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Sample records for selected metal ions

  1. On the Metal Ion Selectivity of Oxoacid Extractants

    SciTech Connect

    Hay, Benjamin; Chagnes, Alexandre; Cote, Gerard

    2013-01-01

    Relationships between metal chelate stability, ligand basicity, and metal ion acidity are reviewed and the general applicability is illustrated by linear correlations between aqueous stability constants and ligand pKa values for 35 metals with 26 ligands. The results confirm that most individual ligands of this type exhibit a stability ordering that correlates with the Lewis acidity of the metal ion. It is concluded that the general metal ion selectivity exhibited by liquid-liquid oxoacid extractants such as carboxylic acids, -diketones, and alkylphosphoric acids reflects the intrinsic affinity of the metal ion for the negative oxygen donor ligand.

  2. Spectroscopic detection of metals ions using a novel selective sensor

    NASA Astrophysics Data System (ADS)

    Peralta-Domínguez, D.; Ramos-Ortiz, G.; Maldonado, J. L.; Rodriguez, M.; Meneses-Nava, M. A.; Barbosa-Garcia, O.; Santillan, R.; Farfan, N.

    2011-09-01

    Colorimetric chemosensors are simple, economical and practical optical approach for detecting toxic metal ions (Hg2+, Pb2+, Ni2+, etc.) in the environment. In this work, we present a simple but highly specific organic compound 4-chloro-2-((E)-((E)-3-(4-(dimethylamino)phenyl)allylidene)amino)phenol (L1) that acts as a colorimetric sensor for divalent metal ions in H2O. The mechanism of the interaction between L1 and various metal-ions has been established by UV-vis absorption and emission spectroscopic experiments that indicate favorable coordination of metal ions with L1 in different solvents. Experimental results indicate that the shape of the electronic transition band of L1 (receptor compound) changed after the interaction with divalent metal-ions, such as Hg2+, Pb2+, Mn2+, Co2+, Cu2+, and Ni2+ in aqueous solution. We found that L1 have a considerable selectivity for Ni2+ ions, even in presence of other metals ions when mixtures of DMSO/H2O as are used as solvents. L1, which has been targeted for sensing transition metal ions, exhibits binding-induced color changes from yellow to pink observed even by the naked eye in presence of Ni2+ ions.

  3. Substrate Profile and Metal-ion Selectivity of Human Divalent Metal-ion Transporter-1*

    PubMed Central

    Illing, Anthony C.; Shawki, Ali; Cunningham, Christopher L.; Mackenzie, Bryan

    2012-01-01

    Divalent metal-ion transporter-1 (DMT1) is a H+-coupled metal-ion transporter that plays essential roles in iron homeostasis. DMT1 exhibits reactivity (based on evoked currents) with a broad range of metal ions; however, direct measurement of transport is lacking for many of its potential substrates. We performed a comprehensive substrate-profile analysis for human DMT1 expressed in RNA-injected Xenopus oocytes by using radiotracer assays and the continuous measurement of transport by fluorescence with the metal-sensitive PhenGreen SK fluorophore. We provide validation for the use of PhenGreen SK fluorescence quenching as a reporter of cellular metal-ion uptake. We determined metal-ion selectivity under fixed conditions using the voltage clamp. Radiotracer and continuous measurement of transport by fluorescence assays revealed that DMT1 mediates the transport of several metal ions that were ranked in selectivity by using the ratio Imax/K0.5 (determined from evoked currents at −70 mV): Cd2+ > Fe2+ > Co2+, Mn2+ ≫ Zn2+, Ni2+, VO2+. DMT1 expression did not stimulate the transport of Cr2+, Cr3+, Cu+, Cu2+, Fe3+, Ga3+, Hg2+, or VO+. 55Fe2+ transport was competitively inhibited by Co2+ and Mn2+. Zn2+ only weakly inhibited 55Fe2+ transport. Our data reveal that DMT1 selects Fe2+ over its other physiological substrates and provides a basis for predicting the contribution of DMT1 to intestinal, nasal, and pulmonary absorption of metal ions and their cellular uptake in other tissues. Whereas DMT1 is a likely route of entry for the toxic heavy metal cadmium, and may serve the metabolism of cobalt, manganese, and vanadium, we predict that DMT1 should contribute little if at all to the absorption or uptake of zinc. The conclusion in previous reports that copper is a substrate of DMT1 is not supported. PMID:22736759

  4. Principles Governing Metal Ion Selectivity in Ion Channel Proteins

    NASA Astrophysics Data System (ADS)

    Lim, Carmay

    2014-03-01

    Our research interests are to (i) unravel the principles governing biological processes and use them to identify novel drug targets and guide drug design, and (ii) develop new methods for studying macromolecular interactions. This talk will provide an overview of our work in these two areas and an example of how our studies have helped to unravel the principles underlying the conversion of Ca2+-selective to Na+-selective channels. Ion selectivity of four-domain voltage-gated Ca2+(Cav) and sodium (Nav) channels, which is controlled by the selectivity filter (SF, the narrowest region of an open pore), is crucial for electrical signaling. Over billions of years of evolution, mutation of the Glu from domain II/III in the EEEE/DEEA SF of Ca2+-selective Cav channels to Lys made these channels Na+-selective. This talk will delineate the physical principles why Lys is sufficient for Na+/Ca2+selectivity and why the DEKA SF is more Na+-selective than the DKEA one.

  5. Selective quenching of benzimidazole derivatives by Cu2+ metal ion

    NASA Astrophysics Data System (ADS)

    Jayabharathi, J.; Thanikachalam, V.; Jayamoorthy, K.; Sathishkumar, R.

    2012-11-01

    It is a very big challenge to develop a Cu2+ selective fluorescent sensor with the ability to exclude the interference of some metal ions such as Fe3+, Mg2+, Ag+, K+ and Na+. Herein, we report a fluorescence quenching of some benzimidazole derivatives (1-6) with Cu2+ metal ion. These benzimidazole derivatives have been shown to bind copper ions resulting in quenching of its fluorescence. The response to Cu2+ is rapid, selective and reversible upon addition of a copper chelator. These benzimidazole derivatives were characterized by 1H, 13C NMR mass and elemental analysis. XRD analysis was carried out for 1-(4-methylbenzyl)-2-p-tolyl-1H-benzo[d]imidazole.

  6. Selected metal ions protect Bacillus subtilis biofilms from erosion.

    PubMed

    Grumbein, S; Opitz, M; Lieleg, O

    2014-08-01

    Many problems caused by bacterial biofilms can be traced back to their high resilience towards chemical perturbations and their extraordinary sturdiness towards mechanical forces. However, the molecular mechanisms that link the mechanical properties of a biofilm with the ability of bacteria to survive in different chemical environments remain enigmatic. Here, we study the erosion stability of Bacillus subtilis (B. subtilis) biofilms in the presence of different chemical environments. We find that these biofilms can utilize the absorption of certain metal ions such as Cu(2+), Zn(2+), Fe(2+), Fe(3+) and Al(3+) into the biofilm matrix to avoid erosion by shear forces. Interestingly, many of these metal ions are toxic for planktonic B. subtilis bacteria. However, their toxic activity is suppressed when the ions are absorbed into the biofilm matrix. Our experiments clearly demonstrate that the biofilm matrix has to fulfill a dual function, i.e. regulating both the mechanical properties of the biofilm and providing a selective barrier towards toxic chemicals.

  7. Measuring and Imaging Metal Ions With Fluorescence-Based Biosensors: Speciation, Selectivity, Kinetics, and Other Issues.

    PubMed

    Thompson, Richard B; Fierke, Carol A

    2017-01-01

    Fluorescence-based biosensors have shown themselves to be a powerful tool for the study of a variety of chemical species in biological systems, notably including metal ions. This chapter provides an overview of several important issues in using such sensors to study metallobiochemistry. These issues include selectivity for the analyte over potential interferents, including those that do not themselves induce a signal, the different forms in which metal ions are found (speciation), the utility of metal ion buffers, and the importance of kinetics in studying metal ion binding reactions. Finally, the chapter briefly discusses some of the issues in understanding whole-organism distribution of metal ions and its control.

  8. Optical metal-organic framework sensor for selective discrimination of some toxic metal ions in water.

    PubMed

    Shahat, Ahmed; Hassan, Hassan M A; Azzazy, Hassan M E

    2013-09-02

    This paper reports the development of a facile and effective approach, based on the use of Zr-based metal-organic frameworks (UiO-66) sensor with micropores geometry, shape and particle morphology for the visual detection and removal of ultra-traces of some toxic metal ions such as Bi(III), Zn(II), Pb(II), Hg(II) and Cd(II). UiO-66 was used as selective carriers for accommodating hydrophobic chromophore probes such as dithizone (DZ) without coupling agent for sensitive and selective discrimination of trace level of toxic analytes. The developed UiO-66 sensor was utilized for the detection of ultra-traces of some toxic metal ions with the naked eye. The new sensor displays high sensitivity and selectivity of a wide range of detectable metals analytes up to 10(-10) mol dm(-3) in solution, in a rapid analyte uptake response (seconds). The developed sensor is stable, cost effective, easy to prepare, and would be useful for rapid detection and removal of ultra-traces of toxic metal ions in water samples.

  9. Lanthanide metal-organic frameworks as selective microporous materials for adsorption of heavy metal ions.

    PubMed

    Jamali, Abbas; Tehrani, Alireza Azhdari; Shemirani, Farzaneh; Morsali, Ali

    2016-06-14

    Four microporous lanthanide metal-organic frameworks (MOFs), namely Ln(BTC)(H2O)(DMF)1.1 (Ln = Tb, Dy, Er and Yb, DMF = dimethylformamide, H3BTC = benzene-1,3,5-tricarboxylic acid), have been used for selective adsorption of Pb(ii) and Cu(ii). Among these MOFs, the Dy-based MOF shows better adsorption property and selectivity toward Pb(ii) and Cu(ii) ions. Adsorption isotherms indicate that sorption of Pb(ii) and Cu(ii) on MOFs is via monolayer coverage. Preconcentration is based on solid-phase extraction in which MOFs were rapidly injected into water samples and adsorption of metal ions was rapid because of good contact with analyte; then adsorbed Pb(ii) and Cu(ii) ions were analyzed by FAAS. The optimized methodology represents good linearity between 1 and 120 μg L(-1) and detection limit of 0.4 and 0.26 μg L(-1) for Pb(ii) and Cu(ii), respectively. Subsequently the method was evaluated for preconcentration of target metal ions in some environmental water samples.

  10. New Proton-Ionizable, Calixarene-Based Ligands for Selective Metal Ion Separations

    SciTech Connect

    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.

  11. Tuning the chemical selectivity of SWNT-FETs for detection of heavy-metal ions.

    PubMed

    Forzani, Erica S; Li, Xiulan; Zhang, Peiming; Tao, Nongjian; Zhang, Ruth; Amlani, Islamshah; Tsui, Raymond; Nagahara, Larry A

    2006-11-01

    A method to functionalize single-walled carbon nanotubes (SWNTs) in a field-effect transistor (FET) device for the selective detection of heavy-metal ions is presented. In this method, peptide-modified polymers were electrochemically deposited onto SWNTs and the selective detection of metal ions was demonstrated by choosing appropriate peptide sequences. The signal transduction mechanism of the peptide-modified SWNT-FETs has also been studied.

  12. The pyridyl group in ligand design for selective metal ion complexation and sensing.

    PubMed

    Hancock, Robert D

    2013-02-21

    Factors in polypyridyl ligands that control their thermodynamic metal ion selectivity in aqueous solution, and their use in selective fluorescent sensing, are examined. Preorganization of polypyridyl ligands ranging from bidentate to tetradentate by bridging benzo groups, as are present in 1,10-phenanthroline (phen) compared to 2,2'-bipyridyl (bpy), is discussed. The role of solvation is considered in relation to the relative affinity of ligands containing pyridyl groups for divalent and trivalent metal ions in aqueous solution. The effects of steric clashes between H atoms on polypyridyl ligands in decreasing complex stability are evaluated, as well as the effect of chelate ring size on metal ion selectivity. Phen ligands with other donor groups present at the 2 and 9 positions, such as alcohols, amides, carboxylates, and oximes are discussed. The design of pyridyl-based ligands for the separation of Am(III) from lanthanide(III) ions is considered, as well as ligands for the removal of metal ions such as Cu(II) or Zn(II) in neurological diseases such as Alzheimer's. The design of pyridyl-based fluorescent sensors for selective sensing of metal ions is examined in terms of the role of spin-orbit coupling constants (ζ), paramagnetism, and steric effects in the development of selective fluorescent sensors that operate via chelation enhanced fluorescence (CHEF). It is concluded that for lighter metal ions with smaller ζ values such as Zn(II) and Ca(II), and to a lesser extent Cd(II), that the CHEF effect can be achieved with pyridyl-containing fluorophores that coordinate directly to the metal ion. The way in which steric effects can be used to decrease the CHEF effect in Zn(II) relative to Cd(II) to enable selective sensing of the latter is analyzed. For heavier metal ions such as Hg(II) and Pb(II), because of their large ζ values which quench fluorescence, it is concluded that the fluorophore should be tethered to the metal-binding part of the sensor, and

  13. Selective retention of basic compounds by metal aquo-ion affinity chromatography.

    PubMed

    Asakawa, Yoshiki; Yamamoto, Eiichi; Asakawa, Naoki

    2014-10-01

    A novel metal aquo-ion affinity chromatography has been developed for the analysis of basic compounds using heat-treated silica gel containing hydrated metal cations (metal aquo-ions) as the packing material. The packing materials of the metal aquo-ion affinity chromatography were prepared by the immobilization of a single metal component such as Fe(III), Al(III), Ag(I), and Ni(II) on silica gel followed by extensive heat treatment. The immobilized metals form aquo-ions to present cation-exchange ability for basic analytes and the cation-exchange ability for basic analytes depends on pKa of the immobilized metal species. In the present study, to evaluate the retention characteristics of metal aquo-ion affinity chromatography, the on-line solid-phase extraction of drugs was investigated. Obtained data clearly evidence the selective retention capability of metal aquo-ion affinity chromatography for basic analytes with sufficient capacity. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Bio-functionalized silver nanoparticles for selective colorimetric sensing of toxic metal ions and antimicrobial studies

    NASA Astrophysics Data System (ADS)

    Vinod Kumar, V.; Anbarasan, S.; Christena, Lawrence Rene; SaiSubramanian, Nagarajan; Philip Anthony, Savarimuthu

    2014-08-01

    Hibiscus Sabdariffa (Gongura) plant extracts (leaves (HL) and stem (HS) were used for the first time in the green synthesis of bio-functionalized silver nanoparticles (AgNPs). The bio-functionality of AgNPs has been successfully utilized for selective colorimetric sensing of potentially health and environmentally hazardous Hg2+, Cd2+ and Pb2+ metal ions at ppm level in aqueous solution. Importantly, clearly distinguishable colour for all three metal ions was observed. The influence of extract preparation condition and pH were also explored on the formation of AgNPs. Both selectivity and sensitivity differed for AgNPs synthesized from different parts of the plant. Direct correlation between the stability of green synthesized AgNPs at different pH and its antibacterial effects has been established. The selective colorimetric sensing of toxic metal ions and antimicrobial effect of green synthesized AgNPs demonstrated the multifunctional applications of green nanotechnology.

  15. Selective detection of heavy metal ions by self assembled chemical field effect transistors

    NASA Astrophysics Data System (ADS)

    Ruan, Hang; Kang, Yuhong; Gladwin, Elizabeth; Claus, Richard O.

    2015-04-01

    Multiple layer-by-layer sensor material modifications were designed and implemented to achieve selectivity of semiconductor based chemical field effect transistors (ChemFETs) to particular heavy metal ions. The ChemFET sensors were fabricated and modified in three ways, with the intent to initially target first mercury and lead ions and then chromium ions, respectively. Sensor characterization was performed with the gate regions of the sensor elements exposed to different concentrations of target heavy metal ion solutions. A minimum detection level in the range of 0.1 ppm and a 10%-90% response time of less than 10 s were demonstrated. By combining layer-by-layer gold nanoparticles and lead ionophores, a sensor is produced that is sensitive and selective not only to chromium but also to Cr3+ and Cr6+. This result supports the claim that high selectivity can be achieved by designing self-assembled bonding for lead, arsenic, chromium, cesium, mercury, and cadmium.

  16. Protein scaffolds for selective enrichment of metal ions

    DOEpatents

    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.

  17. Selective fluorescence sensors for detection of nitroaniline and metal Ions based on ligand-based luminescent metal-organic frameworks

    SciTech Connect

    Yu, Zongchao; Wang, Fengqin; Lin, Xiangyi; Wang, Chengmiao; Fu, Yiyuan; Wang, Xiaojun; Zhao, Yongnan; Li, Guodong

    2015-12-15

    Metal-organic frameworks (MOFs) are porous crystalline materials with high potential for applications in fluorescence sensors. In this work, two solvent-induced Zn(II)–based metal-organic frameworks, Zn{sub 3}L{sub 3}(DMF){sub 2} (1) and Zn{sub 3}L{sub 3}(DMA){sub 2}(H{sub 2}O){sub 3} (2) (L=4,4′-stilbenedicarboxylic acid), were investigated as selective sensing materials for detection of nitroaromatic compounds and metal ions. The sensing experiments show that 1 and 2 both exhibit selective fluorescence quenching toward nitroaniline with a low detection limit. In addition, 1 exhibits high selectivity for detection of Fe{sup 3+} and Al{sup 3+} by significant fluorescence quenching or enhancement effect. While for 2, it only exhibits significant fluorescence quenching effect for Fe{sup 3+}. The results indicate that 1 and 2 are both promising fluorescence sensors for detecting and recognizing nitroaniline and metal ions with high sensitivity and selectivity. - Graphical abstract: Two MOFs have been selected as the fluorescence sensing materials for selectively sensing mitroaromatic compounds and metal ions. The high selectivity makes them promising fluorescence sensors for detecting and recognizing nitroaniline and Fe{sup 3+} or Al{sup 3+}.

  18. Selective extraction of metal ions with polymeric extractants by ion exchange/redox

    DOEpatents

    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.

  19. Selective Separation of Metal Ions via Monolayer Nanoporous Graphene with Carboxyl Groups.

    PubMed

    Li, Zhan; Liu, Yanqi; Zhao, Yang; Zhang, Xin; Qian, Lijuan; Tian, Longlong; Bai, Jing; Qi, Wei; Yao, Huijun; Gao, Bin; Liu, Jie; Wu, Wangsuo; Qiu, Hongdeng

    2016-10-18

    Graphene-coated plastic substrates, such as polyethylene terephthalate (PET), are regularly used in flexible electronic devices. Here we demonstrate a new application of the graphene-coated nanoporous PET membrane for the selective separation of metal ions in an ion exchange manner. Irradiation with swift heavy ions is used to perforate graphene and PET substrate. This process could create graphene nanopores with carboxyl groups, thus forming conical holes in the PET after chemical etching to support graphene nanopores. Therefore, a monolayer nanoporous graphene membrane with a PET substrate is constructed successfully to investigate its ionic selective separation. We find that the permeation ratio of ions strongly depends on the temperature and H(+) concentration in the driving solution. An electric field can increase the permeation ratio of ions through the graphene nanopores, but it inhibits the ion selective separation. Moreover, the structure of the graphene nanopore with carboxyl groups is resolved at the density functional theory level. The results show the asymmetric structure of the nanopore with carboxyl groups, and the analysis indicates that the ionic permeation can be attributed to the ion exchange between metal ions and protons on the two sides of graphene nanopores. These results would be beneficial to the design of membrane separation materials made from graphene with efficient online and offline bulk separation.

  20. Metal nanocrystal/metal-organic framework core/shell nanostructure from selective self-assembly induced by localization of metal ion precursors on nanocrystal surface.

    PubMed

    Ohhashi, Takashi; Tsuruoka, Takaaki; Matsuyama, Tetsuhiro; Takashima, Yohei; Nawafune, Hidemi; Minami, Hideto; Akamatsu, Kensuke

    2015-08-01

    Metal nanocrystal/metal-organic framework core/shell nanostructures have been constructed using metal ion-trapped nanocrystals as scaffolds through a selective self-assembly of framework components on the nanocrystal surfaces. The resulting nanostructures exhibit unique catalytic activity toward nitrophenol analogs.

  1. Selectivity and permeation in calcium release channel of cardiac muscle: alkali metal ions.

    PubMed Central

    Chen, D P; Xu, L; Tripathy, A; Meissner, G; Eisenberg, B

    1999-01-01

    Current was measured from single open channels of the calcium release channel (CRC) of cardiac sarcoplasmic reticulum (over the range +/-180 mV) in pure and mixed solutions (e.g., biionic conditions) of the alkali metal ions Li+, K+, Na+, Rb+, Cs+, ranging in concentration from 25 mM to 2 M. The current-voltage (I-V) relations were analyzed by an extension of the Poisson-Nernst-Planck (PNP) formulation of electrodiffusion, which includes local chemical interaction described by an offset in chemical potential, which likely reflects the difference in dehydration/solvation/rehydration energies in the entry/exit steps of permeation. The theory fits all of the data with few adjustable parameters: the diffusion coefficient of each ion species, the average effective charge distribution on the wall of the pore, and an offset in chemical potential for lithium and sodium ions. In particular, the theory explains the discrepancy between "selectivities" defined by conductance sequence and "selectivities" determined by the permeability ratios (i.e., reversal potentials) in biionic conditions. The extended PNP formulation seems to offer a successful combined treatment of selectivity and permeation. Conductance selectivity in this channel arises mostly from friction: different species of ions have different diffusion coefficients in the channel. Permeability selectivity of an ion is determined by its electrochemical potential gradient and local chemical interaction with the channel. Neither selectivity (in CRC) seems to involve different electrostatic interaction of different ions with the channel protein, even though the ions have widely varying diameters. PMID:10049318

  2. Bio-functionalized silver nanoparticles for selective colorimetric sensing of toxic metal ions and antimicrobial studies.

    PubMed

    Vinod Kumar, V; Anbarasan, S; Christena, Lawrence Rene; SaiSubramanian, Nagarajan; Philip Anthony, Savarimuthu

    2014-08-14

    Hibiscus Sabdariffa (Gongura) plant extracts (leaves (HL) and stem (HS)) were used for the first time in the green synthesis of bio-functionalized silver nanoparticles (AgNPs). The bio-functionality of AgNPs has been successfully utilized for selective colorimetric sensing of potentially health and environmentally hazardous Hg(2+), Cd(2+) and Pb(2+) metal ions at ppm level in aqueous solution. Importantly, clearly distinguishable colour for all three metal ions was observed. The influence of extract preparation condition and pH were also explored on the formation of AgNPs. Both selectivity and sensitivity differed for AgNPs synthesized from different parts of the plant. Direct correlation between the stability of green synthesized AgNPs at different pH and its antibacterial effects has been established. The selective colorimetric sensing of toxic metal ions and antimicrobial effect of green synthesized AgNPs demonstrated the multifunctional applications of green nanotechnology. Copyright © 2014 Elsevier B.V. All rights reserved.

  3. Selective detection of heavy metal ions by self assembled chemical field effect transistors

    SciTech Connect

    Ruan, Hang Kang, Yuhong; Gladwin, Elizabeth; Claus, Richard O.

    2015-04-20

    Multiple layer-by-layer sensor material modifications were designed and implemented to achieve selectivity of semiconductor based chemical field effect transistors (ChemFETs) to particular heavy metal ions. The ChemFET sensors were fabricated and modified in three ways, with the intent to initially target first mercury and lead ions and then chromium ions, respectively. Sensor characterization was performed with the gate regions of the sensor elements exposed to different concentrations of target heavy metal ion solutions. A minimum detection level in the range of 0.1 ppm and a 10%–90% response time of less than 10 s were demonstrated. By combining layer-by-layer gold nanoparticles and lead ionophores, a sensor is produced that is sensitive and selective not only to chromium but also to Cr{sup 3+} and Cr{sup 6+}. This result supports the claim that high selectivity can be achieved by designing self-assembled bonding for lead, arsenic, chromium, cesium, mercury, and cadmium.

