, allowing construction of titration curves, whereas a few resonances fail to titrate. On formation of the Ga/sup III/OTf/2(C 2 O 4 ) ternary complexes, two of the low-field C(2)H resonances in each half-molecule fail to titrate. This behavior implicates the imidazole groups giving rise to these resonances as ligands to the bound metal ion. A third C(2)H resonance in each half-molecule undergoes a marked reduction in pK'/sub a/ on formation of the ternary complex. The imidazole group displaying this resonance is implicated in a proton-relay scheme involved in binding the synergistic anion, oxalate, and a water of hydration on the bound metal ion. The titration curves for the various imidazole resonances have been fit to a four-parameter equation involving estimation of the pK'/sub a/, the limiting chemical shift values, and a Hill constant n. Hill constants of 1, which suggests positive cooperativity in the titration of this residue. The basis for this behavior cannot be rationalized at this time. 13 C NMR studies of [zeta- 13 C]Arg-OTf suggest the Arg side chains may not be intimately involved in formation of the ternary complex

  12. Removal and recovery of metal ions from process and waste streams using polymer filtration

    International Nuclear Information System (INIS)

    Jarvinen, G.D.; Smith, B.F.; Robison, T.W.; Kraus, K.M.; Thompson, J.A.

    1999-01-01

    Polymer Filtration (PF) is an innovative, selective metal removal technology. Chelating, water-soluble polymers are used to selectively bind the desired metal ions and ultrafiltration is used to concentrate the polymer-metal complex producing a permeate with low levels of the targeted metal ion. When applied to the treatment of industrial metal-bearing aqueous process streams, the permeate water can often be reused within the process and the metal ions reclaimed. This technology is applicable to many types of industrial aqueous streams with widely varying chemistries. Application of PF to aqueous streams from nuclear materials processing and electroplating operations will be described

  13. QM/MM Molecular Dynamics Studies of Metal Binding Proteins

    Directory of Open Access Journals (Sweden)

    Pietro Vidossich

    2014-07-01

    Full Text Available Mixed quantum-classical (quantum mechanical/molecular mechanical (QM/MM simulations have strongly contributed to providing insights into the understanding of several structural and mechanistic aspects of biological molecules. They played a particularly important role in metal binding proteins, where the electronic effects of transition metals have to be explicitly taken into account for the correct representation of the underlying biochemical process. In this review, after a brief description of the basic concepts of the QM/MM method, we provide an overview of its capabilities using selected examples taken from our work. Specifically, we will focus on heme peroxidases, metallo-β-lactamases, α-synuclein and ligase ribozymes to show how this approach is capable of describing the catalytic and/or structural role played by transition (Fe, Zn or Cu and main group (Mg metals. Applications will reveal how metal ions influence the formation and reduction of high redox intermediates in catalytic cycles and enhance drug metabolism, amyloidogenic aggregate formation and nucleic acid synthesis. In turn, it will become manifest that the protein frame directs and modulates the properties and reactivity of the metal ions.

  14. Albumin as marker for susceptibility to metal ions in metal-on-metal hip prosthesis patients.

    Science.gov (United States)

    Facchin, F; Catalani, S; Bianconi, E; Pasquale, D De; Stea, S; Toni, A; Canaider, S; Beraudi, A

    2017-04-01

    Metal-on-metal (MoM) hip prostheses are known to release chromium and cobalt (Co), which negatively affect the health status, leading to prosthesis explant. Albumin (ALB) is the main serum protein-binding divalent transition metals. Its binding capacity can be affected by gene mutations or modification of the protein N-terminal region, giving the ischaemia-modified albumin (IMA). This study evaluated ALB, at gene and protein level, as marker of individual susceptibility to Co in MoM patients, to understand whether it could be responsible for the different management of this ion. Co was measured in whole blood, serum and urine of 40 MoM patients. A mutational screening of ALB was performed to detect links between mutations and metal binding. Finally, serum concentration of total ALB and IMA were measured. Serum total ALB concentration was in the normal range for all patients. None of the subjects presented mutations in the investigated gene. Whole blood, serum and urine Co did not correlate with serum total ALB or IMA, although IMA was above the normal limit in most subjects. The individual susceptibility is very important for patients' health status. Despite the limited results of this study, we provide indications on possible future investigations on the toxicological response to Co.

  15. Ag(I), Pb(II) and Hg(II) binding to biomolecules studied by Perturbed Angular Correlation of $\\gamma$-rays (PAC) spectroscopy: Function and toxicity of metal ions in biological systems

    CERN Multimedia

    Metal ions display diverse functions in biological systems and are essential components in both protein structure and function, and in control of biochemical reaction paths and signaling. Similarly, metal ions may be used to control structure and function of synthetic biomolecules, and thus be a tool in the design of molecules with a desired function. In this project we address a variety of questions concerning both the function of metal ions in natural systems, in synthetic biomolecules, and the toxic effect of some metal ions. All projects involve other experimental techniques such as NMR, EXAFS, UV-Vis, fluorescence, and CD spectroscopies providing complementary data, as well as interpretation of the experimental data by quantum mechanical calculations of spectroscopic properties.

  16. Evaluation of immobilized metal-ion affinity chromatography and electrospray ionization tandem mass spectrometry for recovery and identification of copper(II-binding ligands in seawater using the model ligand 8-hydroxyquinoline

    Directory of Open Access Journals (Sweden)

    Richard L Nixon

    2016-11-01

    Full Text Available Complexation by organic ligands dominates the speciation of iron (Fe, copper (Cu, and other bioactive trace metals in seawater, controlling their bioavailability and distribution in the marine environment. Several classes of high-affinity Fe-binding ligands (siderophores have been identified in seawater but the chemical structures of marine Cu-complexing ligands remain unknown. Immobilized metal-ion affinity chromatography (IMAC allows Cu ligands to be isolated from bulk dissolved organic matter (DOM in seawater and separated into fractions which can be characterized independently using electrochemical and spectroscopic techniques. Attempts have been made to combine IMAC with electrospray ionization mass spectrometry (ESI-MS to characterize marine Cu ligands, but results have proven inconclusive due to the lack of tandem mass spectrometry (MS/MS data to confirm ligand recovery. We used 8-hydroxyquinoline (8-HQ, a well-characterized model ligand that forms strong 1:2 metal:ligand complexes with Cu2+ at pH 8 (log β2 = 18.3, to evaluate Cu(II-IMAC and ESI-MS/MS for recovery and identification of copper(II-complexing ligands in seawater. One-litre samples of 0.45µm-filtered surface seawater were spiked with 8-HQ at low concentrations (up to 100 nM and fractionated by IMAC. Fractions eluted with acidified artificial seawater were desalted and re-suspended in methanol via solid-phase extraction (SPE to obtain extracts suitable for ESI-MS analysis. Recovery of 8-HQ by Cu(II-IMAC was confirmed unambiguously by MS/MS and found to average 81% based upon accurate quantitation via multiple reaction monitoring (MRM. Cu(II-IMAC fractionation of unspiked seawater using multiple UV detection wavelengths suggests an optimal fraction size of 2 mL for isolating and analyzing Cu ligands with similar properties.

  17. Functionalization of protein crystals with metal ions, complexes and nanoparticles.

    Science.gov (United States)

    Abe, Satoshi; Maity, Basudev; Ueno, Takafumi

    2018-04-01

    Self-assembled proteins have specific functions in biology. With inspiration provided by natural protein systems, several artificial protein assemblies have been constructed via site-specific mutations or metal coordination, which have important applications in catalysis, material and bio-supramolecular chemistry. Similar to natural protein assemblies, protein crystals have been recognized as protein assemblies formed of densely-packed monomeric proteins. Protein crystals can be functionalized with metal ions, metal complexes or nanoparticles via soaking, co-crystallization, creating new metal binding sites by site-specific mutations. The field of protein crystal engineering with metal coordination is relatively new and has gained considerable attention for developing solid biomaterials as well as structural investigations of enzymatic reactions, growth of nanoparticles and catalysis. This review highlights recent and significant research on functionalization of protein crystals with metal coordination and future prospects. Copyright © 2017 Elsevier Ltd. All rights reserved.

  18. Effective charge of energetic ions in metals

    International Nuclear Information System (INIS)

    Kitagawa, M.; Brandt, W.

    1983-01-01

    The effective charge of energetic ion, as derived from stopping power of metals, is calculated by use of a dielectronic-response function method. The electronic distribution in the ion is described through the variational principle in a statistical approximation. The dependences of effective charge on the ion velocity, atomic number and r/sub s/-value of metal are derived at the low-velocity region. The effective charge becomes larger than the real charge of ion due to the close collisions. We obtain the quasi-universal equation of the fractional effective electron number of ion as a function of the ratio between the ionic size and the minimum distance approach. The comparsion between theoretical and experimental results of the effective charge is performed for the cases of N ion into Au, C and Al. We also discuss the equipartition rule of partially ionized ion at the high-velocity region

  19. MetalionRNA: computational predictor of metal-binding sites in RNA structures.

    Science.gov (United States)

    Philips, Anna; Milanowska, Kaja; Lach, Grzegorz; Boniecki, Michal; Rother, Kristian; Bujnicki, Janusz M

    2012-01-15

    Metal ions are essential for the folding of RNA molecules into stable tertiary structures and are often involved in the catalytic activity of ribozymes. However, the positions of metal ions in RNA 3D structures are difficult to determine experimentally. This motivated us to develop a computational predictor of metal ion sites for RNA structures. We developed a statistical potential for predicting positions of metal ions (magnesium, sodium and potassium), based on the analysis of binding sites in experimentally solved RNA structures. The MetalionRNA program is available as a web server that predicts metal ions for RNA structures submitted by the user. The MetalionRNA web server is accessible at http://metalionrna.genesilico.pl/.

  20. Mechanism of Metal Ion Activation of the Diphtheria Toxin Repressor DtxR

    Energy Technology Data Exchange (ETDEWEB)

    D' Aquino,J.; Tetenbaum-Novatt, J.; White, A.; Berkovitch, F.; Ringe, D.

    2005-01-01

    The diphtheria toxin repressor (DtxR) is a metal ion-activated transcriptional regulator that has been linked to the virulence of Corynebacterium diphtheriae. Structure determination has shown that there are two metal ion binding sites per repressor monomer, and site-directed mutagenesis has demonstrated that binding site 2 (primary) is essential for recognition of the target DNA repressor, leaving the role of binding site 1 (ancillary) unclear. Calorimetric techniques have demonstrated that although binding site 1 (ancillary) has high affinity for metal ion with a binding constant of 2 x 10{sup -7}, binding site 2 (primary) is a low-affinity binding site with a binding constant of 6.3 x 10{sup -4}. These two binding sites act in an independent fashion, and their contribution can be easily dissected by traditional mutational analysis. Our results clearly demonstrate that binding site 1 (ancillary) is the first one to be occupied during metal ion activation, playing a critical role in stabilization of the repressor. In addition, structural data obtained for the mutants Ni-DtxR(H79A, C102D), reported here, and the previously reported DtxR(H79A) have allowed us to propose a mechanism of metal activation for DtxR.

  1. Multiheteromacrocycles that complex metal ions. Third progress report, 1 May 1976--30 April 1977

    International Nuclear Information System (INIS)

    Cram, D.J.

    1977-01-01

    The overall objective of this research is to design, synthesize and evaluate cyclic and polycyclic host organic compounds for their abilities to complex and lipophilize guest metal ions, their complexes and clusters. Host organic compounds consist of strategically placed solvating, coordinating and ion-pairing sites tied together by covalent bonds through hydrocarbon units around cavities shaped to be occupied by guest metal ions, or metal ions plus their ligands. Specificity in complexation is sought by matching the following properties of host and guest: cavity and metal ion sizes; geometric arrangements of binding sites; numbers of binding sites; characters of binding sites; and valences. The specific compounds synthesized and their complexing and lipophilizing properties are summarized

  2. Metal ion sorption by untreated and chemically treated biomass

    Energy Technology Data Exchange (ETDEWEB)

    Kilbane, J.J.; Xie, J.

    1992-12-31

    The metal-binding ability of biosorbents is well known; however, in comparison with commercial ion-exchange resins the capacity of biosorbents is low. The purpose of this research was to examine chemically modified biosorbents and biosorbents prepared from microorganisms isolated from extreme environments to determine if significant improvements in metal-binding capacity or biosorbents with unique capabilities could be produced. Chemical treatments examined included acid, alkali, carbon disulfide, phosphorus oxychloride, anhydrous formamide, sodium thiosulfate, sodium chloroacetic acid, and phenylsulfonate. Biosorbents were prepared from microorganisms isolated from pristine and acid mine drainage impacted sites and included heterotrophs, methanotrophs, algae, and sulfate reducers. Chemical modification with carbon disulfide, phosphorous oxychloride, and sodium thiosulfate yielded biosorbents with such as much as 74%, 133%, and 155% improvements, respectively, in metal-binding capacity, but the performance of these chemically modified biosorbents deteriorated upon repeated use. A culture isolated from an acid mine drainage impacted site, IGTM17, exhibits about 3-fold higher metal-binding capacity in comparison with other biosorbents examined in this study. IGTM17 also exhibits superior metal-binding ability at decreased pH or in the presence of interfering common cations in comparison with other biosorbents or some commercially available cation exchange resins. Some biosorbents, such as IGTM5, can bind anions. To our knowledge this is the first demonstration of the ability of biosorbents to bind anions. Moreover, preliminary data indicate that the chemical modification of biosorbents may be capable of imparting the ability to selectively bind certain anions. Further research is needed to optimize conditions for the chemical modification and stabilization of biosorbents.

  3. Engineered Bacterial Metal-binding Proteins for Nanoscale Self-assembly and heavy Metal Tolerance

    Science.gov (United States)

    Hall Sedlak, Ruth Amanda

    Implementing biological principles in material synthesis and assembly is one way to expand our abilities to efficiently assemble nanoscale materials and devices. Specifically, recent advances in identifying peptides that bind inorganic materials with high affinity and specificity has spurred investigation of protein models for nanoscale inorganic assembly. This dissertation presents the results of my studies of several E. coli proteins engineered to bind inorganic materials through simple peptide motifs. I demonstrate that these proteins modulate the self-assembly of DNA-based nanostructures and can introduce heavy metal tolerance into metal-sensitive bacteria. Chapter 2 explores use of the engineered F plasmid DNA relaxase/helicase TraI for the self-assembly of complex DNA-protein-gold nanostructures. The full-length protein is engineered with a gold binding motif at an internal permissive site (TraI369GBP1-7x), while a truncated version of TraI is engineered with the same gold binding motif at the C-terminus (TraI361GBP1-7x). Both constructs bind gold nanoparticles while maintaining their DNA binding activity, and transmission electron microscopy reveals TraI369GBP1-7x utilizes its non-specific DNA binding activity to decorate single-stranded and double-stranded DNA with gold nanoparticles. The self assembly principles demonstrated in this work will be fundamental to constructing higher ordered hybrid nanostructures through DNA-protein-nanoparticle interactions. Chapter 3 studies the effects of expressing inorganic binding peptides within cells. I identified a silver binding peptide that, when fused to the periplasmic maltose binding protein, protects E. coli from silver toxicity in batch culture and reduces silver ions to silver nanoparticles within the bacterial periplasm. Engineered metal-ion tolerant microorganisms such as this E. coli could potentially be used in applications ranging from remediation to interrogation of biomolecule-metal interactions in vivo

  4. Upgraded vacuum arc ion source for metal ion implantation

    International Nuclear Information System (INIS)

    Nikolaev, A. G.; Oks, E. M.; Savkin, K. P.; Yushkov, G. Yu.; Brown, I. G.

    2012-01-01

    Vacuum arc ion sources have been made and used by a large number of research groups around the world over the past twenty years. The first generation of vacuum arc ion sources (dubbed ''Mevva,'' for metal vapor vacuum arc) was developed at Lawrence Berkeley National Laboratory in the 1980s. This paper considers the design, performance parameters, and some applications of a new modified version of this kind of source which we have called Mevva-V.Ru. The source produces broad beams of metal ions at an extraction voltage of up to 60 kV and a time-averaged ion beam current in the milliampere range. Here, we describe the Mevva-V.Ru vacuum arc ion source that we have developed at Tomsk and summarize its beam characteristics along with some of the applications to which we have put it. We also describe the source performance using compound cathodes.

  5. Lithium metal doped electrodes for lithium-ion rechargeable chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Gao; Battaglia, Vince; Wang, Lei

    2016-09-13

    An embodiment of the invention combines the superior performance of a polyvinylidene difluoride (PVDF) or polyethyleneoxide (POE) binder, the strong binding force of a styrene-butadiene (SBR) binder, and a source of lithium ions in the form of solid lithium metal powder (SLMP) to form an electrode system that has improved performance as compared to PVDF/SBR binder based electrodes. This invention will provide a new way to achieve improved results at a much reduced cost.

  6. ION EXCHANGE SOFTENING: EFFECTS ON METAL CONCENTRATIONS

    Science.gov (United States)

    A corrosion control pipe loop study to evaluate the effect of ion exchange water softening on metal leaching from household plumbing materials was conducted on two different water qualities having different pH's and hardness levels. The results showed that removing hardness ions ...

  7. Thiophilic metal ion rescue of phosphorothioate interference within the Tetrahymena ribozyme P4-P6 domain.

    OpenAIRE

    Basu, S; Strobel, S A

    1999-01-01

    Divalent metal ions are essential for the folding and catalytic activities of many RNAs. A commonly employed biochemical technique to identify metal-binding sites in RNA is the rescue of Rp alpha-phosphorothioate (PS) interference by the addition of soft divalent metal ions. To access the ability of such experiments to accurately identify metal-ion coordinations within a complex RNA fold, we report metal-rescue results from the Tetrahymena group I intron P4-P6 domain, where the location and c...

  8. Interaction of lactic acid bacteria with metal ions: opportunities for improving food safety and quality.

    Science.gov (United States)

    Mrvčić, Jasna; Stanzer, Damir; Solić, Ema; Stehlik-Tomas, Vesna

    2012-09-01

    Certain species of lactic acid bacteria (LAB), as well as other microorganisms, can bind metal ions to their cells surface or transport and store them inside the cell. Due to this fact, over the past few years interactions of metal ions with LAB have been intensively investigated in order to develop the usage of these bacteria in new biotechnology processes in addition to their health and probiotic aspects. Preliminary studies in model aqueous solutions yielded LAB with high absorption potential for toxic and essential metal ions, which can be used for improving food safety and quality. This paper provides an overview of results obtained by LAB application in toxic metal ions removing from drinking water, food and human body, as well as production of functional foods and nutraceutics. The biosorption abilities of LAB towards metal ions are emphasized. The binding mechanisms, as well as the parameters influencing the passive and active uptake are analyzed.

  9. Interaction of antihypertensive drug amiloride with metal ions in micellar medium using fluorescence spectroscopy

    International Nuclear Information System (INIS)

    Gujar, Varsha; Pundge, Vijaykumar; Ottoor, Divya

    2015-01-01

    Steady state and life time fluorescence spectroscopy have been employed to study the interaction of antihypertensive drug amiloride with biologically important metal ions i.e. Cu 2+ , Fe 2+ , Ni 2+ and Zn 2+ in various micellar media (anionic SDS (sodium dodecyl sulfate), nonionic TX-100 (triton X-100) and cationic CTAB (cetyl trimethyl ammonium bromide)). It was observed that fluorescence properties of drug remain unaltered in the absence of micellar media with increasing concentration of metal ions. However, addition of Cu 2+ , Fe 2+ and Ni 2+ caused fluorescence quenching of amiloride in the presence of anionic micelle, SDS. Binding of drug with metal ions at the charged micellar interface could be the possible reason for this pH-dependent metal-mediated fluorescence quenching. There were no remarkable changes observed due to metal ions addition when drug was present in cationic and nonionic micellar medium. The binding constant and bimolecular quenching constant were evaluated and compared for the drug–metal complexes using Stern–Volmer equation and fluorescence lifetime values. - Highlights: • Interaction of amiloride with biologically important metal ions, Fe 2+ , Cu 2+ , Ni 2+ and Zn 2+ . • Monitoring the interaction in various micelle at different pH by fluorescence spectroscopy. • Micelles acts as receptor, amiloride as transducer and metal ions as analyte in the present system. • Interaction study provides pH dependent quenching and binding mechanism of drug with metal ions

  10. Metal vapor vacuum arc ion sources

    International Nuclear Information System (INIS)

    Brown, I.G.; Dickinson, M.R.; Galvin, J.E.; Godechot, X.; MacGill, R.A.

    1990-06-01

    We have developed a family of metal vapor vacuum are (MEVVA) high current metal ion sources. The sources were initially developed for the production of high current beams of metal ions for heavy ion synchrotron injection for basic nuclear physics research; more recently they have also been used for metal ion implantation. A number of different embodiments of the source have been developed for these specific applications. Presently the sources operate in a pulsed mode, with pulse width of order 1 ms and repetition rate up to 100 pps. Beam extraction voltage is up to 100 kV, and since the ions produced in the vacuum arc plasma are in general multiply ionized the ion energy is up to several hundred keV. Beam current is up to several Amperes peak and around 10 mA time averaged delivered onto target. Nearly all of the solid metals of the Periodic Table have been use to produce beam. A number of novel features have been incorporated into the sources, including multiple cathodes and the ability to switch between up to 18 separate cathode materials simply and quickly, and a broad beam source version as well as miniature versions. here we review the source designs and their performance. 45 refs., 7 figs

  11. Endonuclease active site plasticity allows DNA cleavage with diverse alkaline Earth and transition metal ions.

    Science.gov (United States)

    Vasu, Kommireddy; Saravanan, Matheshwaran; Nagaraja, Valakunja

    2011-09-16

    A majority of enzymes show a high degree of specificity toward a particular metal ion in their catalytic reaction. However, Type II restriction endonuclease (REase) R.KpnI, which is the first member of the HNH superfamily of REases, exhibits extraordinary diversity in metal ion dependent DNA cleavage. Several alkaline earth and transition group metal ions induce high fidelity and promiscuous cleavage or inhibition depending upon their concentration. The metal ions having different ionic radii and co-ordination geometries readily replace each other from the enzyme's active site, revealing its plasticity. Ability of R.KpnI to cleave DNA with both alkaline earth and transition group metal ions having varied ionic radii could imply utilization of different catalytic site(s). However, mutation of the invariant His residue of the HNH motif caused abolition of the enzyme activity with all of the cofactors, indicating that the enzyme follows a single metal ion catalytic mechanism for DNA cleavage. Indispensability of His in nucleophile activation together with broad cofactor tolerance of the enzyme indicates electrostatic stabilization function of metal ions during catalysis. Nevertheless, a second metal ion is recruited at higher concentrations to either induce promiscuity or inhibit the DNA cleavage. Regulation of the endonuclease activity and fidelity by a second metal ion binding is a unique feature of R.KpnI among REases and HNH nucleases. The active site plasticity of R.KpnI opens up avenues for redesigning cofactor specificities and generation of mutants specific to a particular metal ion.

  12. Metal ions as inflammatory initiators of osteolysis.

    Science.gov (United States)

    Magone, Kevin; Luckenbill, Daniel; Goswami, Tarun

    2015-05-01

    Osteolysis and aseptic loosening currently contribute 75 % of implant failures. Furthermore, with over four million joint replacements projected to be performed in the United States annually, osteolysis and aseptic loosening may continue to pose a significant morbidity. This paper reviews the osteolysis cascade leading to osteoclast activation and bone resorption at the biochemical level. Additionally, the metal ion release mechanism from metallic implants is elucidated. Even though metal ions are not the predominating initiator of osteolysis, they do increase the concentration of key inflammatory cytokines that stimulate osteoclasts and prove to be a contributor to osteolysis and aseptic loosening. Osteolysis is a competitive mechanism among a number of biological reactions, which includes debris release, macrophage and osteoclast activation, an inflammatory response as well as metal ion release. Pharmacological therapy for component loosening has also been reviewed. A non-surgical treatment of osteolysis has not been found in the literature and thus may become an area of future research. Even though this research is warranted, comprehensively understanding the immune response to orthopedic implants and their metallic ions, and thus, creating improved prostheses appears to be the most cost-effective approach to decrease the morbidity related to osteolysis and to design implants with greater longevity. The ionic forms, cytokines, toxicity, gene expression, biological effects, and hypersensitivity responses of metallic elements from metal implants are summarized as well.

  13. Immobilization of Metal Hexacyanoferrate Ion-Exchangers for the Synthesis of Metal Ion Sorbents—A Mini-Review

    Directory of Open Access Journals (Sweden)

    Thierry Vincent

    2015-11-01

    Full Text Available Metal hexacyanoferrates are very efficient sorbents for the recovery of alkali and base metal ions (including radionuclides such as Cs. Generally produced by the direct reaction of metal salts with potassium hexacyanoferrate (the precursors, they are characterized by ion-exchange and structural properties that make then particularly selective for Cs(I, Rb(I and Tl(I recovery (based on their hydrated ionic radius consistent with the size of the ion-exchanger cage, though they can bind also base metals. The major drawback of these materials is associated to their nanometer or micrometer size that makes them difficult to recover in large-size continuous systems. For this reason many techniques have been designed for immobilizing these ion-exchangers in suitable matrices that can be organic (mainly polymers and biopolymers or inorganic (mineral supports, carbon-based matrices. This immobilization may proceed by in situ synthesis or by entrapment/encapsulation. This mini-review reports some examples of hybrid materials synthesized for the immobilization of metal hexacyanoferrate, the different conditionings of these composite materials and, briefly, the parameters to take into account for their optimal design and facilitated use.

  14. Hydrogen molecule binding to unsaturated metal sites in metal-organic frameworks studied by neutron powder diffraction and inelastic neutron scattering

    Science.gov (United States)

    Liu, Yun; Brown, Craig; Neumann, Dan; Dinca, Mircea; Long, Jeffrey; Peterson, Vanessa; Kepert, Cameron

    2007-03-01

    Metal organic framework (MOF) materials have shown considerable potential for hydrogen storage arising from very large surface areas. However, the low binding energy of hydrogen molecules limits its storage capability to very low temperatures (industrial applications. Using neutron powder diffraction (NPD), we have characterized the hydrogen adsorption sites in a selected series of MOF materials with exposed unsaturated metal ions. Direct binding between the unsaturated metal ions and hydrogen molecules is observed and responsible for the enhanced initial hydrogen adsorption enthalpy. The different metals centers in these MOFs show different binding strength and interaction distances between the hydrogen molecule and metal ions. The organic linker also affects the overall H2 binding strength. Inelastic neutron scattering spectra of H2 in these MOFs are also discussed.

  15. Partitioning of metals in different binding phases of tropical estuarine sediments: importance of metal chemistry.

    Science.gov (United States)

    Chakraborty, Parthasarathi; Chakraborty, Sucharita; Vudamala, Krushna; Sarkar, Arindam; Nath, B Nagender

    2016-02-01

    Distribution of metals in different binding phases of estuarine sediments provides chemically significant description of metal-sediment interactions. This study describes the influences of ligand field stabilization energy (LFSE), Jahn-Teller effect, and water exchange rate (k-w) on metal distribution in different binding phases of estuarine sediments. It was found that Cu had highest affinity for organic binding phases in the studied sediments followed by Ni and Pb. However, Pb showed strong association with Fe/Mn oxide phases followed by Ni and Cu. Faster k-w of Cu (II) (1 × 10(9) s(-1)) increased the rate of complex formation of Cu(2+) ion with ligand in the organic phases. The Cu-ligand (from organic phase) complexes gained extra stability by the Jahn-Teller effect. The combined effects of these two phenomena and high ionic potential increased the association of Cu with the organic phases of the sediments than Ni and Pb. The smaller ionic radii of Ni(2+) (0.72 Å) than Pb(2+) (1.20 Å) increase the stability of Ni-ligand complexes in the organic phase of the sediments. High LFSE of Ni(II) (compared with Pb(2+) ions) also make Ni-organic complexes increasingly stable than Pb. High k-w (7 × 10(9) s(-1)) of Pb did not help it to associate with organic phases in the sediments. The high concentration of Pb in the Fe/Mn oxyhydroxide binding phase was probably due to co-precipitation of Pb(2+) and Fe(3+). High surface area or site availability for Pb(2+) ion on Fe oxyhydroxide phase was probably responsible for the high concentration of Pb in Fe/Mn oxyhydroxide phase. Increasing concentrations of Cu in organic phases with the increasing Cu loading suggest that enough binding sites were available for Cu in the organic binding phases of the sediments. This study also describes the influence of nature of sedimentary organic carbon (terrestrial and marine derived OC) in controlling these metal distribution and speciation in marine sediment.

  16. Ion beam analysis of metal ion implanted surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Evans, P.J.; Chu, J.W.; Johnson, E.P.; Noorman, J.T. [Australian Nuclear Science and Technology Organisation, Lucas Heights, NSW (Australia); Sood, D.K. [Royal Melbourne Inst. of Tech., VIC (Australia)

    1993-12-31

    Ion implantation is an established method for altering the surface properties of many materials. While a variety of analytical techniques are available for the characterisation of implanted surfaces, those based on particle accelerators such as Rutherford backscattering (RBS) and nuclear reaction analysis (NRA) provide some of the most useful and powerful for this purpose. Application of the latter techniques to metal ion implantation research at ANSTO will be described with particular reference to specific examples from recent studies. Where possible, the information obtained from ion beam analysis will be compared with that derived from other techniques such as Energy Dispersive X-ray (EDX) and Auger spectroscopies. 4 refs., 5 figs.

  17. Correlations of acute toxicity of metal ions and the covalent/ionic character of their bonds

    Energy Technology Data Exchange (ETDEWEB)

    Turner, J.E.; Williams, M.W.; Jacobson, K.B.; Hingerty, B.E.

    1984-01-01

    We have investigated correlations between physicochemical properties of 24 metal ions and their acute toxicity in mice and Drosophila. A high correlation for a softness parameter suggests that the relative covalent/ionic character of the bonds formed by the metal ions may be important in determining their toxicity. This hypothesis is reinforced by model calculations of metal binding to dinucleotides in water. Since the nature of bonds depends on ligand electronegativity, we searched for correlations involving this parameter. Although electronegativity is useful for interpreting some aspects of metal-ion behavior related to toxicity, it does not yield improved correlations. 8 refs., 3 figs., 1 tab.

  18. Synthesis and metal binding properties of salicylate-, catecholate-, and hydroxypyridinonate-functionalized dendrimers.

    Science.gov (United States)

    Cohen, S M; Petoud, S; Raymond, K N

    2001-01-05

    The synthesis, characterization, and metal-binding studies of chelate-functionalized dendrimers is reported. Salicylate, catecholate, and hydroxypyridinonate bidentate chelators have been coupled to the surface of both poly(propyleneimine) (Astramol) and poly(amidoamine) (Starburst, PAMAM) dendrimers up to the fifth generation (64 endgroups). A general method has been developed for the facile and high quality chromatographic purification of poly(propyleneimine) and poly(amidoamine) dendrimer derivatives. One- and two-dimensional (TOCSY) 1H NMR experiments and electrospray ionization mass spectrometry (ESI-MS) have confirmed the exhaustive coupling of these chelators to the primary amine functionalities of the dendrimers. Spectrophotometric titrations were used to investigate the metal binding ability of these macrochelates. Spectral analysis shows that ferric iron binding to these ligands is localized to the chelating endgroups. The ability of these dendritic polymers to bind large numbers of metal ions may lead to applications as metal sequestering agents for waste remediation technologies.

  19. Polymer filtration systems for dilute metal ion recovery

    Energy Technology Data Exchange (ETDEWEB)

    Smith, B.F.; Robison, T.W.; Jarvinen, G.D.

    1998-12-01

    Scientists at Los Alamos National Laboratory have developed a metal recovery system that meets the global treatment demands for all kinds of industrial and metal-processing streams. The Polymer Filtration (PF) System--a process that is easily operated and robust--offers metal-finishing businesses a convenient and inexpensive way to recover and recycle metal ions in-house, thus reducing materials costs, waste removal costs, and industrial liability. As a valuable economic and environmental asset, the PF System has been named a winner of a 1995 R and D 100 Award. These awards are presented annually by R and D Magazine to the one hundred most significant technical innovations of the year. The PF System is based on the use of water-soluble metal-binding polymers and on advanced ultrafiltration membranes. Customers for this technology will receive new soluble polymers, especially formulated for their waste stream, and the complete PF processing unit: a reaction reservoir, pumps, plumbing, controls, and the advanced ultrafiltration membranes, all in a skid mounted frame. Metal-bearing waste water is treated in the reaction reservoir, where the polymer binds with the metal ions under balanced acid/base conditions. The reservoir fluid is then pumped through the ultrafiltration system--a cartridge packed with ultrafiltration membranes shaped in hollow fibers. As the fluid travels inside the fiber, water and other small molecules--simple salts such as calcium and sodium, for example--pass through the porous membrane walls of the fibers and are discharged through the outlet as permeate. The polymer-bound metal, which is too large to pass through the pores, is both purified and concentrated inside the hollow fibers and is returned to the fluid reservoir for further waste water treatment.

  20. Cleavage reactions of the complex ions derived from self-complementary deoxydinucleotides and alkali-metal ions using positive ion electrospray ionization with tandem mass spectrometry.

    Science.gov (United States)

    Xiang, Yun; Abliz, Zeper; Takayama, Mitsuo

    2004-05-01

    The dissociation reactions of the adduct ions derived from the four self-complementary deoxydinucleotides, d(ApT), d(TpA), d(CpG), d(GpC), and alkali-metal ions were studied in detail by positive ion electrospray ionization multiple-stage mass spectrometry (ESI-MS(n)). For the [M + H](+) ions of the four deoxydinucleotides, elimination of 5'-terminus base or loss of both of 5'-terminus base and a deoxyribose were the major dissociation pathway. The ESI-MS(n) spectra showed that Li(+), Na(+), and Cs(+) bind to deoxydinucleotides mainly by substituting the H(+) of phosphate group, and these alkali-metal ions preferred to bind to pyrimidine bases rather than purine bases. For a given deoxydinucleotide, the dissociation pathway of [M + K](+) ions differed clearly from that of [M + Li](+), [M + Na](+), and [M + Cs](+) ions. Some interesting and characteristic cleavage reactions were observed in the product-ion spectra of [M + K](+) ions, including direct elimination of deoxyribose and HPO(3) from molecular ions. The fragmentation behavior of the [M + K](+) and [M + W](+) (W = Li, Na, Cs) adduct ions depend upon the sequence of bases, the interaction between alkali-metal ions and nucleobases, and the steric hindrance caused by bases.

  1. Multiheteromacrocycles that Complex Metal Ions. Ninth Progress Report (includes results of last three years), 1 May 1980 -- 30 April 1983

    Science.gov (United States)

    Cram, D. J.

    1982-09-15

    The overall objective of this research is to design, synthesize, and evaluate cyclic and polycyclic host organic compounds for the abilities to complex and lipophilize guest metal ions, their complexes, and their clusters. Host organic compounds consist of strategically placed solvating, coordinating, and ion-pairing sites tied together by covalent bonds through hydrocarbon units around cavities shaped to be occupied by guest metal ions, or by metal ions plus their ligands. Specificity in complexation is sought by matching the following properties of host and guest: cavity and metal ion sizes; geometric arrangements of binding sites; numbers of binding sites; characters of binding sites; and valences. The hope is to synthesize new classes of compounds useful in the separation of metal ions, their complexes, and their clusters.

  2. Comparison of molecular mechanics-Poisson-Boltzmann surface area (MM-PBSA) and molecular mechanics-three-dimensional reference interaction site model (MM-3D-RISM) method to calculate the binding free energy of protein-ligand complexes: Effect of metal ion and advance statistical test

    Science.gov (United States)

    Pandey, Preeti; Srivastava, Rakesh; Bandyopadhyay, Pradipta

    2018-03-01

    The relative performance of MM-PBSA and MM-3D-RISM methods to estimate the binding free energy of protein-ligand complexes is investigated by applying these to three proteins (Dihydrofolate Reductase, Catechol-O-methyltransferase, and Stromelysin-1) differing in the number of metal ions they contain. None of the computational methods could distinguish all the ligands based on their calculated binding free energies (as compared to experimental values). The difference between the two comes from both polar and non-polar part of solvation. For charged ligand case, MM-PBSA and MM-3D-RISM give a qualitatively different result for the polar part of solvation.

  3. Exploiting Cancer Metal Metabolism using Anti-Cancer Metal-Binding Agents.

    Science.gov (United States)

    Merlot, Angelica M; Kalinowski, Danuta S; Kovacevic, Zaklina; Jansson, Patric J; Sahni, Sumit; Huang, Michael L; Lane, Darius L; Lok, Hiu; Richardson, Des R

    2017-07-05

    Metals are vital cellular elements necessary for multiple indispensable biological processes of living organisms, including energy transduction and cell proliferation. Interestingly, alterations in metal levels and also changes in the expression of proteins involved in metal metabolism have been demonstrated in a variety of cancers. Considering this and the important role of metals for cell growth, the development of drugs that sequester metals have become an attractive target for the development of novel anti-cancer agents. Interest in this field has surged with the design and development of new generations of chelators of the thiosemicarbazone class. These ligands have shown potent anti-cancer and anti-metastatic activity in vitro and in vivo. Due to their efficacy and safe toxicological assessment, some of these agents have recently entered multi-center clinical trials as therapeutics for advanced and resistant tumors. This review highlights the role, and changes in homeostasis, of metals in cancer and emphasizes the pre-clinical development and clinical assessment of metal ion-binding agents, namely, thiosemicarbazones, as anti-tumor agents. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

  4. Electrospray Ionization Mass Spectrometry: From Cluster Ions to Toxic metal Ions in Biology

    Energy Technology Data Exchange (ETDEWEB)

    Lentz, Nicholas B. [Iowa State Univ., Ames, IA (United States)

    2007-01-01

    This dissertation focused on using electrospray ionization mass spectrometry to study cluster ions and toxic metal ions in biology. In Chapter 2, it was shown that primary, secondary and quarternary amines exhibit different clustering characteristics under identical instrument conditions. Carbon chain length also played a role in cluster ion formation. In Chapters 3 and 4, the effects of solvent types/ratios and various instrumental parameters on cluster ion formation were examined. It was found that instrument interface design also plays a critical role in the cluster ion distribution seen in the mass spectrum. In Chapter 5, ESI-MS was used to investigate toxic metal binding to the [Gln11]-amyloid β-protein fragment (1-16). Pb and Cd bound stronger than Zn, even in the presence of excess Zn. Hg bound weaker than Zn. There are endless options for future work on cluster ions. Any molecule that is poorly ionized in positive ion mode can potentially show an increase in ionization efficiency if an appropriate anion is used to produce a net negative charge. It is possible that drug protein or drug/DNA complexes can also be stabilized by adding counter-ions. This would preserve the solution characteristics of the complex in the gas phase. Once in the gas phase, CID could determine the drug binding location on the biomolecule. There are many research projects regarding toxic metals in biology that have yet to be investigated or even discovered. This is an area of research with an almost endless future because of the changing dynamics of biological systems. What is deemed safe today may show toxic effects in the future. Evolutionary changes in protein structures may render them more susceptible to toxic metal binding. As the understanding of toxicity evolves, so does the demand for new toxic metal research. New instrumentation designs and software make it possible to perform research that could not be done in the past. What was undetectable yesterday will

  5. Binding of ligands to the catalytic zinc ion in horse liver alcohol dehydrogenase.

    Science.gov (United States)

    Syvertsen, C; McKinley-McKee, J S

    1984-01-01

    The affinity of nitrogen and sulfur ligands for the catalytic zinc ion in horse liver alcohol dehydrogenase has been investigated by their influence on the affinity labeling reaction with iodoacetate. All the nitrogen compounds including ammonia, a primary and a secondary amine, and heterocycles containing a pyridine-type nitrogen with the exception of 2,2-dipyridyl were found to activate the affinity labeling reaction. Activation results from inner-sphere ligand coordination to the catalytic zinc ion. Closely related pyridine compounds gave a regular increase in affinity for the enzyme with increasing basicity, as expected for coordination to a metal ion. The sulfur compounds penicillamine and mercaptoethanol also activated the affinity labeling reaction, but dimercaptopropanol bound very tightly as a bidentate inhibited the reaction. The anions hydrosulfide, diethyldithiocarbamate, and cyanide coordinated to the catalytic zinc ion, whereas azide, thiocyanate, tetrazole, and iodide complexed the anion-binding site. The anionic metal ligands increased the rate of inactivation of the enzyme with iodoacetamide by binding to the catalytic zinc ion, while the binding of iodoacetate to the anion-binding site was prevented.

  6. Specificity of the metalloregulator CueR for monovalent metal ions

    DEFF Research Database (Denmark)

    Szunyogh, Dániel; Szokolai, Hajnalka; Thulstrup, Peter Waaben

    2015-01-01

    (II) , and Hg(II) binding to model systems encompassing the metal-ion-binding loop of CueR from E. coli and V. cholerae. In the presence of Ag(I) , a conserved cysteine residue displays a pKa value for deprotonation of the thiol that is close to the physiological pH value. This property is only observed...

  7. Extraction and Binding Efficiency of Calix[8]arene Derivative Toward Selected Transition Metals

    Directory of Open Access Journals (Sweden)

    Imdadullah Qureshi

    2008-12-01

    Full Text Available In this article we have explored the extraction efficiency as well as binding ability of calix[8]arene derivative (3 for selected transition metal ions (Co2+, Cd2+, Ni2+, Pb2+ and Cu2+. Picrate salt solutions of these metals were used in the liquid-liquid extraction experiments. It is apparent from the results that ligand 3 shows appreciable high extraction of transition metal cations, with the relative order Pb2+>Cu2+>Ni2+>Co2+>Cd2+ being observed. Highest extraction efficiency has been observed for Pb2+ and Cu2+ i.e. 95 and 91% respectively. The significant extraction and complexation ability for these metal ions may be attributed to the nature, size, structure and geometry of both ligand and metal ions.

  8. Three Metal Ions Participate in the Reaction Catalyzed by T5 Flap Endonuclease*S⃞

    Science.gov (United States)

    Syson, Karl; Tomlinson, Christopher; Chapados, Brian R.; Sayers, Jon R.; Tainer, John A.; Williams, Nicholas H.; Grasby, Jane A.

    2008-01-01

    Protein nucleases and RNA enzymes depend on divalent metal ions to catalyze the rapid hydrolysis of phosphate diester linkages of nucleic acids during DNA replication, DNA repair, RNA processing, and RNA degradation. These enzymes are widely proposed to catalyze phosphate diester hydrolysis using a “two-metal-ion mechanism.” Yet, analyses of flap endonuclease (FEN) family members, which occur in all domains of life and act in DNA replication and repair, exemplify controversies regarding the classical two-metal-ion mechanism for phosphate diester hydrolysis. Whereas substrate-free structures of FENs identify two active site metal ions, their typical separation of >4 Å appears incompatible with this mechanism. To clarify the roles played by FEN metal ions, we report here a detailed evaluation of the magnesium ion response of T5FEN. Kinetic investigations reveal that overall the T5FEN-catalyzed reaction requires at least three magnesium ions, implying that an additional metal ion is bound. The presence of at least two ions bound with differing affinity is required to catalyze phosphate diester hydrolysis. Analysis of the inhibition of reactions by calcium ions is consistent with a requirement for two viable cofactors (Mg2+ or Mn2+). The apparent substrate association constant is maximized by binding two magnesium ions. This may reflect a metal-dependent unpairing of duplex substrate required to position the scissile phosphate in contact with metal ion(s). The combined results suggest that T5FEN primarily uses a two-metal-ion mechanism for chemical catalysis, but that its overall metallobiochemistry is more complex and requires three ions. PMID:18697748

  9. Study of the Interactions Between Transition Metal Ions and Peptides by CALIFORNIUM-252 Plasma Desorption Mass Spectrometry

    Science.gov (United States)

    Hu, Zhaohong

    This dissertation focuses on the study of interactions between transition metal ions (Cu(II), Zn(II), Pd(II), Pt(II)) and peptides (bradykinins and angiotensins). Chapter I provides an overview on the fundamental issues related to and techniques used for studying transition metal ion -peptide/protein complexes. It also reviews different mass spectroscopic techniques used for metal ion-peptide studies. Chapter II delineates the principle of ^{252 }Cf-PDMS instrumentation and the sample preparation methods utilized for this dissertation research. In order to study metal ion-peptide complexes with PDMS, it is essential to define the relationship between complex structures identified from PD mass spectra and complexes formed in solution phase. Chapter III includes the studies of the effects of solution conditions on the detection of metal ion-peptide complexes in PDMS. Solution pH is the most important factor for determining the formation of a complex. Reaction time, reactant concentration, and reaction temperature all display distinct influences on PDMS results. It demonstrates that the PDMS results are closely correlated with the complexes pre-formed in aqueous solution. Chapter IV provides ample spectroscopic data on peptides and their metal ion complexes. The metal ion -containing molecular ions observed provide information on numbers of metal ion-binding sites in a peptide and metal ion-affinity of the peptide. By analyzing fragmentation patterns, amino acid residues and functional groups involved in metal ion binding in a peptide can be identified.

  10. Parkinson disease protein DJ-1 binds metals and protects against metal-induced cytotoxicity.

    Science.gov (United States)

    Björkblom, Benny; Adilbayeva, Altynai; Maple-Grødem, Jodi; Piston, Dominik; Ökvist, Mats; Xu, Xiang Ming; Brede, Cato; Larsen, Jan Petter; Møller, Simon Geir

    2013-08-02

    The progressive loss of motor control due to reduction of dopamine-producing neurons in the substantia nigra pars compacta and decreased striatal dopamine levels are the classically described features of Parkinson disease (PD). Neuronal damage also progresses to other regions of the brain, and additional non-motor dysfunctions are common. Accumulation of environmental toxins, such as pesticides and metals, are suggested risk factors for the development of typical late onset PD, although genetic factors seem to be substantial in early onset cases. Mutations of DJ-1 are known to cause a form of recessive early onset Parkinson disease, highlighting an important functional role for DJ-1 in early disease prevention. This study identifies human DJ-1 as a metal-binding protein able to evidently bind copper as well as toxic mercury ions in vitro. The study further characterizes the cytoprotective function of DJ-1 and PD-mutated variants of DJ-1 with respect to induced metal cytotoxicity. The results show that expression of DJ-1 enhances the cells' protective mechanisms against induced metal toxicity and that this protection is lost for DJ-1 PD mutations A104T and D149A. The study also shows that oxidation site-mutated DJ-1 C106A retains its ability to protect cells. We also show that concomitant addition of dopamine exposure sensitizes cells to metal-induced cytotoxicity. We also confirm that redox-active dopamine adducts enhance metal-catalyzed oxidation of intracellular proteins in vivo by use of live cell imaging of redox-sensitive S3roGFP. The study indicates that even a small genetic alteration can sensitize cells to metal-induced cell death, a finding that may revive the interest in exogenous factors in the etiology of PD.

  11. Parkinson Disease Protein DJ-1 Binds Metals and Protects against Metal-induced Cytotoxicity*

    Science.gov (United States)

    Björkblom, Benny; Adilbayeva, Altynai; Maple-Grødem, Jodi; Piston, Dominik; Ökvist, Mats; Xu, Xiang Ming; Brede, Cato; Larsen, Jan Petter; Møller, Simon Geir

    2013-01-01

    The progressive loss of motor control due to reduction of dopamine-producing neurons in the substantia nigra pars compacta and decreased striatal dopamine levels are the classically described features of Parkinson disease (PD). Neuronal damage also progresses to other regions of the brain, and additional non-motor dysfunctions are common. Accumulation of environmental toxins, such as pesticides and metals, are suggested risk factors for the development of typical late onset PD, although genetic factors seem to be substantial in early onset cases. Mutations of DJ-1 are known to cause a form of recessive early onset Parkinson disease, highlighting an important functional role for DJ-1 in early disease prevention. This study identifies human DJ-1 as a metal-binding protein able to evidently bind copper as well as toxic mercury ions in vitro. The study further characterizes the cytoprotective function of DJ-1 and PD-mutated variants of DJ-1 with respect to induced metal cytotoxicity. The results show that expression of DJ-1 enhances the cells' protective mechanisms against induced metal toxicity and that this protection is lost for DJ-1 PD mutations A104T and D149A. The study also shows that oxidation site-mutated DJ-1 C106A retains its ability to protect cells. We also show that concomitant addition of dopamine exposure sensitizes cells to metal-induced cytotoxicity. We also confirm that redox-active dopamine adducts enhance metal-catalyzed oxidation of intracellular proteins in vivo by use of live cell imaging of redox-sensitive S3roGFP. The study indicates that even a small genetic alteration can sensitize cells to metal-induced cell death, a finding that may revive the interest in exogenous factors in the etiology of PD. PMID:23792957

  12. short communication binding of nickel and zinc ions with activated ...

    African Journals Online (AJOL)

    a

    ABSTRACT. Activated carbon was prepared from sugar cane fibre by carbonizing at 500 oC for 30 minutes. ... Equilibrium sorption of nickel and zinc ions by the activated carbon was studied using a range of metal ion .... which means that limited sorption cycles will be required in the treatment of waste water containing the ...

  13. A computational study of adsorption of divalent metal ions on graphene oxide

    Directory of Open Access Journals (Sweden)

    Somphob Thompho

    2017-12-01

    Full Text Available Adsorption of divalent metal ions (Pb2+,Cd2+, Zn2+,Cu2+ on graphene oxide (GO was studied using density functional theory (DFT. Adsorption geometries and energies, as well as the nature of the binding energy, were calculated for the interaction of divalent metal ions with oxygen-containing groups on the surface of GO. The configurations of the complexes were modeled by placing the divalent metal ions above the center and perpendicular to the surface. Binding of Cu2+ to the GO sheet was predicted to be much stronger than that for other divalent metal ions. Calculated results show good agreement with experimental observations and provide useful information for environmental pollution cleanup.

  14. Requirement for transient metal ions revealed through computational analysis for DNA polymerase going in reverse

    Science.gov (United States)

    Perera, Lalith; Freudenthal, Bret D.; Beard, William A.; Shock, David D.; Pedersen, Lee G.; Wilson, Samuel H.

    2015-01-01

    DNA polymerases facilitate faithful insertion of nucleotides, a central reaction occurring during DNA replication and repair. DNA synthesis (forward reaction) is “balanced,” as dictated by the chemical equilibrium by the reverse reaction of pyrophosphorolysis. Two closely spaced divalent metal ions (catalytic and nucleotide-binding metals) provide the scaffold for these reactions. The catalytic metal lowers the pKa of O3′ of the growing primer terminus, and the nucleotide-binding metal facilitates substrate binding. Recent time-lapse crystallographic studies of DNA polymerases have identified an additional metal ion (product metal) associated with pyrophosphate formation, leading to the suggestion of its possible involvement in the reverse reaction. Here, we establish a rationale for a role of the product metal using quantum mechanical/molecular mechanical calculations of the reverse reaction in the confines of the DNA polymerase β active site. Additionally, site-directed mutagenesis identifies essential residues and metal-binding sites necessary for pyrophosphorolysis. The results indicate that the catalytic metal site must be occupied by a magnesium ion for pyrophosphorolysis to occur. Critically, the product metal site is occupied by a magnesium ion early in the pyrophosphorolysis reaction path but must be removed later. The proposed dynamic nature of the active site metal ions is consistent with crystallographic structures. The transition barrier for pyrophosphorolysis was estimated to be significantly higher than that for the forward reaction, consistent with kinetic activity measurements of the respective reactions. These observations provide a framework to understand how ions and active site changes could modulate the internal chemical equilibrium of a reaction that is central to genome stability. PMID:26351676

  15. Selective metal binding by Vanabin2 from the vanadium-rich ascidian, Ascidia sydneiensis samea.

    Science.gov (United States)

    Kawakami, Norifumi; Ueki, Tatsuya; Matsuo, Koichi; Gekko, Kunihiko; Michibata, Hitoshi

    2006-07-01

    Vanadium-binding proteins, or Vanabins, have recently been isolated from the vanadium-rich ascidian, Ascidia sydneiensis samea. Recent reports indicate that Vanabin2 binds twenty V(IV) ions at pH 7.5, and that it has a novel bow-shaped conformation. However, the role of Vanabin2 in vanadium accumulation by the ascidian has not yet been determined. In the present study, the effects of acidic pH on selective metal binding to Vanabin2 and on the secondary structure of Vanabin2 were examined. Vanabin2 selectively bound to V(IV), Fe(III), and Cu(II) ions under acidic conditions. In contrast, Co(II), Ni(II), and Zn(II) ions were bound at pH 6.5 but not at pH 4.5. Changes in pH had no detectable effect on the secondary structure of Vanabin2 under acidic conditions, as determined by circular dichroism spectroscopy, and little variation in the dissociation constant for V(IV) ions was observed in the pH range 4.5-7.5, suggesting that the binding state of the ligands is not affected by acidification. Taken together, these results suggest that the reason for metal ion dissociation upon acidification is attributable not to a change in secondary structure but, rather, that it is caused by protonation of the amino acid ligands that complex with V(IV) ions.

  16. Fluorescence signalling of the transition metal ions: Design strategy ...

    Indian Academy of Sciences (India)

    on fluorescence signalling systems for the transition metal ions. It is shown that even simple fluorophore-spacer-receptor systems can display excellent off-on fluorescence signalling towards the quenching metal ions when the fluorophore ...

  17. Pyrrolo-dC Metal-Mediated Base Pairs in the Reverse Watson-Crick Double Helix: Enhanced Stability of Parallel DNA and Impact of 6-Pyridinyl Residues on Fluorescence and Silver-Ion Binding.

    Science.gov (United States)

    Yang, Haozhe; Mei, Hui; Seela, Frank

    2015-07-06

    Reverse Watson-Crick DNA with parallel-strand orientation (ps DNA) has been constructed. Pyrrolo-dC (PyrdC) nucleosides with phenyl and pyridinyl residues linked to the 6 position of the pyrrolo[2,3-d]pyrimidine base have been incorporated in 12- and 25-mer oligonucleotide duplexes and utilized as silver-ion binding sites. Thermal-stability studies on the parallel DNA strands demonstrated extremely strong silver-ion binding and strongly enhanced duplex stability. Stoichiometric UV and fluorescence titration experiments verified that a single (2py) PyrdC-(2py) PyrdC pair captures two silver ions in ps DNA. A structure for the PyrdC silver-ion base pair that aligns 7-deazapurine bases head-to-tail instead of head-to-head, as suggested for canonical DNA, is proposed. The silver DNA double helix represents the first example of a ps DNA structure built up of bidentate and tridentate reverse Watson-Crick base pairs stabilized by a dinuclear silver-mediated PyrdC pair. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Polyatomic ions from a high current ion implanter driven by a liquid metal ion source

    Science.gov (United States)

    Pilz, W.; Laufer, P.; Tajmar, M.; Böttger, R.; Bischoff, L.