  4. Interaction of selected divalent metal ions with human ataxin-3 Q36.

    PubMed

    Stawoska, Iwona; Wesełucha-Birczyńska, Aleksandra; Regonesi, Maria Elena; Riva, Matteo; Tortora, Paolo; Stochel, Grazyna

    2009-11-01

    The mode of interaction of ataxin-3 Q36 (AT-3 Q36) with selected endogenous and exogenous metal ions, namely, Zn(2+), Cu(2+), Ni(2+), and Cd(2+), was examined. Metal-ion-induced structural changes of the protein were monitored by fluorescence as well as Fourier transform Raman spectroscopy. We found that the cations tested lead to a decrease in alpha-helical content and a concurrent increase in beta-sheet as well as undefined (beta-turn and random-coil) structures. The most evident effect was observed for copper and nickel cations. After titration with these cations, the AT3 Q36 secondary structure content (27% alpha-helices in the presence of either ion, 31 and 27% beta-sheets for Cu(2+) and Ni(2+), respectively) was similar to that observed for the aggregated form of the protein (27% alpha-helices, 36% beta-sheets). Using the 1-anilinonaphthalene-8-sulfonate hydrophobic fluorescence probe, we showed that the presence of the metal ions tested led to the formation of solvent-exposed hydrophobic patches of AT-3 Q36, and that such an effect decreased with increasing ionic radius.

  5. Rice straw modified by click reaction for selective extraction of noble metal ions.

    PubMed

    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.

  6. Categoric prediction of metal ion mechanisms in the active sites of 17 select type II restriction endonucleases.

    PubMed

    Advani, Sonia; Mishra, Puneet; Dubey, Shraddha; Thakur, Samridhi

    2010-11-12

    Recently determined crystal structures of type II restriction endonucleases have produced a plethora of information on the basis for target site sequence selectivity. The positioning and role of metal ions in DNA recognition sites might reflect important properties of protein-DNA interaction. Although acidic and basic groups in the active sites can be identified, and in some cases divalent-metal binding sites delineated, a convincing picture clarifying the way in which the attacking hydroxide ion is generated, and the leaving group stabilized, has not been elucidated for any of the enzymes. We have examined the interatomic distances between metal ions and proposed key catalytic residues in the binding sites of seventeen type II restriction endonucleases whose crystal structures are documented in literature. The summary and critical evaluation of structural assignments and predictions made earlier have been useful to group these enzymes. All the enzymes used for this study have been categorized on the basis of the number of metal ions identified in their crystal structures. Among 17 experimentally characterized (not putative) type II REases, whose apparently full-length sequences are available in REBASE, we predict 8 (47%) to follow the single metal ion mechanism, 5 to follow the two metal ion mechanism, 2, the three metal ion mechanism, 1, the four metal ion mechanism and 1 the six metal ion mechanism. Copyright © 2010 Elsevier Inc. All rights reserved.

  7. Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometric analysis of metal-ion selected dynamic protein libraries.

    PubMed

    Cooper, Helen J; Case, Martin A; McLendon, George L; Marshall, Alan G

    2003-05-07

    The application of electrospray ionization (ESI) Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry to the investigation of the relative stabilities (and thus packing efficiencies) of Fe-bound trihelix peptide bundles is demonstrated. Small dynamic protein libraries are created by metal-ion assisted assembly of peptide subunits. Control of the trimeric aggregation state is coupled to stability selection by exploiting the coordination requirements of Fe(2+) in the presence of bidentate 2,2'-bipyridyl ligands covalently appended to the peptide monomers. At limiting metal-ion concentration, the most thermodynamically stable, optimally packed peptide trimers dominate the mass spectrum. The identities of optimally stable candidate trimers observed in the ESI FT-ICR mass spectra are confirmed by resynthesis of exchange-inert analogues and measurement of their folding free energies. The peptide composition of the trimers may be determined by infrared multiphoton dissociation (IRMPD) MS(3) experiments. Additional sequence information for the peptide subunits is obtained from electron capture dissociation (ECD) of peptides and metal-bound trimers. The experiments also suggest the presence of secondary structure in the gas phase, possibly due to partial retention of the solution-phase coiled coil structure.

  8. Selective nitrogen capture by porous hybrid materials containing accessible transition metal ion sites

    NASA Astrophysics Data System (ADS)

    Yoon, Ji Woong; Chang, Hyunju; Lee, Seung-Joon; Hwang, Young Kyu; Hong, Do-Young; Lee, Su-Kyung; Lee, Ji Sun; Jang, Seunghun; Yoon, Tae-Ung; Kwac, Kijeong; Jung, Yousung; Pillai, Renjith S.; Faucher, Florian; Vimont, Alexandre; Daturi, Marco; Férey, Gérard; Serre, Christian; Maurin, Guillaume; Bae, Youn-Sang; Chang, Jong-San

    2017-05-01

    Selective dinitrogen binding to transition metal ions mainly covers two strategic domains: biological nitrogen fixation catalysed by metalloenzyme nitrogenases, and adsorptive purification of natural gas and air. Many transition metal-dinitrogen complexes have been envisaged for biomimetic nitrogen fixation to produce ammonia. Inspired by this concept, here we report mesoporous metal-organic framework materials containing accessible Cr(III) sites, able to thermodynamically capture N2 over CH4 and O2. This fundamental study integrating advanced experimental and computational tools confirmed that the separation mechanism for both N2/CH4 and N2/O2 gas mixtures is driven by the presence of these unsaturated Cr(III) sites that allows a much stronger binding of N2 over the two other gases. Besides the potential breakthrough in adsorption-based technologies, this proof of concept could open new horizons to address several challenges in chemistry, including the design of heterogeneous biomimetic catalysts through nitrogen fixation.

  9. Major-ion and selected trace-metal chemistry of the Biscayne Aquifer, Southeast Florida

    USGS Publications Warehouse

    Radell, M.J.; Katz, B.G.

    1991-01-01

    The major-ion and selected trace-metal chemistry of the Biscayne aquifer was characterized as part of the Florida Ground-Water Quality Monitoring Network Program, a multiagency cooperative effort concerned with delineating baseline water quality for major aquifer systems in the State. The Biscayne aquifer is unconfined and serves as the sole source of drinking water for more than 3 million people in southeast Florida. The Biscayne aquifer consists of highly permeable interbedded limestone and sandstone of Pleistocene and Pliocene age underlying most of Dade and Broward Counties and parts of Palm Beach and Monroe Counties. The high permeability is largely caused by extensive carbonate dissolution. Water sampled from 189 wells tapping the Biscayne aquifer was predominantly a calcium bicarbonate type with some mixed types occurring in coastal areas and near major canals. Major - ion is areally uniform throughout the aquifer. According to nonparametric statistical tests of major ions and dissolved solids, the concentrations of calcium, sodium, bicarbonate, and dissolved solids increased significantly with well depth ( 0.05 significance level ), probably a result of less circulation at depth. Potassium and nitrate concentrations decreased significantly with depth. Although the source of recharge to the aquifer varies seasonally, there was no statistical difference in the concentration of major ions in pared water samples from 27 shallow wells collected during wet and dry seasons. Median concentrations for barium, chromium, copper, lead, and manganese were below maximum or secondary maximum contaminant levels set by the US Environmental Protection Agency. The median iron concentration only slightly exceeded the secondary maximum contaminant level. The concentration of barium was significantly related (0.05 significance level) to calcium and bicarbonate concentration. No distinct areal pattern or vertical distribution of the selected trace metals was evident in water from

  10. Synthesis and Ion-Exchange Properties of Graphene Th(IV) Phosphate Composite Cation Exchanger: Its Applications in the Selective Separation of Lead Metal Ions.

    PubMed

    Rangreez, Tauseef Ahmad; Asiri, Abdullah M; Alhogbi, Basma G; Naushad, Mu

    2017-07-24

    In this study, graphene Th(IV) phosphate was prepared by sol-gel precipitation method. The ion-exchange behavior of this cation-exchanger was studied by investigating properties like ion-exchange capacity for various metal ions, the effect of eluent concentration, elution behavior, and thermal effect on ion-exchange capacity (IEC). Several physicochemical properties as Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD) study, thermal studies, scanning electron microscopy (SEM) and transmission electron microscopy (TEM) studies were also carried out. The material possessed an IEC of 1.56 meq·dry·g(-1) of the exchanger and was found to be nano-composite. The selectivity studies showed that the material is selective towards Pb(II) ions. The selectivity of this cation-exchanger was demonstrated in the binary separation of Pb(II) ions from mixture with other metal ions. The recovery was found to be both quantitative and reproducible.

  11. Heterogeneous behavior of metalloproteins toward metal ion binding and selectivity: insights from molecular dynamics studies.

    PubMed

    Gogoi, Prerana; Chandravanshi, Monika; Mandal, Suraj Kumar; Srivastava, Ambuj; Kanaujia, Shankar Prasad

    2016-07-01

    About one-third of the existing proteins require metal ions as cofactors for their catalytic activities and structural complexities. While many of them bind only to a specific metal, others bind to multiple (different) metal ions. However, the exact mechanism of their metal preference has not been deduced to clarity. In this study, we used molecular dynamics (MD) simulations to investigate whether a cognate metal (bound to the structure) can be replaced with other similar metal ions. We have chosen seven different proteins (phospholipase A2, sucrose phosphatase, pyrazinamidase, cysteine dioxygenase (CDO), plastocyanin, monoclonal anti-CD4 antibody Q425, and synaptotagmin 1 C2B domain) bound to seven different divalent metal ions (Ca(2+), Mg(2+), Zn(2+), Fe(2+), Cu(2+), Ba(2+), and Sr(2+), respectively). In total, 49 MD simulations each of 50 ns were performed and each trajectory was analyzed independently. Results demonstrate that in some cases, cognate metal ions can be exchanged with similar metal ions. On the contrary, some proteins show binding affinity specifically to their cognate metal ions. Surprisingly, two proteins CDO and plastocyanin which are known to bind Fe(2+) and Cu(2+), respectively, do not exhibit binding affinity to any metal ion. Furthermore, the study reveals that in some cases, the active site topology remains rigid even without cognate metals, whereas, some require them for their active site stability. Thus, it will be interesting to experimentally verify the accuracy of these observations obtained computationally. Moreover, the study can help in designing novel active sites for proteins to sequester metal ions particularly of toxic nature.

  12. Membranes based on polymer miscibility for selective transport and separation of metallic ions.

    PubMed

    Zioui, Djamila; Arous, Omar; Mameri, Nabil; Kerdjoudj, Hacène; Sebastian, M San; Vilas, J L; Nunes-Pereira, J; Lanceros-Méndez, Senentxu

    2017-08-15

    Polymer inclusion membranes (PIM) used for selective transport and separation of metallic ions have emerged in recent times. Their expansion depends on the method of preparation and their suitable structure and physico-chemical characteristics. In this paper, a novel category of membranes for ions separation is reported. The membranes were synthesized by thermally induced phase separation using a mixture of polyvinylidene fluoride (PVDF) and cellulose triacetate (CTA) plasticized by tris(2-ethylhexyl) phosphate (TEHP) and with di-(2-ethylhexyl) phosphoric acid (D2EHPA) incorporated into the polymer as carrier to increase specific interactions between polymers. PIM membrane exhibited a hydrophobic (∼100°) and thermally stable up to ∼200°C porous homogenous structure. The transport of Ni(II), Zn(II) and Pb(II) from aqueous solutions was studied by competitive transport across polymer inclusion membranes (PIM). Competitive transport of ions in solution across PIM provide the selectivity order: Ni(2+) (45%)>Pb(2+) (35%)>Zn(2+) (5%). A long-term transport experiment was carried out to study the durability of the system. Copyright © 2017 Elsevier B.V. All rights reserved.

  13. Protein Signatures That Promote Operator Selectivity among Paralog MerR Monovalent Metal Ion Regulators*

    PubMed Central

    Humbert, María V.; Rasia, Rodolfo M.; Checa, Susana K.; Soncini, Fernando C.

    2013-01-01

    Two paralog transcriptional regulators of the MerR family, CueR and GolS, are responsible for monovalent metal ion sensing and resistance in Salmonella enterica. Although similar in sequence and also in their target binding sites, these proteins differ in signal detection and in the set of target genes they control. Recently, we demonstrated that selective promoter recognition depends on the presence of specific bases located at positions 3′ and 3 within the operators they interact with. Here, we identify the amino acid residues within the N-terminal DNA-binding domain of these sensor proteins that are directly involved in operator discrimination. We demonstrate that a methionine residue at position 16 of GolS, absolutely conserved among GolS-like proteins but absent in all CueR-like xenologs, is the key to selectively recognize operators that harbor the distinctive GolS-operator signature, whereas the residue at position 19 finely tunes the regulator/operator interaction. Furthermore, swapping these residues switches the set of genes recognized by these transcription factors. These results indicate that co-evolution of a regulator and its cognate operators within the bacterial cell provides the conditions to avoid cross-recognition and guarantees the proper response to metal injury. PMID:23733186

  14. Construction of three lanthanide metal-organic frameworks: Synthesis, structure, magnetic properties and highly selective sensing of metal ions

    NASA Astrophysics Data System (ADS)

    Zhang, Xiu-Mei; Li, Peng; Gao, Wei; Liu, Feng; Liu, Jie-Ping

    2016-12-01

    Three lanthanide metal-organic frameworks (Ln-MOFs), [Ln(TZI)(H2O)4]·3H2O (Ln=Gd (1) and Tb (2) and Dy (3), H3TZI=5-(1H-tetrazol-5-yl)isophthalic acid), have been synthesized under hydrothermal conditions. Single crystal X-ray diffraction reveals that 1-3 are isostructural and display a 1D double chain based on dinuclear motifs with (μ-COO)2 double bridges. Magnetic studies indicate antiferromagnetic interactions in 1, ferromagnetic interactions in 2 and 3. Furthermore, compound 3 displays a slow relaxation behavior. Compound 2 exhibits intense characteristic green emission of Tb(III) ions in the solid state, which can be observed by the naked eye under UV light. Interestingly, 2 can selectively sense Pb2+ and Fe3+ ions through luminescence enhancement and quenching, respectively. The luminescence quenching mechanisms have been investigated in detail. The study on luminescence Ln-MOFs as a probe for sensing Pb2+ and Fe3+ ions is exceedingly rare example.

  15. Removal of selected metal ions from aqueous solution using modified corncobs.

    PubMed

    Vaughan, T; Seo, C W; Marshall, W E

    2001-06-01

    The objective of this study was to convert corncobs to metal ion adsorbents for wastewater treatment. Ground corncobs were modified with either 0.6 M citric acid (CA) or 1.0 M phosphoric acid (PA) to help improve their natural adsorption capacity. The effect of a combination of wash and modification treatment was tested for corncob adsorption efficiency with five different metal ions (cadmium, copper, lead, nickel, zinc) individually or in a mixed solution containing each metal at a 20 mM concentration. Results were compared to those of commercial resins Amberlite IRC-718, Amberlite 200, Duolite GT-73 and carboxymethylcellulose (CMC). Modified corncobs showed the same adsorption efficiency as Duolite GT-73 for cadmium, copper, nickel and zinc ions and had greater adsorption than CMC for nickel and zinc ions. For mixed metals, the modified corncobs exhibited the same adsorption efficiency as Duolite GT-73 for cadmium and copper ions and the same or higher adsorption than Amberlite IRC-718 for lead ions. Adsorption capacities of modified samples were compared to those of Amberlite IRC-718, Amberlite 200 and Duolite GT-73. Commercial resins generally had higher adsorption capacities than modified corncobs. However, the adsorption capacity of modified corncobs for copper and lead ions was equivalent to Duolite GT-73, but was lower than for Amberlite IRC-718 or Amberlite 200. Depending on the specific metal ion and the presence or absence of other metal ions, chemically modified corncobs were at least equivalent in adsorption properties to all of the commercial cation exchange resins examined in this study.

  16. Highly selectively monitoring heavy and transition metal ions by a fluorescent sensor based on dipeptide.

    PubMed

    Neupane, Lok Nath; Thirupathi, Ponnaboina; Jang, Sujung; Jang, Min Jung; Kim, Jung Hwa; Lee, Keun-Hyeung

    2011-09-15

    Fluorescent sensor (DMH) based on dipeptide was efficiently synthesized in solid phase synthesis. The dipeptide sensor shows sensitive response to Ag(I), Hg(II), and Cu(II) among 14 metal ions in 100% aqueous solution. The fluorescent sensor differentiates three heavy metal ions by response type; turn on response to Ag(I), ratiometric response to Hg(II), and turn off detection of Cu(II). The detection limits of the sensor for Ag(I) and Cu(II) were much lower than the EPA's drinking water maximum contaminant levels (MCL). Specially, DMH penetrated live cells and detected intracellular Ag(+) by turn on response. We described the fluorescent change, binding affinity, detection limit for the metal ions. The study of a heavy metal-responsive sensor based on dipeptide demonstrates its potential utility in the environment field.

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

    PubMed

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

    2017-03-06

    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.

  18. Biochemical and structural characterization of Salmonella typhimurium glyoxalase II: new insights into metal ion selectivity.

    PubMed

    Campos-Bermudez, Valeria A; Leite, Ney Ribeiro; Krog, Renata; Costa-Filho, Antonio J; Soncini, Fernando C; Oliva, Glaucius; Vila, Alejandro J

    2007-10-02

    Glyoxalase II is a hydrolytic enzyme part of the glyoxalase system, responsible for detoxifying several cytotoxic compounds employing glutathione. Glyoxalase II belongs to the superfamily of metallo-beta-lactamases, with a conserved motif able to bind up to two metal ions in their active sites, generally zinc. Instead, several eukaryotic glyoxalases II have been characterized with different ratios of iron, zinc, and manganese ions. We have expressed a gene coding for a putative member of this enzyme superfamily from Salmonella typhimurium that we demonstrate, on the basis of its activity, to be a glyoxalase II, named GloB. Recombinant GloB expressed in Escherichia coli was purified with variable amounts of iron, zinc, and manganese. All forms display similar activities, as can be shown from protein expression in minimal medium supplemented with specific metal ions. The crystal structure of GloB solved at 1.4 A shows a protein fold and active site similar to those of its eukaryotic homologues. NMR and EPR experiments also reveal a conserved electronic structure at the metal site. GloB is therefore able to accommodate these different metal ions and to carry out the hydrolytic reaction with similar efficiencies in all cases. The metal promiscuity of this enzyme (in contrast to other members of the same superfamily) can be accounted for by the presence of a conserved Asp residue acting as a second-shell ligand that is expected to increase the hardness of the metal binding site, therefore favoring iron uptake in glyoxalases II.

  19. Synthesis and Ion-Exchange Properties of Graphene Th(IV) Phosphate Composite Cation Exchanger: Its Applications in the Selective Separation of Lead Metal Ions

    PubMed Central

    Rangreez, Tauseef Ahmad; Alhogbi, Basma G.; Naushad, Mu.

    2017-01-01

    In this study, graphene Th(IV) phosphate was prepared by sol–gel precipitation method. The ion-exchange behavior of this cation-exchanger was studied by investigating properties like ion-exchange capacity for various metal ions, the effect of eluent concentration, elution behavior, and thermal effect on ion-exchange capacity (IEC). Several physicochemical properties as Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD) study, thermal studies, scanning electron microscopy (SEM) and transmission electron microscopy (TEM) studies were also carried out. The material possessed an IEC of 1.56 meq·dry·g−1 of the exchanger and was found to be nano-composite. The selectivity studies showed that the material is selective towards Pb(II) ions. The selectivity of this cation-exchanger was demonstrated in the binary separation of Pb(II) ions from mixture with other metal ions. The recovery was found to be both quantitative and reproducible. PMID:28737717

  20. Protein selectivity with immobilized metal ion-tacn sorbents: chromatographic studies with human serum proteins and several other globular proteins.

    PubMed

    Jiang, W; Graham, B; Spiccia, L; Hearn, M T

    1998-01-01

    The chromatographic selectivity of the immobilized chelate system, 1,4,7-triazocyclononane (tacn), complexed with the borderline metal ions Cu2+, Cr3+, Mn2+, Co2+, Zn2+, and Ni2+ has been investigated with hen egg white lysozyme, horse heart cytochrome c, and horse skeletal muscle myoglobin, as well as proteins present in partially fractionated preparations of human plasma. The effects of ionic strength and pH of the loading and elution buffers on protein selectivities of these new immobilized metal ion affinity chromatographic (IMAC) systems have been examined. The results confirm that immobilized Mn;pl-tacn sorbents exhibit a novel type of IMAC behavior with proteins. In particular, the chromatographic properties of these immobilized M(n+)-tacn ligand systems were significantly different compared to the IMAC behavior observed with other types of immobilized tri- and tetradentate chelating ligands, such as iminodiacetic acid, O-phosphoserine, or nitrilotriacetic acid, when complexed with borderline metal ions. The experimental results have consequently been evaluated in terms of the additional contributions to the interactive processes mediated by effects other than solely the conventional lone pair Lewis soft acid-Lewis soft base coordination interactions, typically found for the IMAC of proteins with borderline and soft metal ions, such as Cu2+ or Ni2+.

  1. C-H functionalization: thoroughly tuning ligands at a metal ion, a chemist can greatly enhance catalyst's activity and selectivity.

    PubMed

    Shul'pin, Georgiy B

    2013-09-28

    This brief essay consists of a few "exciting stories" devoted to relations within a metal-complex catalyst between a metal ion and a coordinated ligand. When, as in the case of a human couple, the rapport of the partners is cordial and a love cements these relations, a chemist finds an ideal married couple, in other words he obtains a catalyst of choice which allows him to functionalize C-H bonds very efficiently and selectively. Examples of such lucky marriages in the catalytic world of ions and ligands are discussed here. Activity of the catalyst is characterized by turnover number (TON) or turnover frequency (TOF) as well as by yield of a target product. Introducing a chelating N,N- or N,O-ligand to the catalyst molecule (this can be an iron or manganese derivative) sharply enhances its activity. However, the activity of vanadium derivatives (with additionally added to the solution pyrazinecarboxylic acid, PCA) as well as of various osmium complexes does not dramatically depend on the nature of ligands surrounding metal ions. Complexes of these metals are very efficient catalysts in oxidations with H2O2. Osmium derivatives are record-holders exhibiting extremely high TONs whereas vanadium complexes are on the second position. Finally, elegant examples of alkane functionalization on the ions of non-transition metals (aluminium, gallium etc.) are described when one ligand within the metal complex (namely, hydroperoxyl ligand HOO(-)) helps other ligand of this complex (H2O2 molecule coordinated to the metal) to disintegrate into two species, generating very reactive hydroxyl radical. Hydrogen peroxide molecule, even ligated to the metal ion, is perfectly stable without the assistance of the neighboring HOO(-) ligand. This ligand can be easily oxidized donating an electron to its partner ligand (H2O2). In an analogous case, when the central ion in the catalyst is a transition metal, this ion changing its oxidation state can donate an electron to the coordinated H2O2

  2. Selectivity and permeation of alkali metal ions in K+-channels.

    PubMed

    Furini, Simone; Domene, Carmen

    2011-06-24

    Ion conduction in K(+)-channels is usually described in terms of concerted movements of K(+) progressing in a single file through a narrow pore. Permeation is driven by an incoming ion knocking on those ions already inside the protein. A fine-tuned balance between high-affinity binding and electrostatic repulsive forces between permeant ions is needed to achieve efficient conduction. While K(+)-channels are known to be highly selective for K(+) over Na(+), some K(+) channels conduct Na(+) in the absence of K(+). Other ions are known to permeate K(+)-channels with a more moderate preference and unusual conduction features. We describe an extensive computational study on ion conduction in K(+)-channels rendering free energy profiles for the translocation of three different alkali ions and some of their mixtures. The free energy maps for Rb(+) translocation show at atomic level why experimental Rb(+) conductance is slightly lower than that of K(+). In contrast to K(+) or Rb(+), external Na(+) block K(+) currents, and the sites where Na(+) transport is hindered are characterized. Translocation of K(+)/Na(+) mixtures is energetically unfavorable owing to the absence of equally spaced ion-binding sites for Na(+), excluding Na(+) from a channel already loaded with K(+). Copyright © 2011 Elsevier Ltd. All rights reserved.

  3. Altering the Peptide Binding Selectivity of Polymeric Reverse Micelle Assemblies via Metal Ion Loading.

    PubMed

    Wang, Meizhe; Zhao, Bo; Gao, Jingjing; He, Huan; Castellanos, Laura J; Thayumanavan, S; Vachet, Richard W

    2017-08-31

    Supramolecular reverse micelle assemblies, formed by amphiphilic copolymers, can selectively encapsulate molecules in their interiors depending on the functional groups present in the polymers. Altering the binding selectivity of these materials typically requires the synthesis of alternate functional groups. Here, we demonstrate that the addition of Zr(IV) ions to the interiors of reverse micelles having phosphonate functional groups transforms the supramolecular materials from ones that selectively bind positively charged peptides into materials that selectively bind phosphorylated peptides. We also show that the binding selectivity of these reverse micelle assemblies can be further tuned by varying the fractions of phosphonate groups in the copolymer structure. The optimized reverse micelle materials can selectively transfer and bind phosphorylated peptides from aqueous solutions over a wide range of pH conditions and can selectively enrich phosphorylated peptides even in complicated mixtures.

  4. Selection of short peptides with high affinity for various metal ions: Strategies and applications

    SciTech Connect

    Ataai, M.M.; Whiteford, W.K.

    1995-12-01

    The authors have used a random combinatorial library to generate an immensely diverse population of candidate peptides and have screened the library, using novel strategies, for selection of peptides of displaying high affinity towards a target metal. As the pool of available binding candidates, we have employed a hexapeptide library, containing essentially all the possible combination of sequences for a hexapeptide, expressed on surface of phage. Our experiments with copper demonstrated that our amplification and selection procedure is very effective. Out of 20 clones sequenced, after four rounds of amplification and selection 18 shared the same sequence. The corresponding peptide which contain two histidines was then synthesized and its binding affinity for copper was assessed. The results revealed that the selected peptide has a very high affinity for copper; its affinity is significantly higher than any hexapeptide which we are aware of including six adjacent histidine, (his)6, frequently used as an affinity tag in bioseparation. Selection of short peptides with high affinity and selectivity for arsenic, mercury, and lead is also underway. We envision important application of this work including discovery of highly effective drugs for treating metal toxicity replacing the chelating agents currently in use, and development of inexpensive whole cell adsorbents for toxicity replacing the chelating agents currently in use, and development of inexpensive whole cell adsorbents for the removal of toxic metals from dilute aqueous streams because dead cells or isolated cell wall, covered by the desired metal-binding domain may serve as high affinity and high capacity metal adsorbents. Other potential application will also be discussed in this presentation.

  5. Mapping of heavy metal ion sorption to cell-extracellular polymeric substance-mineral aggregates by using metal-selective fluorescent probes and confocal laser scanning microscopy.

    PubMed

    Hao, Likai; Li, Jianli; Kappler, Andreas; Obst, Martin

    2013-11-01

    Biofilms, organic matter, iron/aluminum oxides, and clay minerals bind toxic heavy metal ions and control their fate and bioavailability in the environment. The spatial relationship of metal ions to biomacromolecules such as extracellular polymeric substances (EPS) in biofilms with microbial cells and biogenic minerals is complex and occurs at the micro- and submicrometer scale. Here, we review the application of highly selective and sensitive metal fluorescent probes for confocal laser scanning microscopy (CLSM) that were originally developed for use in life sciences and propose their suitability as a powerful tool for mapping heavy metals in environmental biofilms and cell-EPS-mineral aggregates (CEMAs). The benefit of using metal fluorescent dyes in combination with CLSM imaging over other techniques such as electron microscopy is that environmental samples can be analyzed in their natural hydrated state, avoiding artifacts such as aggregation from drying that is necessary for analytical electron microscopy. In this minireview, we present data for a group of sensitive fluorescent probes highly specific for Fe(3+), Cu(2+), Zn(2+), and Hg(2+), illustrating the potential of their application in environmental science. We evaluate their application in combination with other fluorescent probes that label constituents of CEMAs such as DNA or polysaccharides and provide selection guidelines for potential combinations of fluorescent probes. Correlation analysis of spatially resolved heavy metal distributions with EPS and biogenic minerals in their natural, hydrated state will further our understanding of the behavior of metals in environmental systems since it allows for identifying bonding sites in complex, heterogeneous systems.

  6. Metal alloy and monoelemental nanoclusters in silica formed by sequential ion implantation and annealing in selected atmosphere

    NASA Astrophysics Data System (ADS)

    Ren, F.; Jiang, C. Z.; Chen, H. B.; Shi, Y.; liu, C.; Wang, J. B.

    2004-11-01

    The preparation of metal alloy and monoelemental nanoclusters in silica by Ag, Cu ion sequential implantation and annealing in selected oxidizing or reducing atmosphere is studied. The formation of metastable Ag-Cu alloy is verified in the as-implanted samples by optical absorption spectra, selected area electron diffraction and energy dispersive spectrometer spectrum. The alloy is discomposed at elevated annealing temperature in both oxidizing and reducing atmospheres. The different effects of annealing behaviors on the Ag-Cu alloy nanoclusters are investigated.

  7. Metal Ions in Unusual Valency States.

    ERIC Educational Resources Information Center

    Sellers, Robin M.

    1981-01-01

    Discusses reactivity of metal ions with the primary products of water radiolysis, hyper-reduced metal ions, zero-valent metal ions, unstable divalent ions from the reduction of bivalent ions, hyper-oxidized metal ions, and metal complexes. (CS)

  8. Metal Ions in Unusual Valency States.

    ERIC Educational Resources Information Center

    Sellers, Robin M.

    1981-01-01

    Discusses reactivity of metal ions with the primary products of water radiolysis, hyper-reduced metal ions, zero-valent metal ions, unstable divalent ions from the reduction of bivalent ions, hyper-oxidized metal ions, and metal complexes. (CS)

  9. A preorganized metalloreceptor for alkaline earth ions showing calcium versus magnesium selectivity in water: biological activity of selected metal complexes.

    PubMed

    Amatori, Stefano; Ambrosi, Gianluca; Fanelli, Mirco; Formica, Mauro; Fusi, Vieri; Giorgi, Luca; Macedi, Eleonora; Micheloni, Mauro; Paoli, Paola; Rossi, Patrizia

    2014-08-25

    The N,N'-bis[(3-hydroxy-4-pyron-2-yl)methyl]-N,N'-dimethylethylendiamine (Malten = L) forms the highly stable [CuH(-2)L] species in water, in which the converging maltol oxygen atoms form an electron-rich area able to host hard metal ions. When considering the alkaline earth series (AE), the [Cu(H(-2)L)] species binds all metal ions, with the exception of Mg(2+), exhibiting the relevant property to discriminate Ca(2+) versus Mg(2+) at physiological pH 7.4; the binding of the AE metal is visible to the naked eye. The stability constant values of the trinuclear [AE{Cu(H(-2)L)}2](2+) species formed reach the maximum for Ca(2+) (log K=7.7). Ca(2+) also forms a tetranuclear [Ca{Cu(H(-2)L)}]2(4+) species at a high Ca(2+) concentration. Tri- and tetranuclear calcium complexes show blue- and pink-colored crystals, respectively. [Cu(H(-2)L)] is the most active species in inducing DNA alterations. The DNA damages are compatible with its hydrolytic cleavages. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. A Terbium Metal-Organic Framework for Highly Selective and Sensitive Luminescence Sensing of Hg(2+) Ions in Aqueous Solution.

    PubMed

    Xia, Tifeng; Song, Tao; Zhang, Gege; Cui, Yuanjing; Yang, Yu; Wang, Zhiyu; Qian, Guodong

    2016-12-19

    A series of isomorphic lanthanide metal-organic frameworks (MOFs) Ln(TATAB)⋅(DMF)4 (H2 O)(MeOH)0.5 (LnTATAB, Ln=Eu, Tb, Sm, Dy, Gd; H3 TATAB=4,4',4''-s-triazine-1,3,5-triyltri-p-aminobenzoic acid) have been solvothermally synthesized and structurally characterized. Among these MOFs, TbTATAB exhibits good water stability and a high fluorescence quantum yield. Because mercury ions (Hg(2+) ) have a high affinity to nitrogen atoms, and the space between multiple nitrogen atoms from triazine and imino groups is suitable for interacting with Hg(2+) ions, TbTATAB shows highly selective and sensitive detection of Hg(2+) in aqueous solution with a detection limit of 4.4 nm. Furthermore, it was successfully applied to detect Hg(2+) ions in natural water samples. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Multi-signaling thiocarbohydrazide based colorimetric sensors for the selective recognition of heavy metal ions in an aqueous medium

    NASA Astrophysics Data System (ADS)

    Momidi, Bharath Kumar; Tekuri, Venkatadri; Trivedi, Darshak R.

    2017-06-01

    A series of colorimetric chemosensors R1-R6 have been developed from thiocarbohydrazide derivatives, for the selective detection of heavy metal ions. The structures of the receptors R1-R6 were well characterized by standard spectroscopic techniques like FT-IR, 1H NMR, and ESI-MS. The solid structure of receptor R1 and R2 were derived by single crystal X-ray diffraction (SC-XRD). The cation reorganization abilities of receptors R1-R6 were studied by UV-Vis spectroscopy. The receptors R1, R3 and R4 acts as a tremendous sensitive probe for heavy metal ions (Hg2 +, Cd2 + and Pb2 +) with the μM detection (R1 for Hg2 +, 2.72, R3 for Cd2 +, 3.22, R4 for Hg2 +, Cd2 + & Pb2 +, 0.70, 0.20 & 0.30 μM) and the receptors R2, R5 &R6 are sensitive towards Cu2 + ions with the μM detection (3.34, 0.90 & 1.20 μM) in an aqueous medium among all other tested cations. The receptor R4 shows a multi-color response towards Hg2 +, Cu2 +, Cd2 + and Pb2 + ions. The recognition mechanism, stoichiometric binding ratio and detection limit (DL) have been examined by UV-Visible spectroscopic titration experiments and Benesi-Hildebrand (B-H) plot, receptor R1-R6 sowed 1:1 binding ratio with good binding constant range of 103 to 105 M- 1 with Hg2 +, Cu2 +, Cd2 + and Pb2 + ions metal ions.

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

    PubMed

    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.

  13. Extended study of DETA-functionalized PGMA adsorbent in the selective adsorption behaviors and mechanisms for heavy metal ions of Cu, Co, Ni, Zn, and Cd.

    PubMed

    Liu, Changkun; Bai, Renbi

    2010-10-01

    In this paper, the adsorption selectivity and mechanism of diethylenetriamine (DETA)-functionalized PGMA adsorbent (denoted as P-DETA) toward a number of heavy metal ions, including Cu, Co, Ni, Zn, and Cd ions, were experimentally and analytically examined. Experimental results showed a selective adsorption sequence, based on the adsorption affinity, of Cu>Co>Ni>Zn>Cd ions on P-DETA. X-ray absorption fine structure (XAFS) analysis was used to reveal the adsorption coordination geometry, bond length, and coordination number of each type of metal ion with the DETA group. The analysis indicated that Cu, Ni, and Zn ions formed tetrahedral geometry (fourfold coordination) when adsorbed, while Co ion showed an octahedral geometry (sixfold coordination). However, the coordination geometry for Cd could not be obtained in the analysis due to the lack of reference information. The analysis from EXAFS further confirmed that the ratio of DETA ligand to the adsorbed metal ion was probably 1 for Cu, Ni, or Zn ions, while that ratio was 2 for Co ion. From the stability constant (in the log K form) for a metal ion-DETA ligand coordination (denoted as ML(n), where M indicates a heavy metal ion, and L(n) indicates n numbers of ligands involved), a relationship of log K (CuL)>log K (CoL(2))>log K (NiL)>log K (ZnL)>log K (CdL) is suggested. This sequence is in good correlation with the experimentally derived adsorption selective sequence of Cu>Co>Ni>Zn>Cd ions, indicating that the coordination geometry played an important role in the determination of the adsorption selectivity for heavy metal ions by the polyamine-functionalized adsorbent of P-DETA.

  14. Quantum chemical study of the photolysis mechanisms of sulfachloropyridazine and the influence of selected divalent metal ions.

    PubMed

    Shah, Shaheen; Zhang, Heming; Song, Xuedan; Hao, Ce

    2015-11-01

    Sulfonamides have been found in aquatic environments. Degradation of sulfachloropyridazine (SCP) mainly proceeds through direct and indirect photolysis in the aquatic environment. However, the mechanisms underlying the triplet photolysis of SCP and the influence of metal ions on the photolysis mechanism have not yet been fully explained. In this study, we elucidated the triplet photolysis mechanisms of SCP and the effects of three selected metal ions (Zn(2+), Ca(2+), and Cu(2+)) on the SCP photolysis mechanisms using quantum chemical calculation. Optimization of molecular structures and reaction pathways analysis of SCP were carried out at the B3LYP/6-31+G(d,p) level of theory. Two minimum energy pathways were investigated in the triplet photolysis of SCP. In Step 2 of Path-I, the photolysis product of SCP is a sulfur dioxide extrusion product, (4-(3-chloro-6-iminopyridazine-1(6H)-yl)aniline). The estimated activation energies of Step 2 and Step 3 of Path-I were much higher than in Path-II. Therefore, Path-II was found as the lowest energy pathway to obtain the SCP photoproducts, and Step 2 of Path-II was confirmed as the rate-determining step (RDS) in the photolysis mechanism of SCP. For the RDS of Path-II, computations with the three metal ions complexes (IM1-Cu(2+), IM1-Ca(2+), and IM1-Zn(2+)) show that the metal ions Cu(2+) and Ca(2+) promote triplet-sensitized photolysis of SCP by reducing the activation energy of RDS of Path-II, whereas Zn(2+) showed an inhibitory effect in photolysis of SCP by increasing the activation energy. Copyright © 2015. Published by Elsevier Ltd.

  15. A Water-Stable Metal-Organic Framework for Highly Sensitive and Selective Sensing of Fe(3+) Ion.

    PubMed

    Hou, Bing-Lei; Tian, Dan; Liu, Jiang; Dong, Long-Zhang; Li, Shun-Li; Li, Dong-Sheng; Lan, Ya-Qian

    2016-10-17

    A new metal-organic framework [Zn5(hfipbb)4(trz)2(H2O)2] (NNU-1) [H2hfipbb = 4,4'-(hexafluoroisopropylidene)bis(benzoic acid), Htrz = 1H-1,2,3-triazole] was assembled by hydrothermal synthesis. Single-crystal X-ray diffraction analysis reveals that NNU-1 displays a twofold interpenetrating three-dimensional (3D) framework with a {4(24)·6(4)}-bcu topology. Interestingly, the 3D framework contains a two-dimensional (2D) layered structure that consists of alternating left- and right-handed double helical chains. On the basis of the hydrophobic -CF3 groups from H2hfipbb ligand, NNU-1 possesses excellent stability in water. It is worth noting that NNU-1 not only shows a highly selective fluorescence quenching effect to Fe(3+) ion in aqueous solution but also resists the interference of other metals including Fe(2+) ion. Accordingly, NNU-1 probably functions as a potential promising fluorescence sensor for detecting Fe(3+) ion with high sensitivity and selectivity.

  16. Mapping of Heavy Metal Ion Sorption to Cell-Extracellular Polymeric Substance-Mineral Aggregates by Using Metal-Selective Fluorescent Probes and Confocal Laser Scanning Microscopy

    PubMed Central

    Li, Jianli; Kappler, Andreas; Obst, Martin

    2013-01-01

    Biofilms, organic matter, iron/aluminum oxides, and clay minerals bind toxic heavy metal ions and control their fate and bioavailability in the environment. The spatial relationship of metal ions to biomacromolecules such as extracellular polymeric substances (EPS) in biofilms with microbial cells and biogenic minerals is complex and occurs at the micro- and submicrometer scale. Here, we review the application of highly selective and sensitive metal fluorescent probes for confocal laser scanning microscopy (CLSM) that were originally developed for use in life sciences and propose their suitability as a powerful tool for mapping heavy metals in environmental biofilms and cell-EPS-mineral aggregates (CEMAs). The benefit of using metal fluorescent dyes in combination with CLSM imaging over other techniques such as electron microscopy is that environmental samples can be analyzed in their natural hydrated state, avoiding artifacts such as aggregation from drying that is necessary for analytical electron microscopy. In this minireview, we present data for a group of sensitive fluorescent probes highly specific for Fe3+, Cu2+, Zn2+, and Hg2+, illustrating the potential of their application in environmental science. We evaluate their application in combination with other fluorescent probes that label constituents of CEMAs such as DNA or polysaccharides and provide selection guidelines for potential combinations of fluorescent probes. Correlation analysis of spatially resolved heavy metal distributions with EPS and biogenic minerals in their natural, hydrated state will further our understanding of the behavior of metals in environmental systems since it allows for identifying bonding sites in complex, heterogeneous systems. PMID:23974141

  17. Ion-selective electrode in determining fluorine in binary fluorides of metals of groups II-V

    SciTech Connect

    Mishchenko, V.T.; Mukomel', V.L.; Polvektov, N.S.; Shilova, L.P.; Tselik, E.I.

    1986-01-01

    The authors have developed a method of determining fluorine by ion-selective electrode techniques in specimens containing mixtures of the fluorides of magnesium and the rare-earth elements (REE), as well as scandium and bismuth. The specimens after treatment at high temperatures are sparingly soluble at room temperature in water and also in aqueous solutions of acids and bases. The authors found that a mixture of KNaCO/sub 3/ and K/sub 2/S/sub 2/O/sub 8/ with a mass ratio of 2:1 was an effective flux for MgF/sub 2/-MeF/sub 3/ specimens, where Me is an REE ion. The combined method of analyzing binary mixtures of fluorides (Mg and REE, Sc and Bi) which provides satisfactory accuracy and reliability in determining the fluoride and two different metals whose compounds may have various ratios in the samples.

  18. Ion-Selective Electrodes.

    ERIC Educational Resources Information Center

    Arnold, Mark A.; Meyerhoff, Mark E.

    1984-01-01

    Literature on ion-selective electrodes (ISEs) is reviewed in seven sections: books, conferences, reviews; potentiometric membrane electrodes; glass and solid-state membrane electrodes; liquid and polymer membrane ISEs; coated wire electrodes, ion-selective field effect transistors, and microelectrodes; gas sensors and selective bioelectrode…

  19. Ion-Selective Electrodes.

    ERIC Educational Resources Information Center

    Arnold, Mark A.; Meyerhoff, Mark E.

    1984-01-01

    Literature on ion-selective electrodes (ISEs) is reviewed in seven sections: books, conferences, reviews; potentiometric membrane electrodes; glass and solid-state membrane electrodes; liquid and polymer membrane ISEs; coated wire electrodes, ion-selective field effect transistors, and microelectrodes; gas sensors and selective bioelectrode…

  20. Metal complex formation with 1,10-diaza-4,7,13,16-tetraoxacyclooctadecane-N,N'-diacetic acid: an approach to potential lanthanide ion selective reagents

    SciTech Connect

    Chang, C.A.; Rowland, M.E.

    1983-12-21

    The principles of designing lanthanide (Ln) ion selective macrocyclic reagents are discussed. Factors such as the size of the metal ion, the cavity size of the ligand, the stereochemical constraint imposed on the ligand, and the overall coordination number of the multidentate ligand are considered. On the basis of these principles, the macromonocyclic ligand 1,10-diaza-4,7,13,16-tetraoxacyclooctadecane-N,N'-diacetic acid (dacda) has been prepared and characterized. stability constants of dacda complexes of various metal ions are reported. Except for a few metal ions such as copper (II), lead (II), and cadmium (II), dacda shows unique selectivity toward lanthanide ions as a group. Also, for the first time in aqueous solution for a multidentate ligand, the stability constants for Ln-ligand complexes decrease with increasing atomic number for heavy lanthanides and remain roughly unchanged for the lighter lanthanides. These data are discussed, and the structures of the complexes are proposed. 3 figures, 1 table.

  1. A single serine residue determines selectivity to monovalent metal ions in metalloregulators of the MerR family.

    PubMed

    Ibáñez, María M; Checa, Susana K; Soncini, Fernando C

    2015-05-01

    MerR metalloregulators alleviate toxicity caused by an excess of metal ions, such as copper, zinc, mercury, lead, cadmium, silver, or gold, by triggering the expression of specific efflux or detoxification systems upon metal detection. The sensor protein binds the inducer metal ion by using two conserved cysteine residues at the C-terminal metal-binding loop (MBL). Divalent metal ion sensors, such as MerR and ZntR, require a third cysteine residue, located at the beginning of the dimerization (α5) helix, for metal coordination, while monovalent metal ion sensors, such as CueR and GolS, have a serine residue at this position. This serine residue was proposed to provide hydrophobic and steric restrictions to privilege the binding of monovalent metal ions. Here we show that the presence of alanine at this position does not modify the activation pattern of monovalent metal sensors. In contrast, GolS or CueR mutant sensors with a substitution of cysteine for the serine residue respond to monovalent metal ions or Hg(II) with high sensitivities. Furthermore, in a mutant deleted of the Zn(II) exporter ZntA, they also trigger the expression of their target genes in response to either Zn(II), Cd(II), Pb(II), or Co(II). Specificity in a stressor's recognition is essential for mounting an appropriate response. MerR metalloregulators trigger the expression of specific resistance systems upon detection of heavy metal ions. Two groups of these metalloregulators can be distinguished, recognizing either +1 or +2 metal ions, depending on the presence of a conserved serine in the former or a cysteine in the latter. Here we demonstrate that the serine residue in monovalent metal ion sensors excludes divalent metal ion detection, as its replacement by cysteine renders a pan-metal ion sensor. Our results indicate that the spectrum of signals detected by these sensors is determined not only by the metal-binding ligand availability but also by the metal-binding cavity flexibility

  2. A Single Serine Residue Determines Selectivity to Monovalent Metal Ions in Metalloregulators of the MerR Family

    PubMed Central

    Ibáñez, María M.

    2015-01-01

    ABSTRACT MerR metalloregulators alleviate toxicity caused by an excess of metal ions, such as copper, zinc, mercury, lead, cadmium, silver, or gold, by triggering the expression of specific efflux or detoxification systems upon metal detection. The sensor protein binds the inducer metal ion by using two conserved cysteine residues at the C-terminal metal-binding loop (MBL). Divalent metal ion sensors, such as MerR and ZntR, require a third cysteine residue, located at the beginning of the dimerization (α5) helix, for metal coordination, while monovalent metal ion sensors, such as CueR and GolS, have a serine residue at this position. This serine residue was proposed to provide hydrophobic and steric restrictions to privilege the binding of monovalent metal ions. Here we show that the presence of alanine at this position does not modify the activation pattern of monovalent metal sensors. In contrast, GolS or CueR mutant sensors with a substitution of cysteine for the serine residue respond to monovalent metal ions or Hg(II) with high sensitivities. Furthermore, in a mutant deleted of the Zn(II) exporter ZntA, they also trigger the expression of their target genes in response to either Zn(II), Cd(II), Pb(II), or Co(II). IMPORTANCE Specificity in a stressor's recognition is essential for mounting an appropriate response. MerR metalloregulators trigger the expression of specific resistance systems upon detection of heavy metal ions. Two groups of these metalloregulators can be distinguished, recognizing either +1 or +2 metal ions, depending on the presence of a conserved serine in the former or a cysteine in the latter. Here we demonstrate that the serine residue in monovalent metal ion sensors excludes divalent metal ion detection, as its replacement by cysteine renders a pan-metal ion sensor. Our results indicate that the spectrum of signals detected by these sensors is determined not only by the metal-binding ligand availability but also by the metal-binding cavity

  3. Selective alkaline stripping of metal ions after solvent extraction by base-stable 1,2,3-triazolium ionic liquids.

    PubMed

    Raiguel, Stijn; Depuydt, Daphne; Vander Hoogerstraete, Tom; Thomas, Joice; Dehaen, Wim; Binnemans, Koen

    2017-04-19

    Novel 1,2,3-triazolium ionic liquids with a high base stability were synthesized for use in solvent extraction of first-row transition elements and rare earths from chloride media. The synthesis of these ionic liquids makes use of a recently reported, metal-free multicomponent reaction that allows full substitution of the 1,2,3-triazolium skeleton. The physical and chemical properties of these ionic liquids are compared with those of a trisubstituted analog. Peralkylation of the 1,2,3-triazolium skeleton leads to ionic liquids with superior properties, such as low viscosity, low solubility in water and higher thermal and base stability. Iodide and thiocyanate ionic liquids with peralkylated cations were applied to the solvent extraction of metal ions, and their stability in alkaline media was exploited in the selective stripping of the metals from the loaded ionic liquid phase by alkaline solutions. EXAFS and Raman spectroscopy were performed to gain insight into the extraction mechanism. The applicability of these extraction systems was demonstrated in separations relevant for the recovery of metals from ores and end-of-life products: Fe(iii)/Cu(ii)/Zn(ii) (copper ores, brass scraps) and Fe(iii)/Nd(iii) (rare earth magnets).