    2017-12-01

    High current liquid metal ion sources are well known and found their first application as field emission electric propulsion thrusters in space technology. The aim of this work is the adaption of such kind of sources in broad ion beam technology. Surface patterning based on self-organized nano-structures on, e.g., semiconductor materials formed by heavy mono- or polyatomic ion irradiation from liquid metal (alloy) ion sources (LMAISs) is a very promising technique. LMAISs are nearly the only type of sources delivering polyatomic ions from about half of the periodic table elements. To overcome the lack of only very small treated areas by applying a focused ion beam equipped with such sources, the technology taken from space propulsion systems was transferred into a large single-end ion implanter. The main component is an ion beam injector based on high current LMAISs combined with suited ion optics allocating ion currents in the μA range in a nearly parallel beam of a few mm in diameter. Different types of LMAIS (needle, porous emitter, and capillary) are presented and characterized. The ion beam injector design is specified as well as the implementation of this module into a 200 kV high current ion implanter operating at the HZDR Ion Beam Center. Finally, the obtained results of large area surface modification of Ge using polyatomic Bi2+ ions at room temperature from a GaBi capillary LMAIS will be presented and discussed.

  19. The role of metal ion-ligand interactions during divalent metal ion adsorption.

    Science.gov (United States)

    Eldridge, Daniel S; Crawford, Russell J; Harding, Ian H

    2015-09-15

    A suite of seven different divalent metal ions (Ca(II), Cd(II), Cu(II), Mg(II), Ni(II), Pb(II), Zn(II)) was adsorbed from solution onto two Fe2O3 samples, quartz SiO2 and three different amphoteric polystyrene latices (containing amine and carboxyl functional groups). For the metal oxides, a high correlation was observed between the pH at which 50% of the metal was removed from solution (pH50) and the first hydrolysis constant for the metal ion (pK1). For the polystyrene latices, a much higher correlation was observed between the pH50 and pKc (equilibrium constant describing metal-carboxyl affinity) as opposed to pK1. These observations provide evidence of a strong relationship that exists between a metal's affinity for a particular ligand in solution and for that metal ion's affinity for the same ligand present as part of an adsorbing surface. The isoelectric point of the amphoteric latex surface can be increased by decreasing the carboxyl content of the latex surface. For all 7 metal ions, this resulted in a substantial decrease, for any given pH, in adsorption. We suggest that this may be partly due to the decreased carboxyl content, but is dominantly attributable to the presence of less favorable electrostatic conditions. This, in turn, demonstrates that electrostatics play a controlling role in metal ion adsorption onto amphoteric latex surfaces and, in addition to the nature of the metal ion, also controls the pH at which adsorption takes place. Crown Copyright © 2015. Published by Elsevier Inc. All rights reserved.

  20. Heavy metal ion uptake properties of polystyrene-supported ...

    Indian Academy of Sciences (India)

    Metal ion uptake properties of polystyrene-supported chelating polymer resins functionalized with (i) glycine, (ii) hydroxy benzoic acid, (iii) Schiff base and (iv) diethanol amine have been investigated. The effects of pH, time and initial concentration on the uptake of metal ions have been studied. The uptake of metal ion ...

  1. Binding properties of oxacalix[4]arenes derivatives toward metal cations

    International Nuclear Information System (INIS)

    Mellah, B.

    2006-11-01

    The objective of this work was to establish the binding properties of oxacalix[4]arene derivatives with different numbers of the oxa bridges, functional groups (ketones, pyridine, ester, amide and methoxy) and conformations. Their interactions with alkali and alkaline-earth, heavy and transition metal cations have been evaluated according to different approaches: (i) extraction of corresponding picrates from an aqueous phase into dichloromethane; (ii) determination of the thermodynamic parameters of complexation in methanol and/or acetonitrile by UV-spectrophotometry and micro-calorimetry; (iii) determination of the stoichiometry of the complexes by ESI-MS; (iv) 1 H-NMR titrations allowing to localize the metal ions in the ligand cavity. In a first part dealing on homo-oxacalix[4]arenes, selectivities for Na + , K + , Ca 2+ , Pb 2+ and Mn 2+ of ketones derivatives was shown. The presence of oxa bridge in these derivatives increases their efficiency while decreasing their selectivity with respect to related calixarenes. The pyridine derivative prefers transition and heavy metal cations, in agreement with the presence of the soft nitrogen atoms. In the second part, di-oxacalix[4]arene ester and secondary amide derivatives were shown to be less effective than tertiary amide counterparts but to present high selectivities for Li + , Ba 2+ , Zn 2+ and Hg 2+ . A third part devoted to the octa-homo-tetra-oxacalix[4]arene tetra-methoxy shows that the 1:1 metal complexes formed are generally more stable than those of calixarenes, suggesting the participation of the oxygen atoms of the bridge in the complexation. Selectivity for Cs + , Ba 2+ , Cu 2+ and Hg 2+ were noted. (author)

  2. Characterization of Metal Ion ­ Colloid Interaction: Impact On Colloid-facilitated Transport

    Science.gov (United States)

    Specht, C. H.; Schmitt, D.; Kaulisch, E.-M.; Frimmel, F. H.

    It is generally accepted, that metal transport in natural aquatic systems strongly de- pends on the metal binding form. Besides complex formation with well defined inor- ganic and organic ligands, the interaction with colloidal particles and soil material is one of the most important reactions of metal ions in aquatic systems. Mobile colloids compete with the stationary soil matrix for binding of metal ions and might facili- tate their transport. Important representatives for mineral and organic colloids are clay minerals and natural organic matter (NOM), respectively. In this work, the interaction of metal ions with clay minerals and NOM is characterized by coupling of asymmetric flow field-flow fractionation AF4 to inductively coupled plasma ­ mass spectrometry (ICPMS). A method for separating mineral from organic colloids is presented, which allows to quantify the amount of metals being bound to either colloid. For different metal ions (Cu, Zn, Pb, Pt) and a metalloid (As) a different extent of binding to either colloid was found.The information obtained from the AF4-ICPMS measurements was useful for the understanding of the observations from column experiments which were conducted to quantify the colloid-facilitated metal transport. In column experiments, the transport of the mineral colloids itself and the influence of NOM onto the colloid transport were investigated. Furthermore, the dependance of colloid transport from the ionic strength and the pH value was elucidated. In order to get information about the co-transport of metal ions by organic and mineral colloids, metal ions were adsorbed onto the colloidal material and a distribution coef- ficient of the metal ions between the colloidal phase and the solution was determined. The colloidal suspension containing both, "free" and adsorbed metal ions were then injected onto the column. The direct metal breakthrough caused by colloidal trans- port was detected at the column outlet. The results clearly

  3. Activation of Methane by Gaseous Metal Ions

    Czech Academy of Sciences Publication Activity Database

    Schröder, Detlef

    2010-01-01

    Roč. 49, č. 5 (2010), s. 850-851 ISSN 1433-7851 Grant - others:European Research Council(XE) AdG HORIZOMS Institutional research plan: CEZ:AV0Z40550506 Keywords : C-C coupling * C-H bond activation * gas-phase reactions * metal ions * methane Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 12.730, year: 2010

  4. Binding of iron, zinc, and lead ions from aqueous solution by shea butter (Butyrospermun Parkii) seed husks

    Energy Technology Data Exchange (ETDEWEB)

    Eromosele, I.C.; Otitolaye, O.O. (Federal Univ. of Technology, Yola, Adamawa State (Nigeria))

    1994-08-01

    Several workers have reported on the potential use of agricultural products as substrates for the removal of metal ions from aqueous solutions. These studies demonstrated that considerable amounts of metal ions can be removed from aqueous solutions by cellulosic materials. The merit in the use of the latter is their relative abundance and cheapness compared to conventional materials for the removal of toxic metal ions from waste-waters. In some of the studies, chemical modification of cellulosic materials significantly enhanced their ion-binding properties, providing greater flexibility in their applications to a wide range of heavy metal ions. Shea butter plant (Butyrospermun Parkii) normally grows in the wild within the guinea-savana zone of Nigeria. The seeds are a rich source of edible oils and the husks are usually discarded. The husk is thus available in abundance and, hence, there is reason to examine its ion-binding properties for its possible application in the removal of toxic metal ions from industrial waste-waters. This paper reports on preliminary studies of the sorption of iron, zinc and lead ions from aqueous solution by modified and unmodified shea butter seed husks. 8 refs., 5 figs., 1 tab.

  5. Sensing of heavy metal ions by intrinsic TMV coat protein fluorescence

    Science.gov (United States)

    Bayram, Serene S.; Green, Philippe; Blum, Amy Szuchmacher

    2018-04-01

    We propose the use of a cysteine mutant of TMV coat protein as a signal transducer for the selective sensing and quantification of the heavy metal ions, Cd2+, Pb2+, Zn2+ and Ni2+ based on intrinsic tryptophan quenching. TMV coat protein is inexpensive, can be mass-produced since it is expressed and extracted from E-coli. It also displays several different functional groups, enabling a wide repertoire of bioconjugation chemistries; thus it can be easily integrated into functional devices. In addition, TMV-ion interactions have been widely reported and utilized for metallization to generate organic-inorganic hybrid composite novel materials. Building on these previous observations, we herein determine, for the first time, the TMV-ion binding constants assuming the static fluorescence quenching model. We also show that by comparing TMV-ion interactions between native and denatured coat protein, we can distinguish between chemically similar heavy metal ions such as cadmium and zinc ions.

  6. Structures and energetics of complexation of metal ions with ammonia, water, and benzene: A computational study.

    Science.gov (United States)

    Sharma, Bhaskar; Neela, Y Indra; Narahari Sastry, G

    2016-04-30

    Quantum chemical calculations have been performed at CCSD(T)/def2-TZVP level to investigate the strength and nature of interactions of ammonia (NH3 ), water (H2 O), and benzene (C6 H6 ) with various metal ions and validated with the available experimental results. For all the considered metal ions, a preference for C6 H6 is observed for dicationic ions whereas the monocationic ions prefer to bind with NH3 . Density Functional Theory-Symmetry Adapted Perturbation Theory (DFT-SAPT) analysis has been employed at PBE0AC/def2-TZVP level on these complexes (closed shell), to understand the various energy terms contributing to binding energy (BE). The DFT-SAPT result shows that for the metal ion complexes with H2 O electrostatic component is the major contributor to the BE whereas, for C6 H6 complexes polarization component is dominant, except in the case of alkali metal ion complexes. However, in case of NH3 complexes, electrostatic component is dominant for s-block metal ions, whereas, for the d and p-block metal ion complexes both electrostatic and polarization components are important. The geometry (M(+) -N and M(+) -O distance for NH3 and H2 O complexes respectively, and cation-π distance for C6 H6 complexes) for the alkali and alkaline earth metal ion complexes increases down the group. Natural population analysis performed on NH3 , H2 O, and C6 H6 complexes shows that the charge transfer to metal ions is higher in case of C6 H6 complexes. © 2015 Wiley Periodicals, Inc.

  7. Ion-induced effects on metallic nanoparticles

    International Nuclear Information System (INIS)

    Klimmer, Andreas

    2010-01-01

    This work deals with the ion-irradiation of metallic nanoparticles in combination with various substrates. Particle diameters were systematically varied within the range of 2.5-14 nm, inter-particle distances range from 30-120 nm. Irradiations were performed with various inert gas ions with energies of 200 keV, resulting in an average ion range larger than the particle dimensions and therefore the effects of irradiation are mainly due to creation of structural defects within the particles and the underlying substrate as well. The main part of this work deals with ion-induced burrowing of metallic nanoparticles into the underlying substrate. The use of micellar nanoparticles with sharp size distribution combined with AFM and TEM analysis allows a much more detailed look at this effect than other works on that topic so far. With respect to the particle properties also a detailed look on the effect of irradiation on the particle structure would be interesting, which might lead to a deliberate influence on magnetic properties, for example. Within the context of this work, first successful experiments were performed on FePt particles, showing a significant reduction of the ordering temperature leading to the magnetically interesting, ordered L1 0 phase. (orig.)

  8. Evaluation of complexing agents and column temperature in ion chromatographic separation of alkali metals, alkaline earth metals and transition metals ion

    International Nuclear Information System (INIS)

    Kelkar, Anoop; Pandey, Ashish; Name, Anil B.; Das, D.K.; Behere, P.G.; Mohd Afzal

    2015-01-01

    The aim of ion chromatography method development is the resolution of all metal ions of interests. Resolution can be improved by changing the selectivity. Selectivity in chromatography can be altered by changes in mobile phase (eg eluent type, eluent strength) or through changes in stationary phase. Temperature has been used in altering the selectivity of particularly in reversed phase liquid chromatography and ion exchange chromatography. Present paper describe the retention behaviour of alkali metals, alkaline earth metals and transition metal ions on a silica based carboxylate function group containing analyte column. Alkali metals, alkaline earth metals and transition metal ions were detected by ion conductivity and UV-VIS detectors respectively

  9. Interaction of antihypertensive drug amiloride with metal ions in micellar medium using fluorescence spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Gujar, Varsha; Pundge, Vijaykumar; Ottoor, Divya, E-mail: divya@chem.unipune.ac.in

    2015-05-15

    Steady state and life time fluorescence spectroscopy have been employed to study the interaction of antihypertensive drug amiloride with biologically important metal ions i.e. Cu{sup 2+}, Fe{sup 2+}, Ni{sup 2+} and Zn{sup 2+} in various micellar media (anionic SDS (sodium dodecyl sulfate), nonionic TX-100 (triton X-100) and cationic CTAB (cetyl trimethyl ammonium bromide)). It was observed that fluorescence properties of drug remain unaltered in the absence of micellar media with increasing concentration of metal ions. However, addition of Cu{sup 2+}, Fe{sup 2+} and Ni{sup 2+} caused fluorescence quenching of amiloride in the presence of anionic micelle, SDS. Binding of drug with metal ions at the charged micellar interface could be the possible reason for this pH-dependent metal-mediated fluorescence quenching. There were no remarkable changes observed due to metal ions addition when drug was present in cationic and nonionic micellar medium. The binding constant and bimolecular quenching constant were evaluated and compared for the drug–metal complexes using Stern–Volmer equation and fluorescence lifetime values. - Highlights: • Interaction of amiloride with biologically important metal ions, Fe{sup 2+}, Cu{sup 2+}, Ni{sup 2+} and Zn{sup 2+}. • Monitoring the interaction in various micelle at different pH by fluorescence spectroscopy. • Micelles acts as receptor, amiloride as transducer and metal ions as analyte in the present system. • Interaction study provides pH dependent quenching and binding mechanism of drug with metal ions.

  10. Metal ion effects on enolase activity

    International Nuclear Information System (INIS)

    Lee, M.E.; Nowak, T.

    1986-01-01

    Most metal binding studies with yeast enolase suggest that two metals per monomer are required for catalytic activity. The functions of metal I and metal II have not been unequivocally defined. In a series of kinetic experiments where the concentration of MgII is kept constant at subsaturating levels (1mM), the addition of MnII or of ZnII gives a hyperbolic decrease in activity. The final velocity of these mixed metal systems is the same velocity obtained with either only MnII or ZnII respectively. The concentration of MnII (40 μM) or of Zn (2μM) which gives half maximal effect in the presence of (1mM) MgII is approximately the same as the Km' value for MnII (9μM) or ZnII (3μM) respectively. Direct binding of MnII to enolase in the absence and presence of MgII shows that MnII and MgII compete for the same metal site on enolase. In the presence of 2-phosphoglycerate (2-PGA) and MgII, only a single site is occupied by MnII. Results suggest MnII at site I and MgII at site II. PRR and high resolution 1 H and 31 P NMR studies of enzyme-ligand complexes containing MnII and MgII and MnII are consistent with this model. 31 P measurements allow a measure of the equilibrium constant (0.36) for enolase. Saturation transfer measurements yield net rate constants (k/sub f/ = 0.49s -1 ; k/sub r/ = 1.3s -1 ) for the overall reaction. These values are smaller than k/sub cat/ (38s -1 ) measured under analogous conditions. The cation at site I appears to determine catalytic activity

  11. Interaction of beta-amyloid(1-40) peptide with pairs of metal ions: An electrospray ion trap mass spectrometric model study.

    Science.gov (United States)

    Drochioiu, Gabi; Manea, Marilena; Dragusanu, Mihaela; Murariu, Manuela; Dragan, Ecaterina Stela; Petre, Brandusa Alina; Mezo, Gabor; Przybylski, Michael

    2009-09-01

    The stoichiometries and the affinity toward simple and paired metal ions of synthetic amyloid-beta(1-40) peptide (Abeta1-40) were investigated by electrospray ion trap mass spectrometry (ESI-MS), circular dichroism (CD), and atomic force microscopy (AFM). The results lead to the working hypothesis that pH-dependent metal binding to Abeta1-40 may induce conformational changes, which affect the affinity toward other metals. A significant copper and zinc binding to Abeta1-40 peptide at pH 5.5 was found, whereas nickel ions commonly bind to each molecule of beta-amyloid peptide. Some complexes of Abeta1-40 with more than one nickel ion were identified by ESI-MS. In addition, nickel ions proved to enhance Abeta oligomerization. On increasing pH, up to 12 ions of zinc may bind to a single Abeta molecule. Under the same pH and concentration conditions, the binding pattern of the independent copper and silver ions to Abeta1-40 was different from that of the equimolecular mixture of the two metal ions. One might assume that some conformational changes due to water loss altered the capacity of Abeta peptide to bind certain heavy metal ions. As a consequence, copper-silver interaction with the binding process to Abeta1-40 became highly complex. A competition between silver and nickel ions for Abeta1-40 binding sites at high pH was also observed. New strategies were proposed to identify the characteristic signals for some important metal ion-peptide complexes in the spectra recorded at high pH or high concentrations of metal ions. To explain the formation of such a large number of high metal ion-Abeta complexes, we took into consideration the participation of both histidine residues and free amino groups as well as carboxylate ones in the binding process. Finally, CD and AFM studies supported the mass spectrometric data.

  12. Transparent monolithic metal ion containing nanophase aerogels

    Energy Technology Data Exchange (ETDEWEB)

    Risen, W. M., Jr.; Hu, X.; Ji, S.; Littrell, K.

    1999-12-01

    The formation of monolithic and transparent transition metal containing aerogels has been achieved through cooperative interactions of high molecular weight functionalized carbohydrates and silica precursors, which strongly influence the kinetics of gelation. After initial gelation, subsequent modification of the ligating character of the system, coordination of the group VIII metal ions, and supercritical extraction afford the aerogels. The structures at the nanophase level have been probed by photon and electron transmission and neutron scattering techniques to help elucidate the basis for structural integrity together with the small entity sizes that permit transparency in the visible range. They also help with understanding the chemical reactivities of the metal-containing sites in these very high surface area materials. These results are discussed in connection with new reaction studies.

  13. Alkali metal ion templated transition metal formate framework materials: synthesis, crystal structures, ion migration, and magnetism.

    Science.gov (United States)

    Eikeland, Espen; Lock, Nina; Filsø, Mette; Stingaciu, Marian; Shen, Yanbin; Overgaard, Jacob; Iversen, Bo Brummerstedt

    2014-10-06

    Four transition metal formate coordination polymers with anionic frameworks, namely, Na[Mn(HCOO)3], K[Mn(HCOO)3], Na2[Cu3(HCOO)8], and K2[Cu5(HCOO)12], were synthesized using a mild solution chemistry approach. Multitemperature single-crystal (100-300 K) and powder X-ray diffraction studies of the compounds reveal structures of large diversity ranging from cubic chiral Na-Mn formate to triclinic Na-Cu formate. The structural variety is caused by the nature of the transition metals, the alkali metal ion templation, and the versatility of the formate group, which offers metal-metal coordination through three different O-C-O bridging modes (syn-syn, syn-anti, anti-anti) in addition to metal-metal bridging via a single oxygen atom. The two manganese(II) compounds contain mononuclear, octahedrally coordinated moieties, but the three-dimensional connectivity between the manganese octahedra is very different in the two structures. The two copper frameworks, in contrast, consist of binuclear and mononuclear moieties (Na-Cu formate) and trinuclear and mononuclear moieties (K-Cu formate), respectively. Procrystal electron density analysis of the compounds indicates one-dimensional K(+)-ion conductivity in K-Mn and K-Cu, and the nature of the proposed potassium ion migration is compared with results from similar analysis on known Na(+) and K(+) ion conductors. K-Mn and Na-Mn were tested as cathode materials, but this resulted in poor reversibility due to low conductivity or structural collapse. The magnetic properties of the compounds were studied by vibrating sample magnetometric measurements, and their thermal stabilities were determined by thermogravimetric analysis and differential thermal analysis. Despite structural differences, the metal formates that contain the same transition metal have similar magnetic properties and thermal decomposition pathways, that is, the nature of the transition metal controls the compound properties.

  14. THE ROLES OF METAL IONS IN REGULATION BY RIBOSWITCHES

    OpenAIRE

    Ferré-D'Amaré, Adrian; Winkler, Wade C.

    2011-01-01

    Metal ions are required by all organisms in order to execute an array of essential molecular functions. They play a critical role in many catalytic mechanisms and structural properties. Proper homeostasis of ions is critical; levels that are aberrantly low or high are deleterious to cellular physiology. To maintain stable intracellular pools, metal ion-sensing regulatory (metalloregulatory) proteins couple metal ion concentration fluctuations with expression of genes encoding for cation trans...

  15. Ion mobility studies of carbohydrates as group I adducts: isomer specific collisional cross section dependence on metal ion radius.

    Science.gov (United States)

    Huang, Yuting; Dodds, Eric D

    2013-10-15

    Carbohydrates play numerous critical roles in biological systems. Characterization of oligosaccharide structures is essential to a complete understanding of their functions in biological processes; nevertheless, their structural determination remains challenging in part due to isomerism. Ion mobility spectrometry provides the means to resolve gas phase ions on the basis of their shape-to-charge ratios, thus providing significant potential for separation and differentiation of carbohydrate isomers. Here, we report on the determination of collisional cross sections for four groups of isomeric carbohydrates (including five isomeric disaccharides, four isomeric trisaccharides, two isomeric pentasaccharides, and two isomeric hexasaccharides) as their group I metal ion adducts (i.e., [M + Li](+), [M + Na](+), [M + K](+), [M + Rb](+), and [M + Cs](+)). In all, 65 collisional cross sections were measured, the great majority of which have not been previously reported. As anticipated, the collisional cross sections of the carbohydrate metal ion adducts generally increase with increasing metal ion radius; however, the collisional cross sections were found to scale with the group I cation size in isomer specific manners. Such measurements are of substantial analytical value, as they illustrate how the selection of charge carrier influences carbohydrate ion mobility determinations. For example, certain pairs of isomeric carbohydrates assume unique collisional cross sections upon binding one metal ion, but not another. On the whole, these data suggest a role for the charge carrier as a probe of carbohydrate structure and thus have significant implications for the continued development and application of ion mobility spectrometry for the distinction and resolution of isomeric carbohydrates.

  16. Biosorption of metal ions from aqueous solution and tannery effluent by Bacillus sp. FM1.

    Science.gov (United States)

    Masood, Farhana; Malik, Abdul

    2011-01-01

    The metal binding capacity of Bacillus sp. FM1 isolated from soil irrigated with tannery effluent was assessed using synthetic metal solutions and tannery wastewater. Biosorption of Cr(VI) and Cu(II) ions from aqueous solutions using Bacillus was investigated as a function of pH, initial metal ion concentration and contact time. The optimum adsorption pH value observed for Cr(VI) and Cu(II) ions was 2 and 5, respectively. Metal ion uptake increased with increasing initial metal concentration but no significant difference was observed by increasing the time after 60 min. Maximum uptake capacity of chromium was estimated as 64.102 mg g(-1), and of copper to 78.125 mg g(-1). Equilibrium data were well described by the Langmuir and Freundlich adsorption relations. The presence of functional groups on the cell wall surface of the biomass that may interact with the metal ion was confirmed by Fourier Transform Infrared (FTIR) spectroscopy. The application of Bacillus to remove Cr(VI) and Cu(II) in tannery effluent revealed that the biomass was capable of removing both the metal ions. However, the biosorption performance was slightly lower compared to that of synthetic metal solutions. Several factors may be responsible for this difference. However, the most important factor appears to be the presence of other contaminants such as anions, organics, and other trace metals in the effluent.

  17. Europium ion as a probe for binding sites to carrageenans

    International Nuclear Information System (INIS)

    Ramos, Ana P.; Goncalves, Rogeria R.; Serra, Osvaldo A.; Zaniquelli, Maria Elisabete D.; Wong, Kenneth

    2007-01-01

    Carrageenans, sulfated polysaccharides extracted from red algae, present a coil-helix transition and helix aggregation dependence on the type and concentration of counterions. In this study, we focus attention on a mixed valence counterion system: Eu 3+ /Na + or K + with different gel-forming carrageenans: kappa, iota, and kappa-2. Results of stationary and time-dependent luminescence showed to be a suitable tool to probe ion binding to both the negatively charged sulfate group and the hydroxyl groups present in the biopolymer. For lower europium ion concentrations, a single longer decay emission lifetime was detected, which was attributed to the binding of europium ion to the carrageenan sulfate groups. An additional decay ascribed to europium binding to hydroxyl groups was observed above a threshold concentration, and this decay was dependent on the carrageenan charge density. Symmetry of the europium ion microenvironment was estimated by the ratio between the intensities of its emission bands, which has been shown to depend on the concentration of europium ions and on the specificity of the monovalent counterion bound to the carrageenan

  18. Synthesis, characterization, anti-microbial, DNA binding and cleavage studies of Schiff base metal complexes

    Directory of Open Access Journals (Sweden)

    Poomalai Jayaseelan

    2016-09-01

    Full Text Available A novel Schiff base ligand has been prepared by the condensation between butanedione monoxime with 3,3′-diaminobenzidine. The ligand and metal complexes have been characterized by elemental analysis, UV, IR, 1H NMR, conductivity measurements, EPR and magnetic studies. The molar conductance studies of Cu(II, Ni(II, Co(II and Mn(II complexes showed non-electrolyte in nature. The ligand acts as dibasic with two N4-tetradentate sites and can coordinate with two metal ions to form binuclear complexes. The spectroscopic data of metal complexes indicated that the metal ions are complexed with azomethine nitrogen and oxyimino nitrogen atoms. The binuclear metal complexes exhibit octahedral arrangements. DNA binding properties of copper(II metal complex have been investigated by electronic absorption spectroscopy. Results suggest that the copper(II complex bind to DNA via an intercalation binding mode. The nucleolytic cleavage activities of the ligand and their complexes were assayed on CT-DNA using gel electrophoresis in the presence and absence of H2O2. The ligand showed increased nuclease activity when administered as copper complex and copper(II complex behave as efficient chemical nucleases with hydrogen peroxide activation. The anti-microbial activities and thermal studies have also been studied. In anti-microbial activity all complexes showed good anti-microbial activity higher than ligand against gram positive, gram negative bacteria and fungi.

  19. Validating metal binding sites in macromolecule structures using the CheckMyMetal web server

    Science.gov (United States)

    Zheng, Heping; Chordia, Mahendra D.; Cooper, David R.; Chruszcz, Maksymilian; Müller, Peter; Sheldrick, George M.

    2015-01-01

    Metals play vital roles in both the mechanism and architecture of biological macromolecules. Yet structures of metal-containing macromolecules where metals are misidentified and/or suboptimally modeled are abundant in the Protein Data Bank (PDB). This shows the need for a diagnostic tool to identify and correct such modeling problems with metal binding environments. The "CheckMyMetal" (CMM) web server (http://csgid.org/csgid/metal_sites/) is a sophisticated, user-friendly web-based method to evaluate metal binding sites in macromolecular structures in respect to 7350 metal binding sites observed in a benchmark dataset of 2304 high resolution crystal structures. The protocol outlines how the CMM server can be used to detect geometric and other irregularities in the structures of metal binding sites and alert researchers to potential errors in metal assignment. The protocol also gives practical guidelines for correcting problematic sites by modifying the metal binding environment and/or redefining metal identity in the PDB file. Several examples where this has led to meaningful results are described in the anticipated results section. CMM was designed for a broad audience—biomedical researchers studying metal-containing proteins and nucleic acids—but is equally well suited for structural biologists to validate new structures during modeling or refinement. The CMM server takes the coordinates of a metal-containing macromolecule structure in the PDB format as input and responds within a few seconds for a typical protein structure modeled with a few hundred amino acids. PMID:24356774

  20. Non-Native Metal Ion Reveals the Role of Electrostatics in Synaptotagmin 1-Membrane Interactions.

    Science.gov (United States)

    Katti, Sachin; Nyenhuis, Sarah B; Her, Bin; Srivastava, Atul K; Taylor, Alexander B; Hart, P John; Cafiso, David S; Igumenova, Tatyana I

    2017-06-27

    C2 domains are independently folded modules that often target their host proteins to anionic membranes in a Ca 2+ -dependent manner. In these cases, membrane association is triggered by Ca 2+ binding to the negatively charged loop region of the C2 domain. Here, we used a non-native metal ion, Cd 2+ , in lieu of Ca 2+ to gain insight into the contributions made by long-range Coulombic interactions and direct metal ion-lipid bridging to membrane binding. Using X-ray crystallography, NMR, Förster resonance energy transfer, and vesicle cosedimentation assays, we demonstrate that, although Cd 2+ binds to the loop region of C2A/B domains of synaptotagmin 1 with high affinity, long-range Coulombic interactions are too weak to support membrane binding of individual domains. We attribute this behavior to two factors: the stoichiometry of Cd 2+ binding to the loop regions of the C2A and C2B domains and the impaired ability of Cd 2+ to directly coordinate the lipids. In contrast, electron paramagnetic resonance experiments revealed that Cd 2+ does support membrane binding of the C2 domains in full-length synaptotagmin 1, where the high local lipid concentrations that result from membrane tethering can partially compensate for lack of a full complement of divalent metal ions and specific lipid coordination in Cd 2+ -complexed C2A/B domains. Our data suggest that long-range Coulombic interactions alone can drive the initial association of C2A/B with anionic membranes and that Ca 2+ further augments membrane binding by the formation of metal ion-lipid coordination bonds and additional Ca 2+ ion binding to the C2 domain loop regions.

  1. Synthesis, Characterization and Metal Ion Detection of Novel Fluoroionophores Based on Heterocyclic Substituted Alanines

    Directory of Open Access Journals (Sweden)

    M. Manuela M Raposo

    2007-10-01

    Full Text Available The synthesis of new fluorescent probes containing the thiophene andbenzoxazole moieties combined with an alanine residue is described. The resulting highlyfluorescent heterocyclic alanine derivatives respond via a quenching effect, withparamagnetic Cu(II and Ni(II metal ions and with diamagnetic Hg(II, as shown by theabsorption and steady-state fluorescence spectroscopy studies. The formation ofmononuclear or dinuclear metal complexes was postulated based on the presence of thefree carboxylic acid as binding site and also with the interaction with the donor atoms inthe chromophore. Interaction with other important biological metal ions such as Zn(II,Ca(II and Na(I was also explored.

  2. Heavy metal ion uptake properties of polystyrene-supported ...

    Indian Academy of Sciences (India)

    Unknown

    at pH 6 they are found to be Cd(II) and Cr(VI) selective. Metal ion uptake properties of resins follow Freundlich's equation. The resins are recyclable and are therefore employed for the removal of heavy metal pollutants from industrial waste water. Keywords. Uptake properties; heavy metal ion; selectivity; recyclability. 1.

  3. Systems and methods for producing metal clusters; functionalized surfaces; and droplets including solvated metal ions

    Science.gov (United States)

    Cooks, Robert Graham; Li, Anyin; Luo, Qingjie

    2017-08-01

    The invention generally relates to systems and methods for producing metal clusters; functionalized surfaces; and droplets including solvated metal ions. In certain aspects, the invention provides methods that involve providing a metal and a solvent. The methods additionally involve applying voltage to the solvated metal to thereby produce solvent droplets including ions of the metal containing compound, and directing the solvent droplets including the metal ions to a target. In certain embodiments, once at the target, the metal ions can react directly or catalyze reactions.

  4. MCTBI: a web server for predicting metal ion effects in RNA structures.

    Science.gov (United States)

    Sun, Li-Zhen; Zhang, Jing-Xiang; Chen, Shi-Jie

    2017-08-01

    Metal ions play critical roles in RNA structure and function. However, web servers and software packages for predicting ion effects in RNA structures are notably scarce. Furthermore, the existing web servers and software packages mainly neglect ion correlation and fluctuation effects, which are potentially important for RNAs. We here report a new web server, the MCTBI server (http://rna.physics.missouri.edu/MCTBI), for the prediction of ion effects for RNA structures. This server is based on the recently developed MCTBI, a model that can account for ion correlation and fluctuation effects for nucleic acid structures and can provide improved predictions for the effects of metal ions, especially for multivalent ions such as Mg 2+ effects, as shown by extensive theory-experiment test results. The MCTBI web server predicts metal ion binding fractions, the most probable bound ion distribution, the electrostatic free energy of the system, and the free energy components. The results provide mechanistic insights into the role of metal ions in RNA structure formation and folding stability, which is important for understanding RNA functions and the rational design of RNA structures. © 2017 Sun et al.; Published by Cold Spring Harbor Laboratory Press for the RNA Society.

  5. [Metal ion concentrations in patients with metal-metal bearings in prostheses].

    Science.gov (United States)

    Kretzer, J P; Van Der Straeten, C; Sonntag, R; Müller, U; Streit, M; Moradi, B; Jäger, S; Reinders, J

    2013-08-01

    Increased wear leads to elevated systemic and local metal ion concentrations for patients treated with metal-on-metal bearings. The local metal ion content in the close environment of the joint replacement (e.g. joint aspirate or tissue) is several times higher compared to the systemic metal content (e.g. in blood or serum). As a result of increased metal ion levels, local and systemic effects, such as osteolysis, pseudotumors, sensitization or in rare cases toxicity may occur. Although the definition of a specific threshold to define clinical problems is difficult due to a lack of sensitivity, the systemic metal concentration is frequently measured clinically. Currently a threshold for cobalt and chromium between 4 µg/l and 7 µg/l is under debate. Very high levels (≥ 20 µg/l) or a steady increase over time should be a warning sign; however, metal ion levels should not be interpreted as a single diagnostic tool but rather in the entire context of the clinical, radiological and cross-sectional imaging, metal artefact reduction sequence (MARS) magnetic resonance imaging (MRI), ultrasound and computed tomography (CT) findings.

  6. The roles of metal ions in regulation by riboswitches.

    Science.gov (United States)

    Ferré-D'Amaré, Adrian R; Winkler, Wade C

    2011-01-01

    Metal ions are required by all organisms in order to execute an array of essential molecular functions. They play a critical role in many catalytic mechanisms and structural properties. Proper homeostasis of ions is critical; levels that are aberrantly low or high are deleterious to cellular physiology. To maintain stable intracellular pools, metal ion-sensing regulatory (metalloregulatory) proteins couple metal ion concentration fluctuations with expression of genes encoding for cation transport or sequestration. However, these transcriptional-based regulatory strategies are not the only mechanisms by which organisms coordinate metal ions with gene expression. Intriguingly, a few classes of signal-responsive RNA elements have also been discovered to function as metalloregulatory agents. This suggests that RNA-based regulatory strategies can be precisely tuned to intracellular metal ion pools, functionally akin to metal-loregulatory proteins. In addition to these metal-sensing regulatory RNAs, there is a yet broader role for metal ions in directly assisting the structural integrity of other signal-responsive regulatory RNA elements. In this chapter, we discuss how the intimate physicochemical relationship between metal ions and nucleic acids is important for the structure and function of metal ion- and metabolite-sensing regulatory RNAs.

  7. Interaction of Different Divalent Metal Ions with Lipid Bilayer: Impact on the Encapsulation of Doxorubicin by Lipid Bilayer and Lipoplex Mediated Deintercalation.

    Science.gov (United States)

    Das, Anupam; Adhikari, Chandan; Chakraborty, Anjan

    2017-03-02

    In this article, we investigate the influence of different metal ions (Ca 2+ , Mg 2+ , and Zn 2+ ) on binding of an anticancer drug doxorubicin (DOX) to DMPC bilayer and lipoplex mediated deintercalation of DOX from DOX-DNA complex. Our study reveals that lipid bilayer in the presence of different metal ions displays much higher binding affinity toward DOX than bare lipid bilayer does. Further, this affinity for a particular metal ion increases linearly with metal ion concentration. The steady state and time-resolved fluorescence studies reveal that binding of DOX with lipid bilayer in the presence of different metal ions varies in the order of Ca 2+ > Mg 2+ > Zn 2+ . The rotational relaxation of DOX in the presence of different metal ions takes place in the same order. We explain these phenomena in the light of alteration of the physical properties brought about by metal ions. Moreover, we find that binding pattern of metal ions with lipid head groups influences the intake of DOX in lipid bilayer. We exploit the binding of DOX with bilayer to study the deintercalation of DOX from DOX-DNA complex. We observe that with increase in metal ion concentration the deintercalation increases. Among all metal ions, Ca 2+ appears to be most effective in deintercalation compared to other metal ions. The time-resolved fluorescence anisotropy and circular dichroism measurements indicate that in the presence of Ca 2+ , lipid bilayer offer strongest interaction with DNA while the same is weakest for Zn 2+ . This explains the highest percentage of deintercalation of DOX from drug-DNA complex in the presence of Ca 2+ . Overall the present study demonstrates a new strategy that binding of drug molecules with lipid bilayer and deintercalation of the same from drug-DNA complex can be tuned by modulation of lipid bilayer with different metal ions and their concentration.

  8. Heavy metal ion uptake properties of polystyrene-supported ...

    Indian Academy of Sciences (India)

    Unknown

    concentration on the uptake of metal ions have been studied. The uptake of metal ion depends on pH. The resins are more selective at pH 10 for Pb(II) and Hg(II), whereas at pH 6 they are found to be Cd(II) and Cr(VI) selective. Metal ion uptake properties of resins follow Freundlich's equation. The resins are recyclable and ...

  9. Mechanism of the inhibition of milk xanthine oxidase activity by metal ions: a transient kinetic study.

    Science.gov (United States)

    Mondal, M S; Sau, A K; Mitra, S

    2000-07-14

    The nature and mechanism of the inhibition of the oxidoreductase activity of milk xanthine oxidase (XO) by Cu(2+), Hg(2+) and Ag(+) ions has been studied by steady state and stopped flow transient kinetic measurements. The results show that the nature of the inhibition is noncompetitive. The inhibition constants for Cu(2+) and Hg(2+) are in the micromolar and that for Ag(+) is in the nanomolar range. This suggests that the metal ions have strong affinity towards XO. pH dependence studies of the inhibition indicate that at least two ionisable groups of XO are involved in the binding of these metal ions. The effect of the interaction of the metal ions on the reductive and oxidative half reactions of XO has been investigated, and it is observed that the kinetic parameters of the reductive half reaction are not affected by these metal ions. However, the interaction of these metal ions with XO significantly affects the kinetic parameters of the oxidative half reaction. It is suggested that this may be the main cause for the inhibition of XO activity by the metal ions.

  10. Electrochemical Characterization of Metal-Binding Properties of Metallothioneins Isolated from M. galloprovincialis

    OpenAIRE

    Raspor, Biserka; Pavičić, Jasenka

    1997-01-01

    Amperometric titrations of defined metallothionein concentrations with the standard CdCl2 solution have been performed in seawater samples at pH > 8, in order to define the metal-binding properties of purified mussel metallothionein component. The concentration of the formed Cd-thionein complex has been assessed in the indirect and direct mode. The results on the available ligand concentration CL for complexing Cd2+ ions and the apparent stability constant K, determined by two procedures are ...

  11. Blood metal ion concentrations in metal-on-metal total hip arthroplasty.

    Science.gov (United States)

    Ohtsuru, Tadahiko; Morita, Yuji; Murata, Yasuaki; Shimamoto, Shuji; Munakata, Yutaro; Kato, Yoshiharu

    2017-05-01

    The hip placement with a metal-on-metal (MOM) bearing has been used for both surface replacement and total hip arthroplasty (THA). Use of MOM bearing for hip replacement reduces the wear compared to conventional bearings. We prospectively assessed 30 patients who underwent unilateral MOM THA. A control group of 30 patients who underwent metal-on-polyethylene THA using the implants as the other group, except for bearing, were accessed. Blood samples were collected preoperatively and at 3- , 6- , 9- , 12- , 15- , 18- , and 24-month intervals. Changes in mean blood metal ion concentration were compared between the MOM and metal-on-polyethylene groups. A statistically significant positive correlation was observed between blood cobalt and chromium concentrations in all of the patients. The mean blood ion concentrations of the MOM were significantly higher than those of the metal-on-polyethylene. A statistically significant negative correlation was found between maximum blood cobalt concentration and cup version angle. The maximum blood chromium concentrations in the patients who had larger cup version angles were more likely to decrease. We considered that cup version angle is one of the factors that have the greatest effect on blood metal ion concentration, and the target cup version angle that did not induce an increase in blood metal ion concentrations was approximately 20°.

  12. Sorption of metal ions on synthetic organo-inorganic ion exchanger polyacrylonitrile-Ti(IV) tungstophosphate

    International Nuclear Information System (INIS)

    Haidary, A.; Ahmadi, S. J.; Asadi, M. R.; Asgharizadeh, F.; Ashtari, P.

    2010-01-01

    In this study two Polyacrylonitrile-Ti(IV) tungstophosphate organo-inorganic ion exchangers with different molar ratios have been synthesized. These ion exchangers have been characterized by fourier transform-IR, X- ray diffraction, thermal gravimetric, scanning electron microscopy and CHNSO techniques and their cation exchange capacity bas been measured by continuous method. Distribution coefficients (K d ) for metal ions and radionuclides were determined by batch method and with these ion exchangers, separation of metal ions was achieved on a glass column.

  13. Plasma immersion ion implantation for reducing metal ion release

    Energy Technology Data Exchange (ETDEWEB)

    Diaz, C.; Garcia, J. A.; Maendl, S.; Pereiro, R.; Fernandez, B.; Rodriguez, R. J. [Centro de Ingenieria Avanzada de Superficies AIN, 31191, Cordovilla-Pamplona (Spain); Leibniz-Institut fuer Oberflaechenmodifizierung, 04318 Leipzig (Germany); Universidad de Oviedo, Departamento Quimica Fisica y Analitica (Spain); Centro de Ingenieria Avanzada de Superficies AIN, 31191, Cordovilla-Pamplona (Spain)

    2012-11-06

    Plasma immersion ion implantation of Nitrogen and Oxygen on CoCrMo alloys was carried out to improve the tribological and corrosion behaviors of these biomedical alloys. In order to optimize the implantation results we were carried experiments at different temperatures. Tribocorrosion tests in bovine serum were used to measure Co, Cr and Mo releasing by using Inductively Coupled Plasma Mass Spectrometry analysis after tests. Also, X-ray Diffraction analysis were employed in order to explain any obtained difference in wear rate and corrosion tests. Wear tests reveals important decreases in rate of more than one order of magnitude for the best treatment. Moreover decreases in metal release were found for all the implanted samples, preserving the same corrosion resistance of the unimplanted samples. Finally this paper gathers an analysis, in terms of implantation parameters and achieved properties for industrial implementation of these treatments.

  14. Backscattering of light ions from metal surfaces

    International Nuclear Information System (INIS)

    Verbeek, H.

    1975-07-01

    When a metal target is bombarded with light ions some are implanted and some are reflected from the surface or backscattered from deeper layers. This results in an energy distribution of the backscattered particles which reaches from zero to almost the primary energy. The number of the backscattered particles and their energy, angular, and charge distributions depends largely on the energy and the ion target combination. For high energies (i.e., greater than50 keV for protons) particles are backscattered in a single collision governed by the Rutherford cross section. Protons and He-ions with energies of 100 keV to several MeV are widely used for thin film analysis. For lower energies multiple collisions and the screening of the Coulomb potential have to be taken into account, which makes the theoretical treatment more difficult. This energy region is, however, of special interest in the field of nuclear fusion research. Some recent results for energies below 20 keV are discussed in some detail. (auth)

  15. A Transition Metal-Binding, Trimeric βγ-Crystallin from Methane-Producing Thermophilic Archaea, Methanosaeta thermophila.

    Science.gov (United States)

    Srivastava, Shanti Swaroop; Jamkhindikar, Aditya Anand; Raman, Rajeev; Jobby, Maroor K; Chadalawada, Swathi; Sankaranarayanan, Rajan; Sharma, Yogendra

    2017-03-07

    βγ-Crystallins are important constituents of the vertebrate eye lens, whereas in microbes, they are prevalent as Ca 2+ -binding proteins. In archaea, βγ-crystallins are conspicuously confined to two methanogens, viz., Methanosaeta and Methanosarcina. One of these, i.e., M-crystallin from Methanosarcina acetivorans, has been shown to be a typical Ca 2+ -binding βγ-crystallin. Here, with the aid of a high-resolution crystal structure and isothermal titration calorimetry, we report that "Methallin", a βγ-crystallin from Methanosaeta thermophila, is a trimeric, transition metal-binding protein. It binds Fe, Ni, Co, or Zn ion with nanomolar affinity, which is consistent even at 55 °C, the optimal temperature for the methanogen's growth. At the center of the protein trimer, the metal ion is coordinated by six histidines, two from each protomer, leading to an octahedral geometry. Small-angle X-ray scattering analysis confirms that the trimer seen in the crystal lattice is a biological assembly; this assembly dissociates to monomers upon removal of the metal ion. The introduction of two histidines (S17H/S19H) into a homologous βγ-crystallin, Clostrillin, allows it to bind nickel at the introduced site, though with micromolar affinity. However, because of the lack of a compatible interface, nickel binding could not induce trimerization, affirming that Methallin is a naturally occurring trimer for high-affinity transition metal binding. While βγ-crystallins are known to bind Ca 2+ and form homodimers and oligomers, the transition metal-binding, trimeric Methallin is a new paradigm for βγ-crystallins. The distinct features of Methallin, such as nickel or iron binding, are also possible imprints of biogeochemical changes during the period of its origin.

  16. Theory Meets Experiment: Metal Ion Effects in HCV Genomic RNA Kissing Complex Formation.

    Science.gov (United States)

    Sun, Li-Zhen; Heng, Xiao; Chen, Shi-Jie

    2017-01-01

    The long-range base pairing between the 5BSL3. 2 and 3'X domains in hepatitis C virus (HCV) genomic RNA is essential for viral replication. Experimental evidence points to the critical role of metal ions, especially Mg 2+ ions, in the formation of the 5BSL3.2:3'X kissing complex. Furthermore, NMR studies suggested an important ion-dependent conformational switch in the kissing process. However, for a long time, mechanistic understanding of the ion effects for the process has been unclear. Recently, computational modeling based on the Vfold RNA folding model and the partial charge-based tightly bound ion (PCTBI) model, in combination with the NMR data, revealed novel physical insights into the role of metal ions in the 5BSL3.2-3'X system. The use of the PCTBI model, which accounts for the ion correlation and fluctuation, gives reliable predictions for the ion-dependent electrostatic free energy landscape and ion-induced population shift of the 5BSL3.2:3'X kissing complex. Furthermore, the predicted ion binding sites offer insights about how ion-RNA interactions shift the conformational equilibrium. The integrated theory-experiment study shows that Mg 2+ ions may be essential for HCV viral replication. Moreover, the observed Mg 2+ -dependent conformational equilibrium may be an adaptive property of the HCV genomic RNA such that the equilibrium is optimized to the intracellular Mg 2+ concentration in liver cells for efficient viral replication.

  17. Application of Sargassum biomass to remove heavy metal ions from synthetic multi-metal solutions and urban storm water runoff.

    Science.gov (United States)

    Vijayaraghavan, K; Teo, Ting Ting; Balasubramanian, R; Joshi, Umid Man

    2009-05-30

    The ability of Sargassum sp. to biosorb four metal ions, namely lead, copper, zinc, and manganese from a synthetic multi-solute system and real storm water runoff has been investigated for the first time. Experiments on synthetic multi-solute systems revealed that Sargassum performed well in the biosorption of all four metal ions, with preference towards Pb, followed by Cu, Zn, and Mn. The solution pH strongly affected the metal biosorption, with pH 6 being identified as the optimal condition for achieving maximum biosorption. Experiments at different biosorbent dosages revealed that good biosorption capacity as well as high metal removal efficiency was observed at 3g/L. The biosorption kinetics was found to be fast with equilibrium being attained within 50 min. According to the Langmuir isotherm model, Sargassum exhibited maximum uptakes of 214, 67.5, 24.2 and 20.2mg/g for lead, copper, zinc, and manganese, respectively in single-solute systems. In multi-metal systems, strong competition between four metal ions in terms of occupancy binding sites was observed, and Sargassum showed preference in the order of Pb>Cu>Zn>Mn. The application of Sargassum to remove four heavy metal ions in real storm water runoff revealed that the biomass was capable of removing the heavy metal ions. However, the biosorption performance was slightly lower compared to that of synthetic metal solutions. Several factors were responsible for this difference, and the most important factor is the presence of other contaminants such as anions, organics, and other trace metals in the runoff.

  18. Metal ion complexes with HisGly: comparison with PhePhe and PheGly.

    Science.gov (United States)

    Dunbar, Robert C; Oomens, Jos; Berden, Giel; Lau, Justin Kai-Chi; Verkerk, Udo H; Hopkinson, Alan C; Siu, K W Michael

    2013-06-27

    Gas-phase complexes of five metal ions with the dipeptide HisGly have been characterized by DFT computations and by infrared multiple photon dissociation spectroscopy (IRMPD) using the free electron laser FELIX. Fine agreement is found in all five cases between the predicted IR spectral features of the lowest energy structures and the observed IRMPD spectra in the diagnostic region 1500-1800 cm(-1), and the agreement is largely satisfactory at longer wavelengths from 1000 to 1500 cm(-1). Weak-binding metal ions (K(+), Ba(2+), and Ca(2+)) predominantly adopt the charge-solvated (CS) mode of chelation involving both carbonyl oxygens, an imidazole nitrogen of the histidine side chain, and possibly the amino nitrogen. Complexes with Mg(2+) and Ni(2+) are found to adopt iminol (Im) binding, involving the deprotonated amide nitrogen, with tetradentate chelation. This tetradentate coordination of Ni(II) is the preferred binding mode in the gas phase, against the expectation under condensed-phase conditions that such binding would be sterically unfavorable and overshadowed by other outcomes such as metal ion hydration and formation of dimeric complexes. The HisGly results are compared with corresponding results for the PheAla, PheGly, and PhePhe ligands, and parallel behavior is seen for the dipeptides with N-terminal Phe versus His residues. An exception is the different chelation pattern determined for PhePhe versus HisGly, reflecting the intercalation-type cation binding pocket of the PhePhe ligand. The complexes group into three well-defined spectroscopic patterns: nickel and magnesium, calcium and barium, and potassium. Factors leading to differentiation of these distinct spectroscopic categories are (1) differing propensities for choosing the iminol binding pattern, and (2) single versus double charge on the metal center. Nickel and magnesium ions show similar gas-phase binding behavior, contrasting with their quite different patterns of peptide interaction in

  19. Metal Ion Coordination Essential for Specific Molecular Interactions of Butea monosperma Lectin: ITC and MD Simulation Studies.

    Science.gov (United States)

    Abhilash, J; Haridas, M

    2015-05-01

    Crystal structure of Butea monosperma seed lectin (BML) was analyzed and the metal ion geometry identified. In order to understand the role of metal ions for the structural stability and ligand binding, studies of demetallized protein were carried out. Binding of different ligands like GalNAc, lactose, and galactose onto native and demetallized protein was studied by isothermal titration calorimetry as well as molecular simulation methods. Molecular dynamics was applied to the structure after removing the coordinates of metal ions, to identify the effect of demetallization in silico. Docking studies of different sugar molecules as well as the fungal α-amylase was carried out and compared the interactions in the native and apo states. It was found that metal ions are important for the ligand binding with increased affinity. However, their absence did not make any alteration to the secondary structure. Though the metal ions were not coordinated to the loops contacting the α-amylase, the absence of metal ions reduced the protein-protein binding strength due to long-range changes in irregular structures of the lectin.

  20. Recent Advances in Antimicrobial Hydrogels Containing Metal Ions and Metals/Metal Oxide Nanoparticles

    Directory of Open Access Journals (Sweden)

    Fazli Wahid

    2017-11-01

    Full Text Available Recently, the rapid emergence of antibiotic-resistant pathogens has caused a serious health problem. Scientists respond to the threat by developing new antimicrobial materials to prevent or control infections caused by these pathogens. Polymer-based nanocomposite hydrogels are versatile materials as an alternative to conventional antimicrobial agents. Cross-linking of polymeric materials by metal ions or the combination of polymeric hydrogels with nanoparticles (metals and metal oxide is a simple and effective approach for obtaining a multicomponent system with diverse functionalities. Several metals and metal oxides such as silver (Ag, gold (Au, zinc oxide (ZnO, copper oxide (CuO, titanium dioxide (TiO2 and magnesium oxide (MgO have been loaded into hydrogels for antimicrobial applications. The incorporation of metals and metal oxide nanoparticles into hydrogels not only enhances the antimicrobial activity of hydrogels, but also improve their mechanical characteristics. Herein, we summarize recent advances in hydrogels containing metal ions, metals and metal oxide nanoparticles with potential antimicrobial properties.

  1. Coordination of cassava starch to metal ions and thermolysis of ...

    African Journals Online (AJOL)

    Cassava starch formed Werner-type complexes with ions of metals from the transition groups. This was proven by conductivity and electron paramagnetic resonance measurements. The coordination of starch to central metal ions influenced the thermal decomposition of starch. As a rule complexes started to decompose at ...

  2. COORDINATION OF CASSAVA STARCH TO METAL IONS AND ...

    African Journals Online (AJOL)

    a

    ABSTRACT. Cassava starch formed Werner-type complexes with ions of metals from the transition groups. This was proven by conductivity and electron paramagnetic resonance measurements. The coordination of starch to central metal ions influenced the thermal decomposition of starch. As a rule complexes started to ...

  3. Interaction of Hydroxyproline with Bivalent Metal Ions in Chemical ...

    African Journals Online (AJOL)

    NICO

    The stability constants of the ML and ML2 complex species of some metal ions, namely beryllium(II) and cobalt(II), with hydroxyproline were ... metal ions have several significant applications in biological systems.3–20 Beryllium is one ... 1 filter paper for chromatography was used for the purpose of electrophoresis. An Elico ...

  4. Chromatography Of Metal Ions On Wood Cellulose Impregnated ...

    African Journals Online (AJOL)

    Adsorption chromatography of some heavy metal ions on wood cellulose of saw dust (wood waste dust) modified with hydrochloric acid, urea and thiourea was studied. Atomic absorption spectrophotometry (AAS) was used to determine the initial concentration of solutions of Zn2+, Cu2+, Ni2+, Pb2+, and Fe3+ metal ions.

  5. In vitro cytotoxicity of metallic ions released from dental alloys

    NARCIS (Netherlands)

    Milheiro, A.; Nozaki, K.; Kleverlaan, C.J.; Muris, J.; Miura, H.; Feilzer, A.J.

    2016-01-01

    The cytotoxicity of a dental alloy depends on, but is not limited to, the extent of its corrosion behavior. Individual ions may have effects on cell viability that are different from metals interacting within the alloy structure. We aimed to investigate the cytotoxicity of individual metal ions in

  6. Fluorescence signalling of the transition metal ions: Design strategy ...

    Indian Academy of Sciences (India)

    Unknown

    Abstract. Transition metal ions are notorious for their fluorescence quenching abilities. In this paper, we discuss the design strategies for the development of efficient off-on fluorescence signalling systems for the transition metal ions. It is shown that even simple fluorophore-spacer-receptor systems can display excellent.

  7. Selective recovery of gold and other metal ions from an algal biomass

    Energy Technology Data Exchange (ETDEWEB)

    Darnall, D.W.; Greene, B.; Henzl, M.T.; Hosea, J.M.; McPherson, R.A.; Sneddon, J.; Alexander, M.D.

    1986-02-01

    The authors observed that the pH dependence of the binding of Au/sup 3 +/, Ag/sup +/, and Hg/sup 2 +/ to the algae Chlorella vulgaris is different than the binding of other metal ions. Between pH 5 and 7, a variety of metal ions bind strongly to the cell surface. Most of these algal-bound metal ions can be selectively desorbed by lowering the pH to 2; however, Au/sup 3 +/, Hg/sup 2 +/, and Ag/sup +/ are all bound strongly at pH 2. Addition of a strong ligand at different pHs is required to elute these ions from the algal surface. Algal-bound gold and mercury can be selectively eluted by using mercaptoethanol. An elution scheme is demonstrated for the binding and selective recovery of Cu/sup 2 +/, Zn/sup 2 +/, Au/sup 3 +/, and Hg/sup 2 +/ from an equimolar mixture. 20 references, 2 figures.

  8. Cesium ion bombardment of metal surfaces

    International Nuclear Information System (INIS)

    Tompa, G.S.

    1986-01-01

    The steady state cesium coverage due to cesium ion bombardment of molybdenum and tungsten was studied for the incident energy range below 500 eV. When a sample is exposed to a positive ion beam, the work function decreases until steady state is reached with a total dose of less than ≅10 16 ions/cm 2 , for both tungsten and molybdenum. A steady state minimum work function surface is produced at an incident energy of ≅100 eV for molybdenum and at an incident energy of ≅45 eV for tungsten. Increasing the incident energy results in an increase in the work function corresponding to a decrease in the surface coverage of cesium. At incident energies less than that giving the minimum work function, the work function approaches that of cesium metal. At a given bombarding energy the cesium coverage of tungsten is uniformly less than that of molybdenum. Effects of hydrogen gas coadsorption were also examined. Hydrogen coadsorption does not have a large effect on the steady state work functions. The largest shifts in the work function due to the coadsorption of hydrogen occur on the samples when there is no cesium present. A theory describing the steady-state coverage was developed is used to make predictions for other materials. A simple sticking and sputtering relationship, not including implantation, cannot account for the steady state coverage. At low concentrations, cesium coverage of a target is proportional to the ratio of (1 - β)/γ where β is the reflection coefficient and γ is the sputter yield. High coverages are produced on molybdenum due to implantation and low backscattering, because molybdenum is lighter than cesium. For tungsten the high backscattering and low implantation result in low coverages

  9. Coprecipitation of alkali metal ions with calcium carbonate

    International Nuclear Information System (INIS)

    Okumura, Minoru; Kitano, Yasushi

    1986-01-01

    The coprecipitation of alkali metal ions Li + , Na + , K + and Rb + with calcium carbonate has been studied experimentally and the following results have been obtained: (1) Alkali metal ions are more easily coprecipitated with aragonite than with calcite. (2) The relationship between the amounts of alkali metal ions coprecipitated with aragonite and their ionic radii shows a parabolic curve with a peak located at Na + which has approximately the same ionic radius as Ca 2+ . (3) However, the amounts of alkali metal ions coprecipitated with calcite decrease with increasing ionic radius of alkali metals. (4) Our results support the hypothesis that (a) alkali metals are in interstitial positions in the crystal structure of calcite and do not substitute for Ca 2+ in the lattice, but (b) in aragonite, alkali metals substitute for Ca 2+ in the crystal structure. (5) Magnesium ions in the parent solution increase the amounts of alkali metal ions (Li + , Na + , K + and Rb + ) coprecipitated with calcite but decrease those with aragonite. (6) Sodium-bearing aragonite decreases the incorporation of other alkali metal ions (Li + , K + and Rb + ) into the aragonite. (author)

  10. Which metal or ion? Identification of metals and ions in protein structures

    Czech Academy of Sciences Publication Activity Database

    Dohnálek, Jan

    2014-01-01

    Roč. 70, Supplement /August/ (2014), C1484 ISSN 0108-7673. [Congress and General Assembly of the International Union of Crystallography /23./ - IUCr 2014. 05.08.2014-12.08.2014, Montreal] R&D Projects: GA MŠk(CZ) EE2.3.30.0029; GA MŠk(CZ) ED1.1.00/02.0109 Institutional support: RVO:61389013 Keywords : metal s * ions * structure validation Subject RIV: CE - Biochemistry

  11. Metal ion transport in eukaryotic microorganisms: insights from Saccharomyces cerevisiae.

    Science.gov (United States)

    Eide, D J

    2000-01-01

    Metal ions such as iron, copper, manganese, and zinc are essential nutrients for all eukaryotic microorganisms. Therefore, these organisms possess efficient uptake mechanisms to obtain these nutrients from their extracellular environment. Metal ions must also be transported into intracellular organelles where they function as catalytic and structural cofactors for compartmentalized enzymes. Thus, intracellular transport mechanisms are also present. When present in high levels, metal ions can also be toxic, so their uptake and intracellular transport is tightly regulated at both transcriptional and post-transcriptional levels to limit metal ion overaccumulation and facilitate storage and sequestration. Remarkable molecular insight into these processes has come from recent studies of the yeast Saccharomyces cerevisiae. This organism, which is the primary subject of this chapter, serves as a useful paradigm to understand metal ion metabolism in other eukaryotic microbes.

  12. Selective removal of heavy metal ions by disulfide linked polymer networks.

    Science.gov (United States)

    Ko, Dongah; Lee, Joo Sung; Patel, Hasmukh A; Jakobsen, Mogens H; Hwang, Yuhoon; Yavuz, Cafer T; Hansen, Hans Chr Bruun; Andersen, Henrik R

    2017-06-15

    Heavy metal contaminated surface water is one of the oldest pollution problems, which is critical to ecosystems and human health. We devised disulfide linked polymer networks and employed as a sorbent for removing heavy metal ions from contaminated water. Although the polymer network material has a moderate surface area, it demonstrated cadmium removal efficiency equivalent to highly porous activated carbon while it showed 16 times faster sorption kinetics compared to activated carbon, owing to the high affinity of cadmium towards disulfide and thiol functionality in the polymer network. The metal sorption mechanism on polymer network was studied by sorption kinetics, effect of pH, and metal complexation. We observed that the metal ions-copper, cadmium, and zinc showed high binding affinity in polymer network, even in the presence of competing cations like calcium in water. Copyright © 2017 Elsevier B.V. All rights reserved.

  13. Synthesis of new water-soluble metal-binding polymers: Combinatorial chemistry approach. 1997 mid-year progress report

    International Nuclear Information System (INIS)

    Smith, B.F.

    1997-01-01

    'The first objective of this research is to develop rapid discovery and optimization approaches to new water-soluble chelating polymers. A byproduct of the development approach will be the new, selective, and efficient metal-binding agents. The second objective is to evaluate the concept of using water and organic soluble polymers as new solid supports for combinatorial synthesis. The technology under development, Polymer Filtration (PF), is a technique to selectively remove or recover hazardous and valuable metal ions and radionuclides from various dilute aqueous streams. Not only can this technology be used to remediate contaminated soils and solid surfaces and treat aqueous wastes, it can also be incorporated into facilities as a pollution prevention and waste minimization technology. Polymer Filtration uses water-soluble metal-binding polymers to sequester metal ions in dilute solution. The water-soluble polymers have a sufficiently large molecular size that they can be separated and concentrated using commercial ultrafiltration technology. Water, small organic molecules, and unbound metals pass freely through the ultrafiltration membrane while concentrating the metal-binding polymer. The polymers can then be reused by changing the solution conditions to release the metal ions. The metal-ions are recovered in concentrated form for recycle or disposal using a diafiltration process. The water-soluble polymer can be recycled for further aqueous-stream processing. To advance Polymer Filtration technology to the selectivity levels required for DOE needs. fixture directions in Polymer Filtration must include rapid development, testing, and characterization of new metal-binding polymers. The development of new chelating molecules can be equated to the process of new drugs or new materials discovery. Thus, the authors want to build upon and adapt the combinatorial chemistry approaches developed for rapid molecule generation for the drug industry to the rapid

  14. Synthesis of new water-soluble metal-binding polymers: Combinatorial chemistry approach. 1997 mid-year progress report

    Energy Technology Data Exchange (ETDEWEB)

    Smith, B.F.

    1997-06-01

    'The first objective of this research is to develop rapid discovery and optimization approaches to new water-soluble chelating polymers. A byproduct of the development approach will be the new, selective, and efficient metal-binding agents. The second objective is to evaluate the concept of using water and organic soluble polymers as new solid supports for combinatorial synthesis. The technology under development, Polymer Filtration (PF), is a technique to selectively remove or recover hazardous and valuable metal ions and radionuclides from various dilute aqueous streams. Not only can this technology be used to remediate contaminated soils and solid surfaces and treat aqueous wastes, it can also be incorporated into facilities as a pollution prevention and waste minimization technology. Polymer Filtration uses water-soluble metal-binding polymers to sequester metal ions in dilute solution. The water-soluble polymers have a sufficiently large molecular size that they can be separated and concentrated using commercial ultrafiltration technology. Water, small organic molecules, and unbound metals pass freely through the ultrafiltration membrane while concentrating the metal-binding polymer. The polymers can then be reused by changing the solution conditions to release the metal ions. The metal-ions are recovered in concentrated form for recycle or disposal using a diafiltration process. The water-soluble polymer can be recycled for further aqueous-stream processing. To advance Polymer Filtration technology to the selectivity levels required for DOE needs. fixture directions in Polymer Filtration must include rapid development, testing, and characterization of new metal-binding polymers. The development of new chelating molecules can be equated to the process of new drugs or new materials discovery. Thus, the authors want to build upon and adapt the combinatorial chemistry approaches developed for rapid molecule generation for the drug industry to the rapid

  15. Positive cooperativity of the specific binding between Hg2+ ion and T:T mismatched base pairs in duplex DNA

    International Nuclear Information System (INIS)

    Torigoe, Hidetaka; Miyakawa, Yukako; Ono, Akira; Kozasa, Tetsuo

    2012-01-01

    Highlights: ► Hg 2+ specifically bound with the T:T mismatched base pair at 1:1 molar ratio. ► The binding constant between Hg 2+ and the T:T mismatched base pair was 10 6 M −1 . ► The binding constant was larger than those for nonspecific metal–DNA interactions. ► The binding constant for the second Hg 2+ was larger than that for the first Hg 2+ . ► The positive cooperative binding was observed between Hg 2+ and multiple T:T. - Abstract: Metal-mediated base pairs by the interaction between metal ions and artificial bases in oligonucleotides have been developed for their potential applications in nanotechnology. We recently found that a natural T:T mismatched base pair bound with Hg 2+ ion to form a novel T–Hg–T base pair. Here, we examined the thermodynamic properties of the binding between Hg 2+ and each of the single and double T:T mismatched base pair duplex DNAs by isothermal titration calorimetry. Hg 2+ specifically bound with the T:T mismatched base pair at 1:1 molar ratio with 10 6 M −1 binding constant, which was significantly larger than those for nonspecific metal ion–DNA interactions. In the Hg 2+ –double T:T mismatched base pair interaction, the affinity for the second Hg 2+ binding was significantly larger than that for the first Hg 2+ binding. The positively cooperative binding may be favorable to align multiple Hg 2+ in duplex DNA for the application of the metal-mediated base pairs in nanotechnology.

  16. Removal of toxic metal ions from solution by inactivated cells of plants

    International Nuclear Information System (INIS)

    Raza, R.; Khattak, I.M.

    2006-01-01

    The aim of this paper to present the study of plant Larrea tridentate (bush) that grows abundantly in the desert environment of Hub, Balochistan toward the industrial area of Karachi (Pakistan). The binding of Ni(II), Cd(II), Pb(II), Zn(II), Cr(III), and Cr(VI) to Larrea tridentataroots. Stems, and leaves has been shown to be dependent upon pH, with best binding occurring between pH 5 and 6. This effect in pH suggests that the binding mechanism may be an ion exchange type process. Also, the binding mechanism for these metals is a stable, rapid process which implies that the binding is taking place on the cell wall surface of the creosote bush. Capacity and recovery experiments have demonstrated that Larrea tridentate possessed the ability to bind appreciable amounts of Ni(II), Pb(II), Zn(II), and Cr(III) as compared to other biosorbents. This ability to remove and recover heavy metals from solution indicates the tremendous potential that the creosote bush could have for cleansing the environment and industrial waste effluents from toxic metal ions. (author)

  17. Colorimetric photonic hydrogel aptasensor for the screening of heavy metal ions.

    Science.gov (United States)

    Ye, Bao-Fen; Zhao, Yuan-Jin; Cheng, Yao; Li, Ting-Ting; Xie, Zhuo-Ying; Zhao, Xiang-Wei; Gu, Zhong-Ze

    2012-09-28

    We have developed a robust method for the visual detection of heavy metal ions (such as Hg(2+) and Pb(2+)) by using aptamer-functionalized colloidal photonic crystal hydrogel (CPCH) films. The CPCHs were derived from a colloidal crystal array of monodisperse silica nanoparticles, which were polymerized within the polyacrylamide hydrogel. The heavy metal ion-responsive aptamers were then cross-linked in the hydrogel network. During detection, the specific binding of heavy metal ions and cross-linked single-stranded aptamers in the hydrogel network caused the hydrogel to shrink, which was detected as a corresponding blue shift in the Bragg diffraction peak position of the CPCHs. The shift value could be used to estimate, quantitatively, the amount of the target ion. It was demonstrated that our CPCH aptasensor could screen a wide concentration range of heavy metal ions with high selectivity and reversibility. In addition, these aptasensors could be rehydrated from dried gels for storage and aptamer protection. It is anticipated that our technology may also be used in the screening of a broad range of metal ions in food, drugs and the environment.

  18. Alkali metal ion battery with bimetallic electrode

    Science.gov (United States)

    Boysen, Dane A; Bradwell, David J; Jiang, Kai; Kim, Hojong; Ortiz, Luis A; Sadoway, Donald R; Tomaszowska, Alina A; Wei, Weifeng; Wang, Kangli

    2015-04-07

    Electrochemical cells having molten electrodes having an alkali metal provide receipt and delivery of power by transporting atoms of the alkali metal between electrode environments of disparate chemical potentials through an electrochemical pathway comprising a salt of the alkali metal. The chemical potential of the alkali metal is decreased when combined with one or more non-alkali metals, thus producing a voltage between an electrode comprising the molten the alkali metal and the electrode comprising the combined alkali/non-alkali metals.

  19. Sorption of Molecular Oxygen by Metal-Ion Exchanger Nanocomposites

    Science.gov (United States)

    Krysanov, V. A.; Plotnikova, N. V.; Kravchenko, T. A.

    2018-03-01

    Kinetic features are studied of the chemisorption and reduction of molecular oxygen from water by metal-ion exchanger nanocomposites that differ in the nature of the dispersed metal and state of oxidation. In the Pd equilibrium sorption coefficient for oxygen dissolved in water ranges from 20 to 50, depending on the nature and oxidation state of the metal component.

  20. Metals on the move: zinc ions in cellular regulation and in the coordination dynamics of zinc proteins.

    Science.gov (United States)

    Maret, Wolfgang

    2011-06-01

    Homeostatic control maintains essential transition metal ions at characteristic cellular concentrations to support their physiological functions and to avoid adverse effects. Zinc is especially widely used as a catalytic or structural cofactor in about 3000 human zinc proteins. In addition, the homeostatic control of zinc in eukaryotic cells permits functions of zinc(II) ions in regulation and in paracrine and intracrine signaling. Zinc ions are released from proteins through ligand-centered reactions in zinc/thiolate coordination environments, and from stores in cellular organelles, where zinc transporters participate in zinc loading and release. Muffling reactions allow zinc ions to serve as signaling ions (second messengers) in the cytosol that is buffered to picomolar zinc ion concentrations at steady-state. Muffling includes zinc ion binding to metallothioneins, cellular translocations of metallothioneins, delivery of zinc ions to transporter proteins, and zinc ion fluxes through cellular membranes with the result of removing the additional zinc ions from the cytosol and restoring the steady-state. Targets of regulatory zinc ions are proteins with sites for transient zinc binding, such as membrane receptors, enzymes, protein-protein interactions, and sensor proteins that control gene expression. The generation, transmission, targets, and termination of zinc ion signals involve proteins that use coordination dynamics in the inner and outer ligand spheres to control metal ion association and dissociation. These new findings establish critically important functions of zinc ions and zinc metalloproteins in cellular control.

  1. Protein scaffolds for selective enrichment of metal ions

    Science.gov (United States)

    He, Chuan; Zhou, Lu; Bosscher, Michael

    2016-02-09

    Polypeptides comprising high affinity for the uranyl ion are provided. Methods for binding uranyl using such proteins are likewise provided and can be used, for example, in methods for uranium purification or removal.

  2. Metal-binding thermodynamics of the histidine-rich sequence from the metal-transport protein IRT1 of Arabidopsis thaliana.

    Science.gov (United States)

    Grossoehme, Nicholas E; Akilesh, Shreeram; Guerinot, Mary Lou; Wilcox, Dean E

    2006-10-16

    The widespread ZIP family of transmembrane metal-transporting proteins is characterized by a large intracellular loop that contains a histidine-rich sequence whose biological role is unknown. To provide a chemical basis for this role, we prepared and studied a peptide corresponding to this sequence from the first iron-regulated transporter (IRT1) of Arabidopsis thaliana, which transports Fe2+ as well as Mn2+, Co2+, Zn2+, and Cd2+. Isothermal titration calorimetry (ITC) measurements, which required novel experiments and data analysis, and supporting spectroscopic methods were used to quantify IRT1's metal-binding affinity and associated thermodynamics. The peptide, PHGHGHGHGP, binds metal ions with 1:1 stoichiometry and stabilities that are consistent with the Irving-Williams series. Comparison of the metal-binding thermodynamics of the peptide with those of trien provides new insight about enthalpic and entropic contributions to the stability of the metal-peptide complex. Although Fe2+ and other IRT1-transported metal ions do not bind very tightly, this His-rich sequence has a very high entropy-driven affinity for Fe3+, which may have biological significance.

  3. Crystal structure of glucose isomerase in complex with xylitol inhibitor in one metal binding mode.

    Science.gov (United States)

    Bae, Ji-Eun; Kim, In Jung; Nam, Ki Hyun

    2017-11-04

    Glucose isomerase (GI) is an intramolecular oxidoreductase that interconverts aldoses and ketoses. These characteristics are widely used in the food, detergent, and pharmaceutical industries. In order to obtain an efficient GI, identification of novel GI genes and substrate binding/inhibition have been studied. Xylitol is a well-known inhibitor of GI. In Streptomyces rubiginosus, two crystal structures have been reported for GI in complex with xylitol inhibitor. However, a structural comparison showed that xylitol can have variable conformation at the substrate binding site, e.g., a nonspecific binding mode. In this study, we report the crystal structure of S. rubiginosus GI in a complex with xylitol and glycerol. Our crystal structure showed one metal binding mode in GI, which we presumed to represent the inactive form of the GI. The metal ion was found only at the M1 site, which was involved in substrate binding, and was not present at the M2 site, which was involved in catalytic function. The O 2 and O 4 atoms of xylitol molecules contributed to the stable octahedral coordination of the metal in M1. Although there was no metal at the M2 site, no large conformational change was observed for the conserved residues coordinating M2. Our structural analysis showed that the metal at the M2 site was not important when a xylitol inhibitor was bound to the M1 site in GI. Thus, these findings provided important information for elucidation or engineering of GI functions. Copyright © 2017 Elsevier Inc. All rights reserved.

  4. Initiation of protein association in tofu formation by metal ions.

    Science.gov (United States)

    Arii, Yasuhiro; Takenaka, Yasuyuki

    2014-01-01

    Magnesium and calcium ions are important factors in making tofu. However, the molecular role of these ions remains unclear in tofu formation. We have previously shown that magnesium chloride concentration-dependent produced silken tofu-like (SP) and regular tofu-like (RP) precipitates, but was an inconsequential factor for the retention of tofu. We investigated in this present study, the effect of various metal chlorides on the metal chloride concentration-dependent changes in tofu formation. These changes occurred in a similar manner to that of the magnesium ion, in which SP formation was followed by RP formation. It is interesting that the midpoint concentration for the formation of SP and RP represented a good correlation with the stability constant of EDTA. This correlation demonstrated the possibility that metal ions would interact with the carboxyl groups of soy proteins. We consider from these results that metal ions were the initiators of protein association in tofu formation.

  5. Catalysis using hydrous metal oxide ion exchanges

    Science.gov (United States)

    Dosch, Robert G.; Stephens, Howard P.; Stohl, Frances V.

    1985-01-01

    In a process which is catalyzed by a catalyst comprising an active metal on a carrier, said metal being active as a catalyst for the process, an improvement is provided wherein the catalyst is a hydrous, alkali metal or alkaline earth metal titanate, zirconate, niobate or tantalate wherein alkali or alkaline earth metal cations have been exchanged with a catalytically effective amount of cations of said metal.

  6. Metallic ion release from biocompatible cobalt-based alloy

    Directory of Open Access Journals (Sweden)

    Dimić Ivana D.

    2014-01-01

    Full Text Available Metallic biomaterials, which are mainly used for the damaged hard tissue replacements, are materials with high strength, excellent toughness and good wear resistance. The disadvantages of metals as implant materials are their susceptibility to corrosion, the elastic modulus mismatch between metals and human hard tissues, relatively high density and metallic ion release which can cause serious health problems. The aim of this study was to examine metallic ion release from Co-Cr-Mo alloy in artificial saliva. In that purpose, alloy samples were immersed into artificial saliva with different pH values (4.0, 5.5 and 7.5. After a certain immersion period (1, 3 and 6 weeks the concentrations of released ions were determined using Inductively Coupled Plasma - Mass Spectrophotometer (ICP-MS. The research findings were used in order to define the dependence between the concentration of released metallic ions, artificial saliva pH values and immersion time. The determined released metallic ions concentrations were compared with literature data in order to describe and better understand the phenomenon of metallic ion release from the biocompatible cobalt-based alloy. [Projekat Ministarstva nauke Republike Srbije, br. III 46010 i br. ON 174004

  7. The interaction of human serum albumin with selected lanthanide and actinide ions: Binding affinities, protein unfolding and conformational changes.

    Science.gov (United States)

    Ali, Manjoor; Kumar, Amit; Kumar, Mukesh; Pandey, Badri N

    2016-04-01

    Human serum albumin (HSA), the most abundant soluble protein in blood plays critical roles in transportation of biomolecules and maintenance of osmotic pressure. In view of increasing applications of lanthanides- and actinides-based materials in nuclear energy, space, industries and medical applications, the risk of exposure with these metal ions is a growing concern for human health. In present study, binding interaction of actinides/lanthanides [thorium: Th(IV), uranium: U(VI), lanthanum: La(III), cerium: Ce(III) and (IV)] with HSA and its structural consequences have been investigated. Ultraviolet-visible, Fourier transform-infrared, Raman, Fluorescence and Circular dichroism spectroscopic techniques were applied to study the site of metal ions interaction, binding affinity determination and the effect of metal ions on protein unfolding and HSA conformation. Results showed that these metal ions interacted with carbonyl (CO..:)/amide(N..-H) groups and induced exposure of aromatic residues of HSA. The fluorescence analysis indicated that the actinide binding altered the microenvironment around Trp214 in the subdomain IIA. Binding affinity of U(VI) to HSA was slightly higher than that of Th(IV). Actinides and Ce(IV) altered the secondary conformation of HSA with a significant decrease of α-helix and an increase of β-sheet, turn and random coil structures, indicating a partial unfolding of HSA. A correlation was observed between metal ion's ability to alter HSA conformation and protein unfolding. Both cationic effects and coordination ability of metal ions seemed to determine the consequences of their interaction with HSA. Present study improves our understanding about the protein interaction of these heavy ions and their impact on its secondary structure. In addition, binding characteristics may have important implications for the development of rational antidote for the medical management of health effects of actinides and lanthanides. Copyright © 2016 Elsevier

  8. A New Metal Binding Domain Involved in Cadmium, Cobalt and Zinc Transport

    Energy Technology Data Exchange (ETDEWEB)

    Smith, Aaron T. [Northwestern Univ., Evanston, IL (United States); Barupala, Dulmini [Wayne State Univ., Detroit, MI (United States); Stemmler, Timothy L. [Wayne State Univ., Detroit, MI (United States); Rosenzweig, Amy C. [Northwestern Univ., Evanston, IL (United States)

    2015-07-20

    In the P1B-ATPases, which couple cation transport across membranes to ATP hydrolysis, are central to metal homeostasis in all organisms. An important feature of P1B-ATPases is the presence of soluble metal binding domains (MBDs) that regulate transport activity. Only one type of MBD has been characterized extensively, but bioinformatics analyses indicate that a diversity of MBDs may exist in nature. Here we report the biochemical, structural and functional characterization of a new MBD from the Cupriavidus metallidurans P1B-4-ATPase CzcP (CzcP MBD). The CzcP MBD binds two Cd2+, Co2+ or Zn2+ ions in distinct and unique sites and adopts an unexpected fold consisting of two fused ferredoxin-like domains. Both in vitro and in vivo activity assays using full-length CzcP, truncated CzcP and several variants indicate a regulatory role for the MBD and distinct functions for the two metal binding sites. Moreover, these findings elucidate a previously unknown MBD and suggest new regulatory mechanisms for metal transport by P1B-ATPases.

  9. Rapid and Label-Free Strategy to Isolate Aptamers for Metal Ions.

    Science.gov (United States)

    Qu, Hao; Csordas, Andrew T; Wang, Jinpeng; Oh, Seung Soo; Eisenstein, Michael S; Soh, Hyongsok Tom

    2016-08-23

    Generating aptamers that bind to specific metal ions is challenging because existing aptamer discovery methods typically require chemical labels or modifications that can alter the structure and properties of the ions. In this work, we report an aptamer discovery method that enables us to generate high-quality structure-switching aptamers (SSAs) that undergo a conformational change upon binding a metal ion target, without the requirement of labels or chemical modifications. Our method is more efficient than conventional selection methods because it enables direct measurement of target binding via fluorescence-activated cell sorting (FACS), isolating only the desired aptamers with the highest affinity. Using this strategy, we obtained a highly specific DNA SSA with ∼30-fold higher affinity than the best aptamer for Hg(2+) in the literature. We also discovered DNA aptamers that bind to Cu(2+) with excellent affinity and specificity. Both aptamers were obtained within four rounds of screening, demonstrating the efficiency of our aptamer discovery method. Given the growing availability of FACS, we believe our method offers a general strategy for discovering high-quality aptamers for other ions and small-molecule targets in an efficient and reproducible manner.

  10. Progress in metal ion separation and preconcentration : an overview.

    Energy Technology Data Exchange (ETDEWEB)

    Bond, A. H.

    1998-05-19

    A brief historical perspective covering the most mature chemically-based metal ion separation methods is presented, as is a summary of the recommendations made in the 1987 National Research Council (NRC) report entitled ''Separation and Purification: Critical Needs and Opportunities''. A review of Progress in Metal Ion Separation and Preconcentration shows that advances are occurring in each area of need cited by the NRC. Following an explanation of the objectives and general organization of this book, the contents of each chapter are briefly summarized and some future research opportunities in metal ion separations are presented.

  11. Progress in metal ion separation and preconcentration: an overview

    International Nuclear Information System (INIS)

    Bond, A. H.

    1998-01-01

    A brief historical perspective covering the most mature chemically-based metal ion separation methods is presented, as is a summary of the recommendations made in the 1987 National Research Council (NRC) report entitled ''Separation and Purification: Critical Needs and Opportunities''. A review of Progress in Metal Ion Separation and Preconcentration shows that advances are occurring in each area of need cited by the NRC. Following an explanation of the objectives and general organization of this book, the contents of each chapter are briefly summarized and some future research opportunities in metal ion separations are presented

  12. Effects of complexing compounds on sorption of metal ions to cement

    Energy Technology Data Exchange (ETDEWEB)

    Loevgren, Lars [Umeaa Univ. (Sweden). Inorganic chemistry

    2005-12-15

    This present report is a literature review addressing the effects of complexing ligands on the sorption of radionuclides to solid materials of importance for repositories of radioactive waste. Focus is put on laboratory studies of metal ion adsorption to cement in presence of chelating agents under strongly alkaline conditions. As background information, metal sorption to different mineral and cement phases in ligand free systems is described. Furthermore, surface complexation model (SCM) theories are introduced. According to surface complexation theories these interactions occur at specific binding sites at the particle/water interface. Adsorption of cationic metals is stronger at high pH, and the adsorption of anions occurs preferentially at low pH. The adsorption of ions to mineral surfaces is a result of both chemical bonding and electrostatic attraction between the ions and charged mineral surfaces. By combining uptake data with spectroscopic information the sorption can be explained on a molecular level by structurally sound surface complexation models. Most of the metal sorption studies reviewed are dealing with minerals exhibiting oxygen atoms at their surfaces, mainly oxides of Fe(II,III) and Al(III), and aluminosilicates. Investigations of radionuclides are focused on clay minerals, above all montmorillonite and illite. Which mechanism that is governing the metal ion adsorption to a given mineral is to a large extent depending on the metal adsorbed. For instance, sorption of Ni to montmorillonite can occur by formation of inner-sphere mononuclear surface complexes located at the edges of montmorillonite platelets and by formation of a Ni phyllosilicate phase parallel to montmorillonite layers. Also metal uptake to cement materials can occur by different mechanisms. Cationic metals can both be attached to cement (calcium silicate hydrate, CSH) and hardened cement paste (HCP) by formation of inner-sphere complexes at specific surface sites and by

  13. An Animal Model Using Metallic Ions to Produce Autoimmune Nephritis

    Directory of Open Access Journals (Sweden)

    Roxana Ramírez-Sandoval

    2015-01-01

    Full Text Available Autoimmune nephritis triggered by metallic ions was assessed in a Long-Evans rat model. The parameters evaluated included antinuclear autoantibody production, kidney damage mediated by immune complexes detected by immunofluorescence, and renal function tested by retention of nitrogen waste products and proteinuria. To accomplish our goal, the animals were treated with the following ionic metals: HgCl2, CuSO4, AgNO3, and Pb(NO32. A group without ionic metals was used as the control. The results of the present investigation demonstrated that metallic ions triggered antinuclear antibody production in 60% of animals, some of them with anti-DNA specificity. Furthermore, all animals treated with heavy metals developed toxic glomerulonephritis with immune complex deposition along the mesangium and membranes. These phenomena were accompanied by proteinuria and increased concentrations of urea. Based on these results, we conclude that metallic ions may induce experimental autoimmune nephritis.

  14. Heavy metal ions are potent inhibitors of protein folding.

    Science.gov (United States)

    Sharma, Sandeep K; Goloubinoff, Pierre; Christen, Philipp

    2008-07-25

    Environmental and occupational exposure to heavy metals such as cadmium, mercury and lead results in severe health hazards including prenatal and developmental defects. The deleterious effects of heavy metal ions have hitherto been attributed to their interactions with specific, particularly susceptible native proteins. Here, we report an as yet undescribed mode of heavy metal toxicity. Cd2+, Hg2+ and Pb2+ proved to inhibit very efficiently the spontaneous refolding of chemically denatured proteins by forming high-affinity multidentate complexes with thiol and other functional groups (IC(50) in the nanomolar range). With similar efficacy, the heavy metal ions inhibited the chaperone-assisted refolding of chemically denatured and heat-denatured proteins. Thus, the toxic effects of heavy metal ions may result as well from their interaction with the more readily accessible functional groups of proteins in nascent and other non-native form. The toxic scope of heavy metals seems to be substantially larger than assumed so far.

  15. Structures and metal-binding properties of Helicobacter pylori neutrophil-activating protein with a di-nuclear ferroxidase center.

    Science.gov (United States)

    Yokoyama, Hideshi; Fujii, Satoshi

    2014-06-26

    Helicobacter pylori causes severe diseases, such as chronic gastritis, peptic ulcers, and stomach cancers. H. pylori neutrophil-activating protein (HP-NAP) is an iron storage protein that forms a dodecameric shell, promotes the adhesion of neutrophils to endothelial cells, and induces the production of reactive oxygen radicals. HP-NAP belongs to the DNA-protecting proteins under starved conditions (Dps) family, which has significant structural similarities to the dodecameric ferritin family. The crystal structures of the apo form and metal-ion bound forms, such as iron, zinc, and cadmium, of HP-NAP have been determined. This review focused on the structures and metal-binding properties of HP-NAP. These metal ions bind at the di-nuclear ferroxidase center (FOC) by different coordinating patterns. In comparison with the apo structure, metal loading causes a series of conformational changes in conserved residues among HP-NAP and Dps proteins (Trp26, Asp52, and Glu56) at the FOC. HP-NAP forms a spherical dodecamer with 23 symmetry including two kinds of pores. Metal ions have been identified around one of the pores; therefore, the negatively-charged pore is suitable for the passage of metal ions.

  16. Cucumber Metallothionein-Like 2 (CsMTL2 Exhibits Metal-Binding Properties

    Directory of Open Access Journals (Sweden)

    Yu Pan

    2016-11-01

    Full Text Available We identified a novel member of the metallothionein (MT family, Cucumis sativus metallothionein-like 2 (CsMTL2, by screening a young cucumber fruit complementary DNA (cDNA library. The CsMTL2 encodes a putative 77-amino acid Class II MT protein that contains two cysteine (Cys-rich domains separated by a Cys-free spacer region. We found that CsMTL2 expression was regulated by metal stress and was specifically induced by Cd2+ treatment. We investigated the metal-binding characteristics of CsMTL2 and its possible role in the homeostasis and/or detoxification of metals by heterologous overexpression in Escherichia coli cells. Furthermore, we produced a deletion mutant form of the protein, CsMTL2m, that contained the two Cys-rich clusters but lacked the spacer region, in E. coli. We compared the metal-binding properties of CsMTL2 with those of CsMTL2m, the β domain of human metallothionein-like protein 1 (HsMTXb, and phytochelatin-like (PCL heterologously expressed in E. coli using metal-binding assays. We found that E. coli cells expressing CsMTL2 accumulated the highest levels of Zn2+ and Cd2+ of the four transformed cell types, with levels being significantly higher than those of control cells containing empty vector. E. coli cells expressing CsMTL2 had a higher tolerance for cadmium than for zinc ions. These findings show that CsMTL2 improves metal tolerance when heterologously expressed in E. coli. Future studies should examine whether CsMTL2 improves metal tolerance in planta.

  17. Metal ion removal from aqueous solution using physic seed hull.

    Science.gov (United States)

    Mohammad, Masita; Maitra, Saikat; Ahmad, Naveed; Bustam, Azmi; Sen, T K; Dutta, Binay K

    2010-07-15

    The potential of physic seed hull (PSH), Jantropha curcas L. as an adsorbent for the removal of Cd(2+) and Zn(2+) metal ions from aqueous solution has been investigated. It has been found that the amount of adsorption for both Cd(2+) and Zn(2+) increased with the increase in initial metal ions concentration, contact time, temperature, adsorbent dosage and the solution pH (in acidic range), but decreased with the increase in the particle size of the adsorbent. The adsorption process for both metal ions on PSH consists of three stages-a rapid initial adsorption followed by a period of slower uptake of metal ions and virtually no uptake at the final stage. The kinetics of metal ions adsorption on PSH followed a pseudo-second-order model. The adsorption equilibrium data were fitted in the three adsorption isotherms-Freundlich, Langmuir and Dubinin-Radushkevich isotherms. The data best fit in the Langmuir isotherm indication monolayer chemisorption of the metal ions. The adsorption capacity of PSH for both Zn(2+) and Cd(2+) was found to be comparable with other available adsorbents. About 36-47% of the adsorbed metal could be leached out of the loaded PSH using 0.1M HCl as the eluting medium. 2010 Elsevier B.V. All rights reserved.

  18. Catalytic metal ions and enzymatic processing of DNA and RNA.

    Science.gov (United States)

    Palermo, Giulia; Cavalli, Andrea; Klein, Michael L; Alfonso-Prieto, Mercedes; Dal Peraro, Matteo; De Vivo, Marco

    2015-02-17

    CONSPECTUS: Two-metal-ion-dependent nucleases cleave the phosphodiester bonds of nucleic acids via the two-metal-ion (2M) mechanism. Several high-resolution X-ray structures portraying the two-metal-aided catalytic site, together with mutagenesis and kinetics studies, have demonstrated a functional role of the ions for catalysis in numerous metallonucleases. Overall, the experimental data confirm the general mechanistic hypothesis for 2M-aided phosphoryl transfer originally reported by Steitz and Steitz ( Proc. Natl. Acad. Sci. U.S.A. 1993 , 90 ( 14 ), 6498 - 6502 ). This seminal paper proposed that one metal ion favors the formation of the nucleophile, while the nearby second metal ion facilitates leaving group departure during RNA hydrolysis. Both metals were suggested to stabilize the enzymatic transition state. Nevertheless, static X-ray structures alone cannot exhaustively unravel how the two ions execute their functional role along the enzymatic reaction during processing of DNA or RNA strands when moving from reactants to products, passing through metastable intermediates and high-energy transition states. In this Account, we discuss the role of multiscale molecular simulations in further disclosing mechanistic insights of 2M-aided catalysis for two prototypical enzymatic targets for drug discovery, namely, ribonuclease H (RNase H) and type II topoisomerase (topoII). In both examples, first-principles molecular simulations, integrated with structural data, emphasize a cooperative motion of the bimetal motif during catalysis. The coordinated motion of both ions is crucial for maintaining a flexible metal-centered structural architecture exquisitely tailored to accommodate the DNA or RNA sugar-phosphate backbone during phosphodiester bond cleavage. Furthermore, our analysis of RNase H and the N-terminal domain (PAN) of influenza polymerase shows that classical molecular dynamics simulations coupled with enhanced sampling techniques have contributed to describe

  19. Designer ligands: The search for metal ion selectivity

    Directory of Open Access Journals (Sweden)

    Perry T. Kaye

    2011-03-01

    Full Text Available The paper reviews research conducted at Rhodes University towards the development of metal-selective ligands. The research has focused on the rational design, synthesis and evaluation of novel ligands for use in the formation of copper complexes as biomimetic models of the metalloenzyme, tyrosinase, and for the selective extraction of silver, nickel and platinum group metal ions in the presence of contaminating metal ions. Attention has also been given to the development of efficient, metal-selective molecular imprinted polymers.

  20. Metal ion-mediated agonism and agonist enhancement in melanocortin MC1 and MC4 receptors

    DEFF Research Database (Denmark)

    Holst, Birgitte; Elling, Christian E; Schwartz, Thue W

    2002-01-01

    all MC receptors, are parts of the site. It is concluded that the function of the MC1 and MC4 receptors can be positively modulated by metal ions acting both as partial agonists and as potentiators for other agonists, including the endogenous peptide ligand alpha-MSH at Zn(II) concentrations......An endogenous metal-ion site in the melanocortin MC1 and MC4 receptors was characterized mainly in transiently transfected COS-7 cells. ZnCl(2) alone stimulated signaling through the Gs pathway with a potency of 11 and 13 microm and an efficacy of 50 and 20% of that of alpha...... of the metal ion appeared to be additive, because the maximal cAMP response for alpha-MSH in the presence of Zn(II) was 60% above the maximal response for the peptide alone. The affinity of Zn(II) could be increased through binding of the metal ion in complex with small hydrophobic chelators. The binding...

  1. Ion activity and distribution of heavy metals in acid mine drainage polluted subtropical soils

    International Nuclear Information System (INIS)

    Li Yongtao; Becquer, Thierry; Dai Jun; Quantin, Cecile; Benedetti, Marc F.

    2009-01-01

    The oxidative dissolution of mine wastes gives rise to acidic, metal-enriched mine drainage (AMD) and has typically posed an additional risk to the environment. The poly-metallic mine Dabaoshan in South China is an excellent test site to understand the processes affecting the surrounding polluted agricultural fields. Our objectives were firstly to investigate metal ion activity in soil solution, distribution in solid constituents, and spatial distribution in samples, secondly to determine dominant environment factors controlling metal activity in the long-term AMD-polluted subtropical soils. Soil Column Donnan Membrane Technology (SC-DMT) combined with sequential extraction shows that unusually large proportion of the metal ions are present as free ion in the soil solutions. The narrow range of low pH values prevents any pH effects during the binding onto oxides or organic matter. The differences in speciation of the soil solutions may explain the different soil degradation observed between paddy and non-paddy soils. - First evidence of the real free metal ion concentrations in acid mine drainage context in tropical systems

  2. Modeling metal binding to soils: the role of natural organic matter.

    Science.gov (United States)

    Gustafsson, Jon Petter; Pechová, Pavlina; Berggren, Dan

    2003-06-15

    The use of mechanistically based models to simulate the solution concentrations of heavy metals in soils is complicated by the presence of different sorbents that may bind metals. In this study, the binding of Zn, Pb, Cu, and Cd by 14 different Swedish soil samples was investigated. For 10 of the soils, it was found that the Stockholm Humic Model (SHM) was able to describe the acid-base characteristics, when using the concentrations of "active" humic substances and Al as fitting parameters. Two additional soils could be modeled when ion exchange to clay was also considered, using a component additivity approach. For dissolved Zn, Cd, Ca, and Mg reasonable model fits were produced when the metal-humic complexation parameters were identical for the 12 soils modeled. However, poor fits were obtained for Pb and Cu in Aquept B horizons. In two of the soil suspensions, the Lund A and Romfartuna Bhs, the calculated speciation agreed well with results obtained by using cation-exchange membranes. The results suggest that organic matter is an important sorbent for metals in many surface horizons of soils in temperate and boreal climates, and the necessity of properly accounting for the competition from Al in simulations of dissolved metal concentrations is stressed.

  3. Extraction of complexes of metal ions with pyridine oxyazo compounds

    International Nuclear Information System (INIS)

    Lobanov, F.I.; Nurtaeva, G.K.; Ergozhin, E.E.

    1983-01-01

    Modern state and prospects of the development of investigas tions in the field of extraction of complexes of metal ions (V, In, Cd, Nb, REE, RU, Ta, U, Zr and others) with pyridine oxyazo compoUnds are analyzed. Application of pyridine oxyazo compounds as extraction-photometric reagents is described. Basic methods of oxyazo compounds preparation are considered along with reagent properties and physical-chemical characteristics. Flow diagrams of ion extraction are presented for the above metals. Mechanisms of complexing reactions for metal ions with pyridine oxyazo compounds and stability of forming complexes are considered in detail. Concrete methods of extraction-photometric separation and element determination permitting to find simultaneously several metal ions with similar properties in the case of their joint presence are described

  4. Determination of Heavy Metal Ions in Tobacco and Tobacco Additives

    African Journals Online (AJOL)

    NJD

    aminophenyl)-porphyrin, heavy metal ions. 1. Introduction ..... Application. This method was applied to the determination of Co, Ni, Sn,. Hg, Pb and Cd in the glycerol, tobacco leaf, tobacco sauce and cigarette samples. The samples were prepared ...

  5. Adhesive, abrasive and oxidative wear in ion-implanted metals

    International Nuclear Information System (INIS)

    Dearnaley, G.

    1985-01-01

    Ion implantation is increasingly being used to provide wear resistance in metals and cemented tungsten carbides. Field trials and laboratory tests indicate that the best performance is achieved in mild abrasive wear. This can be understood in terms of the classification of wear modes (adhesive, abrasive, oxidative etc.) introduced by Burwell. Surface hardening and work hardenability are the major properties to be enhanced by ion implantation. The implantation of nitrogen or dual implants of metallic and interstitial species are effective. Recently developed techniques of ion-beam-enhanced deposition of coatings can further improve wear resistance by lessening adhesion and oxidation. In order to support such hard coatings, ion implantation of nitrogen can be used as a preliminary treatment. There is thus emerging a versatile group of related hard vacuum treatments involving intense beams of nitrogen ions for the purpose of tailoring metal surfaces to resist wear. (Auth.)

  6. Metal Ion Selectivity of Kojate Complexes: A Theoretical Study

    Directory of Open Access Journals (Sweden)

    Sarita Singh

    2013-01-01

    Full Text Available Density functional calculations have been performed on four-coordinate kojate complexes of selected divalent metal ions in order to determine the affinity of the metal ions for the kojate ion. The complexation reactions are characterized by high energies, showing that they are highly exothermic. It is found that Ni(II exhibits the highest affinity for the kojate ion, and this is attributed to the largest amount of charge transfer from the ligand to the metal ion. The Ni(II complex has distorted square planar structure. The HOMOs and LUMOs of the complexes are also discussed. All complexes display a strong band at ~1500 cm−1 corresponding to the stretching frequency of the weakened carbonyl bond. Comparison of the complexation energies for the two steps shows that most of the complexation energy is realized in the first step. The energy released in the second step is about one-third that of the first step.

  7. Metal ion separations using reactive membranes

    International Nuclear Information System (INIS)

    Way, J.D.

    1993-01-01

    A membrane is a barrier between two phases. If one component of a mixture moves through the membrane faster than another mixture component, a separation can be accomplished. Membranes are used commercially for many applications including gas separations, water purification, particle filtration, and macromolecule separations (Abelson). There are two points to note concerning this definition. First, a membrane is defined based on its function, not the material used to make the membrane. Secondly, a membrane separation is a rate process. The separation is accomplished by a driving force, not by equilibrium between phases. Liquids that are immiscible with the feed and product streams can also be used as membrane materials. Different solutes will have different solubilities and diffusion coefficients in a liquid. The product of the diffusivity and the solubility is known as the permeability coefficient, which is proportional to the solute flux. Differences in permeability coefficient will produce a separation between solutes at constant driving force. Because the diffusion coefficients in liquids are typically orders of magnitude higher than in polymers, a larger flux can be obtained. Further enhancements can be accomplished by adding a nonvolatile complexation agent to the liquid membrane. One can then have either coupled or facilitated transport of metal ions through a liquid membrane. The author describes two implementations of this concept, one involving a liquid membrane supported on a microporous membrane, and the other an emulsion liquid membrane, where separation occurs to internal receiving phases. Applications and costing studies for this technology are reviewed, and a brief summary of some of the problems with liquid membranes is presented

  8. A versatile MOF-based trap for heavy metal ion capture and dispersion

    OpenAIRE

    Peng, Yaguang; Huang, Hongliang; Zhang, Yuxi; Kang, Chufan; Chen, Shuangming; Song, Li; Liu, Dahuan; Zhong, Chongli

    2018-01-01

    Current technologies for removing heavy metal ions are typically metal ion specific. Herein we report the development of a broad-spectrum heavy metal ion trap by incorporation of ethylenediaminetetraacetic acid into a robust metal-organic framework. The capture experiments for a total of 22 heavy metal ions, covering hard, soft, and borderline Lewis metal ions, show that the trap is very effective, with removal efficiencies of >99% for single-component adsorption, multi-component adsorption, ...

  9. Liquid metal field-emission ion sources and their applications

    International Nuclear Information System (INIS)

    Prewett, P.D.; Jefferies, D.K.

    1980-01-01

    The study of ion emission from liquid metal surfaces under the action of high electric fields has led to the development of ion sources of exceptionally high brightness. The design and operating characteristics of commercially manufactured sources of gallium and gold ions are described. Preliminary focusing and scanning experiments have produced spots estimated to be approximately 0.5 μm diameter at currents approximately 0.2 nA using an electrostatic ion optical system. A focused Ga + beam has been used as an ion microprobe for imaging and for elemental mapping of surfaces by SIMS. (author)

  10. The rice transcription factor IDEF1 directly binds to iron and other divalent metals for sensing cellular iron status.

    Science.gov (United States)

    Kobayashi, Takanori; Itai, Reiko Nakanishi; Aung, May Sann; Senoura, Takeshi; Nakanishi, Hiromi; Nishizawa, Naoko K

    2012-01-01

    Iron is essential for most living organisms and its availability often determines survival and proliferation. The Oryza sativa (rice) transcription factor IDEF1 plays a crucial role in regulating iron deficiency-induced genes involved in iron homeostasis. In the present report, we found characteristic histidine-asparagine repeat and proline-rich regions in IDEF1 and its homolog in Hordeum vulgare (barley), HvIDEF1. An immobilized metal ion affinity chromatography assay revealed that IDEF1 and HvIDEF1 bind to various divalent metals, including Fe(2+) and Ni(2+) . Recombinant IDEF1 protein expressed in Escherichia coli contained mainly Fe and Zn. This metal-binding activity of IDEF1 was almost abolished by deletion of the histidine-asparagine and proline-rich regions, but DNA-binding and trans-activation functions were not impaired by the deletion. Transgenic rice plants constitutively overexpressing IDEF1 without these metal-binding domains failed to cause pleiotropic effects conferred by overexpression of full-length IDEF1, including a low germination rate, impaired seedling growth, tolerance to iron deficiency in hydroponic culture, and enhanced expression of various iron deficiency-inducible genes. Impairment of the transcriptional regulation of IDEF1 by deletion of the metal-binding domains occurred primarily at an early stage of iron deficiency. These results suggest that the histidine-asparagine and proline-rich regions in rice IDEF1 directly bind to divalent metals and sense the cellular metal ion balance caused by changes in iron availability. © 2011 The Authors. The Plant Journal © 2011 Blackwell Publishing Ltd.

  11. Architectural design criteria for f-block metal ion sequestering agents. 1998 annual progress report

    International Nuclear Information System (INIS)

    Dixon, D.A.; Hay, B.P.; Paine, R.T.; Raymond, K.N.; Rogers, R.D.; Roundhill, D.M.

    1998-01-01

    'The objective of this project is to provide a means to optimize ligand architecture for f-block metal recognition. The authors strategy builds on an innovative and successful molecular modeling approach in developing polyether ligand design criteria for the alkali and alkaline earth cations. The hypothesis underlying this proposal is that differences in metal ion binding with multidentate ligands bearing the same number and type of donor groups are primarily attributable to intramolecular steric factors. They propose quantifying these steric factors through the application of molecular mechanics models. The research involves close integration of theoretical and experimental chemistry. The experimental work entails synthesizing novel ligands and experimentally determining structures and binding constants for metal ion complexation by series of ligands in which architecture is systematically varied. The theoretical work entails using electronic structure calculations to parameterize a molecular mechanics force field for a range of metal ions and ligand types. The resulting molecular mechanics force field will be used to predict low energy structures for unidentate, bidentate, and multidentate ligands and their metal complexes through conformational searches. Results will be analyzed to assess the relative importance of several steric factors including optimal M-L length, optimal geometry at the metal center, optimal geometry at the donor atoms (complementarity), and conformation prior to binding (preorganization). An accurate set of criteria for the design of ligand architecture will be obtained from these results. These criteria will enable researchers to target ligand structures for synthesis and thereby dramatically reduce the time and cost associated with metal-specific ligand development.'

  12. [Detection of metal ions in hair after metal-metal hip arthroplasty].

    Science.gov (United States)

    Hernandez-Vaquero, D; Rodríguez de la Flor, M; Fernandez-Carreira, J M; Sariego-Muñiz, C

    2014-01-01

    There is an increase in the levels of metals in the serum and urine after the implantation of some models of metal-metal hip prosthesis. It has recently been demonstrated that there is an association between these levels and the levels found in hair. The aim of this study is to determine the presence of metals in hair, and to find out whether these change over time or with the removal of the implant. The levels of chromium, cobalt and molybdenum were determined in the hair of 45 patients at 3, 4, 5, and 6 years after a hip surface replacement. The mean age was 57.5 years, and two were female. Further surgery was required to remove the replacement and implant a new model with metal-polyethylene friction in 11 patients, 5 of them due to metallosis and a periarticular cyst. The mean levels of metals in hair were chromium 163.27 ppm, cobalt 61.98 ppm, and molybdenum 31.36 ppm, much higher than the levels found in the general population. A decrease in the levels of chromium (43.8%), molybdenum (51.1%), and cobalt (91.1%) was observed at one year in the patients who had further surgery to remove the prosthesis. High concentrations of metals in the hair are observed in hip replacements with metal-metal friction, which decrease when that implant is removed. The determination of metal ions in hair could be a good marker of the metal poisoning that occurs in these arthroplasty models. Copyright © 2014 SECOT. Published by Elsevier Espana. All rights reserved.

  13. Laccase Immobilization by Chelated Metal Ion Coordination Chemistry

    Directory of Open Access Journals (Sweden)

    Qingqing Wang

    2014-09-01

    Full Text Available In this work, amidoxime polyacrylonitrile (AOPAN nanofibrous membrane was prepared by a reaction between PAN nanofibers and hydroxylamine hydrochloride. The AOPAN nanofibrous membranes were used for four metal ions (Fe3+, Cu2+, Ni2+, Cd2+ chelation under different conditions. Further, the competition of different metal ions coordinating with AOPAN nanofibrous membrane was also studied. The AOPAN chelated with individual metal ion (Fe3+, Cu2+, Ni2+, Cd2+ and also the four mixed metal ions were further used for laccase (Lac immobilization. Compared with free laccase, the immobilized laccase showed better resistance to pH and temperature changes as well as improved storage stability. Among the four individual metal ion chelated membranes, the stability of the immobilized enzymes generally followed the order as Fe–AOPAN–Lac > Cu–AOPAN–Lac > Ni–AOPAN–Lac > Cd–AOPAN–Lac. In addition, the immobilized enzyme on the carrier of AOPAN chelated with four mixed metal ions showed the best properties.

  14. Enhancement of metal bioleaching from contaminated sediment using silver ion.

    Science.gov (United States)

    Chen, Shen-Yi; Lin, Jih-Gaw

    2009-01-30

    A silver-catalyzed bioleaching process was used to remove heavy metals from contaminated sediment in this study. The effects of silver concentration added on the performance of bioleaching process were investigated. High pH reduction rate was observed in the bioleaching process with silver ion. The silver ion added in the bioleaching process was incorporated into the lattice of the initial sulfide through a cationic interchange reaction. This resulted in the short lag phase and high metal solubilization in the bioleaching process. The maximum pH reduction rate and the ideal metal solubilization were obtained in the presence of 30 mg/L of silver ion. When the added silver ion was greater than 30 mg/L, the rates of pH reduction and metal solubilization gradually decreased. The solubilization efficiencies of heavy metals (Cu, Zn, Mn, Ni and Cr) were relatively high in the silver-enhanced bioleaching process, except Pb. No apparent effect of silver ion on the growth of sulfur-oxidizing bacteria was found in the bioleaching. These results indicate that the kinetics of metal solubilization can be enhanced by the addition of silver ion.