  4. Polymer-supported sulfonated catechol and linear catechol amide ligands and their use in selective metal ion removal recovery from aqueous solutions

    DOEpatents

    Fish, Richard H.

    1998-01-01

    The present invention concerns the synthesis of several biomimetically important polymer-supported, sulfonated catechol (PS-CATS), sulfonated bis-catechol linear amide (PS-2-6-LICAMS) and sulfonated 3,3-linear tris-catechol amide (PS-3,3-LICAMS) ligands, which chemically bond to modified 6% crosslinked macroporous polystyrene-divinylbenzene beads (PS-DVB). These polymers are useful for the for selective removal and recovery of environmentally and economically important metal ions from aqueous solution, as a function of pH. The Fe.sup.3+ ion selectivity shown for PS-CATS, PS-2-6-LICAMS, and PS-3,3-LICAMS polymer beads in competition with a similar concentration of Cu.sup.2+, Zn.sup.2+, Mn.sup.2+, Ni.sup.2+, Mg.sup.2+, Al.sup.3+, and Cr.sup.3+ ions at pH 1-3. Further, the metal ion selectivity is changed at higher pH values in the absence of Fe.sup.3+ (for example, Hg.sup.2+ at pH 3). The rates of selective removal and recovery of the trivalent metal ions, e.g. Fe.sup.3+ Al.sup.3+ ion etc. with the PS-CATS, PS-2-6-LICAMS, and PS-3,3-LICAMS polymer beads used determined are useful as well as equilibrium selectivity coefficient (K.sub.m) values for all metal competition studies. The chelate effect for the predisposed octahedral PS-3,3-LICAMS polymer pendant ligand is the reason that this ligand has a more pronounced selectivity for Fe.sup.3+ ion in comparison to the PS-CATS polymer beads. The predisposed square planar PS-2,6-LICAMS series of polymer pendant ligands are more selective to divalent metal ions Cu.sup.2+, Zn.sup.2+, Mn.sup.2+, Ni.sup.2+, and Mg.sup.2+, than either PS-CATS or PS-3,3-LICAMS. However, Fe.sup.3+ ion still dominates in competition with other divalent and trivalent metal ions. In the absence of Fe.sup.3+, the polymer ligand is selective for Al.sup.3+, Cu.sup.2+ or Hg.sup.2+. The changing of the cavity size from two CH.sub.2 groups to six CH.sub.2 groups in the PS-2-6-LICAMS polymer pendant ligand series does not effect the order of metal ion

  5. Polymer-supported sulfonated catechol and linear catechol amide ligands and their use in selective metal ion removal recovery from aqueous solutions

    DOEpatents

    Fish, R.H.

    1998-11-10

    The present invention concerns the synthesis of several biomimetically important polymer-supported, sulfonated catechol (PS-CATS), sulfonated bis-catechol linear amide (PS-2-6-LICAMS) and sulfonated 3,3-linear tris-catechol amide (PS-3,3-LICAMS) ligands, which chemically bond to modified 6% crosslinked macroporous polystyrene-divinylbenzene beads (PS-DVB). These polymers are useful for the for selective removal and recovery of environmentally and economically important metal ions from aqueous solution, as a function of pH. The Fe{sup 3+} ion selectivity shown for PS-CATS, PS-2-6-LICAMS, and PS-3,3-LICAMS polymer beads in competition with a similar concentration of Cu{sup 2+}, Zn{sup 2+}, Mn{sup 2+}, Ni{sup 2+}, Mg{sup 2+}, Al{sup 3+}, and Cr{sup 3+} ions at pH 1--3. Further, the metal ion selectivity is changed at higher pH values in the absence of Fe{sup 3+} (for example, Hg{sup 2+} at pH 3). The rates of selective removal and recovery of the trivalent metal ions, e.g. Fe{sup 3+}, Al{sup 3+} ion etc. with the PS-CATS, PS-2-6-LICAMS, and PS-3,3-LICAMS polymer beads used determined are useful as well as equilibrium selectivity coefficient (K{sub m}) values for all metal competition studies. The chelate effect for the predisposed octahedral PS-3,3-LICAMS polymer pendant ligand is the reason that this ligand has a more pronounced selectivity for Fe{sup 3+} ion in comparison to the PS-CATS polymer beads. The predisposed square planar PS-2,6-LICAMS series of polymer pendant ligands are more selective to divalent metal ions Cu{sup 2+}, Zn{sup 2+}, Mn{sup 2+}, Ni{sup 2+}, and Mg{sup 2+}, than either PS-CATS or PS-3,3-LICAMS. However, Fe{sup 3+} ion still dominates in competition with other divalent and trivalent metal ions. In the absence of Fe{sup 3+}, the polymer ligand is selective for Al{sup 3+}, Cu{sup 2+} or Hg{sup 2+}. The changing of the cavity size from two CH{sub 2} groups to six CH{sub 2} groups in the PS-2-6-LICAMS polymer pendant ligand series does not effect

  6. Stripping voltammetry study of ultra-trace toxic metal ions on highly selectively adsorptive porous magnesium oxide nanoflowers.

    PubMed

    Wei, Yan; Yang, Ran; Yu, Xin-Yao; Wang, Lun; Liu, Jin-Huai; Huang, Xing-Jiu

    2012-05-07

    We have demonstrated highly selective and sensitive detection of Pb(II) and Cd(II) using a highly selective adsorptive porous magnesium oxide (MgO) nanoflowers. The MgO nanoflower-modified glassy carbon electrode was electrochemically characterized using cyclic voltammetry; and the anodic stripping voltammetric performance of bound Pb(II) and Cd(II) was evaluated using square wave anodic stripping voltammetry (SWASV) analysis. The MgO nanoflower-modified electrode exhibited excellent sensing performance toward Pb(II) and Cd(II) that was never observed previously at bismuth (Bi)-based electrodes. Simultaneous additions of Pb(II) and Cd(II) were investigated in the linear range from 3.3 to 22 nM for Pb(II) and 40 to 140 nM for Cd(II), and detection limits of 2.1 pM and 81 pM were obtained, respectively. Some foreign ions, such as Cu(II), Zn(II) and Cr(III) do not interfere with the detection of Pb(II) and Cd(II). To the best of our knowledge, this is the first example of a highly adsorptive metal oxide with hierarchical micro/nanostructure that allows the detection of both Pb(II) and Cd(II) ions.

  7. Corrosion studies of various heavy-metal fluoride glasses in liquid water: Application to fluoride-ion-selective electrode

    SciTech Connect

    Ravaine, D.; Perera, G.

    1986-12-01

    The leaching rates of various heavy-metal flouride (HMF) glasses have been investigated in pH-buffered solutions. Measurements of weight losses and fluoride-ion and heavy-metal concentrations in solution have been performed. The agreement between the different experimental methods suggests a congruent dissolution although different time dependencies are observed between the investigated glasses.

  8. Polymer-supported sulfonated catechol and linear catechol amide ligands and their use in selective metal ion removal and recovery from aqueous solutions

    DOEpatents

    Fish, R.H.

    1997-04-22

    The present invention concerns the synthesis of several biomimetically important polymer-supported, sulfonated catechol (PS-CATS), sulfonated bis-catechol linear amide (PS-2-6-LICAMS) and sulfonated 3,3-linear tris-catechol amide (PS-3,3-LICAMS) ligands, which chemically bond to modified 6% crosslinked macroporous polystyrene-divinylbenzene beads (PS-DVB). These polymers are useful for the for selective removal and recovery of environmentally and economically important metal ions from aqueous solution, as a function of pH. The Fe{sup 3+} ion selectivity shown for PS-CATS, PS-2-6-LICAMS, and PS-3,3-LICAMS polymer beads in competition with a similar concentration of Cu{sup 2+}, Zn{sup 2+}, Mn{sup 2+}, Ni{sup 2+}, Mg{sup 2+}, Al{sup 3+}, and Cr{sup 3+} ions at pH 1--3. Further, the metal ion selectivity is changed at higher pH values in the absence of Fe{sup 3+} (for example, Hg{sup 2+} at pH 3). The rates of selective removal and recovery of the trivalent metal ions, e.g. Fe{sup 3+}, Al{sup 3+} ion etc. with the PS-CATS, PS-2-6-LICAMS, and PS-3,3-LICAMS polymer beads use determined are useful as well as equilibrium selectivity coefficient (K{sub m}) values for all metal competition studies. The chelate effect for the predisposed octahedral PS-3,3-LICAMS polymer pendant ligand is the reason that this ligand has a more pronounced selectivity for Fe{sup 3+} ion in comparison to the PS-CATS polymer beads. The predisposed square planar PS-2-6-Mn{sup 2+}, Ni{sup 2+}, and Mg{sup 2+}, than either PS-CATS or PS-3,3-LICAMS. However, Fe{sup 3+} ion still dominates in competition with other divalent and trivalent metal ions. In the absence of Fe{sup 3+}, the polymer ligand is selective for Al{sup 3+}, Cu{sup 2+} or Hg{sup 2+}. The changing of the cavity size from two CH{sub 2} groups to six CH{sub 2} groups in the PS-2-6-LICAMS polymer pendant ligand series does not effect the order of metal ion selectivity. 9 figs.

  9. Polymer-supported sulfonated catechol and linear catechol amide ligands and their use in selective metal ion removal and recovery from aqueous solutions

    DOEpatents

    Fish, Richard H.

    1997-01-01

    The present invention concerns the synthesis of several biomimetically important polymer-supported, sulfonated catechol (PS-CATS), sulfonated bis-catechol linear amide (PS-2-6-LICAMS) and sulfonated 3,3-linear tris-catechol amide (PS-3,3-LICAMS) ligands, which chemically bond to modified 6% crosslinked macroporous polystyrene-divinylbenzene beads (PS-DVB). These polymers are useful for the for selective removal and recovery of environmentally and economically important metal ions from aqueous solution, as a function of pH. The Fe.sup.3+ ion selectivity shown for PS-CATS, PS-2-6-LICAMS, and PS-3,3-LICAMS polymer beads in competition with a similar concentration of Cu.sup.2+, Zn.sup.2+, Mn.sup.2+, Ni.sup.2+,Mg.sup.2+, Al.sup.3+, and Cr.sup.3+ ions at pH 1-3. Further, the metal ion selectivity is changed at higher pH values in the absence of Fe.sup.3+ (for example, Hg.sup.2+ at pH 3). The rates of selective removal and recovery of the trivalent metal ions, e.g. Fe.sup.3+ Al.sup.3+ ion etc. with the PS-CATS, PS-2-6-LICAMS, and PS-3,3-LICAMS polymer beads use determined are useful as well as equilibrium selectivity coefficient (K.sub.m) values for all metal competition studies. The chelate effect for the predisposed octahedral PS-3,3-LICAMS polymer pendant ligand is the reason that this ligand has a more pronounced selectivity for Fe.sup.3+ ion in comparison to the PS-CATS polymer beads. The predisposed square planar PS-2-6-Mn.sup.2+, Ni.sup.2+, and Mg.sup.2+, than either PS-CATS or PS-3,3-LICAMS. However, Fe.sup.3+ ion still dominates in competition with other divalent and trivalent metal ions. In the absence of Fe.sup.3+, the polymer ligand is selective for Al.sup.3+, Cu.sup.2+ or Hg.sup.2+. The changing of the cavity size from two CH.sub.2 groups to six CH.sub.2 groups in the PS-2-6-LICAMS polymer pendant ligand series does not effect the order of metal ion selectivity.

  10. Selective ion source

    DOEpatents

    Leung, Ka-Ngo

    1996-01-01

    A ion source is described wherein selected ions maybe extracted to the exclusion of unwanted ion species of higher ionization potential. Also described is a method of producing selected ions from a compound, such as P.sup.+ from PH.sub.3. The invention comprises a plasma chamber, an electron source, a means for introducing a gas to be ionized by electrons from the electron source, means for limiting electron energy from the electron source to a value between the ionization energy of the selected ion species and the greater ionization energy of an unwanted ion specie, and means for extracting the target ion specie from the plasma chamber. In one embodiment, the electrons are generated in a plasma cathode chamber immediately adjacent to the plasma chamber. A small extractor draws the electrons from the plasma cathode chamber into the relatively positive plasma chamber. The energy of the electrons extracted in this manner is easily controlled. The invention is particularly useful for doping silicon with P.sup.+, AS.sup.+, and B.sup.+ without the problematic presence of hydrogen, helium, water, or carbon oxide ions. Doped silicon is important for manufacture of semiconductors and semiconductor devices.

  11. Selective ion source

    DOEpatents

    Leung, K.N.

    1996-05-14

    A ion source is described wherein selected ions maybe extracted to the exclusion of unwanted ion species of higher ionization potential. Also described is a method of producing selected ions from a compound, such as P{sup +} from PH{sub 3}. The invention comprises a plasma chamber, an electron source, a means for introducing a gas to be ionized by electrons from the electron source, means for limiting electron energy from the electron source to a value between the ionization energy of the selected ion species and the greater ionization energy of an unwanted ion specie, and means for extracting the target ion specie from the plasma chamber. In one embodiment, the electrons are generated in a plasma cathode chamber immediately adjacent to the plasma chamber. A small extractor draws the electrons from the plasma cathode chamber into the relatively positive plasma chamber. The energy of the electrons extracted in this manner is easily controlled. The invention is particularly useful for doping silicon with P{sup +}, As{sup +}, and B{sup +} without the problematic presence of hydrogen, helium, water, or carbon oxide ions. Doped silicon is important for manufacture of semiconductors and semiconductor devices. 6 figs.

  12. Selective metal-ion extraction for multiple-ion liquid-liquid exchange reactions. Final report, June 1, 1979-May 31, 1982

    SciTech Connect

    Tavlarides, L.L.

    1982-01-29

    This research in hydrometallurgical solvent extraction is to develop a fundamental means to predict selectivity during simultaneous solvent extraction of multiple metal ions when the kinetic rates and thermodynamic equilibria both do not favor the desired metal. To this end the chemical kinetics and thermodynamic chemical equilibria models for the system copper-iron-acid sulfate solutions extracted by ..beta..-alkenyl-8-hydroxy quinoline in xylene are studied. These models can be employed with appropriate design equations to predict selectivity factors for two phase contactors. The work completed and in progress during the first half of the third funding period is on chemical equilibria studies for the iron-acid-sulfate-..beta..-alkenyl-8-hydroxy quinoline-xylene system. An aqueous phase ionic equilibrium model is available which can be used to calculate concentration of various Fe(III) ionic species present. Iron extraction data were obtained using both the AKUFVE, a high intensity stirrer with an in line centrifugal separator, and a shaker bath apparatus. Analysis of the data to determine a thermodynamic equilibrium model is in progress.

  13. Immobilization of carboxymethylated polyethylenimine-metal-ion complexes in porous membranes to selectively capture his-tagged protein.

    PubMed

    Ning, Wenjing; Wijeratne, Salinda; Dong, Jinlan; Bruening, Merlin L

    2015-02-04

    Membrane adsorbers rapidly capture tagged proteins because flow through membrane pores efficiently conveys proteins to binding sites. Effective adsorbers, however, require membrane pores coated with thin films that bind multilayers of proteins. This work employs adsorption of polyelectrolytes that chelate metal ions to create functionalized membranes that selectively capture polyhistidine-tagged (His-tagged) proteins with binding capacities equal to those of high-binding commercial beads. Adsorption of functional polyelectrolytes is simpler than previous membrane-modification strategies such as growth of polymer brushes or derivatization of adsorbed layers with chelating moieties. Sequential adsorption of protonated poly(allylamine) (PAH) and carboxymethylated branched polyethylenimine (CMPEI) leads to membranes that bind Ni(2+) and capture ∼60 mg of His-tagged ubiquitin per mL of membrane. Moreover, these membranes enable isolation of His-tagged protein from cell lysates in <15 min. The backbone amine groups in CMPEI likely increase swelling in water to double protein binding compared to films composed of PAH and the chelating polymer poly[(N,N-dicarboxymethyl)allylamine] (PDCMAA), which has a hydrocarbon backbone. Metal leaching from PAH/CMPEI- and PAH/PDCMAA-modified membranes is similar to that from GE Hitrap FF columns. Eluates with 0.5 M imidazole contain <10 ppm of Ni(2+).

  14. Factors controlling metal-ion selectivity in the binding sites of calcium-binding proteins. The metal-binding properties of amide donors. A crystallographic and thermodynamic study.

    PubMed

    Clapp, Laura A; Siddons, Chynthia J; Whitehead, Jason R; VanDerveer, Donald G; Rogers, Robin D; Griffin, Scott T; Jones, S Bart; Hancock, Robert D

    2005-11-14

    angles involving coordinated amides in these sites are large, commonly being in the 150-180 degrees range. This is discussed in terms of the idea that for purely ionic bonding the M-O=C bond angle will approach 180 degrees, while for covalent bonding the angle should be closer to 120 degrees. How this fact might be used by the proteins to control selectivity for different metal ions is discussed.

  15. Separation of metal ions from aqueous solutions

    DOEpatents

    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.

  16. Ion exchange of Pb(2+), Cu(2+), Fe(3+), and Cr(3+) on natural clinoptilolite: selectivity determination and influence of acidity on metal uptake.

    PubMed

    Inglezakis, Vassilis J; Loizidou, Maria D; Grigoropoulou, Helen P

    2003-05-01

    In the present study ion exchange of Pb(2+), Cu(2+), Fe(3+), and Cr(3+) on natural Greek clinoptilolite was examined in terms of selectivity toward the above heavy metals in single- and multicomponent solutions in batch systems. Also examined are the influence of clinoptilolite on solution acidity and the effect of acidity on the ion exchange process. Clinoptilolite increases solution acidity due to the exchange of H(+) cations with the cations initially present in its structure. H(+) cations should be considered as competitive ones in ion exchange processes, and consequently ion exchange of metals is favored at high acidity values. Cu(2+) and Cr(3+) are the most sensitive cations with respect to acidity. Selectivity determination demonstrates that the selectivity at total concentration 0.01 N and acidity 2 in both single- and multicomponent solutions is following the order Pb(2+)>Fe(3+)>Cr(3+) > or =Cu(2+). This order is set since the first days of equilibration. However, Cu(2+) shows remarkable changes in selectivity and generally its uptake and selectivity are increasing with time. On the other hand selectivity in single metal solutions where acidity is not adjusted is following the order Pb(2+)>Cr(3+)>Fe(3+) congruent with Cu(2+).

  17. A bis(3-hydroxy-4-pyridinone)-EDTA derivative as a strong chelator for M3+ hard metal ions: complexation ability and selectivity.

    PubMed

    Gama, Sofia; Dron, Paul; Chaves, Silvia; Farkas, Etelka; Santos, M Amélia

    2009-08-21

    The study of chelating compounds is very important to solve problems related to human metal overload. 3-Hydroxy-3-pyridinones (HP), namely deferiprone, have been clinically used for chelating therapy of Fe and Al over the last decade. A multi-disciplinary search for alternative molecules led us to develop poly-(3-hydroxy-4-pyridinones) to increase metal chelation efficacy. We present herein a complexation study of a new bis-(3-hydroxy-4-pyridinone)-EDTA derivative with a set of M(3+) hard metal ions (M = Fe, Al, Ga), as well as Zn(2+), a biologically relevant metal ion. Thus a systematic aqueous solution equilibrium study was performed using potentiometric and spectroscopic techniques (UV-Vis, NMR methods). These set of results enables the establishment of specific models as well as the determination of thermodynamic stability constants and coordination modes of the metal complexes. The results indicate that this ligand has a higher affinity for chelating to these hard metal ions than deferiprone, and that the coordination occurs mostly through the HP moieties. Furthermore, it was also found that this ligand has a higher selectivity for chelating to M(3+) hard metal ions (M = Fe, Al, Ga) than Zn(2+).

  18. Metal ion mediated molecularly imprinted polymer for selective capturing antibiotics containing beta-diketone structure.

    PubMed

    Qu, Shanshan; Wang, Xiaobo; Tong, Changlun; Wu, Jianmin

    2010-12-24

    A new molecularly imprinted polymer (MIP) targeting to quinolones (Qs) and tetracyclines (TCs) was synthesized using itaconic acid (ITA) and ciprofloxacin (CIP) as a functional monomer and template molecule, respectively. Factors affecting the overall performance of MIP were investigated, and the results showed that Fe(3+) ion play a vital role in the formation of MIP with high molecular imprinting effect. Meanwhile, the chelating ability of monomer, species of template molecule, as well as the molar ratio of monomer and template also contribute to the performance of the obtained MIP. Cyclic voltammetry verified that, with the participation of Fe(3+) ions, a ternary complex of ITA-Fe(3+)-CIP could be formed before polymerization. Compared with conventional MIP prepared from commonly used monomer, methacrylic acid (MAA), the new MIP show significantly enhanced molecular imprinting effect and higher capacity for specific adsorption of target compounds as revealed by static and dynamic binding experiments. The MIP was successfully used as solid-phase extraction (SPE) adsorbent for enriching a broad spectrum of antibiotics containing beta-diketone structure from surface water sample. HPLC detection showed that high recovery rate (78.6-113.6%) was found in these spiked antibiotics, whereas recovery rate for the non structurally related drugs, epinephrine (EP) and dopamine (DOPA), was very low (4.7-7.6%) on the MIP cartridges. The results demonstrate that the MIP prepared by the strategy proposed in this work, could specifically target to a series of structurally related antibiotics containing beta-diketone structure.

  19. A Liquid Chromatography Detector for Transition and Rare-Earth Metal Ions Based on a Cupric Ion-Selective Electrode

    DTIC Science & Technology

    1981-05-01

    selective electrode, satur- ated calanel reference electrode isolated by a "Thirsty Glass" (porous Vycor) plug, and stainless steel hypodermic needle ...by a stainless-steel hypodermic needle . The signal was then fed to an inverting low-pass filter with a time constant (RC) of approximately I sec. This...is used in both cases. The "common" electrode needed for the electrometer is a stainless steel hypodermic needle placed in the beaker. The type of

  20. Catalytic potential of selected metal ions for bioleaching, and potential techno-economic and environmental issues: A critical review.

    PubMed

    Pathak, Ashish; Morrison, Liam; Healy, Mark Gerard

    2017-04-01

    Bioleaching is considered to be a low-cost, eco-friendly technique for leaching valuable metals from a variety of matrixes. However, the inherent slow dissolution kinetics and low metal leaching yields have restricted its wider commercial applicability. Recent advancements in bio-hydrometallurgy have suggested that these critical issues can be successfully alleviated through the addition of a catalyst. The catalyzing properties of a variety of metals ions (Ag(+), Hg(++), Bi(+++), Cu(++), Co(++) etc.) during bioleaching have been successfully demonstrated. In this article, the role and mechanisms of these metal species in catalyzing bioleaching from different minerals (chalcopyrite, complex sulfides, etc.) and waste materials (spent batteries) are reviewed, techno-economic and environmental challenges associated with the use of metals ions as catalysts are identified, and future prospectives are discussed. Based on the analysis, it is suggested that metal ion-catalyzed bioleaching will play a key role in the development of future industrial bio-hydrometallurgical processes. Copyright © 2017 Elsevier Ltd. All rights reserved.