  15. Dissecting electrostatic screening, specific ion binding, and ligand binding in an energetic model for glycine riboswitch folding

    Energy Technology Data Exchange (ETDEWEB)

    Lipfert, Jan; Sim, Adelene Y.L.; Herschlag, Daniel; Doniach, Sebastian (Stanford)

    2010-09-17

    Riboswitches are gene-regulating RNAs that are usually found in the 5{prime}-untranslated regions of messenger RNA. As the sugar-phosphate backbone of RNA is highly negatively charged, the folding and ligand-binding interactions of riboswitches are strongly dependent on the presence of cations. Using small angle X-ray scattering (SAXS) and hydroxyl radical footprinting, we examined the cation dependence of the different folding stages of the glycine-binding riboswitch from Vibrio cholerae. We found that the partial folding of the tandem aptamer of this riboswitch in the absence of glycine is supported by all tested mono- and divalent ions, suggesting that this transition is mediated by nonspecific electrostatic screening. Poisson-Boltzmann calculations using SAXS-derived low-resolution structural models allowed us to perform an energetic dissection of this process. The results showed that a model with a constant favorable contribution to folding that is opposed by an unfavorable electrostatic term that varies with ion concentration and valency provides a reasonable quantitative description of the observed folding behavior. Glycine binding, on the other hand, requires specific divalent ions binding based on the observation that Mg{sup 2+}, Ca{sup 2+}, and Mn{sup 2+} facilitated glycine binding, whereas other divalent cations did not. The results provide a case study of how ion-dependent electrostatic relaxation, specific ion binding, and ligand binding can be coupled to shape the energetic landscape of a riboswitch and can begin to be quantitatively dissected.

  16. Adsorption of strontium (II) metal ions using phosphonate ...

    Indian Academy of Sciences (India)

    analysis and solubility. The synthesized polymer was used for sequestering strontium metal from the aqueous solu- tion. The metal binding was examined by the energy dispersive spectroscopy and scanning electron microscopy for the adsorbed Sr(II). Batch adsorption studies were performed by varying three parameters, ...

  17. Adsorption of strontium (II) metal ions using phosphonate ...

    Indian Academy of Sciences (India)

    The synthesized polymer was used for sequestering strontium metal from the aqueous solu- tion. The metal binding was examined by the energy dispersive spectroscopy and scanning electron microscopy for the adsorbed Sr(II). Batch adsorption studies were performed by varying three parameters, namely initial pH, adsor-.

  18. Chemical Speciation of Some metal ions in Groundwaters of Yola ...

    African Journals Online (AJOL)

    Chemical speciation of some metal ions in groundwaters of Yola area using geochemical model were carried out to determine the water quality of the area using the PHREEQC speciation model. The study findings based on model calculations indicated that free Na+, Ca2+, Mg2+ and K+ ions are present and the ...

  19. Electrical properties of polymer modified by metal ion implantation

    International Nuclear Information System (INIS)

    Wu Yuguang; Zhang Tonghe; Zhang Huixing; Zhang Xiaoji; Deng Zhiwei; Zhou Gu

    2000-01-01

    Polyethylene terephthalate (PET) has been modified by Ag, Cr, Cu and Si ion implantation with a dose range from 1x10 16 to 2x10 17 ions cm -2 using a metal vapor vacuum arc (MEVVA) source. The electrical properties of PET have been changed after metal ion implantation. The resistivity of implanted PET decreased obviously with an increase of ion dose. When metal ion dose of 2x10 17 cm -2 was selected, the resistivity of PET could be less than 10 Ω cm, but when Si ions are implanted, the resistivity of PET would be up to several hundred Ω cm. The results show that the conductive behavior of a metal ion implanted sample is obviously different from Si implantation one. The changes of the structure and composition have been observed with transmission electron microscope (TEM) and X-ray diffraction (XRD). The surface structure is varying after ion implantation and it is believed that the change would cause the improvement of the conductive properties. The mechanism of electrical conduction will be discussed

  20. Effect of ion beam irradiation on metal particle doped polymer ...

    Indian Academy of Sciences (India)

    that the surface roughness increases after ion beam irradiation. Keywords. Composite materials; ion beam irradiation; dielectric properties; X-ray diffraction. 1. Introduction. Various metal fillers were incorporated in polymers to pro- duce novel functionalized composites, which have found extensive applications, such as ...

  1. The kinetics and thermodynamics of adsorption of heavy metal ions ...

    African Journals Online (AJOL)

    Titanium-Pillared and Un-Pillared bentonite clays were studied in order to evaluate the thermodynamics and kinetics of heavy metal ion removal from aqueous solutions. The results showed that the maximum sorption of Cu, Cd, Hg and Pb ions occurred within 30 minutes. A pseudo-second order kinetic model was used to ...

  2. Sorption of toxic metal ions in aqueous environment using ...

    African Journals Online (AJOL)

    2012-03-08

    Mar 8, 2012 ... efficient sorbents for divalent heavy metal ions in aqueous environments as their efficiencies exceeded those of chitosan microspheres, ion-imprinted composites, ..... field strength of 1.67 kV/cm. Under these optimised condi- ..... extraction on modified multiwalled carbon nanotubes. Cent. Eur. J. Chem.

  3. Quantum ion-acoustic wave oscillations in metallic nanowires

    Energy Technology Data Exchange (ETDEWEB)

    Moradi, Afshin, E-mail: a.moradi@kut.ac.ir [Department of Engineering Physics, Kermanshah University of Technology, Kermanshah, Iran and Department of Nano Sciences, Institute for Studies in Theoretical Physics and Mathematics (IPM), Tehran (Iran, Islamic Republic of)

    2015-05-15

    The low-frequency electrostatic waves in metallic nanowires are studied using the quantum hydrodynamic model, in which the electron and ion components of the system are regarded as a two-species quantum plasma system. The Poisson equation as well as appropriate quantum boundary conditions give the analytical expressions of dispersion relations of the surface and bulk quantum ion-acoustic wave oscillations.

  4. Selective metal binding to Cys-78 within endonuclease V causes an inhibition of catalytic activities without altering nontarget and target DNA binding

    International Nuclear Information System (INIS)

    Prince, M.A.; Friedman, B.; Gruskin, E.A.; Schrock, R.D. III; Lloyd, R.S.

    1991-01-01

    T4 endonuclease V is a pyrimidine dimer-specific DNA repair enzyme which has been previously shown not to require metal ions for either of its two catalytic activities or its DNA binding function. However, we have investigated whether the single cysteine within the enzyme was able to bind metal salts and influence the various activities of this repair enzyme. A series of metals (Hg2+, Ag+, Cu+) were shown to inactivate both endonuclease Vs pyrimidine dimer-specific DNA glycosylase activity and the subsequent apurinic nicking activity. The binding of metal to endonuclease V did not interfere with nontarget DNA scanning or pyrimidine dimer-specific binding. The Cys-78 codon within the endonuclease V gene was changed by oligonucleotide site-directed mutagenesis to Thr-78 and Ser-78 in order to determine whether the native cysteine was directly involved in the enzyme's DNA catalytic activities and whether the cysteine was primarily responsible for the metal binding. The mutant enzymes were able to confer enhanced ultraviolet light (UV) resistance to DNA repair-deficient Escherichia coli at levels equal to that conferred by the wild type enzyme. The C78T mutant enzyme was purified to homogeneity and shown to be catalytically active on pyrimidine dimer-containing DNA. The catalytic activities of the C78T mutant enzyme were demonstrated to be unaffected by the addition of Hg2+ or Ag+ at concentrations 1000-fold greater than that required to inhibit the wild type enzyme. These data suggest that the cysteine is not required for enzyme activity but that the binding of certain metals to that amino acid block DNA incision by either preventing a conformational change in the enzyme after it has bound to a pyrimidine dimer or sterically interfering with the active site residue's accessibility to the pyrimidine dimer

  5. Synthesis, structure, DNA/BSA binding and antibacterial studies of NNO tridentate Schiff base metal complexes

    Science.gov (United States)

    Sakthi, Marimuthu; Ramu, Andy

    2017-12-01

    A new salicylaldehyde derived 2,4-diiodo-6-((2-phenylaminoethylimino)methyl)phenol Schiff base(L) and its transition metal complexes of the type MLCl where, M = Cu(II), Ni(II), Co(II), Mn(II) and Zn(II) have been synthesized. The coordination mode of Schiff base holding NNO donor atoms with metal ions was well investigated by elemental analysis, ESI-mass as well as IR, UV-vis, CV and NMR spectral studies. The binding efficiency and mode of these complexes with biological macromolecules viz., herring sperm DNA (HS- DNA) and bovine serum albumin (BSA) have been explored through various spectroscopic techniques. The characteristic changes in absorption, emission and, circular dichroism spectra of the complexes with DNA indicate the noticeable interaction between them. From the all spectral information complexes could interact with DNA via non-intercalation mode of binding. The hyperchromisim in absorption band and hypochromisim in emission intensity of BSA with different complex concentrations shown significant information, and the binding affinity value has been predicted from Stern-Volmer plots. Further, all the complexes could cleave the circular plasmid pUC19 DNA efficiently by using an activator H2O2. The ligand and all metal(II) complexes showed good antibacterial activities. The molecular docking studies of the complexes with DNA were performed in order to make a comparison and conclusion with spectral technic results.

  6. Two-photon-induced reduction of metal ions for fabricating three-dimensional electrically conductive metallic microstructure

    Science.gov (United States)

    Tanaka, Takuo; Ishikawa, Atsushi; Kawata, Satoshi

    2006-02-01

    We developed techniques for fabricating three-dimensional metallic microstructures using two-photon-induced metal-ion reduction. In this process, ions in a metal-ion aqueous solution were directly reduced by a tightly focused femtosecond pulsed laser to fabricate arbitrary three-dimensional structures. A self-standing metallic microstructure with high electrical conductivity was demonstrated.

  7. Selective removal of heavy metal ions by disulfide linked polymer networks

    DEFF Research Database (Denmark)

    Ko, Dongah; Sung Lee, Joo; Patel, Hasmukh A.

    2017-01-01

    Heavy metal contaminated surface water is one of the oldest pollution problems, which is critical to ecosystems and human health. We devised disulfide linked polymer networks and employed as a sorbent for removing heavy metal ions from contaminated water. Although the polymer network material has...... a moderate surface area, it demonstrated cadmium removal efficiency equivalent to highly porous activated carbon while it showed 16 times faster sorption kinetics compared to activated carbon, owing to the high affinity of cadmium towards disulfide and thiol functionality in the polymer network. The metal...... sorption mechanism on polymer network was studied by sorption kinetics, effect of pH, and metal complexation. We observed that the metal ions―copper, cadmium, and zinc showed high binding affinity in polymer network, even in the presence of competing cations like calcium in water....

  8. Removal of the metal ions from aqueous solutions by nanoscaled low molecular pectin isolated from seagrass Phyllospadix iwatensis

    International Nuclear Information System (INIS)

    Khozhaenko, Elena; Kovalev, Valeri; Podkorytova, Elena; Khotimchenko, Maksim

    2016-01-01

    Pectins from sea grasses are considered as promising substances with pronounced metal-binding activity. Due to the high molecular weight and heterogeneous structure, the use of pectins for removal of metal ions is difficult. Technology of directed pectin degradation was developed and homogenous degraded nanoscaled pectin polymers were synthesized. Experimental samples of degraded pectin isolated from Phyllospadix iwatensis were tested for their metal binding activity in comparison with native pectin from this seagrass and commercial citrus pectin. The metal uptake of all pectin compounds was highest within the pH range from 4.0 to 6.0. The Langmuir, Freundlich and BET sorption models were applied to describe the isotherms and constants. Results showed that depolymerized pectin exerts highest lead and cadmium binding activity with pronounced affinity. All pectin compounds were suggested to be favorable sorbents. Therefore, it can be concluded that degraded pectin is a prospective material for creation of metal-removing water treatment systems. - Highlights: • Low molecular nanoscaled pectin was obtained using original hydrolysis method • Metal binding activity of pectin compounds was studied in a batch sorption system • Pectins exert highest metal binding activity at pH 6.0 • Metal binding isotherms of all pectins are best described by the Langmuir equation • Low molecular pectin from seagrasses is more effective than high-molecular pectins

  9. Removal of the metal ions from aqueous solutions by nanoscaled low molecular pectin isolated from seagrass Phyllospadix iwatensis

    Energy Technology Data Exchange (ETDEWEB)

    Khozhaenko, Elena [Far Eastern Federal University, School of Biomedicine, 8, Sukhanova str., Vladivostok 690091 (Russian Federation); A.V. Zhirmunsky Institute of Marine Biology Far Eastern Branch of Russian Academy of Sciences, 17, Palchevskgo str., Vladivostok 690059 (Russian Federation); Kovalev, Valeri; Podkorytova, Elena [A.V. Zhirmunsky Institute of Marine Biology Far Eastern Branch of Russian Academy of Sciences, 17, Palchevskgo str., Vladivostok 690059 (Russian Federation); Khotimchenko, Maksim, E-mail: maxkhot@yandex.ru [Far Eastern Federal University, School of Biomedicine, 8, Sukhanova str., Vladivostok 690091 (Russian Federation); A.V. Zhirmunsky Institute of Marine Biology Far Eastern Branch of Russian Academy of Sciences, 17, Palchevskgo str., Vladivostok 690059 (Russian Federation)

    2016-09-15

    Pectins from sea grasses are considered as promising substances with pronounced metal-binding activity. Due to the high molecular weight and heterogeneous structure, the use of pectins for removal of metal ions is difficult. Technology of directed pectin degradation was developed and homogenous degraded nanoscaled pectin polymers were synthesized. Experimental samples of degraded pectin isolated from Phyllospadix iwatensis were tested for their metal binding activity in comparison with native pectin from this seagrass and commercial citrus pectin. The metal uptake of all pectin compounds was highest within the pH range from 4.0 to 6.0. The Langmuir, Freundlich and BET sorption models were applied to describe the isotherms and constants. Results showed that depolymerized pectin exerts highest lead and cadmium binding activity with pronounced affinity. All pectin compounds were suggested to be favorable sorbents. Therefore, it can be concluded that degraded pectin is a prospective material for creation of metal-removing water treatment systems. - Highlights: • Low molecular nanoscaled pectin was obtained using original hydrolysis method • Metal binding activity of pectin compounds was studied in a batch sorption system • Pectins exert highest metal binding activity at pH 6.0 • Metal binding isotherms of all pectins are best described by the Langmuir equation • Low molecular pectin from seagrasses is more effective than high-molecular pectins.

  10. Toxic metals (Ni2+, Pb2+, Hg2+) binding affinity of dissolved organic matter (DOM) derived from different ages municipal landfill leachate

    Science.gov (United States)

    Rikta, S. Y.; Tareq, Shafi M.; Uddin, M. Khabir

    2018-03-01

    Solid waste production is rapidly increasing in Bangladesh and landfill leachate is the consequence of the decomposition of this waste. These leachates contain heavy metals and significant amount of dissolved organic matter (DOM). DOM is known to have considerable role in heavy metals speciation. Hence, it is important to characterize DOM/leachate and evaluate toxic metals binding affinity of DOM. The objectives of this study were to characterize the DOM in landfill leachate through physico-chemical and optical analyses and to investigate the toxic metals (Ni2+, Pb2+ and Hg2+) binding affinity of three different ages (fresh sample L-1, young sample L-2 and mature sample L-3) DOM samples. Results suggested that leachate is a potential pollutant which contained very high organic pollutant load. Conditional stability constant (Log K) and percentages of fluorophores that correspond to metal binding (% f) values indicated that young DOM sample (L-2) had the highest binding affinity to all the three metals ions. In general, DOM samples showed the following order affinity to the metal ions; Ni2+ binding affinity: L-2 > L-3 > L-1, Pb2+ binding affinity: L-2 > L-3 > L-1 and Hg2+ binding affinity: L-2 > L-1 > L-3.

  11. [Metal ions: important co-players in aseptic loosening].

    Science.gov (United States)

    Cadosch, D; Schlett, C L; Gautschi, O P; Frei, H C; Filgueira, L

    2010-08-01

    The aims of this review were to discuss the different mechanisms of biocorrosion of orthopaedic metal implants in the human body, as well as the effects of the released metal ions on bone metabolism and the immune system in regard to their involvement in the pathophysiological mechanisms of aseptic loosening and metal hypersensitivity. Implant failure due to aseptic loosening is thought to occur in about 10-15% of cases. A review of the literature (using PubMed with the search terms: biocorrosion, metal ions and bone metabolism) was performed. Additionally, we discuss our research results in the field of aseptic loosening. Despite a great effort in developing new implants, metal devices used in orthopaedic and trauma surgery remain prone to biocorrosion by several mechanisms including the direct corrosion by osteoclasts, leading to the production of significant amounts of wear particles and metal ions. In addition to the well documented increased osteolytic activity caused by large (in the nanometer range) wear particles, increasing evidence strongly suggests that the released metal ions contribute to the pathophysiological mechanism of aseptic loosening. Metal ions stimulate both the immune system and bone metabolism through a series of direct and indirect pathways leading to an increased osteolytic activity at the bone-implant interface. To date, revision surgery remains the only option for the treatment of a failed orthopaedic implant caused by aseptic loosening. A better understanding of the complex pathophysiological mechanisms (including the effects caused by the released metal ions) of aseptic loosening may have a significant potential in developing novel implants and therapies in order to reduce the incidence of this complication. Georg Thieme Verlag KG Stuttgart, New York.

  12. Algal polysaccharides on lipid Langmuir–Blodgett films and molecular effects upon metal ion contact

    Energy Technology Data Exchange (ETDEWEB)

    Kalinouski de Brito, Audrey; Caseli, Luciano, E-mail: lcaseli@unifesp.br; Nordi, Cristina S.F.

    2013-05-01

    The capability of extracellular polysaccharides released from microorganisms to bind to metal ions is a potential molecular biotechnological tool to produce biosorbents as an alternative for the removal of heavy metals from aquatic environments. In this paper, we exploit the ability of polysaccharides from extracellular polymeric substances produced by phytoplankton adsorbed on lipid monolayers as Langmuir–Blodgett films to interact with silver ions in aqueous environments. The properties of the biomacromolecules after the interaction were investigated with polarisation modulation infrared reflection-absorption spectroscopy and atomic force microscopy. The vibrational spectroscopy technique applied to the Langmuir–Blodgett films before and after contact with silver ions indicated significant changes for the bands related to the chemical groups present in polypeptides and polysaccharides. These changes point to the influence of the metal interaction on the molecular organisation and on the structure of the Langmuir–Blodgett film. Therefore, the behaviour of these biomacromolecules adsorbed at bioinspired interfaces is better understood in terms of properties at the molecular level. This understanding leads to a model in which metal incorporation affects the molecular structure of the ultrathin film. - Highlights: ► Extracellular material released from algae was adsorbed at a lipid monolayer. ► Monolayer changes its rheological properties with material incorporation. ► Changes in proteins and polysaccharides are identified with PM-IRRAS. ► Langmuir–Blodgett films of this composite are sensitive to metal ions in water.

  13. Theory Meets Experiment: Metal Ion Effects in HCV Genomic RNA Kissing Complex Formation

    Directory of Open Access Journals (Sweden)

    Li-Zhen Sun

    2017-12-01

    Full Text Available The long-range base pairing between the 5BSL3. 2 and 3′X domains in hepatitis C virus (HCV genomic RNA is essential for viral replication. Experimental evidence points to the critical role of metal ions, especially Mg2+ ions, in the formation of the 5BSL3.2:3′X kissing complex. Furthermore, NMR studies suggested an important ion-dependent conformational switch in the kissing process. However, for a long time, mechanistic understanding of the ion effects for the process has been unclear. Recently, computational modeling based on the Vfold RNA folding model and the partial charge-based tightly bound ion (PCTBI model, in combination with the NMR data, revealed novel physical insights into the role of metal ions in the 5BSL3.2-3′X system. The use of the PCTBI model, which accounts for the ion correlation and fluctuation, gives reliable predictions for the ion-dependent electrostatic free energy landscape and ion-induced population shift of the 5BSL3.2:3′X kissing complex. Furthermore, the predicted ion binding sites offer insights about how ion-RNA interactions shift the conformational equilibrium. The integrated theory-experiment study shows that Mg2+ ions may be essential for HCV viral replication. Moreover, the observed Mg2+-dependent conformational equilibrium may be an adaptive property of the HCV genomic RNA such that the equilibrium is optimized to the intracellular Mg2+ concentration in liver cells for efficient viral replication.

  14. Sensing of heavy metal ions by intrinsic TMV coat protein fluorescence.

    Science.gov (United States)

    Bayram, Serene S; Green, Philippe; Blum, Amy Szuchmacher

    2018-04-15

    We propose the use of a cysteine mutant of TMV coat protein as a signal transducer for the selective sensing and quantification of the heavy metal ions, Cd 2+ , Pb 2+ , Zn 2+ and Ni 2+ based on intrinsic tryptophan quenching. TMV coat protein is inexpensive, can be mass-produced since it is expressed and extracted from E-coli. It also displays several different functional groups, enabling a wide repertoire of bioconjugation chemistries; thus it can be easily integrated into functional devices. In addition, TMV-ion interactions have been widely reported and utilized for metallization to generate organic-inorganic hybrid composite novel materials. Building on these previous observations, we herein determine, for the first time, the TMV-ion binding constants assuming the static fluorescence quenching model. We also show that by comparing TMV-ion interactions between native and denatured coat protein, we can distinguish between chemically similar heavy metal ions such as cadmium and zinc ions. Copyright © 2018 Elsevier B.V. All rights reserved.

  15. DETERMINATION OF METAL IONS RELEASED BY STAINLESS ...

    African Journals Online (AJOL)

    The amounts of cobalt, iron, manganese, nickel and chromium ions released from new and reused stainless steel arch bar used for maxillomandibular fixation was determined in Hank's solutions of different hydrogen and chloride ions concentrations, whole blood serum and phosphate buffered saline (PBS) in vitro, over a ...

  16. A novel metal ion source for preparing hard coatings

    International Nuclear Information System (INIS)

    Feng, Y.C.; Wong, S.P.

    1999-01-01

    A novel metal ion source, Electron Beam Evaporation Metal Ion Source, has been developed for material modifications. This ion source is based on the electron beam evaporation technology. It can provide gaseous, solid or gaseous and solid mixed intense ion beams for preparing a variety of thin films. In this ion source, a focusing electron beam is used to bombard and vaporize the metal or other solid element within same chamber where the metal or solid atoms are ionized and plasma medium from which ions are extracted is formed by arc discharge. A small aperture diameter extraction system is used for extracting the ion beam from this source. Ion beams of a series of elements, which include C, W, Ta, Mo, Cr, Ti, B, Cu, Ni, Al, Ar, N, C+N, Ti+N, Cr+N, etc., have been extracted. The source has a 3.6 cm extraction diameter. The beam energy ranges from 0.3 to 4 keV for single charge state ions, and the maximum beam current extractable is over 90 mA. The source has been used for preparing hard coatings. The films of carbon nitride and titanium nitride have been synthesized by direct deposition with C+N and Ti+N mixed ion beams. The results have shown to exhibit very high hardness value for carbon nitride films. The microhardness is up to HK 5800 kgf/mm 2 . In comparison with other methods, it is also to exhibit higher hardness value for titanium nitride coating. The highest hardness value obtained for titanium nitride is about 3000 kgf/mm 2 . The AES profile shows that there is a good intermixture between coating and substrate for both films. The principle, structure and performance of this ion source will be described. The preliminary results for forming hard coatings are also presented in this article

  17. Metal ion-assisted self-assembly of complexes for controlled and sustained release of minocycline for biomedical applications

    International Nuclear Information System (INIS)

    Zhang, Zhiling; Wang, Zhicheng; Nong, Jia; Nix, Camilla A; Zhong, Yinghui; Ji, Hai-Feng

    2015-01-01

    This study reports the development of novel drug delivery complexes self-assembled by divalent metal ion-assisted coacervation for controlled and sustained release of a hydrophilic small drug molecule minocycline hydrochloride (MH). MH is a multifaceted agent that has demonstrated therapeutic effects in infection, inflammation, tumor, as well as cardiovascular, renal, and neurological disorders due to its anti-microbial, anti-inflammatory, and cytoprotective properties. However, the inability to translate the high doses used in experimental animals to tolerable doses in human patients limits its clinical application. Localized delivery can potentially expose the diseased tissue to high concentrations of MH that systemic delivery cannot achieve, while minimizing the side effects from systemic exposure. The strong metal ion binding-assisted interaction enabled high drug entrapment and loading efficiency, and stable long term release for more than 71 d. Released MH demonstrated potent anti-biofilm, anti-inflammatory, and neuroprotective activities. Furthermore, MH release from the complexes is pH-sensitive as the chelation between minocycline and metal ions decreases with pH, allowing ‘smart’ drug release in response to the severity of pathology-induced tissue acidosis. This novel metal ion binding-mediated drug delivery mechanism can potentially be applied to other drugs that have high binding affinity for metal ions and may lead to the development of new delivery systems for a variety of drugs. (paper)

  18. Synthesis, Characterization and Metal Ion Detection of Novel Fluoroionophores Based on Heterocyclic Substituted Alanines

    Science.gov (United States)

    Costa, Susana P. G.; Oliveira, Elisabete; Lodeiro, Carlos; Raposo, M. Manuela M.

    2007-01-01

    The synthesis of new fluorescent probes containing the thiophene and benzoxazole moieties combined with an alanine residue is described. The resulting highly fluorescent heterocyclic alanine derivatives respond via a quenching effect, with paramagnetic Cu(II) and Ni(II) metal ions and with diamagnetic Hg(II), as shown by the absorption and steady-state fluorescence spectroscopy studies. The formation of mononuclear or dinuclear metal complexes was postulated based on the presence of the free carboxylic acid as binding site and also with the interaction with the donor atoms in the chromophore. Interaction with other important biological metal ions such as Zn(II), Ca(II) and Na(I) was also explored. PMID:28903216

  19. Heavy metal ion adsorption onto polypyrrole-impregnated porous carbon.

    Science.gov (United States)

    Choi, Moonjung; Jang, Jyongsik

    2008-09-01

    Polypyrrole-impregnated porous carbon was readily synthesized using vapor infiltration polymerization of pyrrole monomers. The results show that the functionalized polymer layer was successfully coated onto the pore surface of carbon without collapse of mesoporous structure. The modified porous carbon exhibited an improved complexation affinity for heavy metal ions such as mercury, lead, and silver ions due to the amine group of polypyrrole. The introduced polypyrrole layer could provide the surface modification to be applied for heavy metal ion adsorbents. Especially, polymer-impregnated porous carbon has an enhanced heavy metal ion uptake, which is 20 times higher than that of adsorbents with amine functional groups. Furthermore, the relationship between the coated polymer amount and surface area was also investigated in regard to adsorption capacity.

  20. Ion binding by humic and fulvic acids: A computational procedure based on functional site heterogeneity and the physical chemistry of polyelectrolyte solutions

    International Nuclear Information System (INIS)

    Marinsky, J.A.; Reddy, M.M.; Ephraim, J.; Mathuthu, A.

    1988-04-01

    Ion binding equilibria for humic and fulvic acids are examined from the point of view of functional site heterogeneity and the physical chemistry of polyelectrolyte solutions. A detailed explanation of the potentiometric properties of synthetic polyelectrolytes and ion-exchange gels is presented first to provide the basis for a parallel consideration of the potentiometric properties exhibited by humic and fulvic acids. The treatment is then extended to account for functional site heterogeneity. Sample results are presented for analysis of the ion-binding reactions of a standard soil fulvic acid (Armadale Horizons Bh) with this approach to test its capability for anticipation of metal ion removal from solution. The ultimate refined model is shown to be adaptable, after appropriate consideration of the heterogeneity and polyelectrolyte factors, to programming already available for the consideration of ion binding by inorganics in natural waters. (orig.)

  1. Binding of Cu(II) ions to peptides studied by fluorescence spectroscopy and isothermal titration calorimetry

    Science.gov (United States)

    Makowska, Joanna; Żamojć, Krzysztof; Wyrzykowski, Dariusz; Uber, Dorota; Wierzbicka, Małgorzata; Wiczk, Wiesław; Chmurzyński, Lech

    2016-01-01

    Steady-state and time-resolved fluorescence quenching measurements supported by Isothermal Titration Calorimetry (ITC) were used to study the interactions of Cu2 + with four peptides. Two of them were taken from the N-terminal part of the FBP28 protein (formin binding protein) WW domain: Tyr-Lys-Thr-Ala-Asp-Gly-Lys-Thr-Tyr-NH2 (D9) and its mutant Tyr-Lys-Thr-Ala-Asn-Gly-Lys-Thr-Tyr-NH2 (D9_M) as well as two mutated peptides from the B3 domain of the immunoglobulin binding protein G derived from Streptococcus: Asp-Val-Ala-Thr-Tyr-Thr-NH2 (J1) and Glu-Val-Ala-Thr-Tyr-Thr-NH2 (J2). The measurements were carried out at 298.15 K in 20 mM 2-(N-morpholino)ethanesulfonic acid (MES) buffer solution with a pH of 6. The fluorescence of all peptides was quenched by Cu2 + ions. The stoichiometry, conditional stability constants and thermodynamic parameters for the interactions of the Cu2 + ions with D9 and D9_M were determined from the calorimetric data. The values of the conditional stability constants were additionally determined from fluorescence quenching measurements and compared with those obtained from calorimetric studies. There was a good correlation between data obtained from the two techniques. On the other hand, the studies revealed that J1 and J2 do not exhibit an affinity towards metal ions. The obtained results prove that fluorescence quenching experiments may be successfully used in order to determine stability constants of complexes with fluorescent ligands. Finally, based on the obtained results, the coordinating properties of the peptides towards the Cu2 + ions are discussed.

  2. Accumulation of some metal ions on Bacillus licheniformis

    International Nuclear Information System (INIS)

    Hafez, M.B.; El-Desouky, W.; Fouad, A.

    2001-01-01

    Pure species of Bacillus licheniformis was used to remove ions from aqueous and simulated waste solutions. Metal ion accumulation on B. licheniformis was fast. Maximum uptake occurred at pH 4± 0.5 and at 25 ± 3 deg C. One gram of dry B. licheniformis was found to accumulate 115 mg cerium, 34 mg copper and 11 mg cobalt from aqueous solutions. The presence of certain foreign ions such as calcium, sodium and potassium decreased the uptake of ions by B. licheniformis, while citrate and EDTA prevent the uptake. Electron microscopic investigations showed that cerium (III), copper (II) and cobalt (II) accumulated extracellulary around the surface wall of B. licheniformis cells. A bio-adsorption mechanism between the metal ions and B. licheniformis cell wall was proposed. (author)

  3. Crystal Structures of Apo and Metal-Bound Forms of the UreE Protein from Helicobacter pylori: Role of Multiple Metal Binding Sites

    Energy Technology Data Exchange (ETDEWEB)

    Shi, Rong; Munger, Christine; Asinas, Abdalin; Benoit, Stephane L.; Miller, Erica; Matte, Allan; Maier, Robert J.; Cygler, Miroslaw (McGill); (Georgia); (Biotech Res.)

    2010-10-22

    The crystal structure of the urease maturation protein UreE from Helicobacter pylori has been determined in its apo form at 2.1 {angstrom} resolution, bound to Cu{sup 2+} at 2.7 {angstrom} resolution, and bound to Ni{sup 2+} at 3.1 {angstrom} resolution. Apo UreE forms dimers, while the metal-bound enzymes are arranged as tetramers that consist of a dimer of dimers associated around the metal ion through coordination by His102 residues from each subunit of the tetramer. Comparison of independent subunits from different crystal forms indicates changes in the relative arrangement of the N- and C-terminal domains in response to metal binding. The improved ability of engineered versions of UreE containing hexahistidine sequences at either the N-terminal or C-terminal end to provide Ni{sup 2+} for the final metal sink (urease) is eliminated in the H102A version. Therefore, the ability of the improved Ni{sup 2+}-binding versions to deliver more nickel is likely an effect of an increased local concentration of metal ions that can rapidly replenish transferred ions bound to His102.

  4. Complexation ion-exchange chromatography of some metal ions on papers impregnated with Ti(IV)-based inorganic ion exchangers.

    Science.gov (United States)

    Sharma, S D; Gupta, R

    2000-02-01

    The chromatographic behavior of 40 metal ions is studied on titanium (IV) arsenate, titanium (IV) phosphate-, titanium (IV) molybdate-, titanium(IV) tungstate-, and titanium(IV) selenite-impregnated papers in 0.1M oxalic, citric, and tartaric acid as mobile phases. Similar studies are carried out on Whatman No. 1 papers for comparison. The ion-exchange capacity of these papers is determined, and their selectivity for different cations is discussed. The mechanism of migration is explained in terms of ion-exchange, precipitation, and adsorption. The prediction of elution sequence from RF values is also checked. The average Ri is found to be almost linearly dependent on the charge of the metal ions. The effect of the pKa of complexing acids on average RF values of 3d series metal ions is explained. A number of binary and ternary separations are achieved.

  5. Metal ions potentiate microglia responsiveness to endotoxin.

    Science.gov (United States)

    Rachmawati, Dessy; Peferoen, Laura A N; Vogel, Daphne Y S; Alsalem, Inás W A; Amor, Sandra; Bontkes, Hetty J; von Blomberg, B Mary E; Scheper, Rik J; van Hoogstraten, Ingrid M W

    2016-02-15

    Oral metal exposure has been associated with diverse adverse reactions, including neurotoxicity. We showed previously that dentally applied metals activate dendritic cells (MoDC) via TLR4 (Ni, Co, Pd) and TLR3 (Au). It is still unknown whether the low levels of dental metals reaching the brain can trigger local innate cells or prime them to become more responsive. Here we tested whether dentally applied metals (Cr, Fe, Co, Ni, Cu, Zn, Au, Hg) activate primary human microglia in vitro and, as a model, monocytic THP-1-cells, in high non-toxic as well as near-physiological concentrations. In addition the effects of 'near-physiological' metal exposure on endotoxin (LPS) responsiveness of these cells were evaluated. IL-8 and IL-6 production after 24h was used as read out. In high, non-toxic concentrations all transition metals except Cr induced IL-8 and IL-6 production in microglia, with Ni and Co providing the strongest stimulation. When using near-physiological doses (up to 10× the normal plasma concentration), only Zn and Cu induced significant IL-8 production. Of note, the latter metals also markedly potentiated LPS responsiveness of microglia and THP-1 cells. In conclusion, transition metals activate microglia similar to MoDCs. In near-physiological concentrations Zn and Cu are the most effective mediators of innate immune activation. A clear synergism between innate responses to Zn/Cu and LPS was observed, shedding new light on the possible relation between oral metal exposure and neurotoxicity. Copyright © 2015. Published by Elsevier B.V.

  6. Adsorption of heavy metal ions by sawdust of deciduous trees.

    Science.gov (United States)

    Bozić, D; Stanković, V; Gorgievski, M; Bogdanović, G; Kovacević, R

    2009-11-15

    The adsorption of heavy metal ions from synthetic solutions was performed using sawdust of beech, linden and poplar trees. The adsorption depends on the process time, pH of the solution, type of ions, initial concentration of metals and the sawdust concentration in suspension. The kinetics of adsorption was relatively fast, reaching equilibrium for less than 20 min. The adsorption equilibrium follows Langmuir adsorption model. The ion exchange mechanism was confirmed assuming that the alkali-earth metals from the adsorbent are substituted by heavy metal ions and protons. On lowering the initial pH, the adsorption capacity decreased, achieving a zero value at a pH close to unity. The maximum adsorption capacity (7-8 mg g(-1) of sawdust) was achieved at a pH between 3.5 and 5 for all the studied kinds of sawdust. The initial concentration of the adsorbate and the concentration of sawdust strongly affect the process. No influence of particles size was evidenced. A degree of adsorption higher than 80% can be achieved for Cu(2+) ions but it is very low for Fe(2+) ions, not exceeding 10%.

  7. Adsorption of heavy metal ions by sawdust of deciduous trees

    International Nuclear Information System (INIS)

    Bozic, D.; Stankovic, V.; Gorgievski, M.; Bogdanovic, G.; Kovacevic, R.

    2009-01-01

    The adsorption of heavy metal ions from synthetic solutions was performed using sawdust of beech, linden and poplar trees. The adsorption depends on the process time, pH of the solution, type of ions, initial concentration of metals and the sawdust concentration in suspension. The kinetics of adsorption was relatively fast, reaching equilibrium for less than 20 min. The adsorption equilibrium follows Langmuir adsorption model. The ion exchange mechanism was confirmed assuming that the alkali-earth metals from the adsorbent are substituted by heavy metal ions and protons. On lowering the initial pH, the adsorption capacity decreased, achieving a zero value at a pH close to unity. The maximum adsorption capacity (7-8 mg g -1 of sawdust) was achieved at a pH between 3.5 and 5 for all the studied kinds of sawdust. The initial concentration of the adsorbate and the concentration of sawdust strongly affect the process. No influence of particles size was evidenced. A degree of adsorption higher than 80% can be achieved for Cu 2+ ions but it is very low for Fe 2+ ions, not exceeding 10%.

  8. Ion conducting fluoropolymer carbonates for alkali metal ion batteries

    Science.gov (United States)

    DeSimone, Joseph M.; Pandya, Ashish; Wong, Dominica; Balsara, Nitash P.; Thelen, Jacob; Devaux, Didier

    2017-09-05

    Liquid or solid electrolyte compositions are described that comprise a homogeneous solvent system and an alkali metal salt dissolved in said solvent system. The solvent system may comprise a fluoropolymer, having one or two terminal carbonate groups covalently coupled thereto. Batteries containing such electrolyte compositions are also described.

  9. IBiSA_Tools: A Computational Toolkit for Ion-Binding State Analysis in Molecular Dynamics Trajectories of Ion Channels.

    Science.gov (United States)

    Kasahara, Kota; Kinoshita, Kengo

    2016-01-01

    Ion conduction mechanisms of ion channels are a long-standing conundrum. Although the molecular dynamics (MD) method has been extensively used to simulate ion conduction dynamics at the atomic level, analysis and interpretation of MD results are not straightforward due to complexity of the dynamics. In our previous reports, we proposed an analytical method called ion-binding state analysis to scrutinize and summarize ion conduction mechanisms by taking advantage of a variety of analytical protocols, e.g., the complex network analysis, sequence alignment, and hierarchical clustering. This approach effectively revealed the ion conduction mechanisms and their dependence on the conditions, i.e., ion concentration and membrane voltage. Here, we present an easy-to-use computational toolkit for ion-binding state analysis, called IBiSA_tools. This toolkit consists of a C++ program and a series of Python and R scripts. From the trajectory file of MD simulations and a structure file, users can generate several images and statistics of ion conduction processes. A complex network named ion-binding state graph is generated in a standard graph format (graph modeling language; GML), which can be visualized by standard network analyzers such as Cytoscape. As a tutorial, a trajectory of a 50 ns MD simulation of the Kv1.2 channel is also distributed with the toolkit. Users can trace the entire process of ion-binding state analysis step by step. The novel method for analysis of ion conduction mechanisms of ion channels can be easily used by means of IBiSA_tools. This software is distributed under an open source license at the following URL: http://www.ritsumei.ac.jp/~ktkshr/ibisa_tools/.

  10. Transformation of triclosan by laccase catalyzed oxidation: The influence of humic acid-metal binding process.

    Science.gov (United States)

    Lu, Junhe; Shi, Yuanyuan; Ji, Yuefei; Kong, Deyang; Huang, Qingguo

    2017-01-01

    Laccase is a widely present extracellular phenoloxidase excreted by fungi, bacteria, and high plants. It is able to catalyze one-electron oxidation of phenolic compounds into radical intermediates that can subsequently couple to each other via covalent bonds. These reactions are believed to play an important role in humification process and the transformation of contaminants containing phenolic functionalities in the environment. In this study, we investigated the kinetics of triclosan transformation catalyzed by laccase. It was found that the rate of triclosan oxidation was first order to the concentrations of both substrate and enzyme. Humic acid (HA) could inhibit the reaction by quenching the radical intermediate of triclosan generated by laccase oxidation. Such inhibition was more significant in the presence of divalent metal cations. This is because that binding to metal ions neutralized the negative charge of HA molecules, thus making them more accessible to laccase molecule that is also negatively charged. Therefore, it has greater chance to quench the radical intermediate that is very unstable and can only diffuse a limited distance after being released from the enzyme catalytic center. Based on these understandings, a reaction model was developed by integration of metal-HA binding equilibriums and kinetic equations. This model precisely predicted the transformation rate of triclosan in the presence of HA and divalent metal ions including Ca 2+ , Mg 2+ , Cd 2+ , Co 2+ , Mn 2+ , Ba 2+ , and Zn 2+ . Overall, this work reveals important insights into laccase catalyzed oxidative coupling process. Copyright © 2016 Elsevier Ltd. All rights reserved.

  11. Metallic ion release after knee prosthesis implantation: a prospective study.

    Science.gov (United States)

    Lons, Adrien; Putman, Sophie; Pasquier, Gilles; Migaud, Henri; Drumez, Elodie; Girard, Julien

    2017-12-01

    Metal-on-metal (MoM) hip replacement bearings produce metallic ions that can cause health complications. Metallic release also occurs with other materials, but data on metallic ion levels after knee arthroplasty are sparse. We postulate that knee replacement generates elevating metallic ions (chromium (Cr), cobalt (Co) and titanium (Ti)) during the first year after implantation. This ongoing prospective study included all patients who underwent the same type of knee arthroplasty between May and December 2013. Cr, Co and Ti levels were measured in whole blood at pre-operation and one-year follow-up (6 and 12 months). Clinical and radiographic data (range of motion, Oxford, International Knee Society (IKS) and satisfaction scores) were recorded. In 90 patients, preoperative Cr, Co and Ti metallic ion levels were respectively 0.45 μg/l, 0.22 μg/l, 2.94 μg/l and increased to 1.27 μg/l, 1.41 μg/l, 4.08 μg/l (p < 0.0001) at last one-year follow-up. Mean Oxford and IKS scores rose, respectively, from 45.9 (30-58) and 24.9 (12-52) to 88.3 (0-168) and 160.8 (93-200) (p < 0.001). After the implantation of knee arthroplasty, we found significant blood elevation of Cr, Co and Ti levels one year after implantation exceeding the normal values. This metallic ion release could lead to numerous effects: allergy, hypersensitivity, etc.

  12. Metal ion mediated photolysis reactions of riboflavin: A kinetic study.

    Science.gov (United States)

    Ahmad, Iqbal; Anwar, Zubair; Ahmed, Sofia; Sheraz, Muhammad Ali; Khattak, Saif-Ur-Rehman

    2017-08-01

    The effect of metal ion complexation on the photolysis of riboflavin (RF) using various metal ions (Ag + , Ni 2+ , Co 2+ , Fe 2+ , Ca 2+ , Cd 2+ , Cu 2+ , Mn 2+ , Pb 2+ , Mg 2+ , Zn 2+ , Fe 3+ ) has been studied. Ultraviolet and visible spectral and fluorimetric evidence has been obtained to confirm the formation of metal-RF complexes. The kinetics of photolysis of RF in metal-RF complexes at pH7.0 has been evaluated. The apparent first-order rate constant (k obs ) for the photolysis of RF and the formation of lumichrome (LC) and lumiflavin (LF) (0.001M phosphate buffer) and LC, LF and cyclodehydroriboflavin (CDRF) (0.2-0.4M phosphate buffer) have been determined. The values of k obs indicate that the rate of photolysis of RF is promoted by divalent and trivalent metal ions. The second-order rate constants (k' ) for the interaction of metal ions with RF are in the order: Zn 2+ >Mg 2+ >Pb 2+ >Mn 2+ >Cu 2+ >Cd 2+ >Fe 2+ >Ca 2+ >Fe 3+ >Co 2+ >Ni 2+ >Ag + . In phosphate buffer (0.2-0.4M), an increase in the metal ion concentration leads to a decrease in the formation of LC compared to that of CDRF by different pathways. The photoproducts of RF have been identified and RF and the photoproducts have simultaneously been assayed by a multicomponent spectrometric method. The mode of photolysis of RF in metal-RF complexes has been discussed. Copyright © 2017 Elsevier B.V. All rights reserved.

  13. Conversion of agonist site to metal-ion chelator site in the beta(2)-adrenergic receptor

    DEFF Research Database (Denmark)

    Elling, C E; Thirstrup, K; Holst, Birgitte

    1999-01-01

    Previously metal-ion sites have been used as structural and functional probes in seven transmembrane receptors (7TM), but as yet all the engineered sites have been inactivating. Based on presumed agonist interaction points in transmembrane III (TM-III) and -VII of the beta(2)-adrenergic receptor,...... as generic, pharmacologic tools to switch 7TM receptors with engineered metal-ion sites on or off at will.......Previously metal-ion sites have been used as structural and functional probes in seven transmembrane receptors (7TM), but as yet all the engineered sites have been inactivating. Based on presumed agonist interaction points in transmembrane III (TM-III) and -VII of the beta(2)-adrenergic receptor......, in this paper we construct an activating metal-ion site between the amine-binding Asp-113 in TM-III-or a His residue introduced at this position-and a Cys residue substituted for Asn-312 in TM-VII. No increase in constitutive activity was observed in the mutant receptors. Signal transduction was activated...

  14. Extraction of metal ions using chemically modified silica gel: a PIXE analysis.

    Science.gov (United States)

    Jal, P K; Dutta, R K; Sudarshan, M; Saha, A; Bhattacharyya, S N; Chintalapudi, S N; K Mishra, B

    2001-08-30

    Organic ligand with carboxyhydrazide functional group was immobilised on the surface of silica gel and the metal binding capacity of the ligand-embedded silica was investigated. The functional group was covalently bonded to the silica matrix through a spacer of methylene groups by sequential reactions of silica gel with dibromobutane, malonic ester and hydrazine in different media. Surface area value of the modified silica was determined. The changes in surface area were correlated with the structural change of the silica surface due to chemical modifications. A mixture solution of metal ions [K(I),Cr(III),Co(II),Ni(II),Cu(II),Zn(II),Hg(II) and U(VI)] was treated with the ligand-embedded silica in 10(-3) M aqueous solution. The measurement of metal extraction capacity of the silica based ligand was done by multielemental analysis of the metal complexes thus formed by using Proton Induced X-ray Emission (PIXE) technique.

  15. Ion beam modification of metals: Compositional and microstructural changes

    Science.gov (United States)

    Was, Gary S.

    Ion implantation has become a highly developed tool for modifying the structure and properties of metals and alloys. In addition to direct implantation, a variety of other ion beam techniques such as ion beam mixing, ion beam assisted deposition and plasma source ion implantation have been used increasingly in recent years. The modifications constitute compositional and microstructural changes in the surface of the metal. This leads to alterations in physical properties (transport, optical, corrosion, oxidation), as well as mechanical properties (strength, hardness, wear resistance, fatigue resistance). The compositional changes brought about by ion bombardment are classified into recoil implantation, cascade mixing, radiation-enhanced diffusion, radiation-induced segregation, Gibbsian adsorption and sputtering which combine to produce an often complicated compositional variation within the implanted layer and often, well beyond. Microstructurally, the phases present are often altered from what is expected from equilibrium thermodynamics giving rise to order-disorder transformations, metastable (crystalline, amorphous or quasicrystalline) phase formation and growth, as well as densification, grain growth, formation of a preferred texture and the formation of a high density dislocation network. All these effects need to be understood before one can determine the effect of ion bombardment on the physical and mechanical properties of metals. This paper reviews the literature in terms of the compositional and microstructural changes induced by ion bombardment, whether by direct implantation, ion beam mixing or other forms of ion irradiation. The topics are introduced as well as reviewed, making this a more pedogogical approach as opposed to one which treats only recent developments. The aim is to provide the tools needed to understand the consequent changes in physical and mechanical properties.

  16. Metal ion leachates and the physico-chemical stability of biotherapeutic drug products.

    Science.gov (United States)

    Kumar, Sandeep; Zhou, Shuxia; Singh, Satish K

    2014-01-01

    Metal ions that leach into biotherapeutic drug product solution during manufacturing and storage, result in contamination that can cause physico-chemical degradation of the active molecule. In this review, we describe various mechanisms by which metal ion leachates can interact with therapeutic proteins and antibodies. Site-specific modifications due to metal catalyzed oxidation (MCO) of the therapeutic proteins cause them to become destabilized and potentially increasingly aggregation prone. We have examined the molecular sequences and structures for three case studies, human relaxin (hRlx), human growth hormone (hGH) and an IgG2 mAb to rationalize the experimental findings related to their MCO. The analysis indicates that metal-binding sites lie in close spatial proximities to predicted aggregation prone regions in these molecules. From the perspective of pharmaceutical development of biotherapeutic drugs, this link between molecular origins of MCO and subsequent aggregation is undesirable. This article further suggests molecular design strategies involving disruption of APRs that may also help mitigate the impact of metal ion leachates on biotherapeutic drug products as well as improving their solubility.

  17. Complementary metal ion specificity of the metal-citrate transporters CitM and CitH of Bacillus subtilis

    NARCIS (Netherlands)

    Krom, BP; Warner, JB; Konings, WN; Lolkema, JS; Warner, Jessica B.

    2000-01-01

    Citrate uptake in Bacillus subtilis is stimulated by a wide range of divalent metal ions. The metal ions were separated into two groups based on the expression pattern of the uptake system. The two groups correlated with the metal ion specificity of two homologous B, subtilis secondary citrate

  18. Metal (Pb, Cd, and Zn) Binding to Diverse Organic Matter Samples and Implications for Speciation Modeling.

    Science.gov (United States)

    Chen, Weibin; Guéguen, Céline; Smith, D Scott; Galceran, Josep; Puy, Jaume; Companys, Encarnació

    2018-04-03

    This study evaluated the influence of dissolved organic matter (DOM) properties on the speciation of Pb, Zn, and Cd. A total of six DOM samples were categorized into autochthonous and allochthonous sources based on their absorbance and fluorescence properties. The concentration of free metal ions ( C M 2+ ) measured by titration using the absence of gradients and Nernstian equilibrium stripping (AGNES) method was compared with that predicted by the Windermere humic aqueous model (WHAM). At the same binding condition (pH, dissolved organic carbon, ionic strength, and total metal concentration) the allochthonous DOM showed a higher level of Pb binding than the autochthonous DOM (84- to 504-fold C Pb 2+ variation). This dependency, however, was less pronounced for Zn (12- to 74-fold C Zn 2+ variation) and least for Cd (2- to 14-fold C Cd 2+ variation). The WHAM performance was affected by source variation through the active DOM fraction ( F). The commonly used F = 1.3 provided reliable C Pb 2+ for allochthonous DOMs and acceptable C Cd 2+ for all DOM, but it significantly under-predicted C Pb 2+ and C Zn 2+ for autochthonous DOM. Adjusting F improved C M 2+ predictions, but the optimum F values were metal-specific (e.g., 0.03-1.9 for Pb), as shown by linear correlations with specific optical indexes. The results indicate a potential to improve WHAM by incorporating rapid measurement of DOM optical properties for site-specific F.

  19. Earthworm Lumbricus rubellus MT-2: Metal Binding and Protein Folding of a True Cadmium-MT

    Directory of Open Access Journals (Sweden)

    Gregory R. Kowald

    2016-01-01

    Full Text Available Earthworms express, as most animals, metallothioneins (MTs—small, cysteine-rich proteins that bind d10 metal ions (Zn(II, Cd(II, or Cu(I in clusters. Three MT homologues are known for Lumbricus rubellus, the common red earthworm, one of which, wMT-2, is strongly induced by exposure of worms to cadmium. This study concerns composition, metal binding affinity and metal-dependent protein folding of wMT-2 expressed recombinantly and purified in the presence of Cd(II and Zn(II. Crucially, whilst a single Cd7wMT-2 species was isolated from wMT-2-expressing E. coli cultures supplemented with Cd(II, expressions in the presence of Zn(II yielded mixtures. The average affinities of wMT-2 determined for either Cd(II or Zn(II are both within normal ranges for MTs; hence, differential behaviour cannot be explained on the basis of overall affinity. Therefore, the protein folding properties of Cd- and Zn-wMT-2 were compared by 1H NMR spectroscopy. This comparison revealed that the protein fold is better defined in the presence of cadmium than in the presence of zinc. These differences in folding and dynamics may be at the root of the differential behaviour of the cadmium- and zinc-bound protein in vitro, and may ultimately also help in distinguishing zinc and cadmium in the earthworm in vivo.

  20. Differential plasma protein binding to metal oxide nanoparticles

    International Nuclear Information System (INIS)

    Deng, Zhou J; Mortimer, Gysell; Minchin, Rodney F; Schiller, Tara; Musumeci, Anthony; Martin, Darren

    2009-01-01

    Nanoparticles rapidly interact with the proteins present in biological fluids, such as blood. The proteins that are adsorbed onto the surface potentially dictate the biokinetics of the nanomaterials and their fate in vivo. Using nanoparticles with different sizes and surface characteristics, studies have reported the effects of physicochemical properties on the composition of adsorbed plasma proteins. However, to date, few studies have been conducted focusing on the nanoparticles that are commonly exposed to the general public, such as the metal oxides. Using previously established ultracentrifugation approaches, two-dimensional gel electrophoresis and mass spectrometry, the current study investigated the binding of human plasma proteins to commercially available titanium dioxide, silicon dioxide and zinc oxide nanoparticles. We found that, despite these particles having similar surface charges in buffer, they bound different plasma proteins. For TiO 2 , the shape of the nanoparticles was also an important determinant of protein binding. Agglomeration in water was observed for all of the nanoparticles and both TiO 2 and ZnO further agglomerated in biological media. This led to an increase in the amount and number of different proteins bound to these nanoparticles. Proteins with important biological functions were identified, including immunoglobulins, lipoproteins, acute-phase proteins and proteins involved in complement pathways and coagulation. These results provide important insights into which human plasma proteins bind to particular metal oxide nanoparticles. Because protein absorption to nanoparticles may determine their interaction with cells and tissues in vivo, understanding how and why plasma proteins are adsorbed to these particles may be important for understanding their biological responses.

  1. Trivalent metal ions based on inorganic compounds with in vitro inhibitory activity of matrix metalloproteinase 13.

    Science.gov (United States)

    Wen, Hanyu; Qin, Yuan; Zhong, Weilong; Li, Cong; Liu, Xiang; Shen, Yehua

    2016-10-01

    Collagenase-3 (MMP-13) inhibitors have attracted considerable attention in recent years and have been developed as a therapeutic target for a variety of diseases, including cancer. Matrix metalloproteinases (MMPs) can be inhibited by a multitude of compounds, including hydroxamic acids. Studies have shown that materials and compounds containing trivalent metal ions, particularly potassium hexacyanoferrate (III) (K3[Fe(CN)6]), exhibit cdMMP-13 inhibitory potential with a half maximal inhibitory concentration (IC50) of 1.3μM. The target protein was obtained by refolding the recombinant histidine-tagged cdMMP-13 using size exclusion chromatography (SEC). The secondary structures of the refolded cdMMP-13 with or without metal ions were further analyzed via circular dichroism and the results indicate that upon binding with metal ions, an altered structure with increased domain stability was obtained. Furthermore, isothermal titration calorimetry (ITC) experiments demonstrated that K3[Fe(CN)6]is able to bind to MMP-13 and endothelial cell tube formation tests provide further evidence for this interaction to exhibit anti-angiogenesis potential. To the best of our knowledge, no previous report of an inorganic compound featuring a MMP-13 inhibitory activity has ever been reported in the literature. Our results demonstrate that K3[Fe(CN)6] is useful as a new effective and specific inhibitor for cdMMP-13 which may be of great potential for future drug screening applications. Copyright © 2016. Published by Elsevier Inc.

  2. A possible role of alkali metal ions in the synthesis of pure-silica molecular sieves

    OpenAIRE

    Goepper, Michelle; Li, Hong-Xin; Davis, Mark E.

    1992-01-01

    Pure-silica ZSM-12 is synthesized in the presence and absence of alkali metal ions; addition of alkali metal ions at constant hydroxide ion concentration increases the crystallization rate of ZSM-12, and it is suggested that alkali metal ions participate in both the nucleation and crystal growth processes.

  3. Radiation hardening of metals irradiated by heavy ions

    International Nuclear Information System (INIS)

    Didyk, A.Yu.; Skuratov, V.A.; Mikhajlova, N.Yu.; Regel', V.R.

    1988-01-01

    The damage dose dependence in the 10 -4 -10 -2 dpa region of radiation hardening of Al, V, Ni, Cu irradiated by xenon ions with 124 MeV energy is investigated using the microhardness technique and transmission electron microscope. It is shown that the pure metals radiation hardening is stimulated for defects clusters with the typical size less than 5 nm, as in the case of neutron and the light charge ion irradiation

  4. Molar absorption coefficients and stability constants of Zincon metal complexes for determination of metal ions and bioinorganic applications.

    Science.gov (United States)

    Kocyła, Anna; Pomorski, Adam; Krężel, Artur

    2017-11-01

    Zincon (ZI) is one of the most common chromophoric chelating probes for the determination of Zn 2+ and Cu 2+ ions. It is also known to bind other metal ions. However, literature data on its binding properties and molar absorption coefficients are rather poor, varying among publications or determined only in certain conditions. There are no systematic studies on Zn 2+ and Cu 2+ affinities towards ZI performed under various conditions. However, this widely commercially available and inexpensive agent is frequently the first choice probe for the measurement of metal binding and release as well as determination of affinity constants of other ligands/macromolecules of interest. Here, we establish the spectral properties and the stability of ZI and its complexes with Zn 2+ , Cu 2+ , Cd 2+ , Hg 2+ , Co 2+ , Ni 2+ and Pb 2+ at multiple pH values from 6 to 9.9. The obtained results show that in water solution the MZI complex is predominant, but in the case of Co 2+ and Ni 2+ , M(ZI) 2 complexes are also formed. The molar absorption coefficient at 618 nm for ZnZI and 599nm for CuZI complexes at pH7.4 in buffered (I=0.1M) water solutions are 24,200 and 26,100M -1 cm -1 , respectively. Dissociation constants of those complexes are 2.09×10 -6 and 4.68×10 -17 M. We also characterized the metal-assisted Zincon decomposition. Our results provide new and reassessed optical and stability data that are applicable to a wide range of chemical and bioinorganic applications including metal ion detection, and quantification and affinity studies of ligands of interest. Accurate values of molar absorption coefficients of Zincon complex with Zn 2+ , Cd 2+ , Hg 2+ , Co 2+ , Ni 2+ , Cu 2+ , and Pb 2+ for rapid metal ion quantification are provided. Zincon stability constants with Zn 2+ and Cu 2+ in a wide pH range were determined. Copyright © 2017 Elsevier Inc. All rights reserved.

  5. A versatile MOF-based trap for heavy metal ion capture and dispersion.

    Science.gov (United States)

    Peng, Yaguang; Huang, Hongliang; Zhang, Yuxi; Kang, Chufan; Chen, Shuangming; Song, Li; Liu, Dahuan; Zhong, Chongli

    2018-01-15

    Current technologies for removing heavy metal ions are typically metal ion specific. Herein we report the development of a broad-spectrum heavy metal ion trap by incorporation of ethylenediaminetetraacetic acid into a robust metal-organic framework. The capture experiments for a total of 22 heavy metal ions, covering hard, soft, and borderline Lewis metal ions, show that the trap is very effective, with removal efficiencies of >99% for single-component adsorption, multi-component adsorption, or in breakthrough processes. The material can also serve as a host for metal ion loading with arbitrary selections of metal ion amounts/types with a controllable uptake ratio to prepare well-dispersed single or multiple metal catalysts. This is supported by the excellent performance of the prepared Pd 2+ -loaded composite toward the Suzuki coupling reaction. This work proposes a versatile heavy metal ion trap that may find applications in the fields of separation and catalysis.

  6. Focused ion beam lithography for rapid prototyping of metallic films

    Energy Technology Data Exchange (ETDEWEB)

    Osswald, Patrick; Kiermaier, Josef; Becherer, Markus; Schmitt-Landsiedel, Doris [Lehrstuhl fuer Technische Elektronik, TU Muenchen, Munich (Germany)

    2010-07-01

    We present FIB-lithography methods for rapid and cost-effective prototyping of metal structures covering the deep-submicron- to the millimeter-range in a single lithography cycle. Focused ion beam (FIB) systems are widely used in semiconductor industry and research facilities for both analytical testing and prototyping. A typical application is to apply electrical contact to micron-sized sensors/particles by FIB induced metal deposition. However, as for E-beam lithography, patterning times for large area bonding pads are unacceptably long, resulting in cost-intensive prototyping. In this work, we optimized FIB lithography processing for negative and positive imaging mode to form metallic structures for large-areas down do the sub-100 nm range. For negative lithography features are defined by implanting Ga{sup +}-ions into a commercial photo resist, without affecting the underlying structures by impinging ions. The structures are highly suitable for following lift-off processing due to the undercut of the resist.Metallic feature size of down to 150 nm are achievable. For positive lithography a PMMA resist is exposed in FIB irradiation. Due to the very low dose (3.10{sup 12} ions/cm{sup 2}) the writing time for an e.g. 100 {mu}m x 100 {mu}m square is approx. 15 seconds. The developed resist is used for subsequent wet chemical etching, obtaining a 100 nm resolution in metal layers.

  7. Smart responsive microcapsules capable of recognizing heavy metal ions.

    Science.gov (United States)

    Pi, Shuo-Wei; Ju, Xiao-Jie; Wu, Han-Guang; Xie, Rui; Chu, Liang-Yin

    2010-09-15

    Smart responsive microcapsules capable of recognizing heavy metal ions are successfully prepared with oil-in-water-in-oil double emulsions as templates for polymerization in this study. The microcapsules are featured with thin poly(N-isopropylacrylamide-co-benzo-18-crown-6-acrylamide) (P(NIPAM-co-BCAm)) membranes, and they can selectively recognize special heavy metal ions such as barium(II) or lead(II) ions very well due to the "host-guest" complexation between the BCAm receptors and barium(II) or lead(II) ions. The stable BCAm/Ba(2+) or BCAm/Pb(2+) complexes in the P(NIPAM-co-BCAm) membrane cause a positive shift of the volume phase transition temperature of the crosslinked P(NIPAM-co-BCAm) hydrogel to a higher temperature, and the repulsion among the charged BCAm/Ba(2+) or BCAm/Pb(2+) complexes and the osmotic pressure within the P(NIPAM-co-BCAm) membranes result in the swelling of microcapsules. Induced by recognizing barium(II) or lead(II) ions, the prepared microcapsules with P(NIPAM-co-BCAm) membranes exhibit isothermal and significant swelling not only in outer and inner diameters but also in the membrane thickness. The proposed microcapsules in this study are highly attractive for developing smart sensors and/or carriers for detection and/or elimination of heavy metal ions. Copyright 2010 Elsevier Inc. All rights reserved.

  8. Adsorption of Metallic Ions onto Chitosan : Equilibrium and Kinetic Studies

    OpenAIRE

    Benavente, Martha

    2008-01-01

    Equilibrium isotherms and the adsorption kinetics of heavy metals onto chitosan were studied experimentally. Chitosan, a biopolymer produced from crustacean shells, has applications in various areas, particularly in drinking water and wastewater treatment due to its ability to remove metallic ions from solutions. The adsorption capacity of chitosan depends on a number of parameters: deacetylation degree, molecular weight, particle size and crystallinity. The purpose of this work was to study ...

  9. DETERMINATION OF METAL IONS RELEASED BY STAINLESS ...

    African Journals Online (AJOL)

    Preferred Customer

    Also taking into account the fact that, in body conditions implant corrosion products are disseminated and eventually eliminated. The result that SS arch bar used in orthodontic appliances corrode in bio-fluids over an extended time interval is of great clinical significance in evaluating their bio-compatibility, the levels of metal.

  10. Structure and mode of action of cyclic lipopeptide pseudofactin II with divalent metal ions.

    Science.gov (United States)

    Janek, Tomasz; Rodrigues, Lígia R; Gudiña, Eduardo J; Czyżnikowska, Żaneta

    2016-10-01

    The interaction of natural lipopeptide pseudofactin II with a series of doubly charged metal cations was examined by matrix-assisted laser-desorption ionization-time of flight (MALDI-TOF) mass spectrometry and molecular modelling. The molecular modelling for metal-pseudofactin II provides information on the metal-peptide binding sites. Overall, Mg(2+), Ca(2+) and Zn(2+) favor the association with oxygen atoms spanning the peptide backbone, whereas Cu(2+) is coordinated by three nitrogens. Circular dichroism (CD) results confirmed that Zn(2+) and Cu(2+) can disrupt the secondary structure of pseudofactin II at high concentrations, while Ca(2+) and Mg(2+) did not essentially affect the structure of the lipopeptide. Interestingly, our results showed that the addition of Zn(2+) and Cu(2+) helped smaller micelles to form larger micellar aggregates. Since pseudofactin II binds metals, we tested whether this phenomena was somehow related to its antimicrobial activity against Staphylococcus epidermidis and Proteus mirabilis. We found that the antimicrobial effect of pseudofactin II was increased by supplementation of culture media with all tested divalent metal ions. Finally, by using Gram-positive and Gram-negative bacteria we showed that the higher antimicrobial activity of metal complexes of pseudofactin II is attributed to the disruption of the cytoplasmic membrane. Copyright © 2016 Elsevier B.V. All rights reserved.

  11. Adsorption of strontium (II) metal ions using phosphonate ...

    Indian Academy of Sciences (India)

    The metal binding was examined by the energy dispersive spectroscopy and scanning electron microscopy for the adsorbed Sr(II). Batch adsorption studies were performed by varying three parameters, namely initial pH, adsorbentdose and the contact time. The reaction kinetics was determined by the Langmuir, Freundlich, ...

  12. (II) metal ions using phosphonate-functionalized polymer

    Indian Academy of Sciences (India)

    The metal binding was examined by the energy dispersive spectroscopy and scanning electron microscopy for the adsorbed Sr(II). Batch adsorption studies were performed by varying three parameters, namely initial pH, adsorbentdose and the contact time. The reaction kinetics was determined by the Langmuir, Freundlich, ...

  13. Sorption of heavy metal ions on new metal-ligand complexes chemically derived from Lycopodium clavatum

    Energy Technology Data Exchange (ETDEWEB)

    Pehlivan, E.; Ersoz, M.; Yildiz, S. [Univ. of Selcuk, Konya (Turkey); Duncan, H.J. [Univ. of Glasgow, Scotland (United Kingdom)

    1994-08-01

    Sorption of heavy metal ions from aqueous solution has been investigated as a function of pH using a novel exchanger system whereby Lycopodium clavatum is functionalized with carboxylate and glyoxime metal-ligand complexes. The new ligand exchangers were prepared using a reaction of diaminosporopollenin with various metal-ligand complexes of glyoxime and monocarboxylic acid. The sorptive behavior of these metal-ligand exchangers and the possibilities to remove and to recover selectively heavy metal cations using these systems are discussed on the basis of their chemical natures and their complexing properties.

  14. Ni2+-based immobilized metal ion affinity chromatography of lactose operon repressor protein from Escherichia coli.

    Science.gov (United States)

    Velkov, Tony; Jones, Alun; Lim, Maria L R

    2008-01-01

    A two-step chromatographic sequence is described for the purification of native lactose operon repressor protein from Escherichia coli cells. The first step involves Ni(2+)-based immobilized metal ion affinity chromatography of the soluble cytoplasmic extract. This method provides superior speed, resolution and yield than the established phosphocellulose cation-exchange chromatographic procedure. Anion-exchange chromatography is used for further purification to >95% purity. The identity and purity of the lactose repressor protein were demonstrated using sodium dodecylsulphate polyacrylamide electrophoresis, crystallization, tryptic finger-printing mass spectrometry, and inducer binding assays. The purified lac repressor exhibited inducer sensitivity for operator DNA binding and undergoes a conformational change upon inducer binding. By all these extensive biochemical criteria, the purified protein behaves exactly as that described for the Escherichia coli lactose operon repressor.

  15. Breast milk metal ion levels in a young and active patient with a metal-on-metal hip prosthesis.

    Science.gov (United States)

    Nelis, Raymond; de Waal Malefijt, Jan; Gosens, Taco

    2013-01-01

    Metal-on-metal resurfacing arthroplasty of the hip has been used increasingly over the last 10 years in younger active patients. The dissolution of the metal wear particles results in measurable increases in cobalt and chromium ions in the serum and urine of patients with a metal-on-metal bearing. We measured the cobalt, chromium, and molybdenum ion levels in urine; serum; and breast milk in a young and active patient with a metal-on-metal hip prosthesis after a pathologic fracture of the femoral neck. Metal-on-metal hip prosthesis leads to increasing levels of molybdenum in breast milk in the short-term follow-up. There are no increasing levels of chromium and cobalt ions in breast milk. Besides the already known elevated concentrations in serum of chromium and cobalt after implantation of a metal-on-metal hip prosthesis, we found no increasing levels of chromium and cobalt in urine. Copyright © 2013 Elsevier Inc. All rights reserved.

  16. Chromium and cobalt ion concentrations in blood and serum following various types of metal-on-metal hip arthroplasties

    DEFF Research Database (Denmark)

    Jantzen, Christopher; Jørgensen, Henrik L; Duus, Benn R

    2013-01-01

    Widely different metal ion concentrations in blood and serum have been reported with metal-on-metal (MoM) implants. We reviewed the literature on blood and serum ion concentrations of chromium (Cr) and cobalt (Co) following various MoM hip arthroplasties.......Widely different metal ion concentrations in blood and serum have been reported with metal-on-metal (MoM) implants. We reviewed the literature on blood and serum ion concentrations of chromium (Cr) and cobalt (Co) following various MoM hip arthroplasties....

  17. Neutralization by metal ions of the toxicity of sodium selenide.

    Directory of Open Access Journals (Sweden)

    Marc Dauplais

    Full Text Available Inert metal-selenide colloids are found in animals. They are believed to afford cross-protection against the toxicities of both metals and selenocompounds. Here, the toxicities of metal salt and sodium selenide mixtures were systematically studied using the death rate of Saccharomyces cerevisiae cells as an indicator. In parallel, the abilities of these mixtures to produce colloids were assessed. Studied metal cations could be classified in three groups: (i metal ions that protect cells against selenium toxicity and form insoluble colloids with selenide (Ag⁺, Cd²⁺, Cu²⁺, Hg²⁺, Pb²⁺ and Zn²⁺, (ii metal ions which protect cells by producing insoluble metal-selenide complexes and by catalyzing hydrogen selenide oxidation in the presence of dioxygen (Co²⁺ and Ni²⁺ and, finally, (iii metal ions which do not afford protection and do not interact (Ca²⁺, Mg²⁺, Mn²⁺ or weakly interact (Fe²⁺ with selenide under the assayed conditions. When occurring, the insoluble complexes formed from divalent metal ions and selenide contained equimolar amounts of metal and selenium atoms. With the monovalent silver ion, the complex contained two silver atoms per selenium atom. Next, because selenides are compounds prone to oxidation, the stabilities of the above colloids were evaluated under oxidizing conditions. 5,5'-dithiobis-(2-nitrobenzoic acid (DTNB, the reduction of which can be optically followed, was used to promote selenide oxidation. Complexes with cadmium, copper, lead, mercury or silver resisted dissolution by DTNB treatment over several hours. With nickel and cobalt, partial oxidation by DTNB occurred. On the other hand, when starting from ZnSe or FeSe complexes, full decompositions were obtained within a few tens of minutes. The above properties possibly explain why ZnSe and FeSe nanoparticles were not detected in animals exposed to selenocompounds.

  18. Effects of Alkali-Metal Ions and Counter Ions in Sn-Beta-Catalyzed Carbohydrate Conversion.

    Science.gov (United States)

    Elliot, Samuel G; Tolborg, Søren; Madsen, Robert; Taarning, Esben; Meier, Sebastian

    2018-02-26

    Alkali-metal ions have recently been shown to strongly influence the catalytic behavior of stannosilicates in the conversion of carbohydrates. An effect of having alkali-metal ions present is a pronounced increase in selectivity towards methyl lactate. Mechanistic details of this effect have remained obscure and are herein addressed experimentally through kinetic experiments and isotope tracking. The presence of alkali-metal ions has a differential effect in competing reaction pathways and promotes the rate of carbon-carbon bond breakage of carbohydrate substrates, but decreases the rates of competing dehydration pathways. Further addition of alkali-metal ions inhibits the activity of Sn-Beta in all major reaction pathways. The alkali-metal effects on product distribution and on the rate of product formation are similar, thus pointing to a kinetic reaction control and to irreversible reaction steps in the main pathways. Additionally, an effect of the accompanying basic anions is shown, supposedly facilitating the cation exchange and eliciting a different concentration-dependent effect to that of neutral alkali-metal salts. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Host Materials for Transition-Metal Ions

    Science.gov (United States)

    1989-09-01

    Phys. 5cr. 25 (1982), 924. J4. L. DiSiplo, E. Tondello, G. De~ichelis, and L. Oleari , Slater-Condon Parameters for Atoms and Ions of the Second...Bnm* Frequently, the point-charge crystal-field components, Anm, indicate the correct phase relations and are used to determine the phases reported in...745. 5. W. L. Bond, Measurement of the Refractive Indices of Several Crystals, J. Appl. Phys. 36 (1965), 1674. 6. G. Burns, E. A. Geiss, B. A

  20. Effect of sulphate and chloride ions on the solvent extraction of some metal ions with liquid cation exchangers

    International Nuclear Information System (INIS)

    Shibata, Junji; Nishimura, Sanji

    1977-01-01

    The extraction of the metal ions from sulphate and chloride solutions with Versatic Acid 911 and di(2-ethyl hexyl) phosphoric acid in benzene was investigated in order to clarify the effect of sulphate and chloride ions on the extraction. Sulphate and chloride ions are not extracted into the organic phase, and they affect metal extraction only by forming the complexes with metal ions in the aqueous phase. The extent of the effect on metal extraction is determined by the kind of metal ions and anionic ligands, and the concentration of ligand ions. Therefore, the difference in extraction behaviour may be explained by the complexing ability of the various anionic ligands present in the aqueous phase. Formation constants of the complexes between metal ions and anionic ligands were computed from these distribution data. (auth.)

  1. Interaction of Hydroxyproline with Bivalent Metal Ions in Chemical ...

    African Journals Online (AJOL)

    Arecent technique involving the use of paper electrophoresis is described for the study of equilibria in binary complex systems in solution. The stability constants of the ML and ML2 complex species of some metal ions, namely beryllium(II) and cobalt(II), with hydroxyproline were determined in 0.1 mol L–1 perchloric acid ...

  2. Speciation and stability of methylene blue-metal-thiocyanate ion ...

    African Journals Online (AJOL)

    The relative stabilities indicate that cobalt is preferred to other two metals in the speciation of ternary complexes comparable with similar complexes in biosystems. This study also provides a method for the spectrophotometric determination of Co(II) and Zn(II) ions at nanogram levels at 25 oC and an ionic strength of 0.15 M.

  3. Dimeric Complexes of Tryptophan with M2+ Metal Ions

    NARCIS (Netherlands)

    Dunbar, R. C.; Steill, J. D.; Polfer, N. C.; Oomens, J.

    2009-01-01

    IRMPD spectroscopy using the FELIX free electron laser and a Fourier transform ICR mass spectrometer was used to characterize the structures of electrosprayed dimer complexes M(2+)Trp(2) of tryptophan with a series of eight doubly charged metal ions, including alkaline earths Ca, Sr, and Ba, and

  4. Synthesis, photophysical and metal ion signalling behaviour of mono

    Indian Academy of Sciences (India)

    Unknown

    Fluorescence decay behaviour of the systems suggests a through-space nature of PET. The systems exhi- bit off–on fluorescence signalling in the aprotic media in the presence of several metal ions, some of which are well known for their fluorescence quenching abilities. Diazacrown derivative, II, appears to be a somewhat ...

  5. Utilization of Plant Refuses as Component of Heavy Metal Ion ...

    African Journals Online (AJOL)

    The ability of the fabricated sensors to detect the presence of heavy metals was analyzed using electrochemical methods like cyclic voltammetry and differential pulse anodic stripping voltammetry. Results showed that the fabricated electrode were able to detect the presence of mercury and lead ions in aqueous solutions ...

  6. Removal of metal ions using dead-end filtration

    African Journals Online (AJOL)

    2005-07-03

    Jul 3, 2005 ... Surfactants due to their high selectivity properties have been used in enhancing membrane filtration for the removal of metal ions in aqueous solutions. Natural surfactants are preferred to synthetic surfactants because the synthetic surfactants have the disadvantage of introducing secondary pollutants into ...

  7. Equilibrium and kinetics studies of metal ion adsorption on dyed ...

    African Journals Online (AJOL)

    Batch equilibration studies were conducted to determine the nature of adsorption of Zn (II) and Cu (II) onto dyed coconut pollens. The nature of adsorption of metal ions was explained using the Langmuir equation. The calculated values of equilibrium parameter indicated favourable adsorption by the adsorbents. Also the ...

  8. Effect of metal ion doping on the photocatalytic activity of ...

    Indian Academy of Sciences (India)

    The activity can be enhanced by the increasing of concentration of the doped metal ions. TiAlPO-5 (4, 8, 12 atom % of Ti) showed the highest photocatalytic activity among all the compounds and its activity was compared to that of Degussa P25 (TiO2). The activity of photocatalysts was correlated with the diffuse reflectance ...

  9. Equilibrium and kinetics studies of metal ion adsorption on dyed ...

    African Journals Online (AJOL)

    GREGO

    2007-04-02

    Apr 2, 2007 ... Batch equilibration studies were conducted to determine the nature of adsorption of Zn (II) and Cu (II) onto dyed coconut pollens. The nature of adsorption of metal ions was explained using the Langmuir equation. The calculated values of equilibrium parameter indicated favourable adsorption by the.

  10. Ion exchangers as adsorbents for removing metals from aquatic media.

    Science.gov (United States)

    Khan, Meraj A; Bushra, Rani; Ahmad, Anees; Nabi, Syed A; Khan, Dilwar A; Akhtar, Arshia

    2014-02-01

    A polyaniline-based composite cation-exchange material was synthesized by way of sol-gel method and studied to explore its analytical and environmental applications. It was characterized by using instrumental analyses [Fourier transform infrared (spectrometer), X-ray, thermogravimetric analysis/differential thermal analysis, standard electron microscopy, and transmission electron microscopy]. Physicochemical studies, such as ion-exchange capacity, pH titrations, and chemical stability, along with effect of eluent concentration and elution, were also performed to exploit the ion-exchange capabilities. pH titration studies showed that the material presents monofunctional strong cation-exchange behavior. This nanocomposite material is semicrystalline in nature and exhibits improved thermal and chemical stability. The partition coefficient studies of different metal ions in the material were performed in demineralised water and different surfactant media, and it was found to be selective for Pb(II) and Hg(II) ions. To exploit the usefulness of the material as an adsorbent, some important quantitative binary separations of metal ions were performed on polyaniline Zr(IV) molybdophosphate columns. This composite cation exchanger can be applied for the treatment of polluted water to remove heavy metals.

  11. Broad-beam, high current, metal ion implantation facility

    International Nuclear Information System (INIS)

    Brown, I.G.; Dickinson, M.R.; Galvin, J.E.; Godechot, X.; MacGill, R.A.

    1990-07-01

    We have developed a high current metal ion implantation facility with which high current beams of virtually all the solid metals of the Periodic Table can be produced. The facility makes use of a metal vapor vacuum arc ion source which is operated in a pulsed mode, with pulse width 0.25 ms and repetition rate up to 100 pps. Beam extraction voltage is up to 100 kV, corresponding to an ion energy of up to several hundred keV because of the ion charge state multiplicity; beam current is up to several Amperes peak and around 10 mA time averaged delivered onto target. Implantation is done in a broad-beam mode, with a direct line-of-sight from ion source to target. Here we describe the facility and some of the implants that have been carried out using it, including the 'seeding' of silicon wafers prior to CVD with titanium, palladium or tungsten, the formation of buried iridium silicide layers, and actinide (uranium and thorium) doping of III-V compounds. 16 refs., 6 figs

  12. Do soft drinks affect metal ions release from orthodontic appliances?

    Science.gov (United States)

    Mikulewicz, Marcin; Wołowiec, Paulina; Loster, Bartłomiej W; Chojnacka, Katarzyna

    2015-01-01

    The effect of orange juice and Coca Cola(®) on the release of metal ions from fixed orthodontic appliances. A continuous flow system designed for in vitro testing of orthodontic appliances was used. Orange juice/Coca Cola(®) was flowing through the system alternately with artificial saliva for 5.5 and 18.5h, respectively. The collected samples underwent a multielemental ICP-OES analysis in order to determine the metal ions release pattern in time. The total mass of ions released from the appliance into orange juice and Coca Cola(®) (respectively) during the experiment was calculated (μg): Ni (15.33; 37.75), Cr (3.604; 1.052), Fe (48.42; ≥ 156.1), Cu (57.87, 32.91), Mn (9.164; 41.16), Mo (9.999; 30.12), and Cd (0.5967; 2.173). It was found that orange juice did not intensify the release of metal ions from orthodontic appliances, whereas Coca Cola(®) caused increased release of Ni ions. Copyright © 2015 Elsevier GmbH. All rights reserved.

  13. Removing coordinated metal ions from proteins: a fast and mild method in aqueous solution.

    Science.gov (United States)

    Carrer, Charlotte; Stolz, Michael; Lewitzki, Erwin; Rittmeyer, Claudia; Kolbesen, Bernd O; Grell, Ernst

    2006-08-01

    Thermodynamic and kinetic studies of metal binding to proteins require the investigation of metal-free proteins, which are often difficult to obtain. We have developed a very fast and mild method to eliminate metal ions from proteins by column chromatography using a commercially available Ni-NTA-type stationary phase. This material, initially designed for protein purification purposes in biotechnology, acts as a strong cation chelator when Ni2+ ions are removed. We have tested this new method with Ca-ATPase, an integral membrane protein exhibiting a strong affinity for Ca2+. By eluting the protein over the Ni2+-free NTA gel, we could remove 95% of the total Ca2+ and obtain an essentially Ca2+-free protein. This method is efficient with only a small amount of NTA gel, and we suggest that it can be applied in general for removal of metal ions from proteins. Moreover, as this procedure can be carried out under mild conditions, the chosen protein kept its enzymatic activity.

  14. Engineering Metal Ion Coordination to Regulate Amyloid Fibril Assembly And Toxicity

    Energy Technology Data Exchange (ETDEWEB)

    Dong, J.; Canfield, J.M.; Mehta, A.K.; Shokes, J.E.; Tian, B.; Childers, W.S.; Simmons, J.A.; Mao, Z.; Scott, R.A.; Warncke, K.; Lynn, D.G.

    2009-06-02

    Protein and peptide assembly into amyloid has been implicated in functions that range from beneficial epigenetic controls to pathological etiologies. However, the exact structures of the assemblies that regulate biological activity remain poorly defined. We have previously used Zn{sup 2+} to modulate the assembly kinetics and morphology of congeners of the amyloid {beta} peptide (A{beta}) associated with Alzheimer's disease. We now reveal a correlation among A{beta}-Cu{sup 2+} coordination, peptide self-assembly, and neuronal viability. By using the central segment of A{beta}, HHQKLVFFA or A{beta}(13-21), which contains residues H13 and H14 implicated in A{beta}-metal ion binding, we show that Cu{sup 2+} forms complexes with A{beta}(13-21) and its K16A mutant and that the complexes, which do not self-assemble into fibrils, have structures similar to those found for the human prion protein, PrP. N-terminal acetylation and H14A substitution, Ac-A{beta}(13-21)H14A, alters metal coordination, allowing Cu{sup 2+} to accelerate assembly into neurotoxic fibrils. These results establish that the N-terminal region of A{beta} can access different metal-ion-coordination environments and that different complexes can lead to profound changes in A{beta} self-assembly kinetics, morphology, and toxicity. Related metal-ion coordination may be critical to the etiology of other neurodegenerative diseases.

  15. Mechanistic Inferences from the Binding of Ligands to LpxC, A Metal-Dependent Deacetylase

    Energy Technology Data Exchange (ETDEWEB)

    Gennadios,H.; Whittington, D.; Li, X.; Fierke, C.; Christianson, D.

    2006-01-01

    The metal-dependent deacetylase LpxC catalyzes the first committed step of lipid A biosynthesis in Gram-negative bacteria. Accordingly, LpxC is an attractive target for the development of inhibitors that may serve as potential new antibiotics for the treatment of Gram-negative bacterial infections. Here, we report the 2.7 Angstroms resolution X-ray crystal structure of LpxC complexed with the substrate analogue inhibitor TU-514 and the 2.0 Angstroms resolution structure of LpxC complexed with imidazole. The X-ray crystal structure of LpxC complexed with TU-514 allows for a detailed examination of the coordination geometry of the catalytic zinc ion and other enzyme-inhibitor interactions in the active site. The hydroxamate group of TU-514 forms a bidentate chelate complex with the zinc ion and makes hydrogen bond interactions with conserved active site residues E78, H265, and T191. The inhibitor C-4 hydroxyl group makes direct hydrogen bond interactions with E197 and H58. Finally, the C-3 myristate moiety of the inhibitor binds in the hydrophobic tunnel of the active site. These intermolecular interactions provide a foundation for understanding structural aspects of enzyme-substrate and enzyme-inhibitor affinity. Comparison of the TU-514 complex with cacodylate and imidazole complexes suggests a possible substrate diphosphate binding site and highlights residues that may stabilize the tetrahedral intermediate and its flanking transition states in catalysis. Evidence of a catalytic zinc ion in the native zinc enzyme coordinated by H79, H238, D242, and two water molecules with square pyramidal geometry is also presented. These results suggest that the native state of this metallohydrolase may contain a pentacoordinate zinc ion, which contrasts with the native states of archetypical zinc hydrolases such as thermolysin and carboxypeptidase A.

  16. Mechanistic inferences from the binding of ligands to LpxC, a metal-dependent deacetylase.

    Science.gov (United States)

    Gennadios, Heather A; Whittington, Douglas A; Li, Xuechen; Fierke, Carol A; Christianson, David W

    2006-07-04

    The metal-dependent deacetylase LpxC catalyzes the first committed step of lipid A biosynthesis in Gram-negative bacteria. Accordingly, LpxC is an attractive target for the development of inhibitors that may serve as potential new antibiotics for the treatment of Gram-negative bacterial infections. Here, we report the 2.7 A resolution X-ray crystal structure of LpxC complexed with the substrate analogue inhibitor TU-514 and the 2.0 A resolution structure of LpxC complexed with imidazole. The X-ray crystal structure of LpxC complexed with TU-514 allows for a detailed examination of the coordination geometry of the catalytic zinc ion and other enzyme-inhibitor interactions in the active site. The hydroxamate group of TU-514 forms a bidentate chelate complex with the zinc ion and makes hydrogen bond interactions with conserved active site residues E78, H265, and T191. The inhibitor C-4 hydroxyl group makes direct hydrogen bond interactions with E197 and H58. Finally, the C-3 myristate moiety of the inhibitor binds in the hydrophobic tunnel of the active site. These intermolecular interactions provide a foundation for understanding structural aspects of enzyme-substrate and enzyme-inhibitor affinity. Comparison of the TU-514 complex with cacodylate and imidazole complexes suggests a possible substrate diphosphate binding site and highlights residues that may stabilize the tetrahedral intermediate and its flanking transition states in catalysis. Evidence of a catalytic zinc ion in the native zinc enzyme coordinated by H79, H238, D242, and two water molecules with square pyramidal geometry is also presented. These results suggest that the native state of this metallohydrolase may contain a pentacoordinate zinc ion, which contrasts with the native states of archetypical zinc hydrolases such as thermolysin and carboxypeptidase A.

  17. Mechanistic Inferences from the Binding of Ligands to LpxC, A Metal-Dependent Deacetylase

    International Nuclear Information System (INIS)

    Gennadios, H.; Whittington, D.; Li, X.; Fierke, C.; Christianson, D.

    2006-01-01

    The metal-dependent deacetylase LpxC catalyzes the first committed step of lipid A biosynthesis in Gram-negative bacteria. Accordingly, LpxC is an attractive target for the development of inhibitors that may serve as potential new antibiotics for the treatment of Gram-negative bacterial infections. Here, we report the 2.7 Angstroms resolution X-ray crystal structure of LpxC complexed with the substrate analogue inhibitor TU-514 and the 2.0 Angstroms resolution structure of LpxC complexed with imidazole. The X-ray crystal structure of LpxC complexed with TU-514 allows for a detailed examination of the coordination geometry of the catalytic zinc ion and other enzyme-inhibitor interactions in the active site. The hydroxamate group of TU-514 forms a bidentate chelate complex with the zinc ion and makes hydrogen bond interactions with conserved active site residues E78, H265, and T191. The inhibitor C-4 hydroxyl group makes direct hydrogen bond interactions with E197 and H58. Finally, the C-3 myristate moiety of the inhibitor binds in the hydrophobic tunnel of the active site. These intermolecular interactions provide a foundation for understanding structural aspects of enzyme-substrate and enzyme-inhibitor affinity. Comparison of the TU-514 complex with cacodylate and imidazole complexes suggests a possible substrate diphosphate binding site and highlights residues that may stabilize the tetrahedral intermediate and its flanking transition states in catalysis. Evidence of a catalytic zinc ion in the native zinc enzyme coordinated by H79, H238, D242, and two water molecules with square pyramidal geometry is also presented. These results suggest that the native state of this metallohydrolase may contain a pentacoordinate zinc ion, which contrasts with the native states of archetypical zinc hydrolases such as thermolysin and carboxypeptidase A

  18. Evolutionary Implications of Metal Binding Features in Different Species’ Prion Protein: An Inorganic Point of View

    Directory of Open Access Journals (Sweden)

    Diego La Mendola

    2014-05-01

    Full Text Available Prion disorders are a group of fatal neurodegenerative conditions of mammals. The key molecular event in the pathogenesis of such diseases is the conformational conversion of prion protein, PrPC, into a misfolded form rich in β-sheet structure, PrPSc, but the detailed mechanistic aspects of prion protein conversion remain enigmatic. There is uncertainty on the precise physiological function of PrPC in healthy individuals. Several evidences support the notion of its role in copper homeostasis. PrPC binds Cu2+ mainly through a domain composed by four to five repeats of eight amino acids. In addition to mammals, PrP homologues have also been identified in birds, reptiles, amphibians and fish. The globular domain of protein is retained in the different species, suggesting that the protein carries out an essential common function. However, the comparison of amino acid sequences indicates that prion protein has evolved differently in each vertebrate class. The primary sequences are strongly conserved in each group, but these exhibit a low similarity with those of mammals. The N-terminal domain of different prions shows tandem amino acid repeats with an increasing amount of histidine residues going from amphibians to mammals. The difference in the sequence affects the number of copper binding sites, the affinity and the coordination environment of metal ions, suggesting that the involvement of prion in metal homeostasis may be a specific characteristic of mammalian prion protein. In this review, we describe the similarities and the differences in the metal binding of different species’ prion protein, as revealed by studies carried out on the entire protein and related peptide fragments.

  19. Cementation of silver ions on metallic copper

    International Nuclear Information System (INIS)

    Jaskula, M.

    2009-01-01

    The silver cementation on metallic copper was investigated in the presence or absence of oxygen. The influence of sulphuric acid and copper sulphate concentration on the silver cement morphology was studied in details, and results were linked with the previously determined kinetics data of the process. The morpgology of silver depopsit was found to be independent of the prosence of oxygen in the system in as well as the sulphuric acide concentration. Contrary, the concentration of copper sulphate strongly influenced the morphology of silver deposite. Two-stage mechanism of cementation was proposed. (authors).

  20. Very broad beam metal ion source for large area ion implantation application

    International Nuclear Information System (INIS)

    Brown, I.; Anders, S.; Dickinson, M.R.; MacGill, R.A.; Yao, X.

    1993-01-01

    The authors have made and operated a very broad beam version of vacuum arc ion source and used it to carry out high energy metal ion implantation of a particularly large substrate. A multiple-cathode vacuum arc plasma source was coupled to a 50 cm diameter beam extractor (multiple aperture, accel-decel configuration) operated at a net extraction voltage of up to 50 kV. The metal ion species chosen were Ni and Ta. The mean ion charge state for Ni and Ta vacuum arc plasmas is 1.8 and 2.9, respectively, and so the mean ion energies were up to about 90 and 145 keV, respectively. The ion source was operated in a repetitively pulsed mode with pulse length 250 μs and repetition rate several pulses per second. The extracted beam had a gaussian profile with FWHM about 35 cm, giving a nominal beam area of about 1,000 cm 2 . The current of Ni or Ta metal ions in the beam was up to several amperes. The targets for the ion implantation were a number of 24-inch long, highly polished Cu rails from an electromagnetic rail gun. The rails were located about 80 cm away from the ion source extractor grids, and were moved across a diameter of the vessel in such a way as to maximize the uniformity of the implant along the rail. The saturation retained dose for Ta was limited to about 4 x 10 16 cm -2 because of the rather severe sputtering, in accordance with the theoretical expectations for these implantation conditions. Here they describe the ion source, the implantation procedure, and the kinds of implants that can be produced in this way

  1. Modification of medical metals by ion implantation of copper

    Science.gov (United States)

    Wan, Y. Z.; Xiong, G. Y.; Liang, H.; Raman, S.; He, F.; Huang, Y.

    2007-10-01

    The effect of copper ion implantation on the antibacterial activity, wear performance and corrosion resistance of medical metals including 317 L of stainless steels, pure titanium, and Ti-Al-Nb alloy was studied in this work. The specimens were implanted with copper ions using a MEVVA source ion implanter with ion doses ranging from 0.5 × 10 17 to 4 × 10 17 ions/cm 2 at an energy of 80 keV. The antibacterial effect, wear rate, and inflexion potential were measured as a function of ion dose. The results obtained indicate that copper ion implantation improves the antibacterial effect and wear behaviour for all the three medical materials studied. However, corrosion resistance decreases after ion implantation of copper. Experimental results indicate that the antibacterial property and corrosion resistance should be balanced for medical titanium materials. The marked deteriorated corrosion resistance of 317 L suggests that copper implantation may not be an effective method of improving its antibacterial activity.

  2. Method for removing metal ions from solution with titanate sorbents

    Science.gov (United States)

    Lundquist, Susan H.; White, Lloyd R.

    1999-01-01

    A method for removing metal ions from solution comprises the steps of providing titanate particles by spray-drying a solution or slurry comprising sorbent titanates having a particle size up to 20 micrometers, optionally in the presence of polymer free of cellulose functionality as binder, said sorbent being active towards heavy metals from Periodic Table (CAS version) Groups IA, IIA, IB, IIB, IIIB, and VIII, to provide monodisperse, substantially spherical particles in a yield of at least 70 percent of theoretical yield and having a particle size distribution in the range of 1 to 500 micrometers. The particles can be used free flowing in columns or beds, or entrapped in a nonwoven, fibrous web or matrix or a cast porous membrane, to selectively remove metal ions from aqueous or organic liquid.

  3. Crystal structures reveal metal-binding plasticity at the metallo-β-lactamase active site of PqqB from Pseudomonas putida

    Energy Technology Data Exchange (ETDEWEB)

    Tu, Xiongying; Latham, John A.; Klema, Valerie J.; Evans III, Robert L.; Li, Chao; Klinman, Judith P.; Wilmot, Carrie M. (UMM); (UCB)

    2017-08-19

    PqqB is an enzyme involved in the biosynthesis of pyrroloquinoline quinone and a distal member of the metallo-β-lactamase (MBL) superfamily. PqqB lacks two residues in the conserved signature motif HxHxDH that makes up the key metal-chelating elements that can bind up to two metal ions at the active site of MBLs and other members of its superfamily. Here, we report crystal structures of PqqB bound to Mn2+, Mg2+, Cu2+, and Zn2+. These structures demonstrate that PqqB can still bind metal ions at the canonical MBL active site. The fact that PqqB can adapt its side chains to chelate a wide spectrum of metal ions with different coordination features on a uniform main chain scaffold demonstrates its metal-binding plasticity. This plasticity may provide insights into the structural basis of promiscuous activities found in ensembles of metal complexes within this superfamily. Furthermore, PqqB belongs to a small subclass of MBLs that contain an additional CxCxxC motif that binds a structural Zn2+. Our data support a key role for this motif in dimerization.

  4. Crystal structures reveal metal-binding plasticity at the metallo-β-lactamase active site of PqqB from Pseudomonas putida.

    Science.gov (United States)

    Tu, Xiongying; Latham, John A; Klema, Valerie J; Evans, Robert L; Li, Chao; Klinman, Judith P; Wilmot, Carrie M

    2017-10-01

    PqqB is an enzyme involved in the biosynthesis of pyrroloquinoline quinone and a distal member of the metallo-β-lactamase (MBL) superfamily. PqqB lacks two residues in the conserved signature motif HxHxDH that makes up the key metal-chelating elements that can bind up to two metal ions at the active site of MBLs and other members of its superfamily. Here, we report crystal structures of PqqB bound to Mn 2+ , Mg 2+ , Cu 2+ , and Zn 2+ . These structures demonstrate that PqqB can still bind metal ions at the canonical MBL active site. The fact that PqqB can adapt its side chains to chelate a wide spectrum of metal ions with different coordination features on a uniform main chain scaffold demonstrates its metal-binding plasticity. This plasticity may provide insights into the structural basis of promiscuous activities found in ensembles of metal complexes within this superfamily. Furthermore, PqqB belongs to a small subclass of MBLs that contain an additional CxCxxC motif that binds a structural Zn 2+ . Our data support a key role for this motif in dimerization.

  5. Recovery of toxic metal ions from washing effluent containing excess aminopolycarboxylate chelant in solution.

    Science.gov (United States)

    Hasegawa, Hiroshi; Rahman, Ismail M M; Nakano, Masayoshi; Begum, Zinnat A; Egawa, Yuji; Maki, Teruya; Furusho, Yoshiaki; Mizutani, Satoshi

    2011-10-15

    Aminopolycarboxylate chelants (APCs) are extremely useful for a variety of industrial applications, including the treatment of toxic metal-contaminated solid waste materials. Because non-toxic matrix elements compete with toxic metals for the binding sites of APCs, an excess of chelant is commonly added to ensure the adequate sequestration of toxic metal contaminants during waste treatment operations. The major environmental impacts of APCs are related to their ability to solubilize toxic heavy metals. If APCs are not sufficiently eliminated from the effluent, the aqueous transport of metals can occur through the introduction of APCs into the natural environment, increasing the magnitude of associated toxicity. Although several techniques that focus primarily on the degradation of APCs at the pre-release step have been proposed, methods that recycle not only the processed water, but also provide the option to recover and reuse the metals, might be economically feasible, considering the high costs involved due to the chelants used in metal ion sequestration. In this paper, we propose a separation process for the recovery of metals from effluents that contain an excess of APCs. Additionally, the option of recycling the processed water using a solid phase extraction (SPE) system with an ion-selective immobilized macrocyclic material, commonly known as a molecular recognition technology (MRT) gel, is presented. Simulated effluents containing As(V), Cd(II), Cr(III), Pb(II) or Se(IV) in the presence of APCs at molar ratios of 1:50 in H2O were studied with a flow rate of 0.2 mL min(-1). The 'captured' ions in the SPE system were quantitatively eluted with HNO3. The effects of solution pH, metal-chelant stability constants and matrix elements were assessed. Better separation performance for the metals was achieved with the MRT-SPE compared to other SPE materials. Our proposed technique offers the advantage of a non-destructive separation of both metal ions and chelants

  6. Ion spectra of the metal vapor vacuum arc ion source with compound and alloy cathodes

    Science.gov (United States)

    Sasaki, Jun; Brown, Ian G.

    1990-01-01

    In metal vapor vacuum arc (MEVVA) ion sources, vacuum arc plasma with cathodes of single, pure elements has been utilized for the production of metal ions. In this study, we have investigated the charge state distributions of ions produced in vacuum arc plasmas in a MEVVA ion source for the case when the cathode is an alloy or a compound material. The ion charge state spectra were analyzed by means of a time-of-flight apparatus. We have compared the ion spectra for a cathode of an alloy or a compound material with its constituent elements: TiC/TiN/TiO2/Ti/C, SiC/Si/C, WC/W/C U/UN/(UN-ZrC)/Zr/C, and brass/Zn/Cu. We find that the MEVVA produces ions of all constituent elements in the compound and the alloy cathodes. The charge state distribution of each element differs, however, from the charge state distribution obtained in the vacuum arc with a cathode made of the pure, single constituent element. Fractional values of the total ion numbers of each constituent element in the extracted beam depart from the stoichiometry of the elements in the cathode material. In an operation with a TiC cathode, we irradiated a 304 stainless-steel plate with the extracted beam. Results from glow-discharge spectroscopy (GDS) of the surface show that both titanium and carbon are implanted in the substrate after the irradiation.

  7. Characterization of Metal Binding in the Active Sites of acireductone dioxygenase Isoforms from Klebsiella ATCC 8724

    Energy Technology Data Exchange (ETDEWEB)

    S Chai; T Ju; M Dang; R Goldsmith; M Maroney; T Pochapsky

    2011-12-31

    The two acireductone dioxygenase (ARD) isozymes from the methionine salvage pathway of Klebsiella ATCC 8724 present an unusual case in which two enzymes with different structures and distinct activities toward their common substrates (1,2-dihydroxy-3-oxo-5-(methylthio)pent-1-ene and dioxygen) are derived from the same polypeptide chain. Structural and functional differences between the two isozymes are determined by the type of M{sup 2+} metal ion bound in the active site. The Ni{sup 2+}-bound NiARD catalyzes an off-pathway shunt from the methionine salvage pathway leading to the production of formate, methylthiopropionate, and carbon monoxide, while the Fe{sup 2+}-bound FeARD catalyzes the on-pathway formation of methionine precursor 2-keto-4-methylthiobutyrate and formate. Four potential protein-based metal ligands were identified by sequence homology and structural considerations. Based on the results of site-directed mutagenesis experiments, X-ray absorption spectroscopy (XAS), and isothermal calorimetry measurements, it is concluded that the same four residues, His96, His98, Glu102 and His140, provide the protein-based ligands for the metal in both the Ni- and Fe-containing forms of the enzyme, and subtle differences in the local backbone conformations trigger the observed structural and functional differences between the FeARD and NiARD isozymes. Furthermore, both forms of the enzyme bind their respective metals with pseudo-octahedral geometry, and both may lose a histidine ligand upon binding of substrate under anaerobic conditions. However, mutations at two conserved nonligand acidic residues, Glu95 and Glu100, result in low metal contents for the mutant proteins as isolated, suggesting that some of the conserved charged residues may aid in transfer of metal from in vivo sources or prevent the loss of metal to stronger chelators. The Glu100 mutant reconstitutes readily but has low activity. Mutation of Asp101 results in an active enzyme that incorporates

  8. Metal ion levels and lymphocyte counts

    DEFF Research Database (Denmark)

    Penny, Jeannette Ø; Varmarken, Jens-Erik; Ovesen, Ole

    2013-01-01

    . RESULTS: The T-lymphocyte counts for both implant types declined over the 2-year period. This decline was statistically significant for CD3(+)CD8(+) in the THA group, with a regression coefficient of -0.04 × 10(9)cells/year (95% CI: -0.08 to -0.01). Regression analysis indicated a depressive effect...... of cobalt ions in particular on T-cells with 2-year whole-blood cobalt regression coefficients for CD3+ of -0.10 (95% CI: -0.16 to -0.04) × 10(9) cells/parts per billion (ppb), for CD3+CD4+ of -0.06 (-0.09 to -0.03) × 10(9) cells/ppb, and for CD3(+)CD8(+) of -0.02 (-0.03 to -0.00) × 10(9) cells...

  9. Fluoroquinolones stimulate the DNA cleavage activity of topoisomerase IV by promoting the binding of Mg(2+) to the second metal binding site.

    Science.gov (United States)

    Oppegard, Lisa M; Schwanz, Heidi A; Towle, Tyrell R; Kerns, Robert J; Hiasa, Hiroshi

    2016-03-01

    Fluoroquinolones target bacterial type IIA topoisomerases, DNA gyrase and topoisomerase IV (Topo IV). Fluoroquinolones trap a topoisomerase-DNA covalent complex as a topoisomerase-fluoroquinolone-DNA ternary complex and ternary complex formation is critical for their cytotoxicity. A divalent metal ion is required for type IIA topoisomerase-catalyzed strand breakage and religation reactions. Recent studies have suggested that type IIA topoisomerases use two metal ions, one structural and one catalytic, to carry out the strand breakage reaction. We conducted a series of DNA cleavage assays to examine the effects of fluoroquinolones and quinazolinediones on Mg(2+)-, Mn(2+)-, or Ca(2+)-supported DNA cleavage activity of Escherichia coli Topo IV. In the absence of any drug, 20-30 mM Mg(2+) was required for the maximum levels of the DNA cleavage activity of Topo IV, whereas approximately 1mM of either Mn(2+) or Ca(2+) was sufficient to support the maximum levels of the DNA cleavage activity of Topo IV. Fluoroquinolones promoted the Topo IV-catalyzed strand breakage reaction at low Mg(2+) concentrations where Topo IV alone could not efficiently cleave DNA. At low Mg(2+) concentrations, fluoroquinolones may stimulate the Topo IV-catalyzed strand breakage reaction by promoting Mg(2+) binding to metal binding site B through the structural distortion in DNA. As Mg(2+) concentration increases, fluoroquinolones may inhibit the religation reaction by either stabilizing Mg(2+) at site B or inhibition the binding of Mg(2+) to site A. This study provides a molecular basis of how fluoroquinolones stimulate the Topo IV-catalyzed strand breakage reaction by modulating Mg(2+) binding. Copyright © 2015 Elsevier B.V. All rights reserved.

  10. Fluoroquinolones stimulate the DNA cleavage activity of topoisomerase IV by promoting the binding of Mg2+ to the second metal binding site

    Science.gov (United States)

    Oppegard, Lisa M.; Schwanz, Heidi A.; Towle, Tyrell R.; Kerns, Robert J.; Hiasa, Hiroshi

    2016-01-01

    Background Fluoroquinolones target bacterial type IIA topoisomerases, DNA gyrase and topoisomerase IV (Topo IV). Fluoroquinolones trap a topoisomerase-DNA covalent complex as a topoisomerase-fluoroquinolone-DNA ternary complex and ternary complex formation is critical for their cytotoxicity. A divalent metal ion is required for type IIA topoisomerase-catalyzed strand breakage and religation reactions. Recent studies have suggested that type IIA topoisomerases use two metal ions, one structural and one catalytic, to carry out the strand breakage reaction. Methods We conducted a series of DNA cleavage assays to examine the effects of fluoroquinolones and quinazolinediones on Mg2+-, Mn2+-, or Ca2+-supported DNA cleavage activity of Esherichia coli Topo IV. Results In the absence of any drug, 20–30 mM Mg2+ was required for the maximum levels of the DNA cleavage activity of Topo IV, whereas approximately 1 mM of either Mn2+ or Ca2+ was sufficient to support the maximum levels of the DNA cleavage activity of Topo IV. Fluoroquinolones promoted the Topo IV-catalyzed strand breakage reaction at low Mg2+ concentrations where Topo IV alone could not efficiently cleave DNA. Conclusions and General Significance At low Mg2+ concentrations, fluoroquinolones may stimulate the Topo IV-catalyzed strand breakage reaction by promoting Mg2+ binding to metal binding site B through the structural distortion in DNA. As Mg2+ concentration increases, fluoroquinolones may inhibit the religation reaction by either stabilizing Mg2+ at site B or inhibition the binding of Mg2+ to site A. This study provides a molecular basis of how fluoroquinolones stimulate the Topo IV-catalyzed strand breakage reaction by modulating Mg2+ binding. PMID:26723176

  11. Comparison of metal ion concentrations and implant survival after total hip arthroplasty with metal-on-metal versus metal-on-polyethylene articulations

    OpenAIRE

    Dahlstrand, Henrik; Stark, André; Wick, Marius C; Anissian, Lucas; Hailer, Nils P; Weiss, Rüdiger J

    2017-01-01

    Background and purpose Large metal-on-metal (MoM) articulations are associated with metal wear and corrosion, leading to increased metal ion concentrations and unacceptable revision rates. There are few comparative studies of 28-mm MoM articulations with conventional metal-on-polyethylene (MoP) couplings. We present a long-term follow-up of a randomized controlled trial comparing MoM versus MoP 28-mm articulations, focused on metal ions and implant survival. Patients and methods 85 patients w...

  12. Development of a four-zone carousel process packed with metal ion-imprinted polymer for continuous separation of copper ions from manganese ions, cobalt ions, and the constituent metal ions of the buffer solution used as eluent.

    Science.gov (United States)

    Jo, Se-Hee; Park, Chanhun; Yi, Sung Chul; Kim, Dukjoon; Mun, Sungyong

    2011-08-19

    A three-zone carousel process, in which Cu(II)-imprinted polymer (Cu-MIP) and a buffer solution were employed as adsorbent and eluent respectively, has been developed previously for continuous separation of Cu²⁺ (product) from Mn²⁺ and Co²⁺ (impurities). Although this process was reported to be successful in the aforementioned separation task, the way of using a buffer solution as eluent made it inevitable that the product stream included the buffer-related metal ions (i.e., the constituent metal ions of the buffer solution) as well as copper ions. For a more perfect recovery of copper ions, it would be necessary to improve the previous carousel process such that it can remove the buffer-related metal ions from copper ions while maintaining the previous function of separating copper ions from the other 2 impure heavy-metal ions. This improvement was made in this study by proposing a four-zone carousel process based on the following strategy: (1) the addition of one more zone for performing the two-step re-equilibration tasks and (2) the use of water as the eluent of the washing step in the separation zone. The operating conditions of such a proposed process were determined on the basis of the data from a series of single-column experiments. Under the determined operating conditions, 3 runs of carousel experiments were carried out. The results of these experiments revealed that the feed-loading time was a key parameter affecting the performance of the proposed process. Consequently, the continuous separation of copper ions from both the impure heavy-metal ions and the buffer-related metal ions could be achieved with a purity of 91.9% and a yield of 92.8% by using the proposed carousel process based on a properly chosen feed-loading time. Copyright © 2011 Elsevier B.V. All rights reserved.

  13. Interaction of Metal Ions with Biomolecular Ligands: How Accurate Are Calculated Free Energies Associated with Metal Ion Complexation?