  1. Effect of selected metal ions on the photocatalytic degradation of bog lake water natural organic matter.

    PubMed

    Espinoza, Luis A Tercero; ter Haseborg, Eike; Weber, Matthias; Karle, Elly; Peschke, Rafael; Frimmel, Fritz H

    2011-01-01

    Herein we report the photocatalytic degradation of natural organic matter from a bog lake (Lake Hohloh, Black Forest, Germany) in the presence of 0, 5, and 10 μmol L(-1) of added Cu(2+), Mn(2+), Zn(2+) and Fe(3+). The reactions were followed by size exclusion chromatography with organic carbon detection (SEC-DOC) and by measurements of low molecular weight organic acids. Addition of Cu(2+) had the largest effect of all four studied metals, leading to a retardation in the molecular size changes in NOM: degradation of the larger molecular weight fraction was inhibited leading to reduced production of smaller molecular weight metabolites. Similarly, addition of Cu(2+) reduced the production of formic and oxalic acids, and reduced the bioavailability of the partially degraded NOM.

  2. Effective and selective recovery of gold and palladium ions from metal wastewater using a sulfothermophilic red alga, Galdieria sulphuraria.

    PubMed

    Ju, Xiaohui; Igarashi, Kensuke; Miyashita, Shin-Ichi; Mitsuhashi, Hiroaki; Inagaki, Kazumi; Fujii, Shin-Ichiro; Sawada, Hitomi; Kuwabara, Tomohiko; Minoda, Ayumi

    2016-07-01

    The demand for precious metals has increased in recent years. However, low concentrations of precious metals dissolved in wastewater are yet to be recovered because of high operation costs and technical problems. The unicellular red alga, Galdieria sulphuraria, efficiently absorbs precious metals through biosorption. In this study, over 90% of gold and palladium could be selectively recovered from aqua regia-based metal wastewater by using G. sulphuraria. These metals were eluted from the cells into ammonium solutions containing 0.2M ammonium salts without other contaminating metals. The use of G. sulphuraria is an eco-friendly and cost-effective way of recovering low concentrations of gold and palladium discarded in metal wastewater. Copyright © 2016 The Authors. Published by Elsevier Ltd.. All rights reserved.

  3. Ionizable calixarene-crown ethers with high selectivity for radium over light alkaline earth metal ions

    SciTech Connect

    Chen, X.; Ji, M.; Fisher, D.R.; Wai, C.M.

    1999-11-15

    {alpha} particle emitters are of increasing interest as the radionuclide attached to monoclonal antibodies of other targeting mechanisms for applications in cell-directed therapy of cancer. {alpha} particles are more effective than {beta}{sup {minus}} particles for cell-killing and promise a more effective treatment of cancer than other forms of radiation. This is because {alpha} particles have high initial energy (4--8 MeV), short path lengths (40--80 {micro}m, or several cell diameters), and consequently greater energy dissipation per unit length. Cell-directed immunotherapy can help improve irradiation of tumor cells while sparing normal tissues. The success of this approach will require effective chemistry for attaching the radionuclide to the antibody. Therefore, a concerted effort has been directed toward the design of chelating agents capable of holding the desired {alpha}-emitting radionuclide, both selectively and with high stability, to the antibody.

  4. Novel metal-ion-mediated, complex-imprinted solid-phase microextraction fiber for the selective recognition of thiabendazole in citrus and soil samples.

    PubMed

    Lian, Haixian; Hu, Yuling; Li, Gongke

    2014-01-01

    A novel metal-ion-mediated complex-imprinted-polymer-coated solid-phase microextraction (SPME) fiber used to specifically recognize thiabendazole (TBZ) in citrus and soil samples was developed. The complex-imprinted polymer was introduced as a novel SPME coating using a "complex template" constructed with Cu(II) ions and TBZ. The recognition and enrichment properties of the coating in water were significantly improved based on the metal ion coordination interaction rather than relying on hydrogen bonding interactions that are commonly applied for the molecularly imprinting technique. Several parameters controlling the extraction performance of the complex-imprinted-polymer-coated fiber were investigated including extraction solvent, pH value, extraction time, metal ion species, etc. Furthermore, SPME coupled with HPLC was developed for detection of TBZ, and the methods resulted in good linearity in the range of 10.0-150.0 ng/mL with a detection limit of 2.4 ng/mL. The proposed method was applied to the analysis of TBZ in spiked soil, orange, and lemon with recoveries of 80.0-86.9% and RSDs of 2.0-8.1%. This research provides an example to prepare a desirable water-compatible and specifically selective SPME coating to extract target molecules from aqueous samples by introducing metal ions as the mediator. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    NASA Astrophysics Data System (ADS)

    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.

  6. Selective and Sensitive Detection of Heavy Metal Ions in 100% Aqueous Solution and Cells with a Fluorescence Chemosensor Based on Peptide Using Aggregation-Induced Emission.

    PubMed

    Neupane, Lok Nath; Oh, Eun-Taex; Park, Heon Joo; Lee, Keun-Hyeung

    2016-03-15

    A fluorescent peptidyl chemosensor for the detection of heavy metal ions in aqueous solution as well as in cells was synthesized on the basis of the peptide receptor for the metal ions using an aggregation-induced emission fluorophore. The peptidyl chemosensor (1) bearing tetraphenylethylene fluorophore showed an exclusively selective turn-on response to Hg(2+) among 16 metal ions in aqueous buffered solution containing NaCl. The peptidyl chemosensor complexed Hg(2+) ions and then aggregated in aqueous buffered solution, resulting in the significant enhancement (OFF-On) of emissions at around 470 nm. The fluorescent sensor showed a highly sensitive response to Hg(2+), and about 1.0 equiv of Hg(2+) was enough for the saturation of the emission intensity change. The detection limit (5.3 nM, R(2) = 0.99) of 1 for Hg(2+) ions was lower than the maximum allowable level of Hg(2+) in drinking water by EPA. Moreover, the peptidyl chemosensor penetrated live cells and detected intracellular Hg(2+) ions by the turn-on response.

  7. Metal ions as enzyme effectors

    NASA Astrophysics Data System (ADS)

    Medyantseva, El'vina P.; Vertlib, Margarita G.; Budnikov, German K.

    1998-03-01

    The role of metal ions as enzyme effectors is considered. Data on inhibitory and activating effects of metal ions are summarised. The dual character of action of the effectors depending on their concentration and the nature of the enzyme is highlighted. The analytical applications of these effects are discussed. The bibliography includes 66 references.

  8. Enhanced metal ion selectivity of 2,9-di-(pyrid-2-yl)-1,10-phenanthroline and its use as a fluorescent sensor for cadmium(II).

    PubMed

    Cockrell, Gregory M; Zhang, Gang; VanDerveer, Donald G; Thummel, Randolph P; Hancock, Robert D

    2008-01-30

    The metal ion complexing properties of the ligand DPP (2,9-di-(pyrid-2-yl)-1,10-phenanthroline) were studied by crystallography, fluorimetry, and UV-visible spectroscopy. Because DPP forms five-membered chelate rings, it will favor complexation with metal ions of an ionic radius close to 1.0 A. Metal ion complexation and accompanying selectivity of DPP is enhanced by the rigidity of the aromatic backbone of the ligand. Cd2+, with an ionic radius of 0.96 A, exhibits a strong CHEF (chelation enhanced fluorescence) effect with 10(-8) M DPP, and Cd2+ concentrations down to 10(-9) M can be detected. Other metal ions that cause a significant CHEF effect with DPP are Ca2+ (10(-3) M) and Na+ (1.0 M), whereas metal ions such as Zn2+, Pb2+, and Hg2+ cause no CHEF effect with DPP. The lack of a CHEF effect for Zn2+ relates to the inability of this small ion to contact all four donor atoms of DPP. The structures of [Cd(DPP)2](ClO4)2 (1), [Pb(DPP)(ClO4)2H2O] (2), and [Hg(DPP)(ClO4)2] (3) are reported. The Cd(II) in 1 is 8-coordinate with the Cd-N bonds to the outer pyridyl groups stretched by steric clashes between the o-hydrogens on these outer pyridyl groups and the central aromatic ring of the second DPP ligand. The 8-coordinate Pb(II) in 2 has two short Pb-N bonds to the two central nitrogens of DPP, with longer bonds to the outer N-donors. The coordination sphere around the Pb(II) is completed by a coordinated water molecule, and two coordinated ClO4(-) ions, with long Pb-O bonds to ClO4(-) oxygens, typical of a sterically active lone pair on Pb(II). The Hg(II) in 3 shows an 8-coordinate structure with the Hg(II) forming short Hg-N bonds to the outer pyridyl groups of DPP, whereas the other Hg-N and Hg-O bonds are rather long. The structures are discussed in terms of the fit of large metal ions to DPP with minimal steric strain. The UV-visible studies of the equilibria involving DPP and metal ions gave formation constants that show that DPP has a higher affinity for metal

  9. High current metal ion implantation

    NASA Astrophysics Data System (ADS)

    Brown, Ian G.

    1990-04-01

    This report summarizes the research and development that has been carried out at Lawrence Berkeley Laboratory to develop a novel kind of high current metal ion source for metallurgical surface modification application. In ion implantation, an energetic ion beam is injected into a solid surface with the result that the surface composition is changed. For the case when the surface is a metal, the tribological properties of the new metallurgical surface can be significantly improved over the unimplanted surface. Previously, however, very intense metal ion beams have not been available, and this has been an impedance to the development of the field. With the MEVVA (Metal Vapor Vacuum Arc) ion source, metal ion beam currents of very high intensity have become available. This report outlines the progress made under the funded program in the four areas addressed: development of the MEVVA ion source for ion implantation application; research on the ion beam characteristics and behavior; development of the ion implantation facility; metallurgical ion implantation research that was performed.

  10. Systematic study of metal ion sorption on selected geologic media. Annual report, October 1978-December 1979. Part 1

    SciTech Connect

    Not Available

    1980-06-01

    Results of research in selection of multiple tracers for enhanced oil recovery systems and ion exchange characteristics of enhanced oi recovery systems concerned with alkaline earth ion-alkali ion equilibria on clay minerals are summarized. An extensive study was completed of the distribution of Na(I) and Ca(II) ions between a common clay, montmorillonite, as well as several other clays, and a series of solutions of constant total ionic strength with varying ionic strength fraction of sodium. Equilibrium quotients for the exchange of sodium and calcium were then calculated and the effects of solution composition, of solution phase activity coefficients, of ionic strength, of degree of purification, and of source of clay were investigated. Distribution coefficients for Sr(II) were determined for a variety of conditions on various clay minerals and oxides. In general for clay minerals, the values of DSR decrease sharply independent of pH. 22 references.

  11. Metal ion substrate inhibition of ferrochelatase.

    PubMed

    Hunter, Gregory A; Sampson, Matthew P; Ferreira, Gloria C

    2008-08-29

    Ferrochelatase catalyzes the insertion of ferrous iron into protoporphyrin IX to form heme. Robust kinetic analyses of the reaction mechanism are complicated by the instability of ferrous iron in aqueous solution, particularly at alkaline pH values. At pH 7.00 the half-life for spontaneous oxidation of ferrous ion is approximately 2 min in the absence of metal complexing additives, which is sufficient for direct comparisons of alternative metal ion substrates with iron. These analyses reveal that purified recombinant ferrochelatase from both murine and yeast sources inserts not only ferrous iron but also divalent cobalt, zinc, nickel, and copper into protoporphyrin IX to form the corresponding metalloporphyrins but with considerable mechanistic variability. Ferrous iron is the preferred metal ion substrate in terms of apparent k(cat) and is also the only metal ion substrate not subject to severe substrate inhibition. Substrate inhibition occurs in the order Cu(2+) > Zn(2+) > Co(2+) > Ni(2+) and can be alleviated by the addition of metal complexing agents such as beta-mercaptoethanol or imidazole to the reaction buffer. These data indicate the presence of two catalytically significant metal ion binding sites that may coordinately regulate a selective processivity for the various potential metal ion substrates.

  12. Functional Determinants of Metal Ion Transport and Selectivity in Paralogous Cation Diffusion Facilitator Transporters CzcD and MntE in Streptococcus pneumoniae.

    PubMed

    Martin, Julia E; Giedroc, David P

    2016-01-19

    Cation diffusion facilitators (CDFs) are a large family of divalent metal transporters that collectively possess broad metal specificity and contribute to intracellular metal homeostasis and virulence in bacterial pathogens. Streptococcus pneumoniae expresses two homologous CDF efflux transporters, MntE and CzcD. Cells lacking mntE or czcD are sensitive to manganese (Mn) or zinc (Zn) toxicity, respectively, and specifically accumulate Mn or Zn, respectively, thus suggesting that MntE selectively transports Mn, while CzcD transports Zn. Here, we probe the origin of this metal specificity using a phenotypic growth analysis of pneumococcal variants. Structural homology to Escherichia coli YiiP predicts that both MntE and CzcD are dimeric and each protomer harbors four pairs of conserved metal-binding sites, termed the A site, the B site, and the C1/C2 binuclear site. We find that single amino acid mutations within both the transmembrane domain A site and the B site in both CDFs result in a cellular metal sensitivity similar to that of the corresponding null mutants. However, multiple mutations in the predicted cytoplasmic C1/C2 cluster of MntE have no impact on cellular Mn resistance, in contrast to the analogous substitutions in CzcD, which do have on impact on cellular Zn resistance. Deletion of the MntE-specific C-terminal tail, present only in Mn-specific bacterial CDFs, resulted in only a modest growth phenotype. Further analysis of MntE-CzcD functional chimeric transporters showed that Asn and Asp in the ND-DD A-site motif of MntE and the most N-terminal His in the HD-HD site A of CzcD (the specified amino acids are underlined) play key roles in transporter metal selectivity. Cation diffusion facilitator (CDF) proteins are divalent metal ion transporters that are conserved in organisms ranging from bacteria to humans and that play important roles in cellular physiology, from metal homeostasis and resistance to type I diabetes in vertebrates. The respiratory

  13. Functional Determinants of Metal Ion Transport and Selectivity in Paralogous Cation Diffusion Facilitator Transporters CzcD and MntE in Streptococcus pneumoniae

    PubMed Central

    Martin, Julia E.

    2016-01-01

    ABSTRACT Cation diffusion facilitators (CDFs) are a large family of divalent metal transporters that collectively possess broad metal specificity and contribute to intracellular metal homeostasis and virulence in bacterial pathogens. Streptococcus pneumoniae expresses two homologous CDF efflux transporters, MntE and CzcD. Cells lacking mntE or czcD are sensitive to manganese (Mn) or zinc (Zn) toxicity, respectively, and specifically accumulate Mn or Zn, respectively, thus suggesting that MntE selectively transports Mn, while CzcD transports Zn. Here, we probe the origin of this metal specificity using a phenotypic growth analysis of pneumococcal variants. Structural homology to Escherichia coli YiiP predicts that both MntE and CzcD are dimeric and each protomer harbors four pairs of conserved metal-binding sites, termed the A site, the B site, and the C1/C2 binuclear site. We find that single amino acid mutations within both the transmembrane domain A site and the B site in both CDFs result in a cellular metal sensitivity similar to that of the corresponding null mutants. However, multiple mutations in the predicted cytoplasmic C1/C2 cluster of MntE have no impact on cellular Mn resistance, in contrast to the analogous substitutions in CzcD, which do have on impact on cellular Zn resistance. Deletion of the MntE-specific C-terminal tail, present only in Mn-specific bacterial CDFs, resulted in only a modest growth phenotype. Further analysis of MntE-CzcD functional chimeric transporters showed that Asn and Asp in the ND-DD A-site motif of MntE and the most N-terminal His in the HD-HD site A of CzcD (the specified amino acids are underlined) play key roles in transporter metal selectivity. IMPORTANCE Cation diffusion facilitator (CDF) proteins are divalent metal ion transporters that are conserved in organisms ranging from bacteria to humans and that play important roles in cellular physiology, from metal homeostasis and resistance to type I diabetes in vertebrates

  14. Metal ion separations by supported liquid membranes

    SciTech Connect

    Gyves, J. de; San Miguel, E.R. de

    1999-06-01

    Carrier-mediated transport through supported liquid membranes is currently recognized as a potentially valuable technology for selective separation and concentration of toxic and valuable metal ions. In this paper, a review of the fundamental aspects concerning metal ion transport and the influencing factors are surveyed in terms of data modeling, membrane efficiency (permeability, selectivity, stability), and data acquisition and evaluation. An account of the information reviewed demonstrates the need for critical reflection on system performances in order to accomplish scaling up operations. On the same basis, an attempt to outline some future trends in the field is presented.

  15. Affinity dialysis - a method of continuous, rapid metal ion separation using dialysis membranes and selective, water-soluble polymers as extractants

    SciTech Connect

    Davis, J.C.; Valus, R.J.; Lawrence, E.G.

    1988-08-01

    A membrane process utilizing dialysis and selective complexation by water-soluble polymers has been developed. This process, termed affinity dialysis, has been shown to be selectively extract and concentrate both cations and anions in a manner similar to ion exchange or solvent extraction. The selective removal of calcium from sodium with selectivity of about 30, removal of chromate ion from dilute streams, and separation of transition metal ions such as Cu/Fe and Cu/Zn have all been successfully demonstrated. Effects of different polymers, polymer concentration, temperature, and flow rates have been studied. The effect of increased polymer concentration is to increase product concentration if appropriate changes in feed, polymer solution, and strip flow rates are made. A continuous polymer solution recycle and regeneration system has been constructed and operated with Cu/Zn and chromate/chloride feed streams. Removal of over 95% of the desired ion in one pass and concentration factors of product over effluent in excess of 100 have been achieved at feed flow rates of 24 gal/d. Product concentrations of greater than 3% from as little as 400 ppm feed have been demonstrated in a continuous process. In addition, the degree of polymer loss to the effluent stream has been shown to be less than 0.01%/d for a typical system. Metal removal from typical feeds is about 0.9 g/m/sup 2/ per 1000 ppm metal in the feed. It is expected that this technique may be useful in the separation of organic and biological materials, as well as for ionic species.

  16. An economically viable method for the removal of selected divalent metal ions from aqueous solutions using activated rice husk.

    PubMed

    Akhtar, Mubeena; Iqbal, Shahid; Kausar, Abida; Bhanger, M I; Shaheen, Muhammad Ashraf

    2010-01-01

    Biosorption of divalent metal ions, i.e. Pb(II), Cd(II), Zn(II) and Cu(II) onto rice husk activated (RHA) is investigated over pH range (1-10) via batch adsorption technique. The chemical and thermal activation of rice husk with 0.1M HNO(3) and 1M K(2)CO(3) at 473 K enhanced the removal efficiency of RHA (35+/-2.1-99+/-0.5%, 33+/-1.2-97+/-0.6%, 32+/-1.3-96+/-0.8% and 28+/-1.8-95+/-0.9% before and after treatment, respectively). The surface area analysis of RHA by BET (Brunauer, Emmett and Teller) nitrogen adsorption method provided pore area and average pore diameter to be 542+/-2.3m(2)g(-1) and 1076+/-5.6 nm respectively. SEM and FTIR analyses of RHA were carried out to determine the surface morphology and functional groups involved in metal binding mechanism, respectively. The adsorption equilibrium was well described by Freundlich, Langmuir and Dubinin-Radushkevish (D-R) isotherm models by employing (4.8-48, 8.9-89, 15.3-153 and 15.7-157)x10(-5)M solution concentrations of sorbates, respectively, at equilibrium time of 20 min at pH 6 and onto 0.2g of sorbent. The kinetics of mass transfer and intra-particle diffusion for metal ions sorption onto RHA were studied with Lagergren and Morris-Weber kinetic models. The numerical values of thermodynamic parameters indicated the exothermic nature, spontaneity and feasibility of the sorption process. The desorption study of metal components from RHA surface was carried out with 0.1M HCl. The sorption mechanism developed illustrates the strong interactions of sorbates with the active sites of the sorbent coupled with efficient and environmentally clean exploitation of rice waste product.

  17. Computational Design of Metal Ion Sequestering Agents

    SciTech Connect

    Hay, Benjamin P.; Rapko, Brian M.

    2005-06-15

    Organic ligands that exhibit a high degree of metal ion recognition are essential precursors for developing separation processes and sensors for metal ions. Since the beginning of the nuclear era, much research has focused on discovering ligands that target specific radionuclides. Members of the Group 1A and 2A cations (e.g., Cs, Sr, Ra) and the f-block metals (actinides and lanthanides) are of primary concern to DOE. Although there has been some success in identifying ligand architectures that exhibit a degree of metal ion recognition, the ability to control binding affinity and selectivity remains a significant challenge. The traditional approach for discovering such ligands has involved lengthy programs of organic synthesis and testing that, in the absence of reliable methods for screening compounds before synthesis, have resulted in much wasted research effort.

  18. Computational Design of Metal Ion Sequestering Agents

    SciTech Connect

    Hay, Benjamin P.; Rapko, Brian M.

    2006-06-01

    Organic ligands that exhibit a high degree of metal ion recognition are essential precursors for developing separation processes and sensors for metal ions. Since the beginning of the nuclear era, much research has focused on discovering ligands that target specific radionuclides. Members of the Group 1A and 2A cations (e.g., Cs, Sr, Ra) and the f-block metals (actinides and lanthanides) are of primary concern to DOE. Although there has been some success in identifying ligand architectures that exhibit a degree of metal ion recognition, the ability to control binding affinity and selectivity remains a significant challenge. The traditional approach for discovering such ligands has involved lengthy programs of organic synthesis and testing that, in the absence of reliable methods for screening compounds before synthesis, have resulted in much wasted research effort.

  19. Computational Design of Metal Ion Sequestering Agents

    SciTech Connect

    Hay, Benjamin P.; Rapko, Brian M.

    2005-06-15

    Organic ligands that exhibit a high degree of metal ion recognition are essential precursors for developing separation processes and sensors for metal ions. Since the beginning of the nuclear era, much research has focused on discovering ligands that target specific radionuclides. Members of the Group 1A and 2A cations (e.g., Cs, Sr, Ra) and the f-block metals (actinides and lanthanides) are of primary concern to DOE. Although there has been some success in identifying ligand architectures that exhibit a degree of metal ion recognition, the ability to control binding affinity and selectivity remains a significant challenge. The traditional approach for discovering such ligands has involved lengthy programs of organic synthesis and testing that, in the absence of reliable methods for screening compounds before synthesis, have resulted in much wasted research effort. This project seeks to enhance and strengthen the traditional approach through computer-aided design of new and improved host molecules. Accurate electronic structure calculations are coupled with experimental data to provide fundamental information about ligand structure and the nature of metal-donor group interactions (design criteria). This fundamental information then is used in a molecular mechanics model (MM) that helps us rapidly screen proposed ligand architectures and select the best members from a set of potential candidates. By using combinatorial methods, molecule building software has been developed that generates large numbers of candidate architectures for a given set of donor groups. The specific goals of this project are: • further understand the structural and energetic aspects of individual donor group- metal ion interactions and incorporate this information within the MM framework • further develop and evaluate approaches for correlating ligand structure with reactivity toward metal ions, in other words, screening capability • use molecule structure building software to generate

  20. Computational Design of Metal Ion Sequestering Agents

    SciTech Connect

    Hay, Benjamin P.; Rapko, Brian M.