    Czech Academy of Sciences Publication Activity Database

    Gutten, Ondrej; Beššeová, Ivana; Rulíšek, Lubomír

    2011-01-01

    Roč. 115, č. 41 (2011), s. 11394-11402 ISSN 1089-5639 R&D Projects: GA MŠk LC512 Institutional research plan: CEZ:AV0Z40550506 Keywords : metal-ion selectivity * theoretical calculations * stability constants Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.946, year: 2011

  14. Kinetic study of heavy metal ions removal by ion exchange in batch conical air spouted bed

    Directory of Open Access Journals (Sweden)

    T.M. Zewail

    2015-03-01

    Full Text Available Spouted bed contactor is a hybrid of fixed and fluidized bed contactors, which retains the advantages of each with good hydrodynamic conditions. The aim of the present study is to investigate the performance of a batch conical air spouted vessel for heavy metal removal by strong cation exchange resins (AMBERJET 1200 Na. The effect of various parameters such as type of heavy metal ions (Ni+2 and Pb+2, contact time, superficial air velocity and initial heavy metal ion concentration on % heavy metal ion removal has been investigated. It has been found that under optimum conditions 98% and 99% removal of Ni+2 and Pb+2 were achieved respectively. Several kinetic models were used to test the experimental data and to examine the controlling mechanism of the sorption process. The present results of Ni+2 and Pb+2 well fit pseudo second order kinetic model with a high correlation coefficient. Both film diffusion and intra-particle diffusion contribute to the ion exchange process. The present study revealed that spouted bed vessel may provide an effective alternative for conducting ion exchange reactions.

  15. Ion conducting polymers and polymer blends for alkali metal ion batteries

    Science.gov (United States)

    DeSimone, Joseph M.; Pandya, Ashish; Wong, Dominica; Vitale, Alessandra

    2017-08-29

    Electrolyte compositions for batteries such as lithium ion and lithium air batteries are described. In some embodiments the compositions are liquid compositions comprising (a) a homogeneous solvent system, said solvent system comprising a perfluropolyether (PFPE) and polyethylene oxide (PEO); and (b) an alkali metal salt dissolved in said solvent system. In other embodiments the compositions are solid electrolyte compositions comprising: (a) a solid polymer, said polymer comprising a crosslinked product of a crosslinkable perfluropolyether (PFPE) and a crosslinkable polyethylene oxide (PEO); and (b) an alkali metal ion salt dissolved in said polymer. Batteries containing such compositions as electrolytes are also described.

  16. Molecular mechanism of ATP binding and ion channel activation in P2X receptors

    Energy Technology Data Exchange (ETDEWEB)

    Hattori, Motoyuki; Gouaux, Eric (Oregon HSU)

    2012-10-24

    P2X receptors are trimeric ATP-activated ion channels permeable to Na{sup +}, K{sup +} and Ca{sup 2+}. The seven P2X receptor subtypes are implicated in physiological processes that include modulation of synaptic transmission, contraction of smooth muscle, secretion of chemical transmitters and regulation of immune responses. Despite the importance of P2X receptors in cellular physiology, the three-dimensional composition of the ATP-binding site, the structural mechanism of ATP-dependent ion channel gating and the architecture of the open ion channel pore are unknown. Here we report the crystal structure of the zebrafish P2X4 receptor in complex with ATP and a new structure of the apo receptor. The agonist-bound structure reveals a previously unseen ATP-binding motif and an open ion channel pore. ATP binding induces cleft closure of the nucleotide-binding pocket, flexing of the lower body {beta}-sheet and a radial expansion of the extracellular vestibule. The structural widening of the extracellular vestibule is directly coupled to the opening of the ion channel pore by way of an iris-like expansion of the transmembrane helices. The structural delineation of the ATP-binding site and the ion channel pore, together with the conformational changes associated with ion channel gating, will stimulate development of new pharmacological agents.

  17. In vitro cytotoxicity of metallic ions released from dental alloys.

    Science.gov (United States)

    Milheiro, Ana; Nozaki, Kosuke; Kleverlaan, Cornelis J; Muris, Joris; Miura, Hiroyuki; Feilzer, Albert J

    2016-05-01

    The cytotoxicity of a dental alloy depends on, but is not limited to, the extent of its corrosion behavior. Individual ions may have effects on cell viability that are different from metals interacting within the alloy structure. We aimed to investigate the cytotoxicity of individual metal ions in concentrations similar to those reported to be released from Pd-based dental alloys on mouse fibroblast cells. Metal salts were used to prepare seven solutions (concentration range 100 ppm-1 ppb) of the transition metals, such as Ni(II), Pd(II), Cu(II), and Ag(I), and the metals, such as Ga(III), In(III), and Sn(II). Cytotoxicity on mouse fibroblasts L929 was evaluated using the MTT assay. Ni, Cu, and Ag are cytotoxic at 10 ppm, Pd and Ga at 100 ppm. Sn and In were not able to induce cytotoxicity at the tested concentrations. Transition metals were able to induce cytotoxic effects in concentrations similar to those reported to be released from Pd-based dental alloys. Ni, Cu, and Ag were the most cytotoxic followed by Pd and Ga; Sn and In were not cytotoxic. Cytotoxic reactions might be considered in the etiopathogenesis of clinically observed local adverse reactions.

  18. Adsorptive Removal of Metal Ions from Water using Functionalized Biomaterials.

    Science.gov (United States)

    Deshpande, Kanchanmala

    2017-01-01

    Synthesis and modification of cost-effective sorbents for removing heavy metals from water resources is an area of significance. It had been reported that materials with biological origins, such as agricultural and animal waste, are excellent alternatives to conventional adsorbents due to their higher affinity, capacity and selectivity towards metal ions. These properties of biomaterials help to reduce or detoxify metal ions concentration in contaminated water to acceptable regulatory standards. Synthesis of novel, efficient, cost effective, eco-friendly biomaterials for heavy metal adsorption from water is still an area of challenge. In this comprehensive review, acompilation of patents as well as published articles is carried out to outline the properties of different biomaterials based on their precursors along withdetailed description of biomaterial morphology and various surface modification approaches. A detailed study of the performance of adsorbents and the role of physical and chemical modification in terms of enhancing their potential for metal adsorption from water is compiled here. The factors affecting adsorption behavior i.e., capacity and affinity of e biomaterials is also compiled. This paper presents a concise review of reported studies on the synthesis and modification of biomaterials, their use for heavy metal removal from waters and future prospects of this technology. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

  19. Liquid metal alloy ion sources—An alternative for focussed ion beam technology

    International Nuclear Information System (INIS)

    Bischoff, Lothar; Mazarov, Paul; Bruchhaus, Lars; Gierak, Jacques

    2016-01-01

    Today, Focused Ion Beam (FIB) processing is nearly exclusively based on gallium Liquid Metal Ion Sources (LMIS). But, many applications in the μm- or nm range could benefit from ion species other than gallium: local ion implantation, ion beam mixing, ion beam synthesis, or Focused Ion Beam Lithography (IBL). Therefore, Liquid Metal Alloy Ion Sources (LMAIS) represent a promising alternative to expand the remarkable application fields for FIB. Especially, the IBL process shows potential advantages over, e.g., electron beam or other lithography techniques: direct, resistless, and three-dimensional patterning, enabling a simultaneous in-situ process control by cross-sectioning and inspection. Taking additionally into account that the used ion species influences significantly the physical and chemical nature of the resulting nanostructures—in particular, the electrical, optical, magnetic, and mechanic properties leading to a large potential application area which can be tuned by choosing a well suited LMAIS. Nearly half of the elements of the periodic table are recently available in the FIB technology as a result of continuous research in this area during the last forty years. Key features of a LMAIS are long life-time, high brightness, and stable ion current. Recent developments could make these sources feasible for nano patterning issues as an alternative technology more in research than in industry. The authors will review existing LMAIS, LMIS other than Ga, and binary and ternary alloys. These physical properties as well as the fabrication technology and prospective domains for modern FIB applications will similarly be reviewed. Other emerging ion sources will be also presented and their performances discussed.

  20. Metal ion dependence of DNA cleavage by SepMI and EhoI restriction endonucleases.

    Science.gov (United States)

    Belkebir, Abdelkarim; Azeddoug, Houssine

    2013-02-22

    Most of type II restriction endonucleases show an absolute requirement for divalent metal ions as cofactors for DNA cleavage. While Mg(2+) is the natural cofactor other metal ions can substitute it and mediate the catalysis, however Ca(2+) (alone) only supports DNA binding. To investigate the role of Mg(2+) in DNA cleavage by restriction endonucleases, we have studied the Mg(2+) and Mn(2+) concentration dependence of DNA cleavage by SepMI and EhoI. Digestion reactions were carried out at different Mg(2+) and Mn(2+) concentrations at constant ionic strength. These enzymes showed different behavior regarding the ions requirement, SepMI reached near maximal level of activity between 10 and 20mM while no activity was detected in the presence of Mn(2+) and in the presence of Ca(2+) cleavage activity was significantly decreased. However, EhoI was more highly active in the presence of Mn(2+) than in the presence of Mg(2+) and can be activated by Ca(2+). Our results propose the two-metal ion mechanism for EhoI and the one-metal ion mechanism for SepMI restriction endonuclease. The analysis of the kinetic parameters under steady state conditions showed that SepMI had a K(m) value for pTrcHisB DNA of 6.15 nM and a V(max) of 1.79×10(-2)nM min(-1), while EhoI had a K(m) for pUC19 plasmid of 8.66 nM and a V(max) of 2×10(-2)nM min(-1). Copyright © 2012 Elsevier GmbH. All rights reserved.

  1. Functional analysis of the citrate activator CitO from Enterococcus faecalis implicates a divalent metal in ligand binding

    Directory of Open Access Journals (Sweden)

    Victor S. Blancato

    2016-02-01

    Full Text Available The regulator of citrate metabolism, CitO, from Enterococcus faecalis belongs to the FCD family within the GntR superfamily. In the presence of citrate, CitO binds to cis-acting sequences located upstream of the cit promoters inducing the expression of genes involved in citrate utilization. The quantification of the molecular binding affinities, performed by isothermal titration calorimetry (ITC, indicated that CitO has a high affinity for citrate (KD= 1.2±0.2 µM, while it did not recognize other metabolic intermediates. Based on a structural model of CitO where a putative small molecule and a metal binding site were identified, it was hypothesized that the metal ion is required for citrate binding. In agreement with this model, citrate binding to CitO sharply decreased when the protein was incubated with EDTA. This effect was reverted by the addition of Ni2+, and Zn2+ to a lesser extent. Structure-based site-directed mutagenesis was conducted and it was found that changes to alanine in residues Arg97 and His191 resulted in decreased binding affinities for citrate, as determined by EMSA and ITC. Further assays using lacZ fusions confirmed that these residues in CitO are involved in sensing citrate in vivo. These results indicate that the molecular modifications induced by a ligand and a metal binding in the C-terminal domain of CitO are required for optimal DNA binding activity, and consequently, transcriptional activation.

  2. Validation of metal-binding sites in macromolecular structures with the CheckMyMetal web server.

    Science.gov (United States)

    Zheng, Heping; Chordia, Mahendra D; Cooper, David R; Chruszcz, Maksymilian; Müller, Peter; Sheldrick, George M; Minor, Wladek

    2014-01-01

    Metals have vital roles in both the mechanism and architecture of biological macromolecules. Yet structures of metal-containing macromolecules in which metals are misidentified and/or suboptimally modeled are abundant in the Protein Data Bank (PDB). This shows the need for a diagnostic tool to identify and correct such modeling problems with metal-binding environments. The CheckMyMetal (CMM) web server (http://csgid.org/csgid/metal_sites/) is a sophisticated, user-friendly web-based method to evaluate metal-binding sites in macromolecular structures using parameters derived from 7,350 metal-binding sites observed in a benchmark data set of 2,304 high-resolution crystal structures. The protocol outlines how the CMM server can be used to detect geometric and other irregularities in the structures of metal-binding sites, as well as how it can alert researchers to potential errors in metal assignment. The protocol also gives practical guidelines for correcting problematic sites by modifying the metal-binding environment and/or redefining metal identity in the PDB file. Several examples where this has led to meaningful results are described in the ANTICIPATED RESULTS section. CMM was designed for a broad audience--biomedical researchers studying metal-containing proteins and nucleic acids--but it is equally well suited for structural biologists validating new structures during modeling or refinement. The CMM server takes the coordinates of a metal-containing macromolecule structure in the PDB format as input and responds within a few seconds for a typical protein structure with 2-5 metal sites and a few hundred amino acids.

  3. Role of metal ions on the activity of Mycobacterium tuberculosis pyrazinamidase.

    Science.gov (United States)

    Sheen, Patricia; Ferrer, Patricia; Gilman, Robert H; Christiansen, Gina; Moreno-Román, Paola; Gutiérrez, Andrés H; Sotelo, Jun; Evangelista, Wilfredo; Fuentes, Patricia; Rueda, Daniel; Flores, Myra; Olivera, Paula; Solis, José; Pesaresi, Alessandro; Lamba, Doriano; Zimic, Mirko

    2012-07-01

    Pyrazinamidase of Mycobacterium tuberculosis catalyzes the conversion of pyrazinamide to the active molecule pyrazinoic acid. Reduction of pyrazinamidase activity results in a level of pyrazinamide resistance. Previous studies have suggested that pyrazinamidase has a metal-binding site and that a divalent metal cofactor is required for activity. To determine the effect of divalent metals on the pyrazinamidase, the recombinant wild-type pyrazinamidase corresponding to the H37Rv pyrazinamide-susceptible reference strain was expressed in Escherichia coli with and without a carboxy terminal. His-tagged pyrazinamidase was inactivated by metal depletion and reactivated by titration with divalent metals. Although Co(2+), Mn(2+), and Zn(2+) restored pyrazinamidase activity, only Co(2+) enhanced the enzymatic activity to levels higher than the wild-type pyrazinamidase. Cu(2+), Fe(2+), Fe(3+), and Mg(2+) did not restore the activity under the conditions tested. Various recombinant mutated pyrazinamidases with appropriate folding but different enzymatic activities showed a differential pattern of recovered activity. X-ray fluorescence and atomic absorbance spectroscopy showed that recombinant wild-type pyrazinamidase expressed in E. coli most likely contained Zn. In conclusion, this study suggests that M. tuberculosis pyrazinamidase is a metalloenzyme that is able to coordinate several ions, but in vivo, it is more likely to coordinate Zn(2+). However, in vitro, the metal-depleted enzyme could be reactivated by several divalent metals with higher efficiency than Zn.

  4. Role of Metal Ions on the Activity of Mycobacterium tuberculosis Pyrazinamidase

    Science.gov (United States)

    Sheen, Patricia; Ferrer, Patricia; Gilman, Robert H.; Christiansen, Gina; Moreno-Román, Paola; Gutiérrez, Andrés H.; Sotelo, Jun; Evangelista, Wilfredo; Fuentes, Patricia; Rueda, Daniel; Flores, Myra; Olivera, Paula; Solis, José; Pesaresi, Alessandro; Lamba, Doriano; Zimic, Mirko

    2012-01-01

    Pyrazinamidase of Mycobacterium tuberculosis catalyzes the conversion of pyrazinamide to the active molecule pyrazinoic acid. Reduction of pyrazinamidase activity results in a level of pyrazinamide resistance. Previous studies have suggested that pyrazinamidase has a metal-binding site and that a divalent metal cofactor is required for activity. To determine the effect of divalent metals on the pyrazinamidase, the recombinant wild-type pyrazinamidase corresponding to the H37Rv pyrazinamide-susceptible reference strain was expressed in Escherichia coli with and without a carboxy terminal. His-tagged pyrazinamidase was inactivated by metal depletion and reactivated by titration with divalent metals. Although Co2+, Mn2+, and Zn2+ restored pyrazinamidase activity, only Co2+ enhanced the enzymatic activity to levels higher than the wild-type pyrazinamidase. Cu2+, Fe2+, Fe3+, and Mg2+ did not restore the activity under the conditions tested. Various recombinant mutated pyrazinamidases with appropriate folding but different enzymatic activities showed a differential pattern of recovered activity. X-ray fluorescence and atomic absorbance spectroscopy showed that recombinant wild-type pyrazinamidase expressed in E. coli most likely contained Zn. In conclusion, this study suggests that M. tuberculosis pyrazinamidase is a metalloenzyme that is able to coordinate several ions, but in vivo, it is more likely to coordinate Zn2+. However, in vitro, the metal-depleted enzyme could be reactivated by several divalent metals with higher efficiency than Zn. PMID:22764307

  5. Ion beam mixing isotopic metal bilayers

    Energy Technology Data Exchange (ETDEWEB)

    Fell, C.J. [Newcastle Univ., NSW (Australia). Dept. of Physics; Kenny, M.J. [CSIRO, Lindfield, NSW (Australia). Div. of Applied Physics

    1993-12-31

    In order to obtain an insight into the mechanisms of ion-solid interactions, bilayer targets can be prepared from two different isotopes. A mixing study SIMS is to be carried out using specially grown monocrystalline bilayers of {sup 58}Ni / {sup 60}Ni. An important aspect of the work is the preparation of high quality single-crystal thin films. The Ni layers will be grown on the (110) surface of pure Ni and verified for crystallinity using Reflection High-Energy Electron Diffraction and Rutherford Backscattering channelling analysis. The Pd bilayers will be grown on a Pd (100) surface. RHEED will be used to confirm the two-dimensional crystallinity of the surface before and after deposition of each layer, and channelling used to confirm bulk film crystallinity. Single crystal substrates are currently being prepared. Analysis of the Ni (110) surface using RHEED at 9 kV shows a streak spacing which corresponds to a lattice spacing of 2.47 {+-} 0.09 Angstroms. 9 refs., 1 fig.

  6. Serum albumin forms a lactoferrin-like soluble iron-binding complex in presence of hydrogen carbonate ions.

    Science.gov (United States)

    Ueno, Hiroshi M; Urazono, Hiroshi; Kobayashi, Toshiya

    2014-02-15

    The iron-lactoferrin complex is a common food ingredient because of its iron-solubilizing capability in the presence of hydrogen carbonate ions. However, it is unclear whether the formation of a stable iron-binding complex is limited to lactoferrin. In this study, we investigated the effects of bovine serum albumin (BSA) on iron solubility and iron-catalyzed lipid oxidation in the presence of hydrogen carbonate ions. BSA could solubilize >100-fold molar equivalents of iron at neutral pH, exceeding the specific metal-binding property of BSA. This iron-solubilizing capability of BSA was impaired by thermally denaturing BSA at ≥ 70 °C for 10 min at pH 8.5. The resulting iron-BSA complex inhibited iron-catalyzed oxidation of soybean oil in a water-in-oil emulsion measured using the Rancimat test. Our study is the first to show that BSA, like lactoferrin, forms a soluble iron-binding complex in the presence of hydrogen carbonate ions. Copyright © 2013 Elsevier Ltd. All rights reserved.

  7. [Applications of metal ions and their complexes in medicine I].

    Science.gov (United States)

    Nagy, László; Csintalan, Gabriella; Kálmán, Eszter; Sipos, Pál; Szvetnik, Attila

    2003-01-01

    The "inorganic medical chemistry" is a rapidly developing field with enormous potential for applications, which offers new possibilities to the pharmaceutical industry. For example, the titanocene dichloride is already in clinical use, and antimetastatic activity of a range of Ru(III) complexes is also well established. There are ways to minimize the toxicity of Gd(III) complexes and therefore they can be safely injected as MRI contrast agents. The so called "ligand design" allows paramagnetic ions to be targeted to specific organs. Such designed ligands also enable the targeting of radiodiagnostic (99mTc) and radiotherapeutic (186Re) isotopes. There is a significant progress in understanding the coordination chemistry and biochemistry of metal ion(s) containing complexes such as Au antiarthritic and Bi antiulcer drugs. Further, currently developing areas include Mn (SOD mimics), V (insulin mimics), Ru (NO scavengers), Ln-based photosensitizers, metal-targeted organic agents and the Fe overload. The expanding knowledge of the role of metals in biochemistry is expected to provide scope for the design of new drugs in many other areas too, for example neuropharmaceutical and antiaffective agents. Progress in coordination chemistry is strongly dependent on understanding not only the thermodynamics of reactions, but also the kinetics of metal complexes under biologically relevant conditions.

  8. Multiheteromacrocycles that Complex Metal Ions. Second Progress Report, 1 May 1975 -- 30 April 1976

    Science.gov (United States)

    Cram, D. J.

    1976-01-15

    Objective is to develop cyclic and polycyclic host organic compounds to complex and lipophilize metal ions. Macrorings were synthesized: (OCH{sub 2} CH{sub 2} O CH{sub 2}COCH{sub 2} COCH{sub 2}){sub 2} and (OCH{sub 2} CH{sub 2} O CH{sub 2} COCH{sub 2} COCH{sub 2}){sub 3}. The smaller ring complexes divalent metals 10{sup 1+9} times better than the open-chain model CH{sub 3} O CH{sub 2} CO CH{sub 2} COCH{sub 2} O CH{sub 3}, and the order in which metal ions are complexed is Cu{sup 2+}, UO{sub 2}{sup 2+} greater than Ni{sup 2+} greater than Fe{sup 2+}, Co{sup 2+}, Zn{sup 2+}, Cd{sup 2+} greater than Mn{sup 2+}. The UO{sub 2}{sup 2+} and Cu{sup 2+} complexes were isolated and characterized. The larger ring complexes trivalent metals 10{sup 0.9-1.7} times better than the open- chain model compound, and the order is La{sup 3+}, Ce{sup 3+} greater than Cr{sup 3+}. Five other macrocycles were also synthesized, and their binding constants with Na, K, NH{sub 4}, and Cs picrates were measured. Six compounds containing one macroring and two inward-pointing ArOH or ArOCH{sub 3} groups were also prepared and tested for binding of Li, Na, K, Rb, and NH{sub 4} picrates. Racemic compounds containing two binaphthyls and its sulfur analog were prepared. Cage-shaped multiheteromacrocycles containing ten O ligand sites or four S and six O ligand sites were prepared and the binding capability of the first compound for picrates studied. Two ring systems with phosphonate ester groups were also prepared. (DLC)

  9. Enrichment of rare earth metal ions by the highly selective adsorption of phytate intercalated layered double hydroxide.

    Science.gov (United States)

    Jin, Cheng; Liu, Huimin; Kong, Xianggui; Yan, Hong; Lei, Xiaodong

    2018-02-27

    Phytate intercalated MgAl layered double hydroxide (MgAl-LDH) was prepared by an anion exchange method with the precursor NO 3 - containing MgAl-LDH. The final as-synthesized product [Mg 0.69 Al 0.31 (OH) 2 ] (phytateNa 6 ) 0.05 (NO 3 ) 0.01 ·mH 2 O (phytate-LDH) has highly selective adsorption ability for some metal ions and can be used to enrich rare earth metal ions in mixed solution, such as Pr 3+ and Ce 3+ from a mixed solution of them with Pb 2+ and Co 2+ . At first, phytate-LDH has good adsorption performance for these ions in single metal ion solutions. At low concentration (below 10 mg L -1 ), all the capture rates of the four metal ions were more than 97%, for highly toxic Pb 2+ it was even up to nearly 100%, and a high capture rate (99.87%) was maintained for Pb 2+ at a high concentration (100 mg L -1 ). When all the four metal ions are co-existing in aqueous solution, the selectivity order is Pb 2+ ≫ Pr 3+ ≈ Ce 3+ > Co 2+ . In a solution containing mixtures of the three metal ions of Pr 3+ , Ce 3+ , and Co 2+ , the selectivity order is Pr 3+ ≈ Ce 3+ ≫ Co 2+ , and in a solution containing mixtures of Pr 3+ with Co 2+ and Ce 3+ with Co 2+ , the selectivity orders are Pr 3+ ≫ Co 2+ and Ce 3+ ≫ Co 2+ , respectively. The high selectivity and adsorption capacities for Pb 2+ , Co 2+ , Pr 3+ , and Ce 3+ result in the efficient removal of Pb 2+ and enrichment of the rare earth metal ions Pr 3+ and Ce 3+ by phytate-LDH. Based on the elemental analysis, it is found that the difference of the adsorption capacities is mainly due to the different coordination number of them with phytate-LDH. With molecular simulation, we believe that the adsorption selectivity is due to the difference of the binding energy between the metal ion and phytate-LDH. Therefore, the phytate-LDH is promising for the enrichment and/or purification of the rare earth metal ions and removal of toxic metal ions from waste water.

  10. Solid State Structures of Alkali Metal Ion Complexes Formed by Low-Molecular-Weight Ligands of Biological Relevance.

    Science.gov (United States)

    Aoki, Katsuyuki; Murayama, Kazutaka; Hu, Ning-Hai

    2016-01-01

    This chapter provides structural data, mainly metal binding sites/modes, observed in crystal structures of alkali metal ion complexes containing low-molecular-weight ligands of biological relevance, mostly obtained from the Cambridge Structural Database (the CSD version 5.35 updated to February 2014). These ligands include (i) amino acids and small peptides, (ii) nucleic acid constituents (excluding quadruplexes and other oligonucleotides), (iii) simple carbohydrates, and (iv) naturally occurring antibiotic ionophores. For some representative complexes of these ligands, some details on the environment of the metal coordination and structural characteristics are described.

  11. A DNAzyme requiring two different metal ions at two distinct sites.

    Science.gov (United States)

    Zhou, Wenhu; Zhang, Yupei; Huang, Po-Jung Jimmy; Ding, Jinsong; Liu, Juewen

    2016-01-08

    Most previously reported RNA-cleaving DNAzymes require only a single divalent metal ion for catalysis. We recently reported a general trivalent lanthanide-dependent DNAzyme named Ce13d. This work shows that Ce13d requires both Na(+) and a trivalent lanthanide (e.g. Ce(3+)), simultaneously. This discovery is facilitated by the sequence similarity between Ce13d and a recently reported Na(+)-specific DNAzyme, NaA43. The Ce13d cleavage rate linearly depends on the concentration of both metal ions. Sensitized Tb(3+) luminescence and DMS footprinting experiments indicate that the guanines in the enzyme loop are important for Na(+)-binding. The Na(+) dissociation constants of Ce13d measured from the cleavage activity assay, Tb(3+) luminescence and DMS footprinting are 24.6, 16.3 and 47 mM, respectively. Mutation studies indicate that the role of Ce(3+) might be replaced by G23 in NaA43. Ce(3+) functions by stabilizing the transition state phosphorane, thus promoting cleavage. G23 competes favorably with low concentration Ce(3+) (below 1 μM). The G23-to-hypoxanthine mutation suggests the N1 position of the guanine as a hydrogen bond donor. Together, Ce13d has two distinct metal binding sites, each fulfilling a different role. DNAzymes can be quite sophisticated in utilizing metal ions for catalysis and molecular recognition, similar to protein metalloenzymes. © The Author(s) 2015. Published by Oxford University Press on behalf of Nucleic Acids Research.

  12. Electron emission during multicharged ion-metal surface interactions

    International Nuclear Information System (INIS)

    Zeijlmans van Emmichoven, P.A.; Havener, C.C.; Hughes, I.G.; Overbury, S.H.; Robinson, M.T.; Zehner, D.M.; Meyer, F.W.

    1992-01-01

    The electron emission during multicharged ion-metal surface interactions will be discussed. The interactions lead to the emission of a significant number of electrons. Most of these electrons have energies below 30 eV. For incident ions with innershell vacancies the emission of Auger electrons that fill these vacancies has been found to occur mainly below the surface. We will present recently measured electron energy distributions which will be used to discuss the mechanisms that lead to the emission of Auger and of low-energy electrons

  13. Wear properties of metal ion implanted 4140 steel

    International Nuclear Information System (INIS)

    Evans, P.J.; Paoloni, F.J.

    1994-01-01

    AISI type 4140 (high tensile) steel has been implanted with tungsten and titanium using a metal vapour vacuum arc ion source. Doses in the range (1-5)x10 16 ionscm -2 were implanted to a depth of approximately 30nm. The relative wear resistance between non-implanted and implanted specimens has been estimated using pin-on-disc and abrasive wear tests. Implantation of titanium decreased the area of wear tracks by a factor of 5 over unimplanted steel. In some cases the steel was also hardened by a liquid carburization treatment before implantation. Abrasion tests revealed a further improvement in wear resistance on this material following ion irradiation. ((orig.))

  14. Development of carbon and metallic nano particle composite materials for the determination of uranium and other heavy metal ions

    International Nuclear Information System (INIS)

    Sahoo, S.; Dey, M.K.; Satpati, A.K.; Reddy, A.V.R.

    2014-01-01

    Carbon and metallic nano particle based composite materials were developed and characterised for the determination of heavy metal ions and uranium in trace concentration levels. Composite material were electrodeposited on the substrate electrode and applied for the electrochemical determination of metal ions. Electrodeposition parameters to synthesise the composite material and the analytical parameters for determination were optimised. (author)

  15. Ions in size-selected aqueous nanodrops: sequential water molecule binding energies and effects of water on ion fluorescence.

    Science.gov (United States)

    Donald, William A; Leib, Ryan D; Demireva, Maria; Williams, Evan R

    2011-11-23

    The effects of water on ion fluorescence were investigated, and average sequential water molecule binding energies to hydrated ions, M(z)(H(2)O)(n), at large cluster size were measured using ion nanocalorimetry. Upon 248-nm excitation, nanodrops with ~25 or more water molecules that contain either rhodamine 590(+), rhodamine 640(+), or Ce(3+) emit a photon with average energies of approximately 548, 590, and 348 nm, respectively. These values are very close to the emission maxima of the corresponding ions in solution, indicating that the photophysical properties of these ions in the nanodrops approach those of the fully hydrated ions at relatively small cluster size. As occurs in solution, these ions in nanodrops with 8 or more water molecules fluoresce with a quantum yield of ~1. Ce(3+) containing nanodrops that also contain OH(-) fluoresce, whereas those with NO(3)(-) do not. This indirect fluorescence detection method has the advantages of high sensitivity, and both the size of the nanodrops as well as their constituents can be carefully controlled. For ions that do not fluoresce in solution, such as protonated tryptophan, full internal conversion of the absorbed 248-nm photon occurs, and the average sequential water molecule binding energies to the hydrated ions can be accurately obtained at large cluster sizes. The average sequential water molecule binding energies for TrpH(+)(H(2)O)(n) and a doubly protonated tripeptide, [KYK + 2H](2+)(H(2)O)(n), approach asymptotic values of ~9.3 (n ≥ 11) and ~10.0 kcal/mol (n ≥ 25), respectively, consistent with a liquidlike structure of water in these nanodrops.

  16. Neutron activation analysis of heavy metal binding by fungal cell walls

    International Nuclear Information System (INIS)

    Crusberg, T.C.; Mayer, J.A.

    1994-01-01

    Aqueous effluents are produced during nuclear power and nuclear weapons development activities which frequently contain low levels of dissolved radioactive nuclides. A number of laboratories are now focusing attention to renewable biological materials to provide traps for low concentrations of dissolved radioactive metal ions in wastewater effluents. The term BIOTRAP can be used to describe such materials, and in this laboratory cell wall preparations of the fungus Penicillium ochro-chloron have been employed to demonstrate their capacity and affinity to reversibly bind and remove copper(2). Since neutron activation analysis (NAA) was readily available, that method was one of several applied to this problem as a suitable analytical methodology to study heavy metal-to-BIOTRAP interactions. Copper and mercury provide good examples of metals which are capable of undergoing activation by thermal neutrons. In NAA, 63 Cu (69.1% natural abundance) is converted to 64 Cu which has a half live of 12.7 hr, and 202 Hg (29.7 % natural abundance) is converted to 203 Hg which has a half life of 46.,6 d

  17. Metal ion toxins and brain aquaporin-4 expression: an overview

    Directory of Open Access Journals (Sweden)

    Adriana eXimenes-Da-Silva

    2016-06-01

    Full Text Available Metal ions such as iron, zinc, and manganese are essential to metabolic functions, protein synthesis, neurotransmission, and antioxidant neuroprotective mechanisms. Conversely, non-essential metals such as mercury and lead are sources of human intoxication due to occupational activities or environmental contamination. Essential or non-essential metal accumulation in the central nervous system (CNS results in changes in blood-brain barrier (BBB permeability, as well as triggering microglia activation and astrocyte reactivity and changing water transport through the cells, which could result in brain swelling. Aquaporin-4 is the main water channel in the CNS, is expressed in astrocyte foot processes in brain capillaries and along the circumventricular epithelium in the ventricles, and has important physiological functions in maintaining brain osmotic homeostasis and supporting brain excitability through regulation of the extracellular space. Some evidence has pointed to a role of AQP4 during metal intoxication in the brain, where it may act in a dual form as a neuroprotector or a mediator of the development of oxidative stress in neurons and astrocytes, resulting in brain swelling and neuronal damage. This mini-review presents the way some metal ions affect changes in AQP4 expression in the CNS and discuss the ways in which water transport in brain cells can be involved in brain damage.

  18. Rice straw modified by click reaction for selective extraction of noble metal ions.

    Science.gov (United States)

    Wang, Jingjing; Wei, Jun; Li, Juan

    2015-02-01

    Rice straw was modified by azide-alkyne click reaction in order to realize selective extraction of noble metal ions. The ability of the modified straw to adsorb Pd(2+) and Pt(4+) was assessed using a batch adsorption technique. It was found that the sorption equilibrium could be reached within 1h and the adsorption capacity increased with temperature for both Pd(2+) and Pt(4+). The maximum sorption capacities for Pd(2+) and Pt(4+) were respectively attained in 1.0 and 0.1 mol/L HCl. The modified straw showed excellent selectivity for noble metal ions in comparison to the pristine straw. In addition, the modified straw was examined as a column packing material for extraction of noble metal ions. It was indicated that 1.0 mL/min was the best flow rate for Pd(2+) and Pt(4+). The modified straw could be repeatedly used for 10 times without any significant loss in the initial binding affinity. Copyright © 2014 Elsevier Ltd. All rights reserved.

  19. The role of metallic ions in nano-bio hybrid catalysts from ab initio first principles

    Science.gov (United States)

    Behera, Sushant; Deb, Pritam

    We employ high-accuracy linear-scaling density functional theory calculations with a near-complete basis set and a minimal parameter implicit solvent model, within the self-consistent calculation, on silver ion assimilated on bacteriorhodopsin (bR) at specific binding sites. The geometry optimization indicates the formation of stable active sites at the interface of nano-bio hybrid and density of states reflects the metallic behavior of the active sites. Detailed kinetics of the catalytic reaction is revealed using ab initio electronic structure calculations. We observed that the metal ion incorporated active sites are more efficient in electrolytic splitting of water than pristine sites due to their less value of Gibbs free energy for hydrogen evolution reaction and strong synergistic effect. The volcano plot analysis and free energy diagram are considered to understan hydrogen evolution efficiency. Moreover, the essential role of metallic ion on catalytic efficiency is elucidated. DBT, Government of India, vide Grant No BT/357/NE/TBP/ 2012. DST, GoI for financial support under INSPIRE Fellowship(IF150325).

  20. Production and Characterization of Desmalonichrome Relative Binding Affinity for Uranyl Ions in Relation to Other Siderophores

    Energy Technology Data Exchange (ETDEWEB)

    Mo, Kai-For; Dai, Ziyu; Wunschel, David S.

    2016-06-24

    Siderophores are Fe binding secondary metabolites that have been investigated for their uranium binding properties. Much of the previous work has focused on characterizing hydroxamate types of siderophores, such as desferrioxamine B, for their uranyl binding affinity. Carboxylate forms of these metabolites hold potential to be more efficient chelators of uranyl, yet they have not been widely studied and are more difficult to obtain. Desmalonichrome is a carboxylate siderophore which is not commercially available and so was obtained from the ascomycete fungus Fusarium oxysporum cultivated under Fe depleted conditions. The relative affinity for uranyl binding of desmalonichrome was investigated using a competitive analysis of binding affinities between uranyl acetate and different concentrations of iron(III) chloride using electrospray ionization mass spectrometry (ESI-MS). In addition to desmalonichrome, three other siderophores, including two hydroxamates (desferrioxamine B and desferrichrome) and one carboxylate (desferrichrome A) were studied to understand their relative affinities for the uranyl ion at two pH values. The binding affinities of hydroxymate siderophores to uranyl ion were found to decrease to a greater degree at lower pH as the concentration of Fe (III) ion increases. On the other hand, lowering pH has little impact on the binding affinities between carboxylate siderophores and uranyl ion. Desmalonichrome was shown to have the greatest relative affinity for uranyl at any pH and Fe(III) concentration. These results suggest that acidic functional groups in the ligands are critical for strong chelation with uranium at lower pH.

  1. The Corrosion Protection of Metals by Ion Vapor Deposited Aluminum

    Science.gov (United States)

    Danford, M. D.

    1993-01-01

    A study of the corrosion protection of substrate metals by ion vapor deposited aluminum (IVD Al) coats has been carried out. Corrosion protection by both anodized and unanodized IVD Al coats has been investigated. Base metals included in the study were 2219-T87 Al, 7075-T6 Al, Titanium-6 Al-4 Vanadium (Ti-6Al-4V), 4130 steel, D6AC steel, and 4340 steel. Results reveal that the anodized IVD Al coats provide excellent corrosion protection, but good protection is also achieved by IVD Al coats that have not been anodized.

  2. Selective extraction of metal ions with polymeric extractants by ion exchange/redox

    Science.gov (United States)

    Alexandratos, Spiro D.

    1987-01-01

    The specification discloses a method for the extraction of metal ions having a reduction potential of above about +0.3 from an aqueous solution. The method includes contacting the aqueous solution with a polymeric extractant having primary phosphinic acid groups, secondary phosphine oxide groups, or both phosphinic acid and phosphine oxide groups.

  3. Kinetic modeling of metal ion transport for desorption of Pb(II) ion ...

    African Journals Online (AJOL)

    The kinetics of desorption of lead (II) ion from metal loaded adsorbent of mercaptoacetic acid modified and unmodified oil palm (Elaeis guineensis) fruit fiber was studied using different solutions, at different contact times. At the end of 25 minutes, 79.19%, 75.99%, 57.14%, 50.56% and 32.72% of Pb2+ were desorbed using ...

  4. COMPARATIVE ANALYSIS FOR METAL BINDING CAPACITY OF CYSTEINE BY USING UV-VIS SPECTROPHOTOMETER

    OpenAIRE

    Shivendu Ranjan; Nandita Dasgupta; Gyanendra Gour; Rashmi Dubey; Kumari Amrita

    2012-01-01

    The metal binding capacity of cysteine with three different metals Nickel, Copper and Lead was studied using UV-Vis spectrophotometer for which absorbance values were taken after interaction of cysteine with metal salt solutions (10ppm and 100ppm). Before taking above absorbance dilution factor was set using cysteine stock. The increase in peak intensity was observed when metal salt solution and metal saltcysteine solution were compared. Based on peak shift and peak intensity finally it can b...

  5. Comparison of metal toxic impacts between aquatic and terrestrial organisms: is the free ion concentration a sufficient descriptor?

    DEFF Research Database (Denmark)

    Owsianiak, Mikolaj; Rosenbaum, Ralph K.; Larsen, Henrik Fred

    2011-01-01

    to be a sufficient indicator of metal toxicity for both aquatic and terrestrial species. With the aim of deriving extrapolations to predict terrestrial toxic impacts of metals from aquatic effect data, we compared copper toxicity of aquatic organisms with that of terrestrial organisms, testing the hypothesis...... of the free metal ion concentration to reflect toxicity, as the presence of protons and other cations reacting with biological binding sites has been shown to affect the toxicity of copper to D. magna. Similar patterns, albeit with smaller variations, are observed for terrestrial organisms. Up to three orders......Characterization of metal toxic impacts in comparative risk assessment and life cycle impact assessment (LCIA) should take into account metal speciation and interactions with soil/water organic constituents, because these mechanisms control metal bioavailability and may influence their toxic...

  6. Chromatography of metal ions with a triazine chelating resin

    Energy Technology Data Exchange (ETDEWEB)

    Wang, W.N.

    1979-05-01

    The synthesis, characterization, and some analytical applications of a new triazine resin are described. Separation of group IB, IIB, VIB, and VIIB metal ions from group VIII metal ions is achieved by this PDT-4 resin. Calcium(II) and magnesium(II) are taken up at pH = 6, 0.1 M acetate and are eluted at pH = 6, 0.1 M sodium nitrate. Copper(II) is retained at pH = 6, 0.1 M acetate and pH = 1 hydrochloric acid and is eluted subsequently by 5 M perchloric acid. Molybdenum(VI) is sorbed selectively from 0.1 N sulfuric acid or hydrochloric acid and is eluted in a tight band by 0.1 N sodium hydroxide. Numerous rapid column chromatographic separations are reported using this new resin, including analysis of NBS standard samples.

  7. Chromatography of metal ions with a triazine chelating resin

    International Nuclear Information System (INIS)

    Wang, W.N.

    1979-05-01

    The synthesis, characterization, and some analytical applications of a new triazine resin are described. Separation of group IB, IIB, VIB, and VIIB metal ions from group VIII metal ions is achieved by this PDT-4 resin. Calcium(II) and magnesium(II) are taken up at pH = 6, 0.1 M acetate and are eluted at pH = 6, 0.1 M sodium nitrate. Copper(II) is retained at pH = 6, 0.1 M acetate and pH = 1 hydrochloric acid and is eluted subsequently by 5 M perchloric acid. Molybdenum(VI) is sorbed selectively from 0.1 N sulfuric acid or hydrochloric acid and is eluted in a tight band by 0.1 N sodium hydroxide. Numerous rapid column chromatographic separations are reported using this new resin, including analysis of NBS standard samples

  8. Multiply charged metal ions in high current pulsed vacuum arcs

    Science.gov (United States)

    Yushkov, G. Yu.; Nikolaev, A. G.; Frolova, V. P.; Oks, E. M.; Rousskikh, A. G.; Zhigalin, A. S.

    2017-12-01

    We show that vacuum arc plasma discharges with a current of several kiloamperes and duration of a few microseconds can generate multiply charged metal ions with charge states greater than 10+. The physical mechanism behind this is discussed, suggesting an optimum arc current for higher charge states depending on the pulse duration and cathode material. Measurements of ion mass-to-charge ratio and images taken with nanosecond resolution suggest that, higher charge state ions are produced at characteristic distances of ˜10 mm from the cathode as the arc current peaks, and the process responsible for their generation is additional ionization as the discharge is pinched by its self-magnetic field. The maximum and mean ion charge states reveal a considerable increase for the all cathode materials studied: magnesium, aluminum, zirconium, tin, tantalum, gold, lead, and bismuth. For bismuth ions, the maximum charge state reaches a record-breaking value of 17+ and the mean of the charge state distribution is 12.6+. The results obtained are of interest for vacuum arc discharge physics and for ion beam technologies.

  9. Discovery of native metal ion sites located on the ferredoxin docking side of photosystem I.

    Energy Technology Data Exchange (ETDEWEB)

    Utschig, L. M.; Chen, L. X.; Poluektov, O. G.; Chemical Sciences and Engineering Division

    2008-03-25

    Photosystem I (PSI) is a large membrane protein that catalyzes light-driven electron transfer across the thylakoid membrane from plastocyanin located in the lumen to ferredoxin in the stroma. Metal analysis reveals that PSI isolated from the cyanobacterial membranes of Synechococcus leopoliensis has a near-stoichiometric 1 molar equiv of Zn2+ per PSI monomer and two additional surface metal ion sites that favor Cu2+ binding. Two-dimensional hyperfine sublevel correlation (HYSCORE) spectroscopy reveals coupling to the so-called remote nitrogen of a single histidine coordinated to one of the Cu2+ centers. EPR and X-ray absorption fine structure (XAFS) studies of 2Cu?PSI complexes reveal the direct interaction of ferredoxin with the Cu2+ centers on PSI, establishing the location of native metal sites on the ferredoxin docking side of PSI. On the basis of these spectroscopic results and previously reported site-directed mutagenesis studies, inspection of the PSI crystal structure reveals a cluster of three highly conserved residues, His(D95), Glu(D103), and Asp(C23), as a likely Cu2+ binding site. The discovery of surface metal sites on the acceptor side of PSI provides a unique opportunity to probe the stromal region of PSI and the interactions of PSI with its reaction partner, the soluble electron carrier protein ferredoxin.

  10. Adsorption of heavy metal ions by activated charcoal

    International Nuclear Information System (INIS)

    Fujikawa, Mitsuo

    1978-01-01

    The adsorption effect was measured for several kinds of heavy metal ions, Pb 2+ , Cd 2+ , Cu 2+ and Zn 2+ by passing them through activated charcoal beds and changing the pH values of solutions. The test procedure is to keep the pH value of solution more than 10 at first, filter heavy metal hydroxide deposit, measure the remaining ion concentration in filtrate, and also test the influence of the addition of alkali to each kind of ions. The individual test procedure for each kind of ions is explained. As for the Cd ions, after the detailed experimental procedure is explained, the adsorption characteristic line is shown as the relation between the adsorption quantity and the equilibrium concentration of Cd 2+ . The similar test procedure and the adsorption characteristic lines are shown and evaluated about Pb 2+ , Cu 2+ and Zn 2+ . These lines are all linear, but have different adsorption quantity and inclination in relation to heavy metal ion concentration. Concerning the influence of pH to adsorption, the characteristics of pH increase are presented, when alkali is added by various quantities to Zn 2+ , Cu 2+ , Pb 2+ and Cd 2+ . The pH of Pb 2+ increased to about 10 by adding 0.4 cc alkali and saturates, but the pH of the other ions did not saturate by adding less than 1.5 cc alkali. When the water containing heavy metals are treated, Cd 2+ , Pb 2+ , Cu 2+ and Zn 2+ are removed almost satisfactorily by passing them through active charcoal filters and keeping pH at 10. The experimental concentrations are 0.05 ppm at pH 10 in Cd, 0.86 ppm at 10.3 in Pb, 0 ppm at pH 9.6 in Cu, 0.06 ppm at pH 8.8 and 12.4 ppm at pH 9.8 in Zn. (Nakai, Y.)

  11. Non-destructive separation of metal ions from wastewater containing excess aminopolycarboxylate chelant in solution with an ion-selective immobilized macrocyclic material.

    Science.gov (United States)

    Hasegawa, Hiroshi; Rahman, Ismail M M; Kinoshita, Sanae; Maki, Teruya; Furusho, Yoshiaki

    2010-03-01

    Although the excellent metal-binding capacities of aminopolycarboxylate chelants (APCs) facilitate their extensive use, pre- and post-toxicity of APCs and their high persistence in aquatic environments evoke concerns. Several treatment techniques with a principal focus on the degradation of APCs at the pre-release step have been proposed. Here, we report a technique for the separation of metal ions from waste solution containing excess APCs using a solid phase extraction system with an ion-selective immobilized macrocyclic material, commonly known as a molecular recognition technology (MRT) gel. Synthetic metal solutions with 100-fold chelant content housed in H2O matrices were used as samples. The MRT gel showed a higher recovery rate compared with other SPE materials at 20 degrees C using a flow rate of 0.2 mL min(-1). The effects of solution pH, metal-chelant stability constants and ionic radii were assessed for 32 metals. Compared to the conventional treatment options for such waste solutions, our proposed technique has the advantage of non-destructive separation of both metal ions and chelants. 2010 Elsevier Ltd. All rights reserved.

  12. Gas porosity in metals and alloys irradiated by helium ions

    International Nuclear Information System (INIS)

    Kalin, B.A.; Korshunov, S.N.; Chernov, I.I.

    1987-01-01

    Experimental studies of the development of gas porosity in metals and alloys during irradiation with helium ions up to high doses and during post-irradiation annealings, are reviewed. The main theoretical problems of the mechanisms of bubble formation and growth, the regularities and peculiarities of bubble development in a thin near-the surface layer during the introduction of helium with the energy of tens of kiloelectron volt, are considered

  13. Topoisomerase IV-quinolone interactions are mediated through a water-metal ion bridge: mechanistic basis of quinolone resistance

    Science.gov (United States)

    Aldred, Katie J.; McPherson, Sylvia A.; Turnbough, Charles L.; Kerns, Robert J.; Osheroff, Neil

    2013-01-01

    Although quinolones are the most commonly prescribed antibacterials, their use is threatened by an increasing prevalence of resistance. The most common causes of quinolone resistance are mutations of a specific serine or acidic residue in the A subunit of gyrase or topoisomerase IV. These amino acids are proposed to serve as a critical enzyme-quinolone interaction site by anchoring a water-metal ion bridge that coordinates drug binding. To probe the role of the proposed water-metal ion bridge, we characterized wild-type, GrlAE85K, GrlAS81F/E85K, GrlAE85A, GrlAS81F/E85A and GrlAS81F Bacillus anthracis topoisomerase IV, their sensitivity to quinolones and related drugs and their use of metal ions. Mutations increased the Mg2+ concentration required to produce maximal quinolone-induced DNA cleavage and restricted the divalent metal ions that could support quinolone activity. Individual mutation of Ser81 or Glu85 partially disrupted bridge function, whereas simultaneous mutation of both residues abrogated protein–quinolone interactions. Results provide functional evidence for the existence of the water-metal ion bridge, confirm that the serine and glutamic acid residues anchor the bridge, demonstrate that the bridge is the primary conduit for interactions between clinically relevant quinolones and topoisomerase IV and provide a likely mechanism for the most common causes of quinolone resistance. PMID:23460203

  14. Selective removal of heavy metal ions by disulfide linked polymer networks

    Energy Technology Data Exchange (ETDEWEB)

    Ko, Dongah [Department of Environmental Engineering, Technical University of Denmark, Miljøvej 113, 2800 Kgs. Lyngby (Denmark); Lee, Joo Sung [Graduate School of EEWS, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 34141 (Korea, Republic of); Patel, Hasmukh A. [Department of Chemistry, Northwestern University, Evanston, IL 60208 (United States); Jakobsen, Mogens H. [Department of Micro and Nano technology, Technical University of Denmark, Ørsteds Plads, 345B, 2800 Kgs. Lyngby (Denmark); Hwang, Yuhoon [Department of Environmental Engineering, Seoul National University of Science and Technology, 232 Gongreung-ro, Nowon-gu, Seoul 01811 (Korea, Republic of); Yavuz, Cafer T. [Graduate School of EEWS, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 34141 (Korea, Republic of); Hansen, Hans Chr. Bruun [Department of Plant and Environmental Sciences, University of Copenhagen, Frederiksberg, Thorvaldsensvej 40, 1871 Frederiksberg C (Denmark); Andersen, Henrik R., E-mail: henrik@ndersen.net [Department of Environmental Engineering, Technical University of Denmark, Miljøvej 113, 2800 Kgs. Lyngby (Denmark)

    2017-06-15

    Highlights: • Disulfide/thiol polymer networks are promising as sorbent for heavy metals. • Rapid sorption and high Langmuir affinity constant (a{sub L}) for stormwater treatment. • Selective sorption for copper, cadmium, and zinc in the presence of calcium. • Reusability likely due to structure stability of disulfide linked polymer networks. - Abstract: Heavy metal contaminated surface water is one of the oldest pollution problems, which is critical to ecosystems and human health. We devised disulfide linked polymer networks and employed as a sorbent for removing heavy metal ions from contaminated water. Although the polymer network material has a moderate surface area, it demonstrated cadmium removal efficiency equivalent to highly porous activated carbon while it showed 16 times faster sorption kinetics compared to activated carbon, owing to the high affinity of cadmium towards disulfide and thiol functionality in the polymer network. The metal sorption mechanism on polymer network was studied by sorption kinetics, effect of pH, and metal complexation. We observed that the metal ions–copper, cadmium, and zinc showed high binding affinity in polymer network, even in the presence of competing cations like calcium in water.

  15. Spectrophotometric determination of some metal ions using hydrazones

    International Nuclear Information System (INIS)

    Mohammed, M. S.

    2000-05-01

    In this research many starting materials were prepared, like methyl salicylate and salicylic acid hydrazide from which different derivatives of hydrazones were synthesized by coupling with carbonyl compounds like benzil monoxime and benzil mono hydrazone which are prepared and others like salicylaldehyde and benzoin. The hydrazones that were synthesized are salicylaldehyde salicylic acid hydrazone, benzoin salicylic acid hydrazone, benzil mono hydrazone salicylic acid hydrazone and benzil monoxime salicylic acid hydrazone. These reagents were determined by different methods, IR spectrophotometric determination, the nitrogen content method and melting point determination. These hydrazones act as ligands for determination of some metal ions by making different coloured complexes that were prepared for eight hydrazones with eight metal ions U (VI), Fe (II), Fe (III), Co (II), V (II), Mo (VI), Ni (II) and Cu (II). These complexes were determined by ultraviolet and visible spectrophotometer (UV/VIS) to detect their absorbance and wavelengths (λ max). The two hydrazones salicylaldehyde salicylic acid-hydrazone and benzoin salicylic acid hydrazone, were selected for determination of five metal ions (Fe (II), Fe (III), U (VI), Ni (II) and Cu (II)), using two micelles sodium n-dodecyl sulphate and pyridinium hexa decyl bromide mono hydrate. Their absorbance and wavelengths were detected using UV/VIS spectrophotometer. (Author)

  16. Adhesive and abrasive wear mechanisms in ion implanted metals

    International Nuclear Information System (INIS)

    Dearnaley, G.

    1985-01-01

    The distinction between adhesive and abrasive wear processes was introduced originally by Burwell during the nineteen-fifties, though some authors prefer to classify wear according to whether it is mild or severe. It is argued here that, on the basis of the performance of a variety of ion implanted metal surfaces, exposed to different modes of wear, the Burwell distinction is a valid one which, moreover, enables us to predict under which circumstances a given treatment will perform well. It is shown that, because wear rates under abrasive conditions are very sensitive to the ratio of the hardness of the surface to that of the abrasive particles, large increases in working life are attainable as a result of ion implantation. Under adhesive wear conditions, the wear rate appears to fall inversely as the hardness increases, and it is advantageous to implant species which will create and retain a hard surface oxide or other continuous film in order to reduce metal-metal contact. By the appropriate combination of physico-chemical changes in an implanted layer it has been possible to reduce wear rates by up to three orders of magnitude. Such rates compensate for the shallow depths achievable by ion implantation. (orig.)

  17. Superhydrogels of nanotubes capable of capturing heavy-metal ions.

    Science.gov (United States)

    Song, Shasha; Wang, Haiqiao; Song, Aixin; Hao, Jingcheng

    2014-01-01

    Self-assembly regulated by hydrogen bonds was successfully achieved in the system of lithocholic acid (LCA) mixed with three organic amines, ethanolamine (EA), diethanolamine (DEA), and triethanolamine (TEA), in aqueous solutions. The mixtures of DEA/LCA exhibit supergelation capability and the hydrogels consist of plenty of network nanotubes with uniform diameters of about 60 nm determined by cryogenic TEM. Interestingly, the sample with the same concentration in a system of EA and LCA is a birefringent solution, in which spherical vesicles and can be transformed into nanotubes as the amount of LCA increases. The formation of hydrogels could be driven by the delicate balance of diverse noncovalent interactions, including electrostatic interactions, hydrophobic interactions, steric effects, van der Waals forces, and mainly hydrogen bonds. The mechanism of self-assembly from spherical bilayer vesicles into nanotubes was proposed. The dried hydrogels with nanotubes were explored to exhibit the excellent capability for capturing heavy-metal ions, for example, Cu(2+), Co(2+), Ni(2+), Pb(2+), and Hg(2+). The superhydrogels of nanotubes from the self-assembly of low-molecular-weight gelators mainly regulated by hydrogen bonds used for the removal of heavy-metal ions is simple, green, and high efficiency, and provide a strategic approach to removing heavy-metal ions from industrial sewage. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Spectrophotometric study of some metal ions using some Schiff's bases

    International Nuclear Information System (INIS)

    Elnager, Nawal Mohomed Ibrahim

    2000-05-01

    In this work two schiff bases namely N,N Bis(benzoyl acetone)-o-phenylene diamine (NNBBPD) and N,N Bis(benzoyl acetone)-isopropylene diamine (NNBBAID) were prepared by direct coupling of benzoyl acetone with o-phenylene and isopropylene diamine respectively. The two reagents were identified by IR spectra, thin layer chromatography (TLC) and determination of the percentage of nitrogen contents (N%). It is found that the two reagents form coloured chelates with Fe (II), Fe (III), Cu (II), U (VI), Ni (II) and Co (II). The two reagents were used for the determination of Fe (II), Fe (III) and U (VI). The formulate of these metal ion complexes were obtained using continuous variations, mole ratio and slope ratio methods. Effect of two micelles, namely sodium n-dodecyl sulphate (SDS) and hexadecyl pyridinum broinide monohydrate (HPB) on metal ion complexes were studied. It is found that both of them increase the solubility and the absorbances of the metal ion complexes with variable effects of the absorption maxima. Calibration curves for Fe (II), Fe (II) and U (VI) were obtained in optimum conditions of pH and micelles solutions. (Author)

  19. Metal negative ion production by a planar magnetron sputter type radio frequency ion source

    Science.gov (United States)

    Yoshioka, K.; Kanda, S.; Kasuya, T.; Wada, M.

    2017-08-01

    A planar magnetron sputter type ion source has been operated to investigate metal negative ion production. Radio frequency power at 13.56 MHz was directly supplied to the planar target made of 2 mm thick Cu disk to maintain plasma discharge and induce DC self-bias to the target for sputtering. Beam profile was obtained and the peak of negative ion beam profile was shifted to 6 mm as the beam traversed the 32 mT magnetic field in the region of the plasma grid. Extraction of Cu- beam was performed and the Cu- beam current was found consisted of two components: Cu-(surface) and Cu-(volume). Negative ion spectra were observed to measure the ratio of the surface component to the volume component. The surface component of Cu- occupied 67% of the total beam at the maximum, while it decreased the fraction down to about 50% as the source pressure was increased.

  20. Structures and physical properties of gaseous metal cationized biological ions.

    Science.gov (United States)

    Burt, Michael B; Fridgen, Travis D

    2012-01-01

    Metal chelation can alter the activity of free biomolecules by modifying their structures or stabilizing higher energy tautomers. In recent years, mass spectrometric techniques have been used to investigate the effects of metal complexation with proteins, nucleobases and nucleotides, where small conformational changes can have significant physiological consequences. In particular, infrared multiple photon dissociation spectroscopy has emerged as an important tool for determining the structure and reactivity of gas-phase ions. Unlike other mass spectrometric approaches, this method is able to directly resolve structural isomers using characteristic vibrational signatures. Other activation and dissociation methods, such as blackbody infrared radiative dissociation or collision-induced dissociation can also reveal information about the thermochemistry and dissociative pathways of these biological ions. This information can then be used to provide information about the structures of the ionic complexes under study. In this article, we review the use of gas-phase techniques in characterizing metal-bound biomolecules. Particular attention will be given to our own contributions, which detail the ability of metal cations to disrupt nucleobase pairs, direct the self-assembly of nucleobase clusters and stabilize non-canonical isomers of amino acids.

  1. Quaternary Benzyltriethylammonium Ion Binding to the Na,K-ATPase: a Tool to Investigate Extracellular K+ Binding Reactions†

    Science.gov (United States)

    Peluffo, R. Daniel; González-Lebrero, Rodolfo M.; Kaufman, Sergio B.; Kortagere, Sandhya; Orban, Branly; Rossi, Rolando C.; Berlin, Joshua R.

    2009-01-01

    This study examined how the quaternary organic ammonium ion, benzyltriethylamine (BTEA), binds to the Na,K-ATPase to produce membrane potential (VM)-dependent inhibition and tested the prediction that such a VM-dependent inhibitor would display electrogenic binding kinetics. BTEA competitively inhibited K+ activation of Na,K-ATPase activity and steady-state 86Rb+ occlusion. The initial rate of 86Rb+ occlusion was decreased by BTEA to a similar degree whether it was added to the enzyme prior to or simultaneously with Rb+, a demonstration that BTEA inhibits the Na,K-ATPase without being occluded. Several BTEA structural analogues reversibly inhibited Na,K-pump current, but none blocked current in a VM-dependent manner except BTEA and its para-nitro derivative, pNBTEA. Under conditions that promoted electroneutral K+-K+ exchange by the Na,K-ATPase, step changes in VM elicited pNBTEA-activated ouabain-sensitive transient currents that had similarities to those produced with the K+ congener, Tl+. pNBTEA- and Tl+-dependent transient currents both displayed saturation of charge moved at extreme negative and positive VM, equivalence of charge moved during and after step changes in VM, and similar apparent valence. The rate constant (ktot) for Tl+-dependent transient current asymptotically approached a minimum value at positive VM. In contrast, ktot for pNBTEA-dependent transient current was a “U”-shaped function of VM with a minimum value near 0 mV. Homology models of the Na,K-ATPase alpha subunit suggested that quaternary amines can bind to two extracellularly-accessible sites, one of them located at K+ binding sites positioned between transmembrane helices 4, 5, and 6. Altogether, these data revealed important information about electrogenic ion binding reactions of the Na,K-ATPase that are not directly measurable during ion transport by this enzyme. PMID:19621894

  2. Removal Process of Heavy Metal Ions from Squid Gut Wastes with Dilute Suluric Acid Leaching and Electrowinning Methods

    OpenAIRE

    嶋影, 和宜; 平井, 伸治; 戸田, 茂雄; 山本, 浩

    2003-01-01

    In order to remove heavy metal ions contained in organic squid gut waste, a novel process has been developed with both dilute suluric acid leaching and electrowinning methods. This process was consisted of three procedures, which are the elimination of greasy component in squid gut wastes, the dissolution of heavy metal ions and the electro-deposition of heavy metal ions. Heavy metal ions contained in organic squid gut wastes are zinc, cadmium and copper ions. Heavy metal ions are leached eas...

  3. Extraction of metal ions by neutral β-diphosphoramides

    International Nuclear Information System (INIS)

    Madic, C.

    1990-01-01

    The extracting ability of β-diphosphoramides of the type R-N[P(O)(NMe 2 ) 2 ] 2 with R=-CH 3 (NIPA), -C 12 H 25 (ODIPA), or -C 16 H 33 (OHDIPA) for metal ions such as lanthanides, uranyl, and the transuranium elements Am(III) and Pu(IV) has been studied. Extraction yields depend on the nature of the ligand, the organic diluent (nitromethane, kerosene, tert-butylbenzene), the concentration of nitric acid in the aqueous phase, and the ligand-to-metal ratio, Q. The results show that the bidentate phosphoramides are very efficient extractants for all of the metals studied, even at low ratios Q. The presence of nitric acid generally enhances the extraction yields. On the other hand, selectivity is rather poor with these ligands. A particular effort has been made to determine the nature of extracted species by NMR spectroscopy

  4. Assessment of the Binding of Protons, Al and Fe to Biochar at Different pH Values and Soluble Metal Concentrations

    Directory of Open Access Journals (Sweden)

    Tan Dang

    2018-01-01

    Full Text Available Biochar can retain large amounts of protons and metals in the drainage water from acid sulfate soils and mine sites. Metal sorption can, however, be influenced by many factors, such as pH and metal composition. This study investigated proton, Al, and Fe retention capacity of eucalyptus biochar (1% w/v at different pH and metal concentrations. In the absence of metals, the biochar had a high proton binding capacity, (up to 0.035 mmol of H+, whereas its capacity to retain hydroxide ions was limited. A batch experiment was carried out at pH 4 and pH 7 with 10−6, 10−5, 10−4, 10−3, and 10−2 M of added Fe or Al. Added metals precipitated considerably prior to addition of the biochar except that Al remained highly soluble at pH 4. The biochar had a high retention capacity for Al and Fe; at high (>1 mM concentrations, over 80% of soluble metals were retained. Metal competition for binding sites of both Al and Fe at different ratios was investigated, but increasing concentrations of one metal did not reduce retention of the other. The results confirmed that biochar has high metal binding capacity under both acidic and neutral conditions.

  5. The kink-turn motif in RNA is dimorphic, and metal ion-dependent

    Science.gov (United States)

    GOODY, TERRY A.; MELCHER, SONYA E.; NORMAN, DAVID G.; LILLEY, DAVID M.J.

    2004-01-01

    The kink-turn (K-turn) is a new motif in RNA structure that was identified by examination of the crystal structures of the ribosome. We examined the structural and dynamic properties of this element in free solution. The K-turn RNA exists in a dynamic equilibrium between a tightly kinked conformation and a more open structure similar to a simple bulge bend. The highly kinked form is stabilized by the noncooperative binding of metal ions, but a significant population of the less-kinked form is present even in the presence of relatively high concentrations of divalent metal ions. The conformation of the tightly kinked population is in excellent agreement with that of the K-turn structures observed in the ribosome by crystallography. The end-to-end FRET efficiency of this species agrees closely with that of the ribosomal K-turn, and the direction of the bend measured by comparative gel electrophoresis also corresponds very well. These results show that the tightly kinked conformation of the K-turn requires stabilization by other factors, possibly by protein binding, for example. The K-turn is therefore unlikely to be of itself a primary organizing feature in RNA. PMID:14730024

  6. Isolation and characterization of iron chelators from turmeric (Curcuma longa): selective metal binding by curcuminoids.

    Science.gov (United States)

    Messner, Donald J; Surrago, Christine; Fiordalisi, Celia; Chung, Wing Yin; Kowdley, Kris V

    2017-10-01

    Iron overload disorders may be treated by chelation therapy. This study describes a novel method for isolating iron chelators from complex mixtures including plant extracts. We demonstrate the one-step isolation of curcuminoids from turmeric, the medicinal food spice derived from Curcuma longa. The method uses iron-nitrilotriacetic acid (NTA)-agarose, to which curcumin binds rapidly, specifically, and reversibly. Curcumin, demethoxycurcumin, and bisdemethoxycurcumin each bound iron-NTA-agarose with comparable affinities and a stoichiometry near 1. Analyses of binding efficiencies and purity demonstrated that curcuminoids comprise the primary iron binding compounds recovered from a crude turmeric extract. Competition of curcuminoid binding to the iron resin was used to characterize the metal binding site on curcumin and to detect iron binding by added chelators. Curcumin-Iron-NTA-agarose binding was inhibited by other metals with relative potency: (>90% inhibition) Cu 2+  ~ Al 3+  > Zn 2+  ≥ Ca 2+  ~ Mg 2+  ~ Mn 2+ (80% by addition of iron to the media; uptake was completely restored by desferoxamine. Ranking of metals by relative potencies for blocking curcumin uptake agreed with their relative potencies in blocking curcumin binding to iron-NTA-agarose. We conclude that curcumin can selectively bind toxic metals including iron in a physiological setting, and propose inhibition of curcumin binding to iron-NTA-agarose for iron chelator screening.

  7. Interaction analysis of chimeric metal-binding green fluorescent protein and artificial solid-supported lipid membrane by quartz crystal microbalance and atomic force microscopy

    International Nuclear Information System (INIS)

    Prachayasittikul, Virapong; Na Ayudhya, Chartchalerm Isarankura; Hilterhaus, Lutz; Hinz, Andreas; Tantimongcolwat, Tanawut; Galla, Hans-Joachim

    2005-01-01

    Non-specific adsorption and specific interaction between a chimeric green fluorescent protein (GFP) carrying metal-binding region and the immobilized zinc ions on artificial solid-supported lipid membranes was investigated using the quartz crystal microbalance technique and the atomic force microscopy (AFM). Supported lipid bilayer, composed of octanethiol and 1,2-dipalmitoyl-sn-glycero-3-phosphocholine/1,2-dioleoyl-sn-glycero-3-[N- (5-amino-1-carboxypentyl iminodiacetic acid)succinyl] (NTA-DOGS)-Zn 2+ , was formed on the gold electrode of quartz resonator (5 MHz). Binding of the chimeric GFP to zinc ions resulted in a rapid decrease of resonance frequency. Reversibility of the process was demonstrated via the removal of metal ions by EDTA. Nanoscale structural orientation of the chimeric GFP on the membrane was imaged by AFM. Association constant of the specific binding to metal ions was 2- to 3-fold higher than that of the non-specific adsorption, which was caused by the fluidization effect of the metal-chelating lipid molecules as well as the steric hindrance effect. This infers a possibility for a further development of biofunctionalized membrane. However, maximization is needed in order to attain closer advancement to a membrane-based sensor device

  8. Study of interactions between metal ions and protein model compounds by energy decomposition analyses and the AMOEBA force field

    Science.gov (United States)

    Jing, Zhifeng; Qi, Rui; Liu, Chengwen; Ren, Pengyu

    2017-10-01

    The interactions between metal ions and proteins are ubiquitous in biology. The selective binding of metal ions has a variety of regulatory functions. Therefore, there is a need to understand the mechanism of protein-ion binding. The interactions involving metal ions are complicated in nature, where short-range charge-penetration, charge transfer, polarization, and many-body effects all contribute significantly, and a quantitative description of all these interactions is lacking. In addition, it is unclear how well current polarizable force fields can capture these energy terms and whether these polarization models are good enough to describe the many-body effects. In this work, two energy decomposition methods, absolutely localized molecular orbitals and symmetry-adapted perturbation theory, were utilized to study the interactions between Mg2+/Ca2+ and model compounds for amino acids. Comparison of individual interaction components revealed that while there are significant charge-penetration and charge-transfer effects in Ca complexes, these effects can be captured by the van der Waals (vdW) term in the AMOEBA force field. The electrostatic interaction in Mg complexes is well described by AMOEBA since the charge penetration is small, but the distance-dependent polarization energy is problematic. Many-body effects were shown to be important for protein-ion binding. In the absence of many-body effects, highly charged binding pockets will be over-stabilized, and the pockets will always favor Mg and thus lose selectivity. Therefore, many-body effects must be incorporated in the force field in order to predict the structure and energetics of metalloproteins. Also, the many-body effects of charge transfer in Ca complexes were found to be non-negligible. The absorption of charge-transfer energy into the additive vdW term was a main source of error for the AMOEBA many-body interaction energies.

  9. How metallic is the binding state of indium hosted by excess-metal chalcogenides in ore deposits?

    Science.gov (United States)

    Ondina Figueiredo, Maria; Pena Silva, Teresa; Oliveira, Daniel; Rosa, Diogo

    2010-05-01

    Discovered in 1863, indium is nowadays a strategic scarce metal used both in classical technologic fields (like low melting-temperature alloys and solders) and in innovative nano-technologies to produce "high-tech devices" by means of new materials, namely liquid crystal displays (LCDs), organic light emitting diodes (OLEDs) and the recently introduced transparent flexible thin-films manufactured with ionic amorphous oxide semiconductors (IAOS). Indium is a typical chalcophile element, seldom forming specific minerals and occurring mainly dispersed within polymetallic sulphides, particularly with excess metal ions [1]. The average content of indium in the Earth's crust is very low but a further increase in its demand is still expected in the next years, thus focusing a special interest in uncovering new exploitation sites through promising polymetallic sulphide ores - e.g., the Iberian Pyrite Belt (IPB) [2] - and in improving recycling technologies. Indium recovery stands mostly on zinc extraction from sphalerite, the natural cubic sulphide which is the prototype of so-called "tetrahedral sulphides" where metal ions fill half of the available tetrahedral sites within the cubic closest packing of sulphur anions where the double of unfilled interstices are available for further in-filling. It is worth remarking that such packing array is particularly suitable for accommodating polymetallic cations by filling closely located interstitial sites [3] as happens in excess-metal tetrahedral sulphides - e.g. bornite, ideally Cu5FeS4, recognized as an In-carrying mineral [4]. Studying the tendency towards In-In interactions able of leading to the formation of polycations would efficiently contribute to understand indium crystal chemistry and the metal binding state in natural chalcogenides. Accordingly, an X-ray absorption near-edge spectroscopy (XANES) study at In L3-edge was undertaken using the instrumental set-up of ID21 beamline at the ESRF (European Synchrotron

  10. Protection of tobacco cells from oxidative copper toxicity by catalytically active metal-binding DNA oligomers.

    Science.gov (United States)

    Iwase, Junichiro; Furukawa, Hiroka; Hiramatsu, Takuya; Bouteau, François; Mancuso, Stefano; Tanaka, Kenichiro; Okazaki, Toshihiko; Kawano, Tomonori

    2014-03-01

    The impact of copper ions on the oxidative and calcium signal transductions, leading to cell death in plant cells, have been documented. Copper induces a series of biological and chemical reactions in plant cells including the oxidative burst reflecting the production of reactive oxygen species and the stimulation of calcium channel opening allowing a transient increase in cytosolic calcium concentrations. These early events, completed within a few minutes after the contact with copper, are known to trigger the development of cell death. The effects of DNA fragments with copper-binding motifs as novel plant cell-protecting agents were assessed using cell suspension cultures of transgenic tobacco (Nicotiana tabacum L., cell line BY-2) expressing the aequorin gene. The addition of GC-rich double-stranded DNA fragments, prior to the addition of copper ions, effectively blocked both the copper-induced calcium influx and cell death. In addition, the DNA-Cu complex examined was shown to possess superoxide-scavenging catalytic activity, suggesting that DNA-mediated protection of the cells from copper toxicity is due to the removal of superoxide. Lastly, a possible mechanism of DNA-Cu interaction and future applications of these DNA fragments in the protection of plant roots from metal toxicity or in aid of phyto-remediation processes are discussed.

  11. Heavy metal ions adsorption from mine waters by sawdust

    Directory of Open Access Journals (Sweden)

    G. Bogdanović

    2009-10-01

    Full Text Available In this work the results on the batch and column adsorption of copper and some associated ions by employing linden and poplar sawdust as a low-cost adsorbent are presented. The mine water from a local abandoned copper mine, as well as synthetic solutions of those ions which are the main constituents of the mine water were both used as a model-system in this study. The adsorption ability of the chosen sawdust to adsorb heavy metal ions is considered as a function of the initial pH of the solution and kind of metal ions. At lower pH of solutions the adsorption percentage (AD % decreases leading to a zero AD % at pH < 1.1. Maximum AD % is achieved at 3.5 < pH < 5. It was found that poplar and linden sawdust have both almost equal adsorption capacities against copper ions. The highest AD % ( ≈80% was achieved for Cu2+, while for Fe2+ it was slightly above 10%. The other considered ions (Zn2+ and Mn2+ were within this interval. The results obtained in the batch mode were verified through the column test by using the real mine water originating from an acid mine drainage (AMD of the copper mine „Cerovo“, RTB Bor. The breakthrough curves are presented as a function of the aqueous phase volume passed through the column allowing having an insight into the column adsorption features. Breakthrough points were determined for copper, manganese and zinc ions. A very high adsorption degree – higher than 99% was achieved in these experiments for all mentioned ions. After completing the adsorption, instead of desorption, the loaded sawdust was drained, dried and burned; the copper bearing ash was then leached with a controlled volume of sulphuric acid solution to concentrate copper therein. The obtained leach solution had the concentration of copper higher than 15 g dm-3 and the amount of H2SO4 high enough to serve as a supporting electrolyte suitable to be treated by the electrowinning for recovery of copper. The technology process based on the column

  12. A simple alkali-metal and noble gas ion source for SIMS equipments with mass separation of the primary ions

    International Nuclear Information System (INIS)

    Duesterhoeft, H.; Pippig, R.

    1986-01-01

    An alkali-metal ion source working without a store of alkali-metals is described. The alkali-metal ions are produced by evaporation of alkali salts and ionization in a low-voltage arc discharge stabilized with a noble gas plasma or in the case of small alkali-metal ion currents on the base of the well known thermic ionization at a hot tungsten wire. The source is very simple in construction and produces a stable ion current of 0.3 μA for more than 100 h. It is possible to change the ion species in a short time. This source is applicable to all SIMS equipments using mass separation for primary ions. (author)

  13. [Metal ions restrain the elimination of 4-tert-octylphenol by delta-MnO2].

    Science.gov (United States)

    Li, Fei-Li; Mou, Hua-Qian

    2013-06-01

    The effect of metal ions on elimination of 4-t-OP by synthetic delta-MnO2 suspension at pH 4.0 was studied. Experiments indicated that the removal of 4-t-OP by delta-MnO2 achieved 100% at reaction time of 150 min. However, the removal of 4-t-OP by delta-MnO2 was restrained when metal ions were added, and the higher concentration of metal ion was, the stronger the inhibition produced. Additionally, there were apparent differences among the inhibitory effect of the tested metal ions. Firstly, Pb2+ and Mn2+ had the strongest effect at pH 4.0, followed by the transition metal ions, then the alkaline earth ions, while the alkali metal ions had little influence on the removal of 4-t-OP by delta-MnO2. Also comparing the adsorption results of metal ions by delta-MnO2, Pb2+ showed the greatest attraction with delta-MnO2, and among the other metal ions, transition metal ions were adsorbed a little more strongly on delta-MnO2 than alkaline earth metal ions. Consequences showed that the inhibitory effects of metal ions were due to their occupying reactive sites on delta-MnO2 surface, which competed with 4-t-OP. Moreover, the dissimilar suppressions were contributed by the different adsorption capacities, surface structure change of MnO2 and the difference of free metal ion percentage in solution as well as metal ions radii.

  14. Why zinc fingers prefer zinc: ligand-field symmetry and the hidden thermodynamics of metal ion selectivity.

    Science.gov (United States)

    Lachenmann, Marcel J; Ladbury, John E; Dong, Jian; Huang, Kun; Carey, Paul; Weiss, Michael A

    2004-11-09

    The zinc finger, a motif of protein-nucleic acid recognition broadly conserved among eukaryotes, is a globular minidomain containing a tetrahedral metal-binding site. Preferential coordination of Zn(2+) (relative to Co(2+)) is proposed to reflect differences in ligand-field stabilization energies (LFSEs) due to complete or incomplete occupancy of d orbitals. LFSE predicts that the preference for Zn(2+) should be purely enthalpic in accord with calorimetric studies of a high-affinity consensus peptide (CP-1; Blasie, C. A., and Berg, J. (2002) Biochemistry 41, 15068-73). Despite its elegance, the general predominance of LFSE is unclear as (i) the magnitude by which CP-1 prefers Zn(2+) is greater than that expected and (ii) the analogous metal ion selectivity of a zinc metalloenzyme (carbonic anhydrase) is driven by changes in entropy rather than enthalpy. Because CP-1 was designed to optimize zinc binding, we have investigated the NMR structure and metal ion selectivity of a natural finger of lower stability derived from human tumor-suppressor protein WT1. Raman spectroscopy suggests that the structure of the WT1 domain is unaffected by interchange of Zn(2+) and Co(2+). As in CP-1, preferential binding of Zn(2+) (relative to Co(2+)) is driven predominantly by differences in enthalpy, but in this case the enthalpic advantage is less than that predicted by LFSE. A theoretical framework is presented to define the relationship between LFSE and other thermodynamic factors, such as metal ion electroaffinities, enthalpies of hydration, and the topography of the underlying folding landscape. The contribution of environmental coupling to entropy-enthalpy compensation is delineated in a formal thermodynamic cycle. Together, these considerations indicate that LFSE provides an important but incomplete description of the stringency and thermodynamic origin of metal-ion selectivity.

  15. Hydration to the poly(oxyethylene) derivative complexes of alkali metal ions and barium ion in 1,2-dichloroethane

    International Nuclear Information System (INIS)

    Kikuchi, Yoichi; Kubota, Mitsuru; Suzuki, Toshio; Sawada, Kiyoshi.

    1994-01-01

    A series of poly(oxyethylene) derivatives (POE compound) complexes of alkali metal and barium ions were extracted into 1,2-dichloroethane (1,2-DCE) by forming ion-pairs with picrate ion. Water molecules were coextracted into 1,2-DCE with the ion-pairs. The mean number of water molecules bound to the POE compound, X H2O,S , and its complex, X H2O,comp , in water saturated with 1,2-DCE was determined by means of aquametry. The X H2O,S value increases with the increase in the number of the oxyethylene units (EO unit) of the POE compound. The X H2O,comp value decreases in the order Li + >Na + >K + ≅Rb + ≅Cs + in any POE compound systems, and increases with the number of EO units of the POE compounds for a given metal ion. These results are interpreted by the hypothesis that the water molecules bound to the complex are those hydrated to the central metal ion, and the hydrated metal ion is surrounded by the EO chain with a helical conformation in the complex. The large number of water molecules are coordinating to the lithium ion complexes and bring about a serious distortion in the helical structure of the complexes. Because of the ion-pair formation with two picrate ions, the X H2O,comp values of barium ion complexes are smaller than those of potassium ion complexes. (author)

  16. Hydration number of alkali metal ions determined by insertion in a conducting polymer

    DEFF Research Database (Denmark)

    Skaarup, Steen

    2008-01-01

    In aqueous solutions, the alkali metals ions are associated with a number of H2O molecules. A distinction is made between a primary solvent shell, (or inner solvation shell), consisting of H2O molecules directly coordinated to the metal ion, and a secondary (or outer) solvation shell, consisting....... The solvation of alkali metal ions has been discussed for many years without a clear consensus. This work presents a systematic study of the hydration numbers of the 5 alkali metal ions, using the electrochemical insertion of the ions in a conducting polymer (polypyrrole containing the large immobile anion DBS...

  17. Adsorption of Heavy Metal Ions from Aqueous Solutions by Bentonite Nanocomposites.

    Science.gov (United States)

    Ma, Jing; Su, Guojun; Zhang, Xueping; Huang, Wen

    2016-08-01

    A series of bentonite nanocomposites have been synthesized by modifying bentonite with hexadecyltrimethylammonium bromide (CTMAB) and the common complexing agents, complexone (ethylene diamine tetraacetic acid, EDTA) or mercaptocomplexant (2-Mercaptobenzothiazole, MBT). These adsorbents are used to remove heavy metal ions (Cu(2+), Zn(2+), Mn(2+),Co(2+)). The Bent-CTMAB-MBT adsorbed metal ions are higher than Bent-CTMAB-EDTA under the same ion concentration in AAS. Compared with the single ion system, the adsorption of the mixed ion system of Cu(2+), Zn(2+), Mn(2+), Co(2+) had decreased differently. In the mixed system, the adsorption of Mn(2+) is significantly lower, but the adsorption of Cu(2+) was highest. The adsorption sequence of these four metal ions was Cu(2+) > Zn(2+) > Co(2+) > Mn(2+), and the selective adsorption was closely related to the hydration energy of heavy metal ions. We could remove more metal ions in different stages with the adsorption sequence.

  18. New Catalytic DNA Biosensors for Radionuclides and Metal ions

    International Nuclear Information System (INIS)

    Lu, Yi

    2003-01-01

    The goals of the project are to develop new catalytic DNA biosensors for simultaneous detection and quantification of bioavailable radionuclides and metal ions, and apply the sensors for on-site, real-time assessment of concentration, speciation and stability of the individual contaminants during and after bioremediation. A negative selection strategy was tested and validated. In vitro selection was shown to yield highly active and specific transition metal ion-dependent catalytic DNA/RNA. A fluorescence resonance energy transfer (FRET) study of in vitro selected DNA demonstrated that the trifluorophore labeled system is a simple and powerful tool in studying complex biomolecules structure and dynamics, and is capable of revealing new sophisticated structural changes. New fluorophore/quenchers in a single fluorosensor yielded improved signal to noise ratio in detection, identification and quantification of metal contaminants. Catalytic DNA fluorescent and colorimetric sensors were shown useful in sensing lead in lake water and in leaded paint. Project results were described in two papers and two patents, and won an international prize

  19. Detection of heavy metal ions in contaminated water by surface plasmon resonance based optical fibre sensor using conducting polymer and chitosan.

    Science.gov (United States)

    Verma, Roli; Gupta, Banshi D

    2015-01-01

    Optical fibre surface plasmon resonance (SPR) based sensor for the detection of heavy metal ions in the drinking water is designed. Silver (Ag) metal and indium tin oxide (ITO) are used for the fabrication of the SPR probe which is further modified with the coating of pyrrole and chitosan composite. The sensor works on the wavelength interrogation technique and is capable of detecting trace amounts of Cd(2+), Pb(2+), and Hg(2+) heavy metal ions in contaminated water. Four types of sensing probes are fabricated and characterised for heavy metal ions out of these pyrrole/chitosan/ITO/Ag coated probe is found to be highly sensitive among all other probes. Further, the cadmium ions bind strongly to the sensing surface than other ions and due to this the sensor is highly sensitive for Cd(2+) ions. The sensor's performance is best for the low concentrations of heavy metal ions and its sensitivity decreases with the increasing concentration of heavy metal ions. Copyright © 2014 Elsevier Ltd. All rights reserved.

  20. Adsorption of aqueous metal ions on cattle-manure-compost based activated carbons.

    Science.gov (United States)

    Zaini, Muhammad Abbas Ahmad; Okayama, Reiko; Machida, Motoi

    2009-10-30

    The objective of this study is to examine the suitability and performance of cattle-manure-compost (CMC) based activated carbons in removing heavy metal ions from aqueous solution. The influence of ZnCl(2) activation ratios and solution pH on the removal of Cu(II) and Pb(II) were studied. Pore texture, available surface functional groups, pH of point zero charge (pH(PZC)), thermogravimetric analysis and elemental compositions were obtained to characterize the activated carbons. Batch adsorption technique was used to determine the metal-binding ability of activated carbons. The equilibrium data were characterized using Langmuir, Freundlich and Redlich-Peterson models. It was found that the uptake of aqueous metal ions by activated carbons could be well described by Langmuir equation. It is suggested that the increase of surface area and mesopore ratio as a result of increasing activation ratios favored the removal of Cu(II), while activated carbon rich in acidic groups showed selective adsorption towards Pb(II). The preferable removal of Cu(II) over Pb(II) could be due to the rich nitrogen content as well as the higher mesoporous surface area in the CMC activated carbons. The impregnated CMC activated carbons also showed a better performance for Cu(II) removal at varying solution pH than Filtrasorb 400 (F400), while a similar performance was observed for Pb(II) removal.

  1. The Effect of Complex Formation upon the Redox Potentials of Metallic Ions. Cyclic Voltammetry Experiments.

    Science.gov (United States)

    Ibanez, Jorge G.; And Others

    1988-01-01

    Describes experiments in which students prepare in situ soluble complexes of metal ions with different ligands and observe and estimate the change in formal potential that the ion undergoes upon complexation. Discusses student formation and analysis of soluble complexes of two different metal ions with the same ligand. (CW)

  2. Modification of solid surface by intense pulsed light-ion and metal-ion beams

    Science.gov (United States)

    Nakagawa, Y.; Ariyoshi, T.; Hanjo, H.; Tsutsumi, S.; Fujii, Y.; Itami, M.; Okamoto, A.; Ogawa, S.; Hamada, T.; Fukumaru, F.

    1989-03-01

    Metal surfaces of Al, stainless-steel and Ti were bombarded with focused intense pulsed proton and carbon ion beams (energy ˜ 80 keV, current density ≲ 1000 A/cm 2, pulse width ˜ 300 ns). Thin titanium carbide layers were produced by carbon-ion irradiation on the titanium surface. The observed molten surface structures and recrystallized layer (20 μm depth) indicated that the surfaces reached high temperatures as a result of the irradiation. The implantation of intense pulsed metal ion beams (Al +, ˜ 20 A/cm 2) with simultaneous deposition of anode metal vapor on Ti and Fe made a mixed layer of AlTi and AlFe of about 0.5 μm depth. Ti and B multilayered films evaporated on glass substrates were irradiated by intense pulsed proton beams of relatively lower current density (10-200 A/cm 2). Ti films containing B atoms above 10 at.% were obtained. When the current density was about 200 A/cm 2 diffraction peaks of TiB 2 appeared.

  3. Formation of negative ions on a metal surface

    International Nuclear Information System (INIS)

    Amersfoort, P.W. van.

    1987-01-01

    In this thesis a fundamental study of the charge exchange process of positive ions on the converter surface is presented. Beams of hydrogen ad cesium ions are scattered from a thoroughly cleaned W(110) surface, under ultra-high vacuum conditions. The cesium coverage of the surface is a controlled parameter. Ch. 2 deals with the negative-ion formation probability for hydrogen atoms. The influence of coabsorption of hydrogen is studied in Ch. 3. These measurements are important for understanding the formation process in plasma sources, because the converter surface is expected to be strongly contaminated with hydrogen. The charge state of scattered cesium particles is investigated in Ch. 4. Knowledge of this parameter is essential for Ch. 5, in which a model study of adsorption of cesium on a metal surface in contact with a plasma is presented. Finally, the negative-ion formation process in a plasma environment is studied in Ch. 6. Measurements done on a hollow-cathode discharge equipped with a novel type of converter, a porous tungsten button, are discussed. Liquid cesium diffuses through this button towards the side in contact with the plasma. (Auth.)

  4. Metal-organic frameworks for lithium ion batteries and supercapacitors

    Energy Technology Data Exchange (ETDEWEB)

    Ke, Fu-Sheng; Wu, Yu-Shan; Deng, Hexiang, E-mail: hdeng@whu.edu.cn

    2015-03-15

    Porous materials have been widely used in batteries and supercapacitors attribute to their large internal surface area (usually 100–1000 m{sup 2} g{sup −1}) and porosity that can favor the electrochemical reaction, interfacial charge transport, and provide short diffusion paths for ions. As a new type of porous crystalline materials, metal-organic frameworks (MOFs) have received huge attention in the past decade due to their unique properties, i.e. huge surface area (up to 7000 m{sup 2} g{sup −1}), high porosity, low density, controllable structure and tunable pore size. A wide range of applications including gas separation, storage, catalysis, and drug delivery benefit from the recent fast development of MOFs. However, their potential in electrochemical energy storage has not been fully revealed. Herein, the present mini review appraises recent and significant development of MOFs and MOF-derived materials for rechargeable lithium ion batteries and supercapacitors, to give a glimpse into these potential applications of MOFs. - Graphical abstract: MOFs with large surface area and high porosity can offer more reaction sites and charge carriers diffusion path. Thus MOFs are used as cathode, anode, electrolyte, matrix and precursor materials for lithium ion battery, and also as electrode and precursor materials for supercapacitors. - Highlights: • MOFs have potential in electrochemical area due to their high porosity and diversity. • We summarized and compared works on MOFs for lithium ion battery and supercapacitor. • We pointed out critical challenges and provided possible solutions for future study.

  5. Metal ion coordination in the E. coli Nudix hydrolase dihydroneopterin triphosphate pyrophosphatase: New clues into catalytic mechanism.

    Directory of Open Access Journals (Sweden)

    Shannon E Hill

    Full Text Available Dihydroneopterin triphosphate pyrophosphatase (DHNTPase, a member of the Mg2+ dependent Nudix hydrolase superfamily, is the recently-discovered enzyme that functions in the second step of the pterin branch of the folate biosynthetic pathway in E. coli. DHNTPase is of interest because inhibition of enzymes in bacterial folate biosynthetic pathways is a strategy for antibiotic development. We determined crystal structures of DHNTPase with and without activating, Mg2+-mimicking metals Co2+ and Ni2+. Four metal ions, identified by anomalous scattering, and stoichiometrically confirmed in solution by isothermal titration calorimetry, are held in place by Glu56 and Glu60 within the Nudix sequence motif, Glu117, waters, and a sulfate ion, of which the latter is further stabilized by a salt bridge with Lys7. In silico docking of the DHNTP substrate reveals a binding mode in which the pterin ring moiety is nestled in a largely hydrophobic pocket, the β-phosphate activated for nucleophilic attack overlays with the crystallographic sulfate and is in line with an activated water molecule, and remaining phosphate groups are stabilized by all four identified metal ions. The structures and binding data provide new details regarding DHNTPase metal requirements, mechanism, and suggest a strategy for efficient inhibition.

  6. Metal ion coordination in the E. coli Nudix hydrolase dihydroneopterin triphosphate pyrophosphatase: New clues into catalytic mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Hill, Shannon E.; Nguyen, Elaine; Ukachukwu, Chiamaka U.; Freeman, Dana M.; Quirk, Stephen; Lieberman, Raquel L.; Boggon, Titus J.

    2017-07-25

    Dihydroneopterin triphosphate pyrophosphatase (DHNTPase), a member of the Mg2+ dependent Nudix hydrolase superfamily, is the recently-discovered enzyme that functions in the second step of the pterin branch of the folate biosynthetic pathway in E. coli. DHNTPase is of interest because inhibition of enzymes in bacterial folate biosynthetic pathways is a strategy for antibiotic development. We determined crystal structures of DHNTPase with and without activating, Mg2+-mimicking metals Co2+ and Ni2+. Four metal ions, identified by anomalous scattering, and stoichiometrically confirmed in solution by isothermal titration calorimetry, are held in place by Glu56 and Glu60 within the Nudix sequence motif, Glu117, waters, and a sulfate ion, of which the latter is further stabilized by a salt bridge with Lys7. In silico docking of the DHNTP substrate reveals a binding mode in which the pterin ring moiety is nestled in a largely hydrophobic pocket, the β-phosphate activated for nucleophilic attack overlays with the crystallographic sulfate and is in line with an activated water molecule, and remaining phosphate groups are stabilized by all four identified metal ions. The structures and binding data provide new details regarding DHNTPase metal requirements, mechanism, and suggest a strategy for efficient inhibition.

  7. Biological removal of metal ions from aqueous process streams

    International Nuclear Information System (INIS)

    Shumate, S.E. II; Strandberg, G.W.; Parrott, J.R. Jr.

    1978-01-01

    Aqueous waste streams from nuclear fuel processing operations may contain trace quantities of heavy metals such as uranium. Conventional chemical and physical treatment may be ineffective or very expensive when uranium concentrations in the range of 10 to 100 g/m 3 must be reduced to 1 g/m 3 or less. The ability of some microorganisms to adsorb or complex dissolved heavy metals offers an alternative treatment method. Uranium uptake by Saccharomyces cerevisiae NRRL Y-2574 and a strain of Pseudomonas aeruginosa was examined to identify factors which might affect a process for the removal of uranium from wastewater streams. At uranium concentrations in the range of 10 to 500 g/m 3 , where the binding capacity of the biomass was not exceeded, temperature, pH, and initial uranium concentration were found to influence the rate of uranium uptake, but not the soluble uranium concentration at equilibrium. 6 figs

  8. Low jitter metal vapor vacuum arc ion source for electron beam ion trap injections

    International Nuclear Information System (INIS)

    Holland, Glenn E.; Boyer, Craig N.; Seely, John F.; Tan, J.N.; Pomeroy, J.M.; Gillaspy, J.D.

    2005-01-01

    We describe a metal vapor vacuum arc (MeVVA) ion source containing eight different cathodes that are individually selectable via the control electronics which does not require moving components in vacuum. Inside the vacuum assembly, the arc plasma is produced by means of a 30 μs pulse (26 kV,125 A) delivering 2.4 mC of charge to the cathode sample material. The trigger jitter is minimized ( 9 ions/cm 2 , measured by an unbiased Faraday cup positioned 20 cm from the extractor grid, at discharge rates up to 5 Hz. The electronic triggering of the discharge is via a fiber optic interface. We present the design, fabrication details, and performance of this MeVVA, recently installed on the National Institute of Standards and Technology electron beam ion trap (EBIT)

  9. Sensitive metal ions (II) determination with resonance Raman method

    Science.gov (United States)

    Yu, Zhi; Bracero, Lucas A.; Chen, Lei; Song, Wei; Wang, Xu; Zhao, Bing

    2013-03-01

    In this paper, a new proposal for the quantitative evaluation of divalent metal ions (M2+) is developed by the use of the competitive resonance Raman (RR)-based method. Upon excitation with light of the appropriate wavelength (532 nm), a strong electric field is generated that couples with the resonance of the complex (zincon-M2+), increasing the character signals of these complexes, resulting in sensitive detection. Herein, the RR probe, zincon-M2+ complex that the RR intensity gets lower with the decreasing of the M2+ concentration, which leads to the transformation of the Raman information. As a result, by using the proposed RR-based method, we could find the liner calibration curves of Cu2+ and Ni2+, which show the potential in quantitative evaluation of an unknown sample. In addition, the abundant fingerprint information shows that RR leads to the successful analysis of a blended solution, which contains two ions: Cu2+ and Ni2+.

  10. Measuring free metal ion concentrations in situ in natural waters using the Donnan Membrane Technique

    NARCIS (Netherlands)

    Kalis, E.J.J.; Weng, L.P.; Dousma, F.; Temminghoff, E.J.M.; Riemsdijk, van W.H.

    2006-01-01

    Metal toxicity is not related to the total but rather to the free or labile metal ion concentration. One of the techniques that can be used to measure several free metal ion concentrations simultaneously is the Donnan Membrane Technique (DMT) in combination with the inductively coupled plasma-mass

  11. PHENOL OXIDATION USING NATURAL ZEOLITE SUPPORTED METAL ION CATALYST

    Directory of Open Access Journals (Sweden)

    Sri Wardhani

    2010-06-01

    Full Text Available Phenol which contained in waste water has to be reduced and it could be done by oxygen oxidation.  In order to increase the rate of reaction it was needed a catalyst. In this research the capability of various catalysts, namely zeolite-Zn(II, zeolite-Cu(II and zeolite-Co(IIin oxidation of phenol has been investigated. The aim of this research was to study the type of metal ion catalyst towards the percentage of oxidated phenol. The oxidation process were carried out in an aqueous phenol of 100 ppm with oxygen flow rate of 200 mL/min. in the presence of catalysts with 0.2M of initial impregnation concentration. The capabilities of catalysts were performed by calculating the activation energy and it was done at two different temperatures, i.e. 70 and 90 oC. The percentage of oxidated phenol was determinated by measuring its concentration using UV-VIS spectrophotometer. In addition, the impregnated metal was calculated by measuring the ion concentration remains in the filtrate solution and it was determined using Atomic Absorption Spectrophotometer. The results showed that metal ion types affected the catalytic activity. The order of phenol oxidationactivity decreased as Co(II > Cu(II > Zn(II. The surface characteristics of catalysts were supported by pore volume and pore diameter i.e 0.009 cm3/g and 16.59 Å for Zn(II whereas specific surface area was 10.32 m2/g for Zn(II, 0.004 cm3/g and 24.37 Å for Cu(II whereas specific surface area was 3.57 m2/g for Cu(II, 0.001 cm3/g and 19.63 Å for Co(II whereas specific surface area was 10.26m2/g for Co(II.   Keywords: phenol,natural zeolite, catalyst, oxidation

  12. Evaluation of ion binding to DNA duplexes using a size-modified Poisson-Boltzmann theory.

    Science.gov (United States)

    Chu, Vincent B; Bai, Yu; Lipfert, Jan; Herschlag, Daniel; Doniach, Sebastian

    2007-11-01

    Poisson-Boltzmann (PB) theory is among the most widely applied electrostatic theories in biological and chemical science. Despite its reasonable success in explaining a wide variety of phenomena, it fails to incorporate two basic physical effects, ion size and ion-ion correlations, into its theoretical treatment. Recent experimental work has shown significant deviations from PB theory in competitive monovalent and divalent ion binding to a DNA duplex. The experimental data for monovalent binding are consistent with a hypothesis that attributes these deviations to counterion size. To model the observed differences, we have generalized an existing size-modified Poisson-Boltzmann (SMPB) theory and developed a new numerical implementation that solves the generalized theory around complex, atomistic representations of biological molecules. The results of our analysis show that good agreement to data at monovalent ion concentrations up to approximately 150 mM can be attained by adjusting the ion-size parameters in the new size-modified theory. SMPB calculations employing calibrated ion-size parameters predict experimental observations for other nucleic acid structures and salt conditions, demonstrating that the theory is predictive. We are, however, unable to model the observed deviations in the divalent competition data with a theory that only accounts for size but neglects ion-ion correlations, highlighting the need for theoretical descriptions that further incorporate ion-ion correlations. The accompanying numerical solver has been released publicly, providing the general scientific community the ability to compute SMPB solutions around a variety of different biological structures with only modest computational resources.

  13. Local coordination of polyvalent metal ions in molten halide mixtures

    International Nuclear Information System (INIS)

    Akdeniz, Z.; Tosi, M.P.

    1989-07-01

    Ample experimental evidence is available in the literature on the geometry and the stability of local coordination for polyvalent metal ions in molten mixtures of their halides with alkali halides. Recent schemes for classifying this evidence are discussed. Dissociation of tetrahedral halocomplexes in good ionic systems can be viewed as a classical Mott problem of bound-state stability in a conducting matrix. More generally, structural coordinates can be constructed from properties of the component elements, to separate out systems with long-lived fourfold or sixfold coordination and to distinguish between these. (author). 11 refs, 1 fig

  14. Studies on the dryolysis reactions of metal ions

    International Nuclear Information System (INIS)

    Baes, C.F. Jr.

    1977-01-01

    Research is reported on metallic ions produced in solutions at low concentrations as mononuclear hydrolysis products. The method for studying the mononuclear species is to measure the solubility of the oxide or hydroxide solid phase that is stable under the conditions of interest. Column solubility measurements of Al(OH) 3 (Gibbsite) in NaCl solution as a function of pH, temperature, and ionic strength are being conducted in order to better establish the stability of the intermediate species Al(OH) 2 + and Al(OH) 3 (aq)

  15. Pb(II) and Hg(II) binding to $\\textit{de novo}$ designed proteins studied by $^{204m}$Pb- and $^{199m}$Hg-Perturbed Angular Correlation of $\\gamma$-rays (PAC) spectroscopy : Clues to heavy metal toxicity

    CERN Multimedia

    2002-01-01

    $\\textit{De novo}$ design of proteins combined with PAC spectroscopy offers a unique and powerful approach to the study of fundamental chemistry of heavy metal-protein interactions, and thus of the mechanisms underlying heavy metal toxicity. In this project we focus on Pb(II) and Hg(II) binding to designed three stranded coiled coil proteins with one or two binding sites, mimicking a variety of naturally occurring thiolate-rich metal ion binding sites in proteins. The $^{204m}$Pb- and $^{199m}$Hg-PAC experiments will complement data already recorded with EXAFS, NMR, UV-Vis and CD spectroscopies.

  16. Binding of heavy metals to derivatives of cholesterol and sodium dodecyl sulfate

    Energy Technology Data Exchange (ETDEWEB)

    Ahmadi, S.; Batchelor, B.; Koseoglu, S.S. [Texas A and M Univ., College Station, TX (United States); Huang, Y.C.

    1995-09-01

    The binding behaviors of five metals (cadmium, copper, nickel, lead, and zinc), individually at pH 6 and collectively at pHs 6 and 3, to deoxycholic acid (DCA) and taurocholic acid (TCA) were compared with those of sodium dodecyl sulfate (SDS) using a continuous diafiltration method. DCA and SDS have been successfully applied in micellar-enhanced ultrafiltration (MEUF) for metal removal from water. In this study, SDS exhibits the strongest binding in the single-component experiments while DCA binds the most in the multicomponent trials. TCA does not show any significant biding compared with DCA and SDS. Overall the molar binding ratios of the mixture at pH 3 were well below those of the other two solutions. This diafiltration technique quantifies the binding characteristics of a surfactant by generating sorption isotherms and determining the intrinsic association constraints with corresponding number of binding sites. These parameters can be useful in designing an efficient MEUF system.

  17. Novel forward osmosis process to effectively remove heavy metal ions

    KAUST Repository

    Cui, Yue

    2014-10-01

    In this study, a novel forward osmosis (FO) process for the removal of heavy metal ions from wastewater was demonstrated for the first time. The proposed FO process consists of a thin-film composite (TFC) FO membrane made from interfacial polymerization on a macrovoid-free polyimide support and a novel bulky hydroacid complex Na4[Co(C6H4O7)2]·r2H2O (Na-Co-CA) as the draw solute to minimize the reverse solute flux. The removal of six heavy metal solutions, i.e., Na2Cr2O7, Na2HAsO4, Pb(NO3)2, CdCl2, CuSO4, Hg(NO3)2, were successfully demonstrated. Water fluxes around 11L/m2/h (LMH) were harvested with heavy metals rejections of more than 99.5% when employing 1M Na-Co-CA as the draw solution to process 2000ppm(1 ppm=1 mg/L) heavy metal solutions at room temperature. This FO performance outperforms most nanofiltration (NF) processes. In addition, the high rejections were maintained at 99.5% when a more concentrated draw solution (1.5M) or feed solution (5000ppm) was utilized. Furthermore, rejections greater than 99.7% were still achieved with an enhanced water flux of 16.5LMH by operating the FO process at 60°C. The impressive heavy metal rejections and satisfactory water flux under various conditions suggest great potential of the newly developed FO system for the treatment of heavy metal wastewater. © 2014 Elsevier B.V.

  18. Use of Raman spectroscopy and chemometrics for the quantification of metal ions attached to Lactobacillus kefir.

    Science.gov (United States)

    Gerbino, E; Mobili, P; Tymczyszyn, E E; Frausto-Reyes, C; Araujo-Andrade, C; Gómez-Zavaglia, A

    2012-02-01

    To set-up an experimental and analytical methodology to evaluate the feasibility of developing simple, accurate and quantitative models based on Raman spectroscopy and multivariate analysis for the quantification of metal ions adsorbed to the bacterial surface of Lactobacillus kefir. One millilitre cultures from two strains of Lact. kefir in the stationary phase were harvested and washed twice with ultra pure water. The bacterial pellets were resuspended into 1 ml solutions of Pb(+2), Cd(+2) or Ni(+2) ranging from 0 to 0·9 mmol l(-1). The suspensions were further incubated for 1 h at 30°C at pH 5·5. After centrifugation, the pellets were kept to register the Raman spectra and the supernatants were used for the analytical determination of Pb(+2) , Cd(+2) and Ni(+2). Micro-organisms nontreated with metal ions were used as controls. Principal component analysis (PCA) was performed over the preprocessed Raman spectra to evaluate whether the clusters obtained could be correlated with the concentration of metal ions attached to the bacterial biomass. After that, partial least squares (PLS) models were calibrated with the aim of quantifying the metal ions adsorbed to the bacterial surface. According to the analytical determinations, the maximum binding capacity of all the metals (q(max)) attained values that are comparable with those observed for other lactic acid bacteria (ca. 0·200 mmol g(-1)). The spectral analysis revealed that the main functional groups involved in the bacteria/metal interaction are carboxylates, phosphates and polysaccharides. In PCA, the first two principal components explain more than 72% variance of the spectral data set contained in the data structure, allowing a clear discrimination among samples of different concentrations. Based on this information and using as reference the results obtained by analytical methods, PLS prediction models were successfully defined for the quantification of Pb(+2), Cd(+2) and Ni(+2) attached to the bacterial

  19. Acetabular bone density and metal ions after metal-on-metal versus metal-on-polyethylene total hip arthroplasty; short-term results

    NARCIS (Netherlands)

    Zijlstra, Wierd P.; van der Veen, Hugo C.; van den Akker-Scheek, Inge; Zee, Mark J. M.; Bulstra, Sjoerd K.; van Raay, Jos J. A. M.

    Information on periprosthetic acetabular bone density is lacking for metal-on-metal total hip arthroplasties. These bearings use cobalt-chromium instead of titanium acetabular components, which could lead to stress shielding and hence periprosthetic bone loss. Cobalt and chromium ions have

  20. Interpretation with a Donnan-based concept of the influence of simple salt concentration on the apparent binding of divalent ions to the polyelectrolytes polystyrenesulfonate and dextran sulfate

    Science.gov (United States)

    Marinsky, J.A.; Baldwin, Robert F.; Reddy, M.M.

    1985-01-01

    It has been shown that the apparent enhancement of divalent metal ion binding to polyions such as polystyrenesulfonate (PSS) and dextran sulfate (DS) by decreasing the ionic strength of these mixed counterion systems (M2+, M+, X-, polyion) can be anticipated with the Donnan-based model developed by one of us (J.A.M.). Ion-exchange distribution methods have been employed to measure the removal by the polyion of trace divalent metal ion from simple salt (NaClO4)-polyion (NaPSS) mixtures. These data and polyion interaction data published earlier by Mattai and Kwak for the mixed counterion systems MgCl2-LiCl-DS and MgCl2-CsCl-DS have been shown to be amenable to rather precise analysis by this model. ?? 1985 American Chemical Society.

  1. Metal ion detection with oligo(ethylene glycol) monolayer-modified gold nanoparticles.

    Science.gov (United States)

    Li, Guangzhao; Yang, Bin; Lu, Zhiqiang; Xia, Sijing; Feng, Hui; Zhu, Xiaoqing; Wang, Anning; Zhu, Jin

    2011-11-01

    Two colorimetric sensors of gold nanoparticles (AuNPs) modified with different oligo(ethylene glycol)-containing organic molecules have been developed to detect metal ions by ultraviolet-visible (UV-vis) extinction spectroscopy. These sensors display different responses to some metal ions. One exhibits high selectivity for Hg2+ over a variety of competitive metal ions and the other one can respond to a multitude of metal ions. These differences might result from the different functionalized end groups of the modified molecules. Coordination effect, pH response, and ionic strength were investigated to understand the mechanism of the responses to metal ions. The results suggested that the colorimetric responses were mainly induced by the coordination effect of the modified organic molecules and the removing of the modified organic molecules caused by metal ions.

  2. Binding of ArgTX-636 in the NMDA receptor ion channel

    DEFF Research Database (Denmark)

    Poulsen, Mette H; Andersen, Jacob; Christensen, Rune

    2015-01-01

    The N-methyl-d-aspartate receptors (NMDARs) constitute an important class of ligand-gated cation channels that are involved in the majority of excitatory neurotransmission in the human brain. Compounds that bind in the NMDAR ion channel and act as blockers are use- and voltage-dependent inhibitor...

  3. Most spin-1/2 transition-metal ions do have single ion anisotropy

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Jia; Whangbo, Myung-Hwan, E-mail: hxiang@fudan.edu.cn, E-mail: mike-whangbo@ncsu.edu [Department of Chemistry, North Carolina State University, Raleigh, North Carolina 27695 (United States); Koo, Hyun-Joo [Department of Chemistry and Research Institute for Basic Sciences, Kyung Hee University, Seoul 130-701 (Korea, Republic of); Xiang, Hongjun, E-mail: hxiang@fudan.edu.cn, E-mail: mike-whangbo@ncsu.edu [Key Laboratory of Computational Physical Sciences (Ministry of Education), State Key Laboratory of Surface Physics, and Department of Physics, Fudan University, Shanghai 200433 (China); Kremer, Reinhard K. [Max-Planck-Institut für Festkörperforschung, Heisenbergstrasse 1, D-70569 Stuttgart (Germany)

    2014-09-28

    The cause for the preferred spin orientation in magnetic systems containing spin-1/2 transition-metal ions was explored by studying the origin of the easy-plane anisotropy of the spin-1/2 Cu{sup 2+} ions in CuCl{sub 2}·2H{sub 2}O, LiCuVO{sub 4}, CuCl{sub 2}, and CuBr{sub 2} on the basis of density functional theory and magnetic dipole-dipole energy calculations as well as a perturbation theory treatment of the spin-orbit coupling. We find that the spin orientation observed for these spin-1/2 ions is not caused by their anisotropic spin exchange interactions, nor by their magnetic dipole-dipole interactions, but by the spin-orbit coupling associated with their crystal-field split d-states. Our study also predicts in-plane anisotropy for the Cu{sup 2+} ions of Bi{sub 2}CuO{sub 4} and Li{sub 2}CuO{sub 2}. The results of our investigations dispel the mistaken belief that magnetic systems with spin-1/2 ions have no magnetic anisotropy induced by spin-orbit coupling.