    2004-06-15

    Organic ligands that exhibit a high degree of metal ion recognition are essential precursors for developing separation processes and sensors for metal ions. Since the beginning of the nuclear era, much research has focused on discovering ligands that target specific radionuclides. Members of the Group 1A and 2A cations (e.g., Cs, Sr, Ra) and the f-block metals (actinides and lanthanides) are of primary concern to DOE. Although there has been some success in identifying ligand architectures that exhibit a degree of metal ion recognition, the ability to control binding affinity and selectivity remains a significant challenge. The traditional approach for discovering such ligands has involved lengthy programs of organic synthesis and testing that, in the absence of reliable methods for screening compounds before synthesis, have resulted in much wasted research effort. This project seeks to enhance and strengthen the traditional approach through computer-aided design of new and improved host molecules. Accurate electronic structure calculations are coupled with experimental data to provide fundamental information about ligand structure and the nature of metal-donor group interactions (design criteria). This fundamental information then is used in a molecular mechanics model (MM) that helps us rapidly screen proposed ligand architectures and select the best members from a set of potential candidates. By using combinatorial methods, molecule building software has been developed that generates large numbers of candidate architectures for a given set of donor groups. The specific goals of this project are: further understand the structural and energetic aspects of individual donor group- metal ion interactions and incorporate this information within the MM framework; further develop and evaluate approaches for correlating ligand structure with reactivity toward metal ions, in other words, screening capability; use molecule structure building software to generate large

  1. Computational Design of Metal Ion Sequestering Agents

    SciTech Connect

    Hay, Benjamin P.; Dixon, David A.; Rapko, Brian M.

    2003-06-01

    Organic ligands that exhibit a high degree of metal ion recognition are essential precursors for developing separation processes and sensors for metal ions. Since the beginning of the nuclear era, much research has focused on discovering ligands that target specific radionuclides. Members of the Group 1A and 2A cations (e.g., Cs, Sr, Ra) and the f-block metals (actinides and lanthanides) are of primary concern to DOE. Although there has been some success in identifying ligand architectures that exhibit a degree of metal ion recognition, the ability to control binding affinity and selectivity remains a significant challenge. The traditional approach for discovering such ligands has involved lengthy programs of organic synthesis and testing that, in the absence of reliable methods for screening compounds before synthesis, have resulted in much wasted research effort. This project seeks to enhance and strengthen the traditional approach through computer-aided design of new and improved host molecules. Accurate electronic structure calculations are coupled with experimental data to provide fundamental information about ligand structure and the nature of metal-donor group interactions (design criteria). This fundamental information then is used in a molecular mechanics model (MM3) that helps us rapidly screen proposed ligand architectures and select the best members from a set of potential candidates. By using combinatorial methods, molecule building software has been developed that generates large numbers of candidate architectures for a given set of donor groups. The specific goals of this project are: (1) further understand the structural and energetic aspects of individual donor group-metal ion interactions and incorporate this information within the MM3 framework; (2) further develop and evaluate approaches for correlating ligand structure with reactivity toward metal ions, in other words, screening capability; (3) use molecule structure building software to

  2. Computational Design of Metal Ion Sequestering Agents

    SciTech Connect

    Hay, Benjamin P.; Dixon, David A.; Rapko, Brian M.

    2002-06-01

    Organic ligands that exhibit a high degree of metal ion recognition are essential precursors for developing separation processes and sensors for metal ions. Since the beginning of the nuclear era, much research has focused on discovering ligands that target specific radionuclides. Members of the Group 1A and 2A cations (e.g., Cs, Sr, Ra) and the f-block metals (actinides and lanthanides) are of primary concern to the U.S. Department of Energy (DOE). Although there has been some success in identifying ligand architectures that exhibit a degree of metal ion recognition, the ability to control binding affinity and selectivity remains a significant challenge. The traditional approach for discovering such ligands has involved lengthy programs of organic synthesis and testing that, in the absence of reliable methods for screening compounds before synthesis, have resulted in much wasted research effort. This project seeks to enhance and strengthen the traditional approach through computer-aided design of new and improved host molecules. Accurate electronic structure calculations are coupled with experimental data to provide fundamental information about ligand structure and the nature of metal-donor group interactions (design criteria). This fundamental information then is used in a molecular mechanics model (MM3) that helps us rapidly screen proposed ligand architectures and select the best members from a set of potential candidates. By using combinatorial methods, molecule building software has been developed that generates large numbers of candidate architectures for a given set of donor groups. The specific objectives of this project are as follows: (1) Further understand the structural and energetic aspects of individual donor group- metal ion interactions and incorporate this information within the framework of MM3. (2) Further develop and evaluate approaches for correlating ligand structure with reactivity toward metal ions, in other words, screening capability. (3

  3. Selective metal ion extraction for multiple ion liquid-liquid exchange reactions. Progress report, DE-AS02-79ER 10406. A001

    SciTech Connect

    Tavlarides, L.L.

    1980-01-01

    The first phase of selecting a model binary system to study was completed. The system selected is Cu(II), Fe(III) acid sulfate solutions extracted by ..beta..-alkenyl 8-hydroxy quinoline (Kelex 100) in xylene. Maximum copper extraction occurs in less than 5 minutes at 30 to 50/sup 0/C. Thermodynamic chemical equilibrium studies with the Fe(III) ion indicate that the ionic charge of the extracted ion is +3 over a limited pH and concentration range. A simplified equilibrium model did not fit the experimental data. A chemical equilibrium model for the aqueous phase was developed. Kinetic studies on the liquid jet recycle reactor are underway. The model proposed to analyze simultaneous extraction of Cu(II) and Fe(III) in a stirred tank extractor was reduced to a set of two nonlinear algebraic equations for idealized kinetic expressions.

  4. Selective Host-Guest Interaction between Metal Ions and Metal-Organic Frameworks Using Dynamic Nuclear Polarization Enhanced Solid-State NMR Spectroscopy

    SciTech Connect

    Guo, Zhiyong; Kobayashi, Takeshi; Wang, Lin-Lin; Goh, Tian Wei; Xiao, Chaoxian; Caporini, Marc A.; Rosay, Melanie; Johnson, Duane D.; Pruski, Marek; Huang, Wenyu

    2014-10-08

    The host–guest interaction between metal ions (Pt²⁺ and Cu²⁺) and a zirconium metal–organic framework (UiO-66-NH₂) was explored using dynamic nuclear polarization-enhanced ¹⁵N{¹H} CPMAS NMR spectroscopy supported by X-ray absorption spectroscopy and density functional calculations. The combined experimental results conclude that each Pt²⁺ coordinates with two NH₂ groups from the MOF and two Cl⁻ from the metal precursor, whereas Cu²⁺ do not form chemical bonds with the NH₂ groups of the MOF framework. Density functional calculations reveal that Pt²⁺ prefers a square-planar structure with the four ligands and resides in the octahedral cage of the MOF in either cis or trans configurations.

  5. Selective Host-Guest Interaction between Metal Ions and Metal-Organic Frameworks using Dynamic Nuclear Polarization Enhanced Solid-State NMR Spectroscopy

    SciTech Connect

    Guo, Zhiyong; Kobayashi, Takeshi; Wang, Lin-Lin; Goh, Tian Wei; Xiao, Chaoxian; Caporini, Marc A; Rosay, Melanie; Johnson, Duane D; Pruski, Marek; Huang, Wenyu

    2014-10-08

    The host–guest interaction between metal ions (Pt2+ and Cu2+) and a zirconium metal–organic framework (UiO-66-NH2) was explored using dynamic nuclear polarization-enhanced 15N{1H} CPMAS NMR spectroscopy supported by X-ray absorption spectroscopy and density functional calculations. The combined experimental results conclude that each Pt2+ coordinates with two NH2 groups from the MOF and two Cl- from the metal precursor, whereas Cu2+ do not form chemical bonds with the NH2 groups of the MOF framework. Density functional calculations reveal that Pt2+ prefers a square-planar structure with the four ligands and resides in the octahedral cage of the MOF in either cis or trans configurations.

  6. Ion plating seals microcracks or porous metal components

    NASA Technical Reports Server (NTRS)

    Spalvins, T.; Buckley, D. H.; Brainard, W. A.

    1972-01-01

    Description of ion plating process is given. Advantage of this process is that any plating metal or alloy can be selected, whereas, for conventional welding, material selection is limited by compatability.

  7. [Metal-tag labeling coupled with high performance liquid chromatography-selected ion monitoring mass spectrometry for absolute quantitation of proteins].

    PubMed

    Li, Jiabin; Zhou, Lianqi; Yan, Hui; Li, Nannan; Hao, Feiran; Tian, Fang; Zhang, Yangjun

    2014-04-01

    A novel method has been established based on metal element chelated tags coupled with high performance liquid chromatography-selected ion monitoring mass spectrometry (HPLC-SIM/MS). The labeling efficiency and stability of metal element chelated tags, the chromatographic retention behavior and MS behavior of the labeled peptides, the linear range and accuracy of this method were examined. The results showed that the metal element chelated tag method has high labeling efficiency and high labeling stability, and the labeled peptides with different kinds of metal tags have consistent chromatographic retention behavior. The method of metal tags coupled with HPLC-SIM/MS has high sensitivity with the limit of quantification (LOQ) up to 1 fmol. The linear range for the method was between 1 fmol to 500 fmol with R2 > 0.99, which means the method has a good linearity. Moreover, this method had an average recovery of 117.01%. The method was used in the absolute quantitation of a protein enolase in Thermoanaerobacter tengcongensis (TTE) with a relative standard deviation of 5.74%, which means high precision. All the results showed that this method is accurate and reliable for the absolute quantitation of proteins. This gives us an alternative for the quantitative determination of proteins in relatively simple biological samples.

  8. Highly selective transport of a uranyl ion through a liquid membrane containing a lipophilic ion-associate of methyltrioctylammonium and hydroxycalix[n]arene-p-sulfonates (n = 6, 8) as metal carriers.

    PubMed

    Kondo, Hirotomo; Nishida, Masashi; Yoshida, Isao

    2002-02-01

    Uranyl ion, UO2(2+), in an aqueous sodium hydrogen carbonate solution of pH 4-8 (source phase) was simultaneously and selectively transported into a dilute sulfuric acid solution (receiving phase) through a membrane (chloroform, bulk) containing a lipophilic ion-associate of methyltrioctylammonium ion and hydroxycalix[n]arene-p-sulfonate ion, 2n (n = 6, 8), MTA+-2n, as a metal carrier. The rate of transport increased in proportion to the concentrations of UO2(2+) in the source phase and carrier in the membrane and along with an increase in the temperature of the system. The rate was also increased along with an increase in the pH of the source phase. None of the other metal ions were transported, or obstructed the transport of UO2(2+), while the presence of large amounts of sodium hydrogencarbonate and sodium chloride in the source phase interfered with the transport by causing a delay in the start of transport.

  9. Selectivity of the highly preorganized tetradentate ligand 2,9-di(pyrid-2-yl)-1,10-phenanthroline for metal ions in aqueous solution, including lanthanide(III) ions and the uranyl(VI) cation.

    PubMed

    Carolan, Ashley N; Cockrell, Gregory M; Williams, Neil J; Zhang, Gang; VanDerveer, Donald G; Lee, Hee-Seung; Thummel, Randolph P; Hancock, Robert D

    2013-01-07

    close in M-N bond lengths to Pm(III), so that an important aspect of the selectivity of polypyridyl type ligands for Am(III) will depend on the above metal ion size-based selectivity. The selectivity patterns of DPP with the alkali-earth metal ions shows a similar preference for Ca(II), which has the most appropriate M-N lengths. The structures of DPP complexes of Zn(II) and Bi(III), as representative of a small and of a large metal ion respectively, are reported. [Zn(DPP)(2)](ClO(4))(2) (triclinic, P1, R = 0.0507) has a six-coordinate Zn(II), with each of the two DPP ligands having one noncoordinated pyridyl group appearing to be π-stacked on the central aromatic ring of the other DPP ligand. [Bi(DPP)(H(2)O)(2)(ClO(4))(2)](ClO(4)) (triclinic, P1, R = 0.0709) has an eight-coordinate Bi, with the coordination sphere composed of the four N donors of the DPP ligand, two coordinated water molecules, and the O donors of two unidentate perchlorates. As is usually the case with Bi(III), there is a gap in the coordination sphere that appears to be the position of a lone pair of electrons on the other side of the Bi from the DPP ligand. The Bi-L bonds become relatively longer as one moves from the side of the Bi containg the DPP to the side where the lone pair is thought to be situated. A DFT analysis of [Ln(tpy)(H(2)O)(n)](3+) and [Ln(DPP)(H(2)O)(5)](3+) complexes is reported. The structures predicted by DFT are shown to match very well with the literature crystal structures for the [Ln(tpy)(H(2)O)(n)](3+) with Ln = La and n = 6, and Ln = Lu with n = 5. This then gives one confidence that the structures for the DPP complexes generated by DFT are accurate. The structures generated by DFT for the [Ln(DPP)(H(2)O)(5)](3+) complexes are shown to agree very well with those generated by MM, giving one confidence in the accuracy of the latter. An analysis of the DFT and MM structures shows the decreasing O--O nonbonded distances as one progresses from La to Lu, with these distances

  10. Metal ion-containing epoxies

    NASA Technical Reports Server (NTRS)

    Stoakley, D. M.; St.clair, A. K.

    1982-01-01

    A variety of metallic and organometallic complexes to be used as potential additives for an epoxy used by the aerospace industry as a composite matrix resin were investigated. A total of 9 complexes were screened for compatibility and for their ability to accelerate or inhibit the cure of a highly crosslinkable epoxy resin. Methods for combining the metallic complexes with the resin were investigated, gel times recorded, and cure exotherms studied by differential scanning calorimetry. Glass transition temperatures of cured metal ion containing epoxy castings were determined by thermomechanical analysis. Thermal stabilities of the castings were determined by thermogravimetric analysis. Mechanical strength and stiffness of these doped epoxies were also measured.

  11. Fluorescent Aromatic Tag-Functionalized MOFs for Highly Selective Sensing of Metal Ions and Small Organic Molecules.

    PubMed

    Zhao, Si-Si; Yang, Jin; Liu, Ying-Ying; Ma, Jian-Fang

    2016-03-07

    By varying the fluorescent tags of resorcin[4]arene-based tetracarboxylic acids from phenyl to naphthyl, two highly luminescent metal-organic frameworks (MOFs), namely, [Zn2(TPC4A)(DMF)(H2O)4]·3H2O (1) and [(CH3)2NH2]2[Zn(TNC4A)]·4H2O (2), were successfully achieved (TPC4A = 2,8,14,20-tetra-phenyl-6,12,18,24-tetra-methoxy-4,10,16,22-tetra-carboxy-methoxy-resorcin[4]arene and TNC4A = 2,8,14,20-tetra-1-naphthal-6,12,18,24-tetra- methoxy-4,10,16,22-tetra-carboxy-methoxy-resorcin[4]arene). Compound 1 features a unique 2D network, while 2 exhibits a fascinating 3D framework. The highly selective detection of small organic molecules as well as Fe(2+) and Fe(3+) was performed for 1 and 2 as fluorescent sensors. Remarkably, luminescent 1 and 2 were used as sensory materials for the sensing of various amine vapors with high selectivity and rapid response. Most strikingly, clear fluorescence "on-off" switch-functions toward small organic molecules as well as amine vapors were also explored for luminescent 1 and 2.

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

    PubMed

    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.

  13. DNA as Sensors and Imaging Agents for Metal Ions

    PubMed Central

    Xiang, Yu

    2014-01-01

    Increasing interests in detecting metal ions in many chemical and biomedical fields have 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 attaching 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 detections. These sensors are highly sensitive (with 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 discs, 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. PMID:24359450

  14. Bioaccumulation of the Selected Metal Ions in Saccharomyces cerevisiae Cells Under Treatment of the Culture with Pulsed Electric Field (PEF).

    PubMed

    Pankiewicz, Urszula; Sujka, Monika; Jamroz, Jerzy

    2015-12-01

    The obtained results demonstrated an influence of PEF on increase in accumulation of various ions in S. cerevisiae cells. Optimization of particular PEF parameters and ions concentrations in the medium caused twofold increase in accumulation of magnesium and zinc ions and 3.5-fold higher accumulation of calcium ions in the cells. In the case of ion couple, accumulation of magnesium and zinc was, respectively, 1.5-fold and twofold higher in comparison to the control cultures. Yeast cells biomass enriched with Mg(2+), Zn(2+), Ca(2+) as well as Mg(2+) and Zn(2+) (simultaneously) may be an alternative for pharmacological supplementation applied in deficiency of these cations.

  15. An Innovative Metal Ions Sensitive “Test Paper” Based on Virgin Nanoporous Silicon Wafer: Highly Selective to Copper(II)

    NASA Astrophysics Data System (ADS)

    Li, Shaoyuan; Chen, Xiuhua; Ma, Wenhui; Ding, Zhao; Zhang, Cong; Chen, Zhengjie; He, Xiao; Shang, Yudong; Zou, Yuxin

    2016-11-01

    Developing an innovative “Test Paper” based on virgin nanoporous silicon (NPSi) which shows intense visible emission and excellent fluorescence stability. The visual fluorescence quenching “Test Paper” was highly selective and sensitive recognizing Cu2+ at μmol/L level. Within the concentration range of 5 × 10-7 ~50 × 10-7mol/L, the linear regression equation of IPL = 1226.3-13.6[CCu2+] (R = 0.99) was established for Cu2+ quantitative detection. And finally, Cu2+ fluorescence quenching mechanism of NPSi prober was proposed by studying the surface chemistry change of NPSi and metal ions immersed-NPSi using XPS characterization. The results indicate that SiHx species obviously contribute to the PL emission of NPSi, and the introduce of oxidization state and the nonradiative recombination center are responsible for the PL quenching. These results demonstrate how virgin NPSi wafer can serve as Cu2+ sensor. This work is of great significant to promote the development of simple instruments that could realize rapid, visible and real-time detection of various toxic metal ions.

  16. An Innovative Metal Ions Sensitive “Test Paper” Based on Virgin Nanoporous Silicon Wafer: Highly Selective to Copper(II)

    PubMed Central

    Li, Shaoyuan; Chen, Xiuhua; Ma, Wenhui; Ding, Zhao; Zhang, Cong; Chen, Zhengjie; He, Xiao; Shang, Yudong; Zou, Yuxin

    2016-01-01

    Developing an innovative “Test Paper” based on virgin nanoporous silicon (NPSi) which shows intense visible emission and excellent fluorescence stability. The visual fluorescence quenching “Test Paper” was highly selective and sensitive recognizing Cu2+ at μmol/L level. Within the concentration range of 5 × 10−7 ~50 × 10−7mol/L, the linear regression equation of IPL = 1226.3-13.6[CCu2+] (R = 0.99) was established for Cu2+ quantitative detection. And finally, Cu2+ fluorescence quenching mechanism of NPSi prober was proposed by studying the surface chemistry change of NPSi and metal ions immersed-NPSi using XPS characterization. The results indicate that SiHx species obviously contribute to the PL emission of NPSi, and the introduce of oxidization state and the nonradiative recombination center are responsible for the PL quenching. These results demonstrate how virgin NPSi wafer can serve as Cu2+ sensor. This work is of great significant to promote the development of simple instruments that could realize rapid, visible and real-time detection of various toxic metal ions. PMID:27821859

  17. Mechanistic Enzyme Models: Pyridoxal and Metal Ions.

    ERIC Educational Resources Information Center

    Hamilton, S. E.; And Others

    1984-01-01

    Background information, procedures, and results are presented for experiments on the pyridoxal/metal ion model system. These experiments illustrate catalysis through Schiff's base formation between aldehydes/ketones and primary amines, catalysis by metal ions, and the predictable manner in which metal ions inhibit or catalyze reactions. (JN)

  18. Mechanistic Enzyme Models: Pyridoxal and Metal Ions.

    ERIC Educational Resources Information Center

    Hamilton, S. E.; And Others

    1984-01-01

    Background information, procedures, and results are presented for experiments on the pyridoxal/metal ion model system. These experiments illustrate catalysis through Schiff's base formation between aldehydes/ketones and primary amines, catalysis by metal ions, and the predictable manner in which metal ions inhibit or catalyze reactions. (JN)

  19. Reversible photodeposition and dissolution of metal ions

    DOEpatents

    Foster, Nancy S.; Koval, Carl A.; Noble, Richard D.

    1994-01-01

    A cyclic photocatalytic process for treating waste water containing metal and organic contaminants. In one embodiment of the method, metal ions are photoreduced onto the photocatalyst and the metal concentrated by resolubilization in a smaller volume. In another embodiment of the method, contaminant organics are first oxidized, then metal ions removed by photoreductive deposition. The present invention allows the photocatalyst to be recycled until nearly complete removal of metal ions and organic contaminants is achieved.

  20. Selective Single-Step Separation of a Mixture of Three Metal Ions by a Triphasic Ionic-Liquid-Water-Ionic-Liquid Solvent Extraction System.

    PubMed

    Vander Hoogerstraete, Tom; Blockx, Jonas; De Coster, Hendrik; Binnemans, Koen

    2015-08-10

    In a conventional solvent extraction system, metal ions are distributed between two immiscible phases, typically an aqueous and an organic phase. In this paper, the proof-of-principle is given for the distribution of metal ions between three immiscible phases, two ionic liquid phases with an aqueous phase in between them. Three-liquid-phase solvent extraction allows separation of a mixture of three metal ions in a single step, whereas at least two steps are required to separate three metals in the case of two-liquid-phase solvent extraction. In the triphasic system, the lower organic phase is comprised of the ionic liquid betainium- or choline bis(trifluoromethylsulfonyl)imide, whereas the upper organic phase is comprised of the ionic liquid trihexyl(tetradecyl)phosphonium bis(trifluoromethylsulfonyl)imide. The triphasic system was used for the separation of a mixture of tin(II), yttrium(III), and scandium(III) ions.

  1. Metallic ions in the equatorial ionosphere

    NASA Technical Reports Server (NTRS)

    Aikin, A. C.; Goldberg, R. A.

    1972-01-01

    Four positive ion composition measurements of the equatorial E region made at Thumba, India, are presented. During the day, the major ions between 90 and 125 km are NO(+) and O2(+). A metallic ion layer centered at 92 km is observed, and found to contain Mg(+), Fe(+), Ca(+), K(+), Al(+), and Na(+) ions. The layer is explained in terms of a similarly shaped latitude distribution of neutral atoms which are photoionized and charge-exchanged with NO(+) and O2(+). Three body reactions form molecular metallic ions which are rapidly lost by dissociative ion-electron recombination. Nighttime observations show downward drifting of the metallic ion layer caused by equatorial dynamo effects. These ions react and form neutral metals which exchange charges with NO(+) and O2(+) to produce an observed depletion of those ions within the metallic ion region.

  2. Process for modifying the metal ion sorption capacity of a medium

    DOEpatents

    Lundquist, Susan H.

    2002-01-01

    A process for modifying a medium is disclosed that includes treating a medium having a metal ion sorption capacity with a solution that includes: A) an agent capable of forming a complex with metal ions; and B) ions selected from the group consisting of sodium ions, potassium ions, magnesium ions, and combinations thereof, to create a medium having an increased capacity to sorb metal ions relative to the untreated medium.

  3. Polymer pendant ligand chemistry. 3. A biomimetic approach to selective metal ion removal and recovery from aqueous solution with polymer-supported sulfonated catechol and linear catechol amide ligands

    SciTech Connect

    Huang, Song-Ping; Li, Wei; Franz, K.J.; Albright, R.L.; Fish, R.H.

    1995-05-24

    The design of organic ligands to selectively remove and recover metal ions from aqueous solution is a new and important area of environmental inorganic chemistry. One approach to designing organic ligands for these purposes is to use biological systems as examples for selective metal ion complexation. Thus, the authors report results on the synthesis of several biomimetically important polymer-supported, sulfonated catechol (PS-CATS), sulfonated bis(catechol) linear amide (PS-2-6-LICAMS), and sulfonated 3.3-linear tris(catechol) amide (PS-3,3-LICAMS) ligands that are chemically bonded to modified 6% cross-linked macroporous polystyrene-divinylbenzene beads (PS-DVB) for selective removal and recovery of environmentally and economically important metal ions from aqueous solution, as a function of pH. The Fe{sup 3+} ion selectivity was dramatically shown for PS-CATS, PS-2-6-LICAMS and PS-3,3-LICAMS polymer beads in competition with a similar concentration of Cu{sup 2+}, Zn{sup 2+}, Mn{sup 2+}, Ni{sup 2+}, Mg{sup 2+}, Al{sup 3+}, and Cr{sup 3+} ions at pH 1-3, while metal ion selectivity could be changed at higher pH values in the absence of Fe{sup 3+} (for example, Hg{sup 2+} at pH 3). Rates of removal and recovery of the Fe{sup 3+} ion with the PS-CATS, PS-2-6LICAMS and PS-3,3-LICAMS polymer beads were also studied as well as relative equilibrium selectivity coefficient (K{sub m}) values for all metal competition studies.

  4. Tetrahydroindazolone substituted 2-aminobenzamides as fluorescent probes: switching metal ion selectivity from zinc to cadmium by interchanging the amino and carbamoyl groups on the fluorophore.

    PubMed

    Jia, Jia; Xu, Qin-Chao; Li, Ri-chen; Tang, Xi; He, Ying-Fang; Zhang, Meng-Yu; Zhang, Yuan; Xing, Guo-Wen

    2012-08-21

    Three fluorescent probes CdABA', CdABA and ZnABA', which are structural isomers of ZnABA, have been designed with N,N-bis(2-pyridylmethyl) ethylenediamine (BPEA) as chelator and 2-aminobenzamide as fluorophore. These probes can be divided into two groups: CdABA, CdABA' for Cd(2+) and ZnABA, ZnABA' for Zn(2+). Although there is little difference in their chemical structures, the two groups of probes exhibit totally different fluorescence properties for preference of Zn(2+) or Cd(2+). In the group of Zn(2+) probes, ZnABA/ZnABA' distinguish Zn(2+) from Cd(2+) with F(Zn)(2+)-F(Cd)(2+) = 1.87-2.00. Upon interchanging the BPEA and carbamoyl groups on the aromatic ring of the fluorophore, the structures of ZnABA/ZnABA' are converted into CdABA/CdABA'. Interestingly, the metal ions selectivity of CdABA/CdABA' was switched to discriminate Cd(2+) from Zn(2+) with F(Cd)(2+)-F(Zn)(2+) = 2.27-2.36, indicating that a small structural modification could lead to a remarkable change of the metal ion selectivity. (1)H NMR titration and ESI mass experiments demonstrated that these fluorescent probers exhibited different coordination modes for Zn(2+) and Cd(2+). With CdABA' as an example, generally, upon addition of Cd(2+), the fluorescence response possesses PET pathway to display no obvious shift of maximum λ(em) in the absence or presence of Cd(2+). However, an ICT pathway could be employed after adding Zn(2+) into the CdABA' solution, resulting in a distinct red-shift of maximal λ(em).

  5. The binding of metal ions to molecularly-imprinted polymers.

    PubMed

    Perera, Rukshan; Ashraf, Syed; Mueller, Anja

    2017-04-01

    Imprinting polymerization is a flexible method to make resins specific for different compounds. Imprinting polymerization involves the polymerization of the resin in the presence of a template, here cadmium ions or arsenate. The template is then removed by washing, leaving specific binding sites in the resin. In water treatment, the removal of toxic metal ions is difficult due to the limited affinity of these ions to ion exchange resins. Imprinting polymerization of ion-exchange resins is used to develop resins with high capacity and some selectivity for cadmium ions or arsenate for water treatment that still function as general ion-exchange resins. A minimum binding capacity of 325 meq/g was achieved for cadmium ions. Competition experiments elucidate the type of bonds present in the imprinting complex. The capacity and bond types for the cadmium ions and arsenate were contrasted. In the case of cadmium, metal-ligand bonds provide significant specificity of binding, although significant binding also occurs to non-specific surface sites. Arsenate ions are larger than cadmium ions and can only bind via ionic and hydrogen bonds, which are weaker than metal-ligand bonds. This results in lower specificity for arsenate. Additionally, diffusion into the resin is a limiting factor due to the larger size of the arsenate ion. These data elucidate the bonds formed between metal ions and the imprinting sites as well as other parameters that increase the capacity for heavy metals and arsenate.

  6. Metal interactions with voltage- and receptor-activated ion channels.

    PubMed Central

    Vijverberg, H P; Oortgiesen, M; Leinders, T; van Kleef, R G

    1994-01-01

    Effects of Pb and several other metal ions on various distinct types of voltage-, receptor- and Ca-activated ion channels have been investigated in cultured N1E-115 mouse neuroblastoma cells. Experiments were performed using the whole-cell voltage clamp and single-channel patch clamp techniques. External superfusion of nanomolar to submillimolar concentrations of Pb causes multiple effects on ion channels. Barium current through voltage-activated Ca channels is blocked by micromolar concentrations of Pb, whereas voltage-activated Na current appears insensitive. Neuronal type nicotinic acetylcholine receptor-activated ion current is blocked by nanomolar concentrations of Pb and this block is reversed at micromolar concentrations. Serotonin 5-HT3 receptor-activated ion current is much less sensitive to Pb. In addition, external superfusion with micromolar concentrations of Pb as well as of Cd and aluminum induces inward current, associated with the direct activation of nonselective cation channels by these metal ions. In excised inside-out membrane patches of neuroblastoma cells, micromolar concentrations of Ca activate small (SK) and big (BK) Ca-activated K channels. Internally applied Pb activates SK and BK channels more potently than Ca, whereas Cd is approximately equipotent to Pb with respect to SK channel activation, but fails to activate BK channels. The results show that metal ions cause distinct, selective effects on the various types of ion channels and that metal ion interaction sites of ion channels may be highly selective for particular metal ions. PMID:7531139

  7. The promise of a specially-designed graft copolymer of acrylic acid onto cellulose as selective sorbent for heavy metal ions.

    PubMed

    Essawy, Hisham A; Mohamed, Magdy F; Ammar, Nabila S; Ibrahim, Hanan S

    2017-10-01

    A specially-designed graft copolymer of acrylic acid onto in-situ formed cellulose-fulvate hybrid showed privileged tendency for uptake of Pb(II) during competitive removal from a mixture containing Cd(II) and Ni(II) within 5min at pH 5. This novel trend is attributed mainly to the crowded high content of coordinating centers within the designed graft copolymer along with the acquired superabsorbency. This provides an outstanding tool to separate some metal ions selectively from mixtures containing multiple ions on kinetic basis. Thus, the designed graft copolymer structure exhibited superior efficiency that reached ∼95% for sole removal of Pb(II). Kinetic modeling for Pb(II) individual removal showed excellent fitting with a pseudo second-order model. Intraparticle diffusion model on the other hand ensured governance of boundary layer effect over diffusion during the removal process due to the superabsorbency feature of the graft copolymer. The experimental findings were described with models such as Freundlich, Langmuir, and Dubinin-Radushkevich. The Langmuir and Freundlich models showed convenience with the adsorption isotherm of Pb(II) onto the developed graft copolymer. Copyright © 2017 Elsevier B.V. All rights reserved.

  8. Metal Ion Sensors Based on DNAzymes and Related DNA Molecules

    PubMed Central

    Kong, Rong-Mei

    2011-01-01

    Metal ion sensors are an important yet challenging field in analytical chemistry. Despite much effort, only a limited number of metal ion sensors are available for practical use because sensor design is often a trial-and-error-dependent process. DNAzyme-based sensors, in contrast, can be developed through a systematic selection that is generalizable for a wide range of metal ions. Here, we summarize recent progress in the design of DNAzyme-based fluorescent, colorimetric, and electrochemical sensors for metal ions, such as Pb2+, Cu2+, Hg2+, and UO22+ In addition, we also describe metal ion sensors based on related DNA molecules, including T-T or C-C mismatches and G-quadruplexes. PMID:21370984

  9. Removal and recovery of toxic metal ions from aqueous waste sites using polymer pendant ligands

    SciTech Connect

    Fish, D.

    1996-10-01

    The purpose of this project is to investigate the use of polymer pendant ligand technology to remove and recover toxic metal ions from DOE aqueous waste sites. Polymer pendant lgiands are organic ligands, anchored to crosslinked, modified divinylbenzene-polystyrene beads, that can selectively complex metal ions. The metal ion removal step usually occurs through a complexation or ion exchange phenomena, thus recovery of the metal ions and reuse of the beads is readily accomplished.

  10. Selective reduction of heavy metals

    SciTech Connect

    Bjorling, G.

    1984-12-11

    The present invention relates to selective reduction of heavy metals out of finey grained, substantially oxidic material by blowing the oxidic material into a furnace together with an amount of reducing agent required for obtaining desired selectivity while simultaneously heat energy is supplied by a gas heated in a plasma generator, the temperature being adjusted to such a level as to correspond to the oxygen potential at which the desired metals are transformed into a particular, isolatable phase as metal melt, metal vapor, speiss or matte and at which the remaining metals enter into a slag phase and can be isolated as slag melt.

  11. Stormwater filtration of toxic heavy metal ions using lignocellulosic materials selection process, fiberization, chemical modification, and mat formation

    Treesearch

    James S. Han

    1999-01-01

    Lignocellulosic materials were evaluated for their effectiveness in filtering toxic heavy metals from stormwater. Kenaf, alfalfa, juniper, and aspen fibers were used as models to evaluate the effectiveness and limitations of chemical modification and the extent of fiber degradation. Individual and mixed aqueous solutions of nickel, copper, zinc, and cadmium in various...

  12. Ion selectivity of graphene nanopores.

    PubMed

    Rollings, Ryan C; Kuan, Aaron T; Golovchenko, Jene A

    2016-04-22

    As population growth continues to outpace development of water infrastructure in many countries, desalination (the removal of salts from seawater) at high energy efficiency will likely become a vital source of fresh water. Due to its atomic thinness combined with its mechanical strength, porous graphene may be particularly well-suited for electrodialysis desalination, in which ions are removed under an electric field via ion-selective pores. Here, we show that single graphene nanopores preferentially permit the passage of K(+) cations over Cl(-) anions with selectivity ratios of over 100 and conduct monovalent cations up to 5 times more rapidly than divalent cations. Surprisingly, the observed K(+)/Cl(-) selectivity persists in pores even as large as about 20 nm in diameter, suggesting that high throughput, highly selective graphene electrodialysis membranes can be fabricated without the need for subnanometer control over pore size.

  13. Ion selectivity of graphene nanopores

    NASA Astrophysics Data System (ADS)

    Rollings, Ryan C.; Kuan, Aaron T.; Golovchenko, Jene A.

    2016-04-01

    As population growth continues to outpace development of water infrastructure in many countries, desalination (the removal of salts from seawater) at high energy efficiency will likely become a vital source of fresh water. Due to its atomic thinness combined with its mechanical strength, porous graphene may be particularly well-suited for electrodialysis desalination, in which ions are removed under an electric field via ion-selective pores. Here, we show that single graphene nanopores preferentially permit the passage of K+ cations over Cl- anions with selectivity ratios of over 100 and conduct monovalent cations up to 5 times more rapidly than divalent cations. Surprisingly, the observed K+/Cl- selectivity persists in pores even as large as about 20 nm in diameter, suggesting that high throughput, highly selective graphene electrodialysis membranes can be fabricated without the need for subnanometer control over pore size.

  14. Ion selectivity of graphene nanopores

    PubMed Central

    Rollings, Ryan C.; Kuan, Aaron T.; Golovchenko, Jene A.

    2016-01-01

    As population growth continues to outpace development of water infrastructure in many countries, desalination (the removal of salts from seawater) at high energy efficiency will likely become a vital source of fresh water. Due to its atomic thinness combined with its mechanical strength, porous graphene may be particularly well-suited for electrodialysis desalination, in which ions are removed under an electric field via ion-selective pores. Here, we show that single graphene nanopores preferentially permit the passage of K+ cations over Cl− anions with selectivity ratios of over 100 and conduct monovalent cations up to 5 times more rapidly than divalent cations. Surprisingly, the observed K+/Cl− selectivity persists in pores even as large as about 20 nm in diameter, suggesting that high throughput, highly selective graphene electrodialysis membranes can be fabricated without the need for subnanometer control over pore size. PMID:27102837

  15. Ion selectivity of graphene nanopores

    SciTech Connect

    Rollings, Ryan C.; Kuan, Aaron T.; Golovchenko, Jene A.

    2016-04-22

    As population growth continues to outpace development of water infrastructure in many countries, desalination (the removal of salts from seawater) at high energy efficiency will likely become a vital source of fresh water. Due to its atomic thinness combined with its mechanical strength, porous graphene may be particularly well-suited for electrodialysis desalination, in which ions are removed under an electric field via ion-selective pores. Here, we show that single graphene nanopores preferentially permit the passage of K+ cations over Cl- anions with selectivity ratios of over 100 and conduct monovalent cations up to 5 times more rapidly than divalent cations. Furthermore, the observed K+/Cl- selectivity persists in pores even as large as about 20 nm in diameter, suggesting that high throughput, highly selective graphene electrodialysis membranes can be fabricated without the need for subnanometer control over pore size.

  16. Ion selectivity of graphene nanopores

    DOE PAGES

    Rollings, Ryan C.; Kuan, Aaron T.; Golovchenko, Jene A.

    2016-04-22

    As population growth continues to outpace development of water infrastructure in many countries, desalination (the removal of salts from seawater) at high energy efficiency will likely become a vital source of fresh water. Due to its atomic thinness combined with its mechanical strength, porous graphene may be particularly well-suited for electrodialysis desalination, in which ions are removed under an electric field via ion-selective pores. Here, we show that single graphene nanopores preferentially permit the passage of K+ cations over Cl- anions with selectivity ratios of over 100 and conduct monovalent cations up to 5 times more rapidly than divalent cations.more » Furthermore, the observed K+/Cl- selectivity persists in pores even as large as about 20 nm in diameter, suggesting that high throughput, highly selective graphene electrodialysis membranes can be fabricated without the need for subnanometer control over pore size.« less

  17. Hematein chelates of unusual metal ions for tinctorial histochemistry.

    PubMed

    Smith, A A

    2010-02-01

    Hematoxylin is oxidized easily to hematein, an excellent stain for metal ions. If it already is bound to a substrate, the metal ion becomes a mordant linking the dye to the substrate. Metal ions added to hematein in solution are chelated by the hematein to form a lake. Most of these chelates stain animal tissues. They usually are bound to the tissue by a combination of hydrogen bonding of the hematein and ionic bonding of the metal ion. When binding of the lake to the tissue occurs by way of the metal ion, the metal ion is a mordant. Mordant staining often is specific. Chromium hematoxylin binds to strong acids; it can be made selective for protein-bound sulfonic acids. Zirconyl hematoxylin is selective for acidic mucins. Mucihematein can be made selective for all acidic mucins or for sulfomucins alone. Bismuth hematoxylin appears to be selective for the guanido group of arginine and there is some evidence that the bonding is covalent. Although it is not a histochemical stain, copper-chrome hematoxylin is an excellent stain for organelles with double membranes, i.e., mitochondria and nuclei.

  18. Liquid metal ion source and alloy

    DOEpatents

    Clark, Jr., William M.; Utlaut, Mark W.; Behrens, Robert G.; Szklarz, Eugene G.; Storms, Edmund K.; Santandrea, Robert P.; Swanson, Lynwood W.

    1988-10-04

    A liquid metal ion source and alloy, wherein the species to be emitted from the ion source is contained in a congruently vaporizing alloy. In one embodiment, the liquid metal ion source acts as a source of arsenic, and in a source alloy the arsenic is combined with palladium, preferably in a liquid alloy having a range of compositions from about 24 to about 33 atomic percent arsenic. Such an alloy may be readily prepared by a combustion synthesis technique. Liquid metal ion sources thus prepared produce arsenic ions for implantation, have long lifetimes, and are highly stable in operation.

  19. Use of ion chromatography for the determination of selected metals in blood serum of patients with type 2 diabetes.

    PubMed

    Błazewicz, Anna; Orlicz-Szczesna, Grazyna; Prystupa, Andrzej; Szczesny, Piotr

    2010-01-01

    Ion chromatography followed by microwave-induced acid digestion was used to evaluate the serum levels of Fe(3+), Cu(2+), Ni(2+), Zn(2+), and Mn(2+) in patients with diagnosed type 2 diabetes and in healthy controls. Recoveries ranged from 98.0% to 102% for Fe(3+), from 89.9% to 100% for Cu(2+), from 87.9% to 102% for Zn(2+), and from 89.6% to 102% for Mn(2+) were determined by examining samples spiked with various amounts of all the studied ions. The time of mineralization longer than 28 min did not affect the assay values. Precision was assessed at four unique concentrations in replicates of six, on four separate occasions. RSD was determined to be 1.16% for Fe(3+), 5.20% for Cu(2+), 2.8% for Zn(2+), and 3.75% for Mn(2+). The accuracy results (values of RSD) were as follows: 5.16% for Fe(3+), 6.35% for Cu(2+), 4.9% for Zn(2+), and 7.23% for Mn(2+). The statistical analysis confirmed that mean concentrations of Fe(3+) and Zn(2+) did not differ significantly from analogous values in the control group. Patients who additionally suffered from hypertension had higher copper concentrations compared with diabetic patients. For diabetics the presence of Mn(2+) was not stated (LOD values amounting to 0.006 microg/mL). Ni(2+) was not detectable for either the studied group or the control group (LOD=0.006 microg/mL).

  20. Separation of platinum group metal ions by Donnan dialysis

    SciTech Connect

    Brajter, K.; Slonawska, K.; Cox, J.A.

    1985-10-01

    Separations of metal ions on the basis of Donnan dialysis across anion-exchange membranes should be possible if the receiver electrolyte composition favors the formation of selected anionic complexes of the sample metal ions. Moreover, such a separation has the possibility of being better suited from some applications than batch or column experiments with anion-exchange resins. The above hypothesis are tested on the platinum-group metal ions, Pt(IV), Rh(III), Pd(II), Ir(III), and Ir(IV). 13 references, 4 tables.

  1. Water quality in Indiana: trends in concentrations of selected nutrients, metals, and ions in streams, 2000-10

    USGS Publications Warehouse

    Risch, Martin R.; Bunch, Aubrey R.; Vecchia, Skip V.; Martin, Jeffrey D.; Baker, Nancy T.

    2014-01-01

    Statistically significant trends were identified that included 167 downward trends and 83 upward trends. The Kankakee River Basin had the most significant upward trends while the most significant downward trends were in the Whitewater River Basin, the Lake Michigan Basin, and the Patoka River Basin. For most constituents, a majority of sites had significant downward trends. Two streams in the Lake Michigan Basin have shown substantial decreases in most constituents. The West Fork White River near Indianapolis, Indiana, showed increases in nitrate and phosphorus and the Kankakee River Basin showed increases in copper, zinc, chloride, sulfate, and hardness. Upward trends in nutrients were identified at a few sites, but most nutrient trends were downward. Upward trends in metals corresponded with relatively small concentration increases while downward trends involved considerably larger concentration changes. Downward trends in chloride, sulfate, and suspended solids were observed statewide, but upward trends in hardness were observed in the northern half of Indiana.

  2. Low specificity of metal ion binding in the metal ion core of a folded RNA.

    PubMed

    Travers, Kevin J; Boyd, Nathan; Herschlag, Daniel

    2007-08-01

    The structure and activity of nucleic acids depend on their interactions with metal ions. Fundamental to these interactions is the degree of specificity observed between the metal ions and nucleic acids, and a complete description of nucleic acid folding requires that we understand the nature of the interactions with metal ions, including specificity. The prior demonstration that high concentrations of monovalent cations prevent nonspecific association of divalent ions with nucleic acids provides a novel and powerful means to examine site-specific metal ion binding isolated from complicating effects of the ion atmosphere. Using these high monovalent cation solution conditions we have monitored the affinity of a series of divalent metal ions for two site-specific metal ion binding sites in the P4-P6 domain of the Tetrahymena group I intron ribozyme. The metal ion core of this highly structured RNA binds two divalent metal ions under these conditions. Despite multiple metal ion-RNA interactions observed in the X-ray crystallographic structure of P4-P6 RNA at the metal ion binding sites, these sites exhibit low specificity among Mn(2+), Mg(2+), Ca(2+), Ni(2+), and Zn(2+). Nevertheless, the largest divalent metal ions tested, Sr(2+) and Ba(2+), were excluded from binding, exhibiting affinities at least two orders of magnitude weaker than observed for the other metal ions. Thus, a picture emerges of two metal ion binding sites, each with a high tolerance for metal ions with different properties but also with limits to accommodation. These limits presumably arise from steric or electrostatic features of the metal ion binding sites.

  3. Hydrated metal ions in the gas phase.

    PubMed

    Beyer, Martin K

    2007-01-01

    Studying metal ion solvation, especially hydration, in the gas phase has developed into a field that is dominated by a tight interaction between experiment and theory. Since the studied species carry charge, mass spectrometry is an indispensable tool in all experiments. Whereas gas-phase coordination chemistry and reactions of bare metal ions are reasonably well understood, systems containing a larger number of solvent molecules are still difficult to understand. This review focuses on the rich chemistry of hydrated metal ions in the gas phase, covering coordination chemistry, charge separation in multiply charged systems, as well as intracluster and ion-molecule reactions. Key ideas of metal ion solvation in the gas phase are illustrated with rare-gas solvated metal ions.

  4. Adhesive bonding of ion beam textured metals and fluoropolymers

    NASA Technical Reports Server (NTRS)

    Mirtich, M. J.; Sovey, J. S.

    1978-01-01

    An electron bombardment argon ion source was used to ion etch various metals and fluoropolymers. The metal and fluoropolymers were exposed to (0.5 to 1.0) keV Ar ions at ion current densities of (0.2 to 1.5) mA/sq cm for various exposure times. The resulting surface texture is in the form of needles or spires whose vertical dimensions may range from tenths to hundreds of micrometers, depending on the selection of beam energy, ion current density, and etch time. The bonding of textured surfaces is accomplished by ion beam texturing mating pieces of either metals or fluoropolymers and applying a bonding agent which wets in and around the microscopic cone-like structures. After bonding, both tensile and shear strength measurements were made on the samples. Also tested, for comparison's sake, were untextured and chemically etched fluoropolymers. The results of these measurements are presented.

  5. Highly Selective Bifunctional Luminescent Sensor toward Nitrobenzene and Cu(2+) Ion Based on Microporous Metal-Organic Frameworks: Synthesis, Structures, and Properties.

    PubMed

    Yang, Lirong; Lian, Chen; Li, Xuefei; Han, Yuyang; Yang, Lele; Cai, Ting; Shao, Caiyun

    2017-05-24

    Two metal-organic frameworks (MOFs), namely, [Ni(DTP)(H2O)]n (I) and [Cd2(DTP)2(bibp)1.5]n (II) (H2DPT = 4'-(4-(3,5-dicarboxylphenoxy) phenyl)-4,2':6',4″-terpyridine; bibp = 1,3-di(1H-imidazol-1-yl)propane), that present structural diversity were solvothermally prepared. Single-crystal X-ray diffraction analysis indicates that they consist of {NiN2O4} building units (for I) and {CdO4N2} and {CdO3N3} building units (for II), which are further linked by multicarboxylate H2DPT to construct microporous three-dimensional frameworks. The remarkable character of these frameworks is that coordination polymer II demonstrates highly selective and sensitive bifunctional luminescent sensor toward nitrobenzene and Cu(2+) ion. The fluorescence quenching mechanism of II caused by nitrobenzene is ascribed to electron transfer from electron-rich (II) to electron-deficient nitrobenzene. The result was also evidenced by the density functional theory. Furthermore, anti-ferromagnetic as well as electrochemical characters of Ni-MOF (I) were also investigated in this paper.

  6. Treatment of model solutions and wastewater containing selected hazardous metal ions using a chitin/lignin hybrid material as an effective sorbent.