  4. Spectrofluorometric and Molecular Modeling Studies on Binding of Nitrite Ion with Bovine Hemoglobin: Effect of Nitrite Ion on Amino Acid Residues

    Science.gov (United States)

    Madrakian, T.; Bagheri, H.; Afkhami, A.

    2015-05-01

    The interaction between nitrite ion and bovine hemoglobin was investigated by a spectrofluorometric technique. The experimental results indicated that the interaction causes a static quenching of the fluorescence of bovine hemoglobin, that the binding reaction is spontaneous, and that H-bonding interactions play a major role in binding of this ion to bovine hemoglobin. The formation constant for this interaction was calculated. Based on Förster's theory of nonradiative energy transfer, the binding distance between this ion and bovine hemoglobin was determined. Furthermore, the interaction of nitrite ion with tyrosine and tryptophan was investigated with synchronous fluorescence. There was no significant shift of the maximum emission wavelength with interactions of the mentioned ion with bovine hemoglobin, which implies that interaction of nitrite ion with bovine hemoglobin does not affect the microenvironment around the tryptophan and tyrosine residues. Furthermore, the effect of nitrite ion on amino acid residues of bovine hemoglobin was studied by a molecular docking technique.

  5. Effects of heavy metal ions on EDTA-sensitive cell contacts of Dictyostelium discoideum

    OpenAIRE

    Yoshida, Motonobu

    2000-01-01

    [Synopsis] The effects of heavy metal ions on the EDTA-sensitive cell contacts, which exist from growthphase stage of Dictyostelium discoideum, was investigated. EDTA-sensitive cell contacts of cells at the growth-phase stage were analyzed in the presence of heavy metal ions. Heavy metal ions Hg^, Cd^ and Cu^ inhibited EDTA-sensitive cell contacts at concentrations higher than 10^M, whereas Pb^ did not show any recognizable effects at the same concentration range. The possible mechanisms of a...

  6. Spectral characterization, optical band gap calculations and DNA binding of some binuclear Schiff-base metal complexes derived from 2-amino-ethanoic acid and acetylacetone

    Science.gov (United States)

    Hussien, Mostafa A.; Nawar, Nagwa; Radwan, Fatima M.; Hosny, Nasser Mohammed

    2015-01-01

    Bi-nuclear metal complexes derived from the reaction of Cu(II), Co(II), Ni(II) and Zn(II) acetates with the Schiff-base ligand (H2L) resulted from the condensation of 2-amino-ethanoic acid (glycine) and acetylacetone have been synthesized and characterized by elemental analyses, Raman spectra, FT-IR, ES-MS, UV-Vis., 1H NMR, ESR, thermal analyses (TG, DTG and DTA) and magnetic measurements. The results showed that, the Schiff base ligand can bind two metal ions in the same time. It coordinates to the first metal ion as mono-negative bi-dentate through azomethine nitrogen and enolic carbonyl after deprotonation. At the same time, it binds to the second metal ion via carboxylate oxygen after deprotonation. The thermodynamic parameters E∗, ΔH∗, ΔG∗ and ΔS∗ have been calculated by Coats-Redfern (CR) and Horowitz-Metzger (HM) methods. The optical band gaps of the isolated complexes have been calculated from absorption spectra and the results indicated semi-conducting nature of the investigated complexes. The interactions between the copper (II) complex and calf thymus DNA (CT-DNA) have been studied by UV spectra. The results confirm that the Cu(II) complex binds to CT-DNA.

  7. Electrospray droplet exposure to organic vapors: metal ion removal from proteins and protein complexes.

    Science.gov (United States)

    DeMuth, J Corinne; McLuckey, Scott A

    2015-01-20

    The exposure of aqueous nanoelectrospray droplets to various organic vapors can dramatically reduce sodium adduction on protein ions in positive ion mass spectra. Volatile alcohols, such as methanol, ethanol, and isopropanol lead to a significant reduction in sodium ion adduction but are not as effective as acetonitrile, acetone, and ethyl acetate. Organic vapor exposure in the negative ion mode, on the other hand, has essentially no effect on alkali ion adduction. Evidence is presented to suggest that the mechanism by which organic vapor exposure reduces alkali ion adduction in the positive mode involves the depletion of alkali metal ions via ion evaporation of metal ions solvated with organic molecules. The early generation of metal/organic cluster ions during the droplet desolvation process results in fewer metal ions available to condense on the protein ions formed via the charged residue mechanism. These effects are demonstrated with holomyoglobin ions to illustrate that the metal ion reduction takes place without detectable protein denaturation, which might be revealed by heme loss or an increase in charge state distribution. No evidence is observed for denaturation with exposure to any of the organic vapors evaluated in this work.

  8. Immobilised metal-ion affinity chromatography purification of histidine-tagged recombinant proteins : a wash step with a low concentration of EDTA

    NARCIS (Netherlands)

    Westra, DF; Welling, GW; Koedijk, DGAM; Scheffer, AJ; The, TH; Welling-Wester, S

    2001-01-01

    Immobilised metal-ion affinity chromatography (IMAC) is widely used for the purification of recombinant proteins in which a poly-histidine tag is introduced. However, other proteins may also bind to IMAC columns. We describe the use of a washing buffer with a low concentration of EDTA (0.5 mM) for

  9. Evaluation of cationite efficiency during extraction of heavy metal ions from diluted solutions

    OpenAIRE

    Gomelya, Nikolai; Ivanova, Veronika; Galimova, Valentina; Nosachova, Julia; Shabliy, Tatiana

    2017-01-01

    Ion exchange is one of the methods that has been successfully employed in industry for extracting heavy metals from wastewater. We conducted research into ion-exchange processes of extraction of heavy metal ions on the weak- and strong-acid cationites from distilled and tap water. Heavy metal ion concentration was less than 1 mg/dm3. We established that in all cases efficiency of water treatment decreased at a decrease in the starting concentration of a metal. The process took place regardles...

  10. Application of monocarboxylic acids for the extraction of metal ions-literature survey

    International Nuclear Information System (INIS)

    Brzozka, Z.; Rozycki, C.

    1980-01-01

    In the paper there is presented a literature review concerning the application of monocarboxylic acids for extraction of metal ions. The following problems are discussed: characteristic of monocarboxylic acids and their mixtures, the equilibria between the acid solution in organic solvent and aqueous phase, the mechanism of acid partition, complexes of carboxylic acids and metal ions in aqueous phase, mechanism of extraction by means of carboxylic acids as well as the problems concerning the extraction of individual metal ions. Data about the extraction of metal ions are presented in table. The 138 references are given. (author)

  11. Use of divalent metal ions in the DNA cleavage reaction of topoisomerase IV

    Science.gov (United States)

    Pitts, Steven L.; Liou, Grace F.; Mitchenall, Lesley A.; Burgin, Alex B.; Maxwell, Anthony; Neuman, Keir C.; Osheroff, Neil

    2011-01-01

    It has long been known that type II topoisomerases require divalent metal ions in order to cleave DNA. Kinetic, mutagenesis and structural studies indicate that the eukaryotic enzymes utilize a novel variant of the canonical two-metal-ion mechanism to promote DNA scission. However, the role of metal ions in the cleavage reaction mediated by bacterial type II enzymes has been controversial. Therefore, to resolve this critical issue, this study characterized the DNA cleavage reaction of Escherichia coli topoisomerase IV. We utilized a series of divalent metal ions with varying thiophilicities in conjunction with oligonucleotides that replaced bridging and non-bridging oxygen atoms at (and near) the scissile bond with sulfur atoms. DNA scission was enhanced when thiophilic metal ions were used with substrates that contained bridging sulfur atoms. In addition, the metal-ion dependence of DNA cleavage was sigmoidal in nature, and rates and levels of DNA cleavage increased when metal ion mixtures were used in reactions. Based on these findings, we propose that topoisomerase IV cleaves DNA using a two-metal-ion mechanism in which one of the metal ions makes a critical interaction with the 3′-bridging atom of the scissile phosphate and facilitates DNA scission by the bacterial type II enzyme. PMID:21300644

  12. Nanoparticles reduce nickel allergy by capturing metal ions

    Science.gov (United States)

    Vemula, Praveen Kumar; Anderson, R. Rox; Karp, Jeffrey M.

    2011-05-01

    Approximately 10% of the population in the USA suffer from nickel allergy, and many are unable to wear jewellery or handle coins and other objects that contain nickel. Many agents have been developed to reduce the penetration of nickel through skin, but few formulations are safe and effective. Here, we show that applying a thin layer of glycerine emollient containing nanoparticles of either calcium carbonate or calcium phosphate on an isolated piece of pig skin (in vitro) and on the skin of mice (in vivo) prevents the penetration of nickel ions into the skin. The nanoparticles capture nickel ions by cation exchange, and remain on the surface of the skin, allowing them to be removed by simple washing with water. Approximately 11-fold fewer nanoparticles by mass are required to achieve the same efficacy as the chelating agent ethylenediamine tetraacetic acid. Using nanoparticles with diameters smaller than 500 nm in topical creams may be an effective way to limit the exposure to metal ions that can cause skin irritation.

  13. Accelerated electron exchange between U4+ and UO22+ by foreign metal ions

    International Nuclear Information System (INIS)

    Obanawa, Heiichiro; Onitsuka, Hatsuki; Takeda, Kunihiko

    1990-01-01

    The rate constant of U 4+ -UO 2 2+ electron exchange (k et ) was increased by more than 100 times in the presence of various metal ions. The larger rate constant was observed for the smaller difference of the standard reduction potential strength between metal ion and UO 2 2+ ion (Δμ θ e ). Detailed investigation of the electron exchange reaction in the presence of Mo 5+ suggested that the mechanism of the electron transfer reaction catalyzed by metal ions is the outer-sphere type independent of U-Clcomplex ions. (author)

  14. Removal of the metal ions from aqueous solutions by nanoscaled low molecular pectin isolated from seagrass Phyllospadix iwatensis.

    Science.gov (United States)

    Khozhaenko, Elena; Kovalev, Valeri; Podkorytova, Elena; Khotimchenko, Maksim

    2016-09-15

    Pectins from sea grasses are considered as promising substances with pronounced metal-binding activity. Due to the high molecular weight and heterogeneous structure, the use of pectins for removal of metal ions is difficult. Technology of directed pectin degradation was developed and homogenous degraded nanoscaled pectin polymers were synthesized. Experimental samples of degraded pectin isolated from Phyllospadix iwatensis were tested for their metal binding activity in comparison with native pectin from this seagrass and commercial citrus pectin. The metal uptake of all pectin compounds was highest within the pH range from 4.0 to 6.0. The Langmuir, Freundlich and BET sorption models were applied to describe the isotherms and constants. Results showed that depolymerized pectin exerts highest lead and cadmium binding activity with pronounced affinity. All pectin compounds were suggested to be favorable sorbents. Therefore, it can be concluded that degraded pectin is a prospective material for creation of metal-removing water treatment systems. Copyright © 2016 Elsevier B.V. All rights reserved.

  15. New Proton-Ionizable, Calixarene-Based Ligands for Selective Metal Ion Separations

    Energy Technology Data Exchange (ETDEWEB)

    Bartsch, Richard A.

    2012-06-04

    The project objective was the discovery of new ligands for performing metal ion separations. The research effort entailed the preparation of new metal ion complexing agents and polymers and their evaluation in metal ion separation processes of solvent extraction, synthetic liquid membrane transport, and sorption. Structural variations in acyclic, cyclic, and bicyclic organic ligands were used to probe their influence upon the efficiency and selectivity with which metal ion separations can be performed. A unifying feature of the ligand structures is the presence of one (or more) side arm with a pendent acidic function. When a metal ion is complexed within the central cavity of the ligand, ionization of the side arm(s) produces the requisite anion(s) for formation of an overall electroneutral complex. This markedly enhances extraction/transport efficiency for separations in which movement of aqueous phase anions of chloride, nitrate, or sulfate into an organic medium would be required. Through systematic structural variations, new ligands have been developed for efficient and selective separations of monovalent metal ions (e.g., alkali metal, silver, and thallium cations) and of divalent metal ion species (e.g., alkaline earth metal, lead, and mercury cations). Research results obtained in these fundamental investigations provide important insight for the design and development of ligands suitable for practical metal ion separation applications.

  16. In Vitro Antioxidant versus Metal Ion Chelating Properties of Flavonoids: A Structure-Activity Investigation

    Science.gov (United States)

    Cherrak, Sabri Ahmed; Mokhtari-Soulimane, Nassima; Berroukeche, Farid; Bensenane, Bachir; Cherbonnel, Angéline; Merzouk, Hafida; Elhabiri, Mourad

    2016-01-01

    Natural flavonoids such as quercetin, (+)catechin and rutin as well as four methoxylated derivatives of quercetin used as models were investigated to elucidate their impact on the oxidant and antioxidant status of human red blood cells (RBCs). The impact of these compounds against metal toxicity was studied as well as their antiradical activities with DPPH assay. Antihemolytic experiments were conducted on quercetin, (+)catechin and rutin with excess of Fe, Cu and Zn (400 μM), and the oxidant (malondialdehyde, carbonyl proteins) and antioxidant (reduced glutathione, catalase activity) markers were evaluated. The results showed that Fe and Zn have the highest prooxidant effect (37 and 33% of hemolysis, respectively). Quercetin, rutin and (+)catechin exhibited strong antioxidant properties toward Fe, but this effect was decreased with respect to Zn ions. However, the Cu showed a weak antioxidant effect at the highest flavonoid concentration (200 μM), while a prooxidant effect was observed at the lowest flavonoid concentration (100 μM). These results are in agreement with the physico-chemical and antiradical data which demonstrated that binding of the metal ions (for FeNTA: (+)Catechin, KLFeNTA = 1.6(1) × 106 M-1 > Rutin, KLFeNTA = 2.0(9) × 105 M-1 > Quercetin, KLFeNTA = 1.0(7) × 105 M-1 > Q35OH, KLFeNTA = 6.3(8.7) × 104 M-1 > Quercetin3’4’OH and Quercetin 3OH, KLFeNTA ~ 2 × 104 M-1) reflects the (anti)oxidant status of the RBCs. This study reveals that flavonoids have both prooxidant and antioxidant activity depending on the nature and concentration of the flavonoids and metal ions. PMID:27788249

  17. Prostate cancer outcome and tissue levels of metal ions

    Science.gov (United States)

    Sarafanov, A.G.; Todorov, T.I.; Centeno, J.A.; MacIas, V.; Gao, W.; Liang, W.-M.; Beam, C.; Gray, Marion A.; Kajdacsy-Balla, A.

    2011-01-01

    BACKGROUNDThere are several studies examining prostate cancer and exposure to cadmium, iron, selenium, and zinc. Less data are available on the possible influence of these metal ions on prostate cancer outcome. This study measured levels of these ions in prostatectomy samples in order to examine possible associations between metal concentrations and disease outcome.METHODSWe obtained formalin fixed paraffin embedded tissue blocks of prostatectomy samples of 40 patients with PSA recurrence, matched 1:1 (for year of surgery, race, age, Gleason grading, and pathology TNM classification) with tissue blocks from 40 patients without recurrence (n = 80). Case–control pairs were compared for the levels of metals in areas adjacent to tumors. Inductively coupled plasma-mass spectrometry (ICP-MS) was used for quantification of Cd, Fe, Zn, and Se.RESULTSPatients with biochemical (PSA) recurrence of disease had 12% lower median iron (95 µg/g vs. 111 µg/g; P = 0.04) and 21% lower zinc (279 µg/g vs. 346 µg/g; P = 0.04) concentrations in the normal-appearing tissue immediately adjacent to cancer areas. Differences in cadmium (0.489 µg/g vs. 0.439 µg/g; 4% higher) and selenium (1.68 µg/g vs. 1.58 µg/g; 5% higher) levels were not statistically significant in recurrence cases, when compared to non-recurrences (P = 0.40 and 0.21, respectively).CONCLUSIONSThere is an association between low zinc and low iron prostate tissue levels and biochemical recurrence in prostate cancer. Whether these novel findings are a cause or effect of more aggressive tumors, or whether low zinc and iron prostatic levels raise implications for therapy, remains to be investigated. 

  18. Metal carbonates as anode materials for lithium ion batteries

    International Nuclear Information System (INIS)

    Shao, Lianyi; Ma, Rui; Wu, Kaiqiang; Shui, Miao; Lao, Mengmeng; Wang, Dongjie; Long, Nengbing; Ren, Yuanlong; Shu, Jie

    2013-01-01

    Highlights: •Metal carbonates are probable anode materials for lithium ion batteries. •CoCO 3 /C composite can deliver an initial discharge capacity of 2096.6 mAh g −1 . •Co, Li 2 CO 3 , Li 2 O, and low-valence carbon are final lithiated products for CoCO 3 . -- Abstract: Six metal carbonates (Li 2 CO 3 , Na 2 CO 3 , SrCO 3 , BaCO 3 , K 2 CO 3 , CoCO 3 ) are tested and compared as anode materials for lithium ion batteries. The electrochemical results show that only CoCO 3 is electrochemically active material and can deliver a high initial capacity of 1425.9 mAh g −1 . The lithium storage mechanism in CoCO 3 is studied by ex situ X-ray diffraction technique, ex situ infrared method, ex situ X-ray photoelectron spectroscopy and in situ X-ray diffraction technique. It is found that the electrochemical reactions between CoCO 3 and Li firstly result in the formation of metal Co and Li 2 CO 3 , and then partial Li 2 CO 3 is further reduced into carbon (C 0 ), low-valence carbon (C 2+ ), and Li 2 O. It also demonstrates that the electrochemical reaction between CoCO 3 and Li is a partially reversible process. Based on these electrochemical results, it is obvious that narrow potential range can acquire a better reversibility for CoCO 3 /Li batteries by suppressing particle pulverization. Besides, the comparison of CoCO 3 , ball-milled CoCO 3 and ball-milled CoCO 3 /C composite also indicates that smaller active particle and carbon buffer are beneficial to obtain better cycling performance and higher reversible capacity

  19. How Native and Alien Metal Cations Bind ATP: Implications for Lithium as a Therapeutic Agent

    Science.gov (United States)

    Dudev, Todor; Grauffel, Cédric; Lim, Carmay

    2017-02-01

    Adenosine triphosphate (ATP), the major energy currency of the cell, exists in solution mostly as ATP-Mg. Recent experiments suggest that Mg2+ interacts with the highly charged ATP triphosphate group and Li+ can co-bind with the native Mg2+ to form ATP-Mg-Li and modulate the neuronal purine receptor response. However, it is unclear how the negatively charged ATP triphosphate group binds Mg2+ and Li+ (i.e. which phosphate group(s) bind Mg2+/Li+) and how the ATP solution conformation depends on the type of metal cation and the metal-binding mode. Here, we reveal the preferred ATP-binding mode of Mg2+/Li+ alone and combined: Mg2+ prefers to bind ATP tridentately to each of the three phosphate groups, but Li+ prefers to bind bidentately to the terminal two phosphates. We show that the solution ATP conformation depends on the cation and its binding site/mode, but it does not change significantly when Li+ binds to Mg2+-loaded ATP. Hence, ATP-Mg-Li, like Mg2+-ATP, can fit in the ATP-binding site of the host enzyme/receptor, activating specific signaling pathways.

  20. Regulation of the heavy metal pump AtHMA4 by a metal-binding autoinhibitory domain

    DEFF Research Database (Denmark)

    Bækgaard, Lone; Roed, Maria Dalgaard; Zhang, Yang

    Heavy metal pumps, or P1B ATPases, are important for heavy metal homeostasis in most cells. In general, these pumps contain extended N- and/or C-termini with one or more metal-binding domains (MBDs), but the role of the extended termini is still not clear. The Arabidopsis thaliana Zn2+-ATPase At......HMA4 contains a very long C-terminus with 13 cysteine pairs and an 11 amino acid residue long histidine stretch at the end. To ascertain the role of the potentially metal-binding domains in the C-terminus of AtHMA4, the C-terminal region alone was expressed in yeast. This resulted in increased Zn...

  1. Metal centre effects on HNO binding in porphyrins and the electronic origin: metal's electronic configuration, position in the periodic table, and oxidation state.

    Science.gov (United States)

    Yang, Liu; Fang, Weihai; Zhang, Yong

    2012-04-21

    HNO binds to many different metals in organometallic and bioinorganic chemistry. To help understand experimentally observed metal centre effects, a quantum chemical investigation was performed, revealing clear general binding trends with respect to metal centre characteristics and the electronic origin for the first time. This journal is © The Royal Society of Chemistry 2012

  2. Use of algae for removing heavy metal ions from wastewater: progress and prospects.

    Science.gov (United States)

    Mehta, S K; Gaur, J P

    2005-01-01

    Many algae have immense capability to sorb metals, and there is considerable potential for using them to treat wastewaters. Metal sorption involves binding on the cell surface and to intracellular ligands. The adsorbed metal is several times greater than intracellular metal. Carboxyl group is most important for metal binding. Concentration of metal and biomass in solution, pH, temperature, cations, anions and metabolic stage of the organism affect metal sorption. Algae can effectively remove metals from multi-metal solutions. Dead cells sorb more metal than live cells. Various pretreatments enhance metal sorption capacity of algae. CaCl2 pretreatment is the most suitable and economic method for activation of algal biomass. Algal periphyton has great potential for removing metals from wastewaters. An immobilized or granulated biomass-filled column can be used for several sorption/desorption cycles with unaltered or slightly decreased metal removal. Langmuir and Freundlich models, commonly used for fitting sorption data, cannot precisely describe metal sorption since they ignore the effect of pH, biomass concentration, etc. For commercial application of algal technology for metal removal from wastewaters, emphasis should be given to: (i) selection of strains with high metal sorption capacity, (ii) adequate understanding of sorption mechanisms, (iii) development of low-cost methods for cell immobilization, (iv) development of better models for predicting metal sorption, (v) genetic manipulation of algae for increased number of surface groups or over expression of metal binding proteins, and (vi) economic feasibility.

  3. Heavy metal ion removal by adsorption on to biological materials

    International Nuclear Information System (INIS)

    Jansson-Charrier, M.; Guibal, E.; Le Cloirec, P.; Surjous, R.

    1994-01-01

    The development of regulations constraints in the industrial waste-waters management leads to the study of new treatment processes, using raw or functionalized biological materials. These processes show competitive performances in metal ion sorption efficiency for the low metal content effluents. Uptake capacities of Uranium as high as 400 mg.g -1 chitosan, equivalent to the double of the uptake capacity of fungal origin biomass, can be reached. The application of these processes to real mine wastewaters gives efficiency coefficient upper to 90%, the residual concentrations are compatible to a direct injection into the environment. The grafting of functional groups onto the chitosan scales up the sorption performances to uptake capacity upper than 600 mg.g -1 polymer. pH, metal concentration are cited as major parameters, particle size influences both uptake kinetics and sorption equilibrium, in the case of the uranium accumulation by chitosan. The desorption of uranium from the sorbent allows the valorization of uranium and the re-use of the sorbent. (authors). 21 refs., 10 figs

  4. Towards metals analysis using corona discharge ionization ion mobility spectrometry.

    Science.gov (United States)

    Jafari, Mohammad T; Saraji, Mohammad; Sherafatmand, Hossein

    2016-02-25

    For the first time, the capability of corona discharge ionization ion mobility spectrometry (CD-IMS) in the determination of metal complex was evaluated. The extreme simplicity of dispersive liquid-liquid microextraction (DLLME) coupled to the high sensitivity of CD-IMS measurement could make this combination really useful for simple, rapid, and sensitive determination of metals in different samples. In this regard, mercury, as a model metal, was complexed with diethyldithiocarbamate (DEDTC), and then extracted into the carbon tetrachloride using DLLME. Some parameters affecting the extraction efficiency, including the type and volume of the extraction solvent, the type and volume of the disperser solvent, the concentration of the chelating agent, salt addition and, pH were exhaustively investigated. Under the optimized condition, the enrichment factor was obtained to be 142. The linear range of 0.035-10.0 μg mL(-1) with r(2) = 0.997 and the detection limit of 0.010 μg mL(-1) were obtained. The relative standard deviation values were calculated to be lower than 4% and 8% for intra-day and inter-day, respectively. Finally, the developed method was successfully applied for the extraction and determination of mercury in various real samples. The satisfactory results revealed the capability of the proposed method in trace analysis without tedious derivatization or hydride generation. Copyright © 2016 Elsevier B.V. All rights reserved.

  5. Outcome of revision arthroplasty for failed metal-on-metal total hip replacements; is there a relation with metal ions?

    Science.gov (United States)

    Iqbal, Hafiz J; Al-Azzani, Waheeb A K; Jackson-Taylor, Esther; Clatworthy, Elizabeth; John, Alun

    2017-05-12

    We aimed to assess the early outcome following revision arthroplasty for failed metal-on-metal (MoM) total hip replacements (THR) due to adverse reaction to metal debris (ARMD). We reviewed 106 consecutive revision arthroplasties. Case notes and radiological investigations were reviewed to assess the complications. Oxford Hip Score (OHS) and Euroqol (EQ-5D-3L) scores were used to assess the functional outcome and improvement of quality of life. At a mean follow-up of 20 months (12-48 months), the mean OHS was 28.7. Pain improved in 61% patients. A majority of patients were in level 2 for all the EQ-5D-3L dimensions. The overall complication rate was 16%. Survivorship free from further revision for any cause was 94.3% at 48 months. There was no correlation between pre-revision blood metal ions and the final outcome. Revision surgery for failed MoM hip replacement due to ARMD is associated with a relatively higher rate of complications and risk of chronic pain. There is poor correlation between serum metal ions and development of ARMD and outcome following revision surgery.

  6. Surface modification by metal ion implantation forming metallic nanoparticles in an insulating matrix

    International Nuclear Information System (INIS)

    Salvadori, M.C.; Teixeira, F.S.; Sgubin, L.G.; Cattani, M.; Brown, I.G.

    2014-01-01

    Highlights: • Metal nanoparticles can be produced through metallic ion implantation in insulating substrate, where the implanted metal self-assembles into nanoparticles. • The nanoparticles nucleate near the maximum of the implantation depth profile, that can be estimated by computer simulation using the TRIDYN. • Nanocomposites, obtained by this way, can be produced in different insulator materials. More specifically we have studied Au/PMMA (polymethylmethacrylate), Pt/PMMA, Ti/alumina and Au/alumina systems. • The nanocomposites were characterized by measuring the resistivity of the composite layer as function of the dose implanted, reaching the percolation threshold. • Excellent agreement was found between the experimental results and the predictions of the theory. - Abstract: There is special interest in the incorporation of metallic nanoparticles in a surrounding dielectric matrix for obtaining composites with desirable characteristics such as for surface plasmon resonance, which can be used in photonics and sensing, and controlled surface electrical conductivity. We have investigated nanocomposites produced by metal ion implantation into insulating substrates, where the implanted metal self-assembles into nanoparticles. The nanoparticles nucleate near the maximum of the implantation depth profile (projected range), which can be estimated by computer simulation using the TRIDYN code. TRIDYN is a Monte Carlo simulation program based on the TRIM (Transport and Range of Ions in Matter) code that takes into account compositional changes in the substrate due to two factors: previously implanted dopant atoms, and sputtering of the substrate surface. Our study show that the nanoparticles form a bidimentional array buried a few nanometers below the substrate surface. We have studied Au/PMMA (polymethylmethacrylate), Pt/PMMA, Ti/alumina and Au/alumina systems. Transmission electron microscopy of the implanted samples show that metallic nanoparticles form in

  7. Simple molecular model for the binding of antibiotic molecules to bacterial ion channels

    Science.gov (United States)

    Mafé, Salvador; Ramírez, Patricio; Alcaraz, Antonio

    2003-10-01

    A molecular model aimed at explaining recent experimental data by Nestorovich et al. [Proc. Natl. Acad. Sci. USA 99, 9789 (2002)] on the interaction of ampicillin molecules with the constriction zone in a channel of the general bacterial porin, OmpF (outer membrane protein F), is presented. The model extends T. L. Hill's theory for intermolecular interactions in a pair of binding sites [J. Am. Chem. Soc. 78, 3330 (1956)] by incorporating two binding ions and two pairs of interacting sites. The results provide new physical insights on the role of the complementary pattern of the charge distributions in the ampicillin molecule and the narrowest part of the channel pore. Charge matching of interacting sites facilitates drug binding. The dependence of the number of ampicillin binding events per second with the solution pH and salt concentration is explained qualitatively using a reduced number of fundamental concepts.

  8. Metal binding ability of glutathione transferases conserved between two animal species, the vanadium-rich ascidian Ascidia sydneiensis samea and the schistosome Schistosoma japonicum.

    Science.gov (United States)

    Yoshinaga, Masafumi; Ueki, Tatsuya; Michibata, Hitoshi

    2007-09-01

    Glutathione transferases (GSTs) are multifunctional enzymes found in many organisms. We recently identified vanadium-binding GSTs, designated AsGSTs, from the vanadium-rich ascidian, Ascidia sydneiensis samea. In this study, the metal-selectivity of AsGST-I was investigated. Immobilized metal ion affinity chromatography (IMAC) analysis revealed that AsGST-I binds to V(IV), Fe(III), and Cu(II) with high affinity in the following order Cu(II)>V(IV)>Fe(III), and to Co(II), Ni(II), and Zn(II) with low affinity. The GST activity of AsGST-I was inhibited dose-dependently by not V(IV) but Cu(II). A competition experiment demonstrated that the binding of V(IV) to AsGST-I was not inhibited by Cu(II). These results suggest that AsGST-I has high V(IV)-selectivity, which can confer the specific vanadium accumulation of ascidians. Because there are few reports on the metal-binding ability of GSTs, we performed the same analysis on SjGST (GST from the schistosome, Schistosoma japonicum). SjGST also demonstrated metal-binding ability although the binding pattern differed from that of AsGST-I. The GST activity of SjGST was inhibited by Cu(II) only, as that of AsGST-I. Our results indicate a possibility that metal-binding abilities of GSTs are conserved among organisms, at least animals, which is suggestive of a new role for these enzymes in metal homeostasis or detoxification.

  9. Some aspects of metallic ion chemistry and dynamics in the mesosphere and thermosphere

    Science.gov (United States)

    Mathews, J. D.

    1987-01-01

    The relationship between the formation of sporadic layers of metallic ion and the dumping of these ions into the upper mesosphere is discussed in terms of the tidal wind, classical (i.e., windshear) and other more complex, perhaps highly nonlinear layer formation mechanisms, and a possible circulation mechanism for these ions. Optical, incoherent scatter radar, rocket, and satellite derived evidence for various layer formation mechanisms and for the metallic ion circulation system is reviewed. The results of simple one dimensional numerical model calculations of sporadic E and intermediate layer formation are presented along with suggestions for more advanced models of intense or blanketing sporadic E. The flux of metallic ions dumped by the tidal wind system into the mesosphere is estimated and compared with estimates of total particle flux of meteoric origin. Possible effects of the metallic ion flux and of meteoric dust on D region ion chemistry are discussed.

  10. Thermosensitive gels incorporating polythioether units for the selective extraction of class b metal ions.

    Science.gov (United States)

    Chayama, K; Morita, Y; Iwatsuki, S

    2010-10-22

    Novel temperature-responsive copolymers of N-isopropylacrylamide and monoaza-tetrathioether derivative, were synthesized for the selective extraction of soft metal ions such as silver(I), copper(I), gold(III) and palladium(II) ion. The ratio between N-isopropylacrylamide group and monoaza-tetrathioether group in the copolymer was determined. The ratio between N-isopropylacrylamide group and monoaza-tetrathioether group varied in the range of 66:1-187:1. Each lower critical solution temperature (LCST) of the polymer solution was determined spectrophotometrically by the relative absorbance change at 750 nm via temperature of the polymer solution. Metal ion extraction using the copolymer with appropriate counter anions such as picrate ion, nitrate or perchlorate ion was examined. Soft metal ions such as silver(I), copper(I), gold(III) and palladium(II) ion were extracted selectively into the solid polymer phase. The extraction efficiency of a metal ion such as silver ion increased as the increase of the ratio of the monoaza-tetrathioether group to N-isopropylacrylamide group in the polymer. The quantitative extraction of class b metal ions as well as the liquid-liquid extraction of metal ions with monoaza-tetrathioether molecule was performed. Copyright © 2010 Elsevier B.V. All rights reserved.

  11. Metal ions, not metal-catalyzed oxidative stress, cause clay leachate antibacterial activity.

    Directory of Open Access Journals (Sweden)

    Caitlin C Otto

    Full Text Available Aqueous leachates prepared from natural antibacterial clays, arbitrarily designated CB-L, release metal ions into suspension, have a low pH (3.4-5, generate reactive oxygen species (ROS and H2O2, and have a high oxidation-reduction potential. To isolate the role of pH in the antibacterial activity of CB clay mixtures, we exposed three different strains of Escherichia coli O157:H7 to 10% clay suspensions. The clay suspension completely killed acid-sensitive and acid-tolerant E. coli O157:H7 strains, whereas incubation in a low-pH buffer resulted in a minimal decrease in viability, demonstrating that low pH alone does not mediate antibacterial activity. The prevailing hypothesis is that metal ions participate in redox cycling and produce ROS, leading to oxidative damage to macromolecules and resulting in cellular death. However, E. coli cells showed no increase in DNA or protein oxidative lesions and a slight increase in lipid peroxidation following exposure to the antibacterial leachate. Further, supplementation with numerous ROS scavengers eliminated lipid peroxidation, but did not rescue the cells from CB-L-mediated killing. In contrast, supplementing CB-L with EDTA, a broad-spectrum metal chelator, reduced killing. Finally, CB-L was equally lethal to cells in an anoxic environment as compared to the aerobic environment. Thus, ROS were not required for lethal activity and did not contribute to toxicity of CB-L. We conclude that clay-mediated killing was not due to oxidative damage, but rather, was due to toxicity associated directly with released metal ions.

  12. Novel synthetic phytochelatin-based capacitive biosensor for heavy metal ion detection.

    Science.gov (United States)

    Bontidean, Ibolya; Ahlqvist, Josefin; Mulchandani, Ashok; Chen, Wilfred; Bae, Weon; Mehra, Rajesh K; Mortari, Alessia; Csöregi, Elisabeth

    2003-05-01

    A novel capacitance biosensor based on synthetic phytochelatins for sensitive detection of heavy metals is described. Synthetic phytochelatin (Glu-Cys)(20)Gly (EC20) fused to the maltose binding domain protein was expressed in Escherichia coli and purified for construction of the biosensor. The new biosensor was able to detect Hg(2+), Cd(2+), Pb(2+), Cu(2+) and Zn(2+) ions in concentration range of 100 fM-10 mM, and the order of sensitivity was S(Zn)>S(Cu)>S(Hg)>S(Cd) congruent with S(Pb). The biological sensing element of the sensor could be regenerated using EDTA and the storage stability of the biosensor was 15 days.

  13. Process for the displacement of cyanide ions from metal-cyanide complexes

    Science.gov (United States)

    Smith, Barbara F.; Robinson, Thomas W.

    1997-01-01

    The present invention relates to water-soluble polymers and the use of such water-soluble polymers in a process for the displacement of the cyanide ions from the metal ions within metal-cyanide complexes. The process waste streams can include metal-cyanide containing electroplating waste streams, mining leach waste streams, mineral processing waste streams, and related metal-cyanide containing waste streams. The metal ions of interest are metals that give very strong complexes with cyanide, mostly iron, nickel, and copper. The physical separation of the water-soluble polymer-metal complex from the cyanide ions can be accomplished through the use of ultrafiltration. Once the metal-cyanide complex is disrupted, the freed cyanide ions can be recovered for reuse or destroyed using available oxidative processes rendering the cyanide nonhazardous. The metal ions are released from the polymer, using dilute acid, metal ion oxidation state adjustment, or competing chelating agents, and collected and recovered or disposed of by appropriate waste management techniques. The water-soluble polymer can then be recycled. Preferred water-soluble polymers include polyethyleneimine and polyethyleneimine having a catechol or hydroxamate group.

  14. A new design of the sputter type metal ion source and its characteristics of ion beam extraction

    International Nuclear Information System (INIS)

    Kim, W.; Choi, B.H.; Jin, J.T.; Jung, K.S.; Do, S.H.; Chung, K.H.

    1993-01-01

    In an attempt to get a high current metal ion beam of various solid elements including refractory metals, a gaseous duoPIGatron ion source was modified by placing a grid type cathode and a sputter target in the PIG chamber. Tungsten mesh was adopted as the cathode grid, and Ar gas was used for a support gas for sputter induction. For Cu, Fe, and Al, ion current and ratio of the metal ion were obtained at various conditions of sputtering voltage, support gas pressure, arc current, magnet current, and beam extraction voltage. Results showed that the metal current density is linearly changed with the sputtering voltage and magnet current. Ratio of the metal ion in the total current is larger at lower support gas pressure. Current densities for Al, Cu, and Fe were 4 mA/cm 2 , 5.5 mA/cm 2 , and 2 mA/cm 2 , respectively, at an arc current of 3 A, extraction voltage of 20 kV, and a sputtering voltage of 1 kV. Ratios of the metals in the extracted ion currents were 9%, 8%, and 5% for Al, Cu, and Fe, respectively

  15. High energy metal ion implantation using 'Magis', a novel, broad-beam, Marx-generator-based ion source

    International Nuclear Information System (INIS)

    Anders, A.; Brown, I.G.; Dickinson, M.R.; MacGill, R.A.

    1996-08-01

    Ion energy of the beam formed by an ion source is proportional to extractor voltage and ion charge state. Increasing the voltage is difficult and costly for extraction voltage over 100 kV. Here we explore the possibility of increasing the charge states of metal ions to facilitate high-energy, broad beam ion implantation at a moderate voltage level. Strategies to enhance the ion charge state include operating in the regimes of high-current vacuum sparks and short pulses. Using a time-of-flight technique we have measured charge states as high as 7+ (73 kA vacuum spark discharge) and 4+ (14 kA short pulse arc discharge), both for copper, with the mean ion charge states about 6.0 and 2.5, respectively. Pulsed discharges can conveniently be driven by a modified Marx generator, allowing operation of ''Magis'' with a single power supply (at ground potential) for both plasma production and ion extraction

  16. Ion-irradiation studies of cascade damage in metals

    International Nuclear Information System (INIS)

    Averback, R.S.

    1982-03-01

    Ion-irradiation studies of the fundamental aspects of cascade damage in metals are reviewed. The emphasis of these studies has been the determination of the primary state of damage (i.e. the arrangement of atoms in the cascade region prior to thermal migration of defects). Progress has been made towards understanding the damage function (i.e. the number of Frenkel pairs produced as a function of primary recoil atom energy), the spatial configuration of vacancies and interstitials in the cascade and the cascade-induced mixing of atoms. It is concluded for these studies that the agitation of the lattice in the vicinity of energetic displacement cascades stimulates the defect motion and that such thermal spike motion induces recombination and clustering of Frenkel defects. 9 figures

  17. New generation of composite inorganic ion-exchangers with polyacrylonitrile binding matrix

    International Nuclear Information System (INIS)

    Sebesta, F.; John, J.; Motl, A.; Uvirova, K.; Smrckova, S.

    1998-01-01

    General procedure for treatment of powdered inorganic ion-exchangers using binding polymer - modified polyacrylonitrile (PAN) into beads suitable for the application in column packed beds was proposed earlier. These composite ion-exchangers were tested for many applications, some of them are used in the full-scale treatment of liquid radioactive wastes and/or for radioanalytical purposes. New generation of the composite ion-exchangers was developed to improve their volume exchange capacity and mechanical strength. Further, composite absorbers with new active components or their mixtures were prepared. The possibility of preparation of magnetic composite adsorbers and magnetic composite ion-exchangers was also studied. The new prepared materials were mainly tested for their application in caesium separation from highly active acidic waste streams. The efficiency of AMP-PAN (ammonium molybdophosphate active component) and ferrocyanides based composite ion-exchangers for caesium separation was studied in more details. Possibilities of regeneration of the above mentioned composite ion-exchangers were also studied. In preliminary experiments, mercury sorption from model mixed radioactive wastes onto ferro- and ferricyanide based absorbers was tested. The new generation of composite ion-exchangers with hydrated titanium oxide or sodium titanate as active component was tested for strontium separation from alkaline solutions. (author)

  18. An Aqueous Metal-ion Capacitor with Oxidised Carbon Nanotubes and Metallic Zinc Electrodes

    Directory of Open Access Journals (Sweden)

    Yuheng Tian

    2016-10-01

    Full Text Available An aqueous metal ion capacitor comprising of a zinc anode, an oxidized carbon nanotubes (oCNTs cathode and a zinc sulfate electrolyte is reported. Since the shuttling cation is Zn2+, this typical metal ion capacitor is named as zinc-ion capacitor (ZIC. The ZIC integrates the divalent zinc stripping/plating chemistry with the surface-enabled pseudocapacitive cation adsorption/desorption on oCNTs. The surface chemistry and crystallographic structure of oCNTs were extensively characterized by combining X-ray photoelectron spectroscopy, Fourier-transformed infrared spectroscopy, Raman spectroscopy and X-ray powder diffraction. The function of the surface oxygen groups in surface cation storage was elucidated by a series of electrochemical measurement and the surface-enabled ZIC showed better performance than the ZIC with an un-oxidized CNT cathode. The reaction mechanism at the oCNT cathode involves the additional reversible Faradaic process, while the CNTs merely show electric double layer capacitive behavior involving a non-Faradaic process. The aqueous hybrid ZIC comprising the oCNT cathode exhibited a specific capacitance of 20 mF cm-2 (corresponding to 53 F g-1 in the range of 0-1.8 V at 10 mV s-1 and a stable cycling performance up to 5000 cycles.

  19. A control on hydrophobic and hydrophilic interactions between HEWL and metal Schiff-base complexes comprising of different metal ions and ligands

    Energy Technology Data Exchange (ETDEWEB)

    Koley Seth, Banabithi; Ray, Aurkie; Basu, Samita, E-mail: samita.basu@saha.ac.in

    2015-05-15

    The structural effects of different copper(II) and nickel(II) Schiff base complexes on hen egg white lysozyme (HEWL) have been investigated through steady state and time resolved absorption and fluorescence, and circular dichroism spectroscopy. The Schiff base ligands with N{sub 4} donor atoms show both hydrophobic and hydrophilic interactions, however hydrophilic interaction prevails with ligands having N{sub 2}O{sub 2} donor atoms. Variation of metal ions from Cu{sup 2+} to Ni{sup 2+} with each type of Schiff base ligand increases the probability of hydrophilic over hydrophobic interactions, which supports their significance in regulating the binding affinity between HEWL and metal complexes. On photo-excitation the complexes comprising of Cu{sup 2+} ion instead of Ni{sup 2+} ion and ligands with N{sub 4} donor system rather than N{sub 2}O{sub 2} donor system, increases the probability of intersystem crossing to populate the corresponding triplet state as observed from laser flash photolysis study. The better binding affinity of nickel complexes with different selectivities compared to copper complexes towards HEWL emphasizes the potentiality of less explored nickel complexes in drug–protein interactions. - Highlights: • Ni{sup II} and Cu{sup II} -Schiff base complexes bind hen egg white lysozyme spontaneously. • Both hydrophobic and hydrophilic interactions are effective for N{sub 4} ligands. • For N{sub 2}O{sub 2} ligands the hydrophilic is predominant over hydrophobic interaction. • Binding affinity and selectivity of Ni{sup II}-complexes are better than Cu{sup II}-complexes. • Replacement of Cu{sup 2+} by Ni{sup 2+} in a ligand enhances chance of hydrophilic interaction.

  20. The ion-electron correlation function in liquid metals

    International Nuclear Information System (INIS)

    Takeda, S.; Tamaki, S.; Waseda, Y.

    1985-01-01

    The structure factors of liquid Zn at 723 K, Sn at 523 K and Bi at 573 K have been determined by neutron diffraction with sufficient accuracy and compared with those of X-ray diffraction. A remarkable difference in the structural information between the two methods is clearly found around the first peak region as well as in the slightly varied peak positions, and it is apparently larger than the experimental errors. With these facts in mind, a new method evaluating the ion-electron correlation function in liquid metals has been proposed by using the measured structural data of X-rays and neutrons, with the help of theoretical values of the electron-electron correlation function by he Utsumi-Ichimaru scheme. This method has been applied to liquid Zn, Sn and Bi, and the radial distribution function of valence electrons around an ion has been estimated, from which the ionic radius and the schematic diagram of the electron distribution map are obtained. The ionic radii evaluated in this work have been found to agree well with those proposed by Pauling. (author)

  1. Alzheimer’s disease: How metal ions define β-amyloid function

    DEFF Research Database (Denmark)

    Kepp, Kasper Planeta

    2017-01-01

    Alzheimer’s disease is increasingly recognized to be linked to the function and status of metal ions, and recently, the amyloid hypothesis has been strongly intertwined with the metal ion hypothesis; in fact, these two hypotheses fit well together and are not mutually contradictory. This review...

  2. Effect of pH, various divalent metal ion and different substrates on ...

    African Journals Online (AJOL)

    EZUGWU ARINZE LINUS

    Key words: Glucoamylase, pH, metal ions, Aspergillus niger, tiger nut starch, amylopectin. INTRODUCTION. Glucoamylase (α-1 ... glycosidic bonds from the non-reducing ends of starch and 1,6-alpha-glucsidic linkages in ..... stable at neutral pH 7.0, it is more likely to readily form neucleophilichydroxide ions with metals by ...

  3. Measuring free metal ion concentrations in multicomponent solutions using Donnan Membrane Technique

    NARCIS (Netherlands)

    Kalis, E.J.J.; Temminghoff, E.J.M.; Weng, L.P.; Riemsdijk, van W.H.

    2007-01-01

    Among speciation techniques that are able to measure free metal ion concentrations, the Donnan membrane technique (DMT) has the advantage that it can measure many different free metal ion concentrations simultaneously in a multicomponent sample. Even though the DMT has been applied to several

  4. Development of an Electrochemical Metal-Ion Biosensor Using Self-Assembled Peptide Nanofibrils

    DEFF Research Database (Denmark)

    Viguier, Bruno; Zor, Kinga; Kasotakis, Emmanouil

    2011-01-01

    This article describes the combination of self-assembled peptide nanofibrils with metal electrodes for the development of an electrochemical metal-ion biosensor. The biological nanofibrils were immobilized on gold electrodes and used as biorecognition elements for the complexation with copper ion...

  5. Cooperative binding of copper(I) to the metal binding domains in Menkes disease protein

    DEFF Research Database (Denmark)

    Jensen, P Y; Bonander, N; Møller, L B

    1999-01-01

    spectroscopy, and their copper(I) binding properties have been determined. Structure prediction derived from far-UV CD indicates that the secondary structure is similar in the three proteins and dominated by beta-sheet. The tryptophan fluorescence maximum is blue-shifted in the constructs containing two...... and six MBDs relative to the monomer, suggesting more structurally buried tryptophan(s), compared to the single MBD construct. Copper(I) binding has been studied by equilibrium dialysis under anaerobic conditions. We show that the copper(I) binding to constructs containing two and six domains...... is cooperative, with Hill coefficients of 1.5 and 4, respectively. The apparent affinities are described by K(0.5), determined to be 65 microM and 19 microM for constructs containing two and six domains, respectively. Our data reveal a unique regulation of Menkes protein upon a change in copper(I) concentration...

  6. Role of the Water–Metal Ion Bridge in Mediating Interactions between Quinolones and Escherichia coli Topoisomerase IV

    Science.gov (United States)

    2015-01-01

    Although quinolones have been in clinical use for decades, the mechanism underlying drug activity and resistance has remained elusive. However, recent studies indicate that clinically relevant quinolones interact with Bacillus anthracis (Gram-positive) topoisomerase IV through a critical water–metal ion bridge and that the most common quinolone resistance mutations decrease drug activity by disrupting this bridge. As a first step toward determining whether the water–metal ion bridge is a general mechanism of quinolone–topoisomerase interaction, we characterized drug interactions with wild-type Escherichia coli (Gram-negative) topoisomerase IV and a series of ParC enzymes with mutations (S80L, S80I, S80F, and E84K) in the predicted bridge-anchoring residues. Results strongly suggest that the water–metal ion bridge is essential for quinolone activity against E. coli topoisomerase IV. Although the bridge represents a common and critical mechanism that underlies broad-spectrum quinolone function, it appears to play different roles in B. anthracis and E. coli topoisomerase IV. The water–metal ion bridge is the most important binding contact of clinically relevant quinolones with the Gram-positive enzyme. However, it primarily acts to properly align clinically relevant quinolones with E. coli topoisomerase IV. Finally, even though ciprofloxacin is unable to increase levels of DNA cleavage mediated by several of the Ser80 and Glu84 mutant E. coli enzymes, the drug still retains the ability to inhibit the overall catalytic activity of these topoisomerase IV proteins. Inhibition parallels drug binding, suggesting that the presence of the drug in the active site is sufficient to diminish DNA relaxation rates. PMID:25115926

  7. Metal Ions Removal Using Nano Oxide Pyrolox™ Material

    Science.gov (United States)

    Gładysz-Płaska, A.; Skwarek, E.; Budnyak, T. M.; Kołodyńska, D.

    2017-02-01

    The paper presents the use of Pyrolox™ containing manganese nano oxides used for the removal of Cu(II), Zn(II), Cd(II), and Pb(II) as well as U(VI) ions. Their concentrations were analyzed using the atomic absorption spectrometer SpectrAA 240 FS (Varian) as well as UV-vis method. For this purpose the static kinetic and equilibrium studies were carried out using the batch technique. The effect of solution pH, shaking time, initial metal ion concentrations, sorbent dosage, and temperature was investigated. The equilibrium data were analyzed using the sorption isotherm models proposed by Freundlich, Langmuir-Freundlich, Temkin, and Dubinin-Radushkevich. The kinetic results showed that the pseudo second order kinetic model was found to correlate the experimental data well. The results indicate that adsorption of Cu(II), Zn(II), Cd(II), and Pb(II) as well as U(VI) ions is strongly dependent on pH. The value of pH 4-7 was optimal adsorption. The time to reach the equilibrium was found to be 24 h, and after this time, the sorption percentage reached about 70%. Kinetics of Cu(II), Zn(II), Cd(II), Pb(II), and U(VI) adsorption on the adsorbent can be described by the pseudo second order rate equation. Nitrogen adsorption/desorption, infrared spectroscopy (FTIR), and scanning electron microscopy (SEM) measurements for adsorbent characterization were performed. Characteristic points of the double layer determined for the studied Pyrolox™ sample in 0.001 mol/dm3 NaCl solution are pHPZC = 4 and pHIEP < 2.

  8. Analysis of Supercritical-Extracted Chelated Metal Ions From Mixed Organic-Inorganic Samples

    Science.gov (United States)

    Sinha, Mahadeva P. (Inventor)

    1996-01-01

    Organic and inorganic contaminants of an environmental sample are analyzed by the same GC-MS instrument by adding an oxidizing agent to the sample to oxidize metal or metal compounds to form metal ions. The metal ions are converted to chelate complexes and the chelate complexes are extracted into a supercritical fluid such as CO2. The metal chelate extract after flowing through a restrictor tube is directly injected into the ionization chamber of a mass spectrometer, preferably containing a refractory metal filament such as rhenium to fragment the complex to release metal ions which are detected. This provides a fast, economical method for the analysis of metal contaminants in a sample and can be automated. An organic extract of the sample in conventional or supercritical fluid solvents can be detected in the same mass spectrometer, preferably after separation in a supercritical fluid chromatograph.

  9. Water-soluble polymers for recovery of metal ions from aqueous streams

    Science.gov (United States)

    Smith, Barbara F.; Robison, Thomas W.

    1998-01-01

    A process of selectively separating a target metal contained in an aqueous solution by contacting the aqueous solution containing a target metal with an aqueous solution including a water-soluble polymer capable of binding with the target metal for sufficient time whereby a water-soluble polymer-target metal complex is formed, and, separating the solution including the water-soluble polymer-target metal complex from the solution is disclosed.

  10. The sorption of metal ions on nanoscale zero-valent iron

    OpenAIRE

    Suponik Tomasz; Popczyk Marcin; Pierzyna Piotr

    2017-01-01

    The injection of the colloidal suspensions of nano-iron (nZVI) into an aquifer is a novel method of removing metal ions from acidic water. In the batch tests, the equilibrium study of the sorption of metal ions, Cu(II) and Zn(II), on Green Tea nanoscale Zero-Valent Ion (GT-nZVI) was carried out. The sorption of metal ions on this reactive material was described using the Langmuir, Freundlich and Sips models. This last model described in a better way the sorption equilibrium in the tested rang...

  11. An artificial tongue fluorescent sensor array for identification and quantitation of various heavy metal ions.

    Science.gov (United States)

    Xu, Wang; Ren, Changliang; Teoh, Chai Lean; Peng, Juanjuan; Gadre, Shubhankar Haribhau; Rhee, Hyun-Woo; Lee, Chi-Lik Ken; Chang, Young-Tae

    2014-09-02

    Herein, a small-molecule fluorescent sensor array for rapid identification of seven heavy metal ions was designed and synthesized, with its sensing mechanism mimicking that of a tongue. The photoinduced electron transfer and intramolecular charge transfer mechanism result in combinatorial interactions between sensor array and heavy metal ions, which lead to diversified fluorescence wavelength shifts and emission intensity changes. Upon principle component analysis (PCA), this result renders clear identification of each heavy metal ion on a 3D spatial dispersion graph. Further exploration provides a concentration-dependent pattern, allowing both qualitative and quantitative measurements of heavy metal ions. On the basis of this information, a "safe-zone" concept was proposed, which provides rapid exclusion of versatile hazardous species from clean water samples based on toxicity characteristic leaching procedure standards. This type of small-molecule fluorescent sensor array could open a new avenue for multiple heavy metal ion detection and simplified water quality analysis.

  12. Role of metal ions in the destruction of TATP: theoretical considerations.

    Science.gov (United States)

    Dubnikova, Faina; Kosloff, Ronnie; Oxley, Jimmie C; Smith, James L; Zeiri, Yehuda

    2011-09-29

    The safe decomposition of solid TATP (triacetone triperoxide) explosive is examined theoretically. The route to destruction starts with formation of metal complexes between a metal ion and the TATP molecule. The second step is decomposition of the molecules into stable final products. We examined the structure and stability of both metal ion (including Na(+), Cu(+), Cu(2+), Co(2+), and Zn(2+)) and proton complexes with TAT