    PubMed

    Bartczak, Przemysław; Klapiszewski, Łukasz; Wysokowski, Marcin; Majchrzak, Izabela; Czernicka, Weronika; Piasecki, Adam; Ehrlich, Hermann; Jesionowski, Teofil

    2017-12-15

    A chitin/lignin material with defined physicochemical and morphological properties was used as an effective adsorbent of environmentally toxic metals from model systems. Particularly significant is its use in the neutralization of real industrial wastes. The ions Ni(2+), Cu(2+), Zn(2+) and Pb(2+) were adsorbed on the functional sorbent, confirming the high sorption capacity of the newly obtained product, primarily due to the presence on its surface of numerous active functional groups from the component biopolymers. The kinetics of the process of ion adsorption from model solution were investigated, and the experimental data were found to fit significantly better to a type 1 pseudo-second-order kinetic model, as confirmed by the high correlation coefficient of 0.999 for adsorption of both nickel(II) copper(II) zinc(II) and lead(II) ions. The experimental data obtained on the basis of adsorption isotherms corresponded to the Langmuir model. The sorption capacity of the chitin/lignin material was measured at 70.41 mg(Ni(2+))/g, 75.70 mg(Cu(2+))/g, 82.41 mg(Zn(2+))/g and 91.74 mg(Pb(2+))/g. Analysis of thermodynamic parameters confirmed the endothermic nature of the process. It was also shown that nitric acid is a very effective desorbing (regenerating) agent, enabling the chitin/lignin material to be reused as an effective sorbent of metal ions. The sorption abilities of the chitin/lignin system with respect to particular metal ions can be ordered in the sequence Ni(2+)ions of nickel(II), copper(II), zinc(II) and lead(II) from wastewater obtained from galvanization and battery production plants, confirming the ability of the chitin/lignin sorbent to adsorb harmful ions from real industrial wastes. Copyright © 2017 Elsevier Ltd. All rights reserved.

  7. Pseudo ribbon metal ion beam source

    SciTech Connect

    Stepanov, Igor B. Ryabchikov, Alexander I.; Sivin, Denis O.; Verigin, Dan A.

    2014-02-15

    The paper describes high broad metal ion source based on dc macroparticle filtered vacuum arc plasma generation with the dc ion-beam extraction. The possibility of formation of pseudo ribbon beam of metal ions with the parameters: ion beam length 0.6 m, ion current up to 0.2 A, accelerating voltage 40 kV, and ion energy up to 160 kV has been demonstrated. The pseudo ribbon ion beam is formed from dc vacuum arc plasma. The results of investigation of the vacuum arc evaporator ion-emission properties are presented. The influence of magnetic field strength near the cathode surface on the arc spot movement and ion-emission properties of vacuum-arc discharge for different cathode materials are determined. It was shown that vacuum-arc discharge stability can be reached when the magnetic field strength ranges from 40 to 70 G on the cathode surface.

  8. Ion-selective electrodes for gold and silver determination.

    PubMed

    Petrukhin, O M; Avdeeva, E N; Shavnya, Y V; Yankauskas, V P; Kazlauskas, R M; Bychkov, A S; Zolotov, Y A

    1987-01-01

    Some new ion-selective electrodes for silver and gold are described. They are based on the ion-associate species formed by the cyanide, chloride or thiourea complexes of the metals, with hydrophobic anions or cations, as appropriate. The electrodes have been applied to the determination of gold and silver in various technological process solutions in industry.

  9. Ion selectivity of crown ethers investigated by UV and IR spectroscopy in a cold ion trap.

    PubMed

    Inokuchi, Yoshiya; Boyarkin, Oleg V; Kusaka, Ryoji; Haino, Takeharu; Ebata, Takayuki; Rizzo, Thomas R

    2012-04-26

    Electronic and vibrational spectra of benzo-15-crown-5 (B15C5) and benzo-18-crown-6 (B18C6) complexes with alkali metal ions, M(+)•B15C5 and M(+)•B18C6 (M = Li, Na, K, Rb, and Cs), are measured using UV photodissociation (UVPD) and IR-UV double resonance spectroscopy in a cold, 22-pole ion trap. We determine the structure of conformers with the aid of density functional theory calculations. In the Na(+)•B15C5 and K(+)•B18C6 complexes, the crown ethers open the most and hold the metal ions at the center of the ether ring, demonstrating an optimum matching in size between the cavity of the crown ethers and the metal ions. For smaller ions, the crown ethers deform the ether ring to decrease the distance and increase the interaction between the metal ions and oxygen atoms; the metal ions are completely surrounded by the ether ring. In the case of larger ions, the metal ions are too large to enter the crown cavity and are positioned on it, leaving one of its sides open for further solvation. Thermochemistry data calculated on the basis of the stable conformers of the complexes suggest that the ion selectivity of crown ethers is controlled primarily by the enthalpy change for the complex formation in solution, which depends strongly on the complex structure.

  10. Ion exchange selectivity for cross-linked polyacrylic acid

    NASA Technical Reports Server (NTRS)

    May, C. E.; Philipp, W. H.

    1983-01-01

    The ion separation factors for 21 common metal ions with cross-linked polyacrylic acid were determined as a function of pH and the percent of the cross-linked polyacrylic acid neutralized. The calcium ion was used as a reference. At a pH of 5 the decreasing order of affinity of the ions for the cross-linked polyacrylic acid was found to be: Hg++, Fe+++, Pb++, Cr+++, Cu++, Cd++, Al+++, Ag+, Zn++, Ni++, Mn++, Co++, Ca++, Sr++, Ba++, Mg++, K+, Rb+, Cs+, Na+, and Li+. Members of a chemical family exhibited similar selectivities. The Hg++ ion appeared to be about a million times more strongly bound than the alkali metal ions. The relative binding of most of the metal ions varied with pH; the very tightly and very weakly bound ions showed the largest variations with pH. The calcium ion-hydrogen ion equilibrium was perturbed very little by the presence of the other ions. The separation factors and selectivity coefficients are discussed in terms of equilibrium and thermodynamic significance.

  11. Accumulation of metal ions by pectinates

    NASA Astrophysics Data System (ADS)

    Deiana, S.; Deiana, L.; Palma, A.; Premoli, A.; Senette, C.

    2009-04-01

    (II). Surprisingly, simultaneous sorption tests and SEM analyses indicate that a different mechanism regulates the sorption of Cu(II) and Pb(II) by PGAE1. In fact, the amount of Pb(II) sorbed (0.92 moles mg-1of PGAE1) by PGAE1 was nearly independent by the presence of Cu(II) ions, at least at the three different concentrations tested, that indicates a higher affinity of Pb(II). Such an aspect was further confirmed by exchange experiments. Samples of PGAE1 saturated with 1.96 moles mg-1of Cu(II) or 2.01 moles mg-1of Pb(II) were put in contact with 100 mL of solutions containing 97.3 moles of Pb(II) or 99.4 moles Cu(II), respectively. The exchange kinetics show that about 80% of Cu(II) was stochiometrically exchanged by Pb(II). In contrast, only about 10% of Pb(II) complexed by PGAE1 was exchanged by Cu(II). The kinetics of simultaneous sorption of all the metal ions tested indicate that Pb(II) is selectively sorbed by the PGAE1 gels. Cd(II) and Zn(II) show a similar affinity towards PGAE1. Thus, in the simultaneous presence of these ions, their selectivity towards this matrix follows the order: Pb > Cu > Cd ? Zn. Sorption of Cr(III) in the presence of the ions considered was not possible to carry out due to interference phenomena. The sorption of the same ions by 50 mg of PGAE2 evidences that the amount of Cu(II), Pb(II), and Cr(III) sorbed is markedly lower than that found for PGAE1. By considering that two carboxylic groups are involved in the complexation of a metal ion, the data show that such a stoichiometry is respected only for Pb(II). The amount of Cu(II) sorbed is about 50% lower than that of Pb(II) at all the pH values tested whereas those of Zn(II) and Cd(II) are negligible whereas that of Cr(III) is the highest. The different behaviour of Cu(II) compared to Pb(II) can be explained taking into account for both hydrophobic and steric effects of the methyl groups as well as to their different charge density. Thus, it can be concluded that the accumulation of metals at the

  12. Supramolecular recognition control of polyethylene glycol modified N-doped graphene quantum dots: tunable selectivity for alkali and alkaline-earth metal ions.

    PubMed

    Yang, Siwei; Sun, Jing; Zhu, Chong; He, Peng; Peng, Zheng; Ding, Guqiao

    2016-02-07

    The graphene quantum dot based fluorescent probe community needs unambiguous evidence about the control on the ion selectivity. In this paper, polyethylene glycol modified N-doped graphene quantum dots (PN-GQDs) were synthesized by alkylation reaction between graphene quantum dots and organic halides. We demonstrate the tunable selectivity and sensitivity by controlling the supramolecular recognition through the length and the end group size of the polyether chain on PN-GQDs. The relationship formulae between the selectivity/detection limit and polyether chains are experimentally deduced. The polyether chain length determines the interaction between the PN-GQDs and ions with different ratios of charge to radius, which in turn leads to a good selectivity control. Meanwhile the detection limit shows an exponential growth with the size of end groups of the polyether chain. The PN-GQDs can be used as ultrasensitive and selective fluorescent probes for Li(+), Na(+), K(+), Mg(2+), Ca(2+) and Sr(2+), respectively.

  13. Colored thin films for specific metal ion detection.

    PubMed

    Schauer, Caroline L; Chen, Mu-San; Price, Ronald R; Schoen, Paul E; Ligler, Frances S

    2004-08-15

    This paper describes the investigation of chitosan and poly(allylamine) (PAH) for the creation of a multi-film, color-based dipstick for the detection of metal ions in solution. Thin, colored films of chitosan and PAH cross-linked with hexamethylene 1,6-di(aminocarboxysulfonate) (HDACS) are created where color is due to film thickness and optical interference effects. The films are investigated for their ability to selectively detect aqueous metal ions via changes in thickness and/or color. Chitosan-HDACS films were selective for Cr(VI) over all other metal ions tested including Cr(acac)3 and Cr(NO3)3 x 9H2O, and PAH-HDACS films were selective for Cu(II) and Cu(I) salts over all other metal ions tested. The irreversible, selective changes due to metal ion solutions were not caused by varying the pH. Potomac River water was also tested using the two films, with results indicating the presence of Cu(II) in the aqueous sample.

  14. Liquid-liquid extraction of metal ions, DFT and TD-DFT analysis of some 1,2,4-triazole Schiff Bases with high selectivity for Pb(II) and Fe(II)

    NASA Astrophysics Data System (ADS)

    Khoutoul, Mohamed; Lamsayah, Morad; Al-blewi, Fawzia F.; Rezki, Nadjet; Aouad, Mohamed Reda; Mouslim, Messali; Touzani, Rachid

    2016-06-01

    Liquid-liquid extraction of metal ions using some 1,2,4-triazole Schiff base derivatives as new extractants was studied. Fe2+, Zn2+, Cu2+, Co2+, Cd2+ and Pb2+ were extracted from the aqueous phase into the organic phase and the extractability for each metal ion was determined by atomic absorption. Interestingly, a competitive extraction was also investigated and then examined at different pH in order to explore the effect of the different substituent groups on metal extraction. Accordingly, high selectivity towards Fe2+ (90.1%) and Pb2+ (94.3%) provided respectively by the presence of electron withdrawing group and electron donor group was attained. In addition, geometry optimizations of the ground and excited-states of the ligands in order to get better insight into the geometry and the electronic structure were carried out by means of DFT and TD-DFT calculations.

  15. Sorption of metal ions on alumina

    SciTech Connect

    Baumgarten, E.; Kirchhausen-Duesing, U.

    1997-10-01

    The adsorption of metal ions on aluminas is of great interest in different fields such as geochemistry, oceanography, limnology, and pollution control. Precipitation and adsorption of metal ions (Co(II), Ni(II), Cu(II), and Cr(III)) on {gamma}-alumina were investigated experimentally. A surface chemical reaction model to calculate concentrations of aluminum ions, metal ions, and pH as variables depending on amount of alumina, volume of liquid and gas phase, initial metal concentration, and amount of acid or base added is presented. In the case of Co(II) the pH dependence of rest concentrations with and without alumina is equal; adsorption may be disregarded. For the other ions adsorption is important. Considering the charge of the surface does not improve the fit. In the pH region, where adsorption leads to lower rest concentrations than precipitation, adsorption may be described by a Henry isotherm.

  16. Ion exchange extraction of heavy metals from wastewater sludges.

    PubMed

    Al-Enezi, G; Hamoda, M F; Fawzi, N

    2004-01-01

    Heavy metals are common contaminants of some industrial wastewater. They find their way to municipal wastewaters due to industrial discharges into the sewerage system or through household chemicals. The most common heavy metals found in wastewaters are lead, copper, nickel, cadmium, zinc, mercury, arsenic, and chromium. Such metals are toxic and pose serious threats to the environment and public health. In recent years, the ion exchange process has been increasingly used for the removal of heavy metals or the recovery of precious metals. It is a versatile separation process with the potential for broad applications in the water and wastewater treatment field. This article summarizes the results obtained from a laboratory study on the removal of heavy metals from municipal wastewater sludges obtained from Ardhiya plant in Kuwait. Data on heavy metal content of the wastewater and sludge samples collected from the plant are presented. The results obtained from laboratory experiments using a commercially available ion exchange resin to remove heavy metals from sludge were discussed. A technique was developed to solubilize such heavy metals from the sludge for subsequent treatment by the ion exchange process. The results showed high efficiency of extraction, almost 99.9%, of heavy metals in the concentration range bound in wastewater effluents and sludges. Selective removal of heavy metals from a contaminated wastewater/sludge combines the benefits of being economically prudent and providing the possibility of reuse/recycle of the treated wastewater effluents and sludges.

  17. Ion selectivity in the selectivity filters of acid-sensing ion channels.

    PubMed

    Dudev, Todor; Lim, Carmay

    2015-01-19

    Sodium-selective acid sensing ion channels (ASICs), which belong to the epithelial sodium channel (ENaC) superfamily, are key players in many physiological processes (e.g. nociception, mechanosensation, cognition, and memory) and are potential therapeutic targets. Central to the ASIC's function is its ability to discriminate Na(+) among cations, which is largely determined by its selectivity filter, the narrowest part of an open pore. However, it is unclear how the ASIC discriminates Na(+) from rival cations such as K(+) and Ca(2+) and why its Na(+)/K(+) selectivity is an order of magnitude lower than that of the ENaC. Here, we show that a well-tuned balance between electrostatic and solvation effects controls ion selectivity in the ASIC1a SF. The large, water-filled ASIC1a pore is selective for Na(+) over K(+) because its backbone ligands form more hydrogen-bond contacts and stronger electrostatic interactions with hydrated Na(+) compared to hydrated K(+). It is selective for Na(+) over divalent Ca(2+) due to its relatively high-dielectric environment, which favors solvated rather than filter-bound Ca(2+). However, higher Na(+)-selectivity could be achieved in a narrow, rigid pore lined by three weak metal-ligating groups, as in the case of ENaC, which provides optimal fit and interactions for Na(+) but not for non-native ions.

  18. Comparative study of metal and non-metal ion implantation in polymers: Optical and electrical properties

    NASA Astrophysics Data System (ADS)

    Resta, V.; Quarta, G.; Farella, I.; Maruccio, L.; Cola, A.; Calcagnile, L.

    2014-07-01

    The implantation of 1 MeV metal (63Cu+, 107Ag+, 197Au+) and non-metal (4He+, 12C+) ions in a polycarbonate (PC) matrix has been studied in order to evaluate the role of ion species in the modification of optical and electrical properties of the polymer. When the ion fluence is above ∼1 × 1013 ions cm-2, the threshold for latent tracks overlapping is overcome and π-bonded carbon clusters grow and aggregate forming a network of conjugated Cdbnd C bonds. For fluences around 1 × 1017 ions cm-2, the aggregation phenomena induce the formation of amorphous carbon and/or graphite like structures. At the same time, nucleation of metal nanoparticles (NPs) from implanted species can take place when the supersaturation threshold is overcome. The optical absorption of the samples increases in the visible range and the optical band gap redshifts from 3.40 eV up to 0.70 eV mostly due to the carbonization process and the formation of C0x clusters and cluster aggregates. Specific structures in the extinction spectra are observed when metal ions are selected in contrast to the non-metal ion implanted PC, thus revealing the possible presence of noble metal based NPs interstitial to the C0x cluster network. The corresponding electrical resistance decreases much more when metal ions are implanted with at least a factor of 2 orders of magnitude difference than the non-metal ions based samples. An absolute value of ∼107 Ω/sq has been measured for implantation with metals at doses higher than 5 × 1016 ions cm-2, being 1017 Ω/sq the corresponding sheet resistance for pristine PC.

  19. Metal Ion Modeling Using Classical Mechanics.

    PubMed

    Li, Pengfei; Merz, Kenneth M

    2017-02-08

    Metal ions play significant roles in numerous fields including chemistry, geochemistry, biochemistry, and materials science. With computational tools increasingly becoming important in chemical research, methods have emerged to effectively face the challenge of modeling metal ions in the gas, aqueous, and solid phases. Herein, we review both quantum and classical modeling strategies for metal ion-containing systems that have been developed over the past few decades. This Review focuses on classical metal ion modeling based on unpolarized models (including the nonbonded, bonded, cationic dummy atom, and combined models), polarizable models (e.g., the fluctuating charge, Drude oscillator, and the induced dipole models), the angular overlap model, and valence bond-based models. Quantum mechanical studies of metal ion-containing systems at the semiempirical, ab initio, and density functional levels of theory are reviewed as well with a particular focus on how these methods inform classical modeling efforts. Finally, conclusions and future prospects and directions are offered that will further enhance the classical modeling of metal ion-containing systems.

  20. Metal Ion Modeling Using Classical Mechanics

    PubMed Central

    2017-01-01

    Metal ions play significant roles in numerous fields including chemistry, geochemistry, biochemistry, and materials science. With computational tools increasingly becoming important in chemical research, methods have emerged to effectively face the challenge of modeling metal ions in the gas, aqueous, and solid phases. Herein, we review both quantum and classical modeling strategies for metal ion-containing systems that have been developed over the past few decades. This Review focuses on classical metal ion modeling based on unpolarized models (including the nonbonded, bonded, cationic dummy atom, and combined models), polarizable models (e.g., the fluctuating charge, Drude oscillator, and the induced dipole models), the angular overlap model, and valence bond-based models. Quantum mechanical studies of metal ion-containing systems at the semiempirical, ab initio, and density functional levels of theory are reviewed as well with a particular focus on how these methods inform classical modeling efforts. Finally, conclusions and future prospects and directions are offered that will further enhance the classical modeling of metal ion-containing systems. PMID:28045509

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

    PubMed

    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.

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

    SciTech Connect

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

    1999-06-13

    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.

  3. ION EXCHANGE SOFTENING: EFFECTS ON METAL CONCENTRATIONS

    EPA Science Inventory

    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 ...

  4. ION EXCHANGE SOFTENING: EFFECTS ON METAL CONCENTRATIONS

    EPA Science Inventory

    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 ...

  5. Evolution of Metal Selectivity in Templated Protein Interfaces

    PubMed Central

    Brodin, Jeffrey D.; Medina-Morales, Annette; Ni, Thomas; Salgado, Eric N.; Ambroggio, Xavier I.; Tezcan, F. Akif

    2010-01-01

    Selective binding by metalloproteins to their cognate metal ions is essential to cellular survival. How proteins originally acquired the ability to selectively bind metals and evolved a diverse array of metal-centered functions despite the availability of only a few metal-coordinating functionalities remains an open question. Using a rational design approach (Metal-Templated Interface Redesign), we describe the transformation of a monomeric electron transfer protein, cytochrome cb562, into a tetrameric assembly (C96RIDC-1) that stably and selectively binds Zn2+, and displays a metal-dependent conformational change reminiscent of a signaling protein. A thorough analysis of the metal binding properties of C96RIDC-14 reveals that it can also stably harbor other divalent metals with affinities that rival (Ni2+) or even exceed (Cu2+) those of Zn2+ on a per site basis. Nevertheless, this analysis suggests that our templating strategy also introduces an increased bias towards binding a higher number of Zn2+ ions (4 high affinity sites) versus Cu2+ or Ni2+ (2 high affinity sites), ultimately leading to the exclusive selectivity of C96RIDC-14 for Zn2 over those ions. More generally, our results indicate that an initial metal-driven nucleation event followed by the formation of a stable protein architecture around the metal provides a straightforward path for generating structural and functional diversity. PMID:20515031

  6. Accumulation of heavy-metal ions by Zoogloea ramigera.

    PubMed

    Norberg, A B; Persson, H

    1984-03-01

    Biomass has been produced from glucose using the organism Zoogloea ramigera 115. This biomass has been used to remove copper, cadmium, and uranyl ions from water solutions. The metal uptake was studied with two different methods: either by spectrophotometric measurements on the solutions after flocculation or by potentiometric measurements with amalgam electrodes in order to follow the entire complex formation. The metal-biopolymer interaction in 0.1M NaClO(4) is practically the same as when no neutral salt is added. The metal uptake is dependent on pH and is selective. A reversible process suitable for metal complexation is described.

  7. Driven evolution of a constitutional dynamic library of molecular helices toward the selective generation of [2 x 2] gridlike arrays under the pressure of metal ion coordination.

    PubMed

    Giuseppone, Nicolas; Schmitt, Jean-Louis; Lehn, Jean-Marie

    2006-12-27

    Constitutional dynamics, self-assembly, and helical-folding control are brought together in the efficient Sc(OTf)3/microwave-catalyzed transimination of helical oligohydrazone strands, yielding highly diverse dynamic libraries of interconverting constituents through assembly, dissociation, and exchange of components. The transimination-type mechanism of the ScIII-promoted exchange, as well as its regioselectivity, occurring only at the extremities of the helical strands, allow one to perform directional terminal polymerization/depolymerization processes when starting with dissymmetric strands. A particular library is subsequently brought to express quantitatively [2 x 2] gridlike metallosupramolecular arrays in the presence of ZnII ions by component recombination generating the correct ligand from the dynamic set of interconverting strands. This behavior represents a process of driven evolution of a constitutional dynamic chemical system under the pressure (coordination interaction) of an external effector (metal ions).

  8. Metal-ion recycle technology for metal electroplating waste waters

    SciTech Connect

    Sauer, N.N.; Smith, B.F.

    1993-06-01

    As a result of a collaboration with Boeing Aerospace, the authors have begun a program to identify suitable treatments or to develop new treatments for electroplating baths. The target baths are mixed-metal or alloy baths that are being integrated into the Boeing electroplating complex. These baths, which are designed to replace highly toxic chromium and cadmium baths, contain mixtures of two metals, either nickel-tungsten, nickel-zinc, or zinc-tin. This report reviews the literature and details currently available on emerging technologies that could affect recovery of metals from electroplating baths under development by Boeing Aerospace. This literature survey summarizes technologies relevant to the recovery of metals from electroplating processes. The authors expanded the scope to investigate single metal ion recovery technologies that could be applied to metal ion recovery from alloy baths. This review clearly showed that the electroplating industry has traditionally relied on precipitation and more recently on electrowinning as its waste treatment methods. Despite the almost ubiquitous use of precipitation to remove contaminant metal ions from waste electroplating baths and rinse waters, this technology is clearly no longer feasible for the electroplating industry for several reasons. First, disposal of unstabilized sludge is no longer allowed by law. Second, these methods are no longer adequate as metal-removal techniques because they cannot meet stringent new metal discharge limits. Third, precious resources are being wasted or discarded because these methods do not readily permit recovery of the target metal ions. As a result, emerging technologies for metal recovery are beginning to see application to electroplating waste recycle. This report summarizes current research in these areas. Included are descriptions of various membrane technologies, such as reverse osmosis and ultrafiltration, ion exchange and chelating polymer technology, and electrodialysis.

  9. Antileishmanial Activity of Disulfiram and Thiuram Disulfide Analogs in an Ex Vivo Model System Is Selectively Enhanced by the Addition of Divalent Metal Ions

    PubMed Central

    Peniche, Alex G.; Renslo, Adam R.; Melby, Peter C.

    2015-01-01

    Current treatments for cutaneous and visceral leishmaniasis are toxic, expensive, difficult to administer, and limited in efficacy and availability. Disulfiram has primarily been used to treat alcoholism. More recently, it has shown some efficacy as therapy against protozoan pathogens and certain cancers, suggesting a wide range of biological activities. We used an ex vivo system to screen several thiuram disulfide compounds for antileishmanial activity. We found five compounds (compound identifier [CID] 7188, 5455, 95876, 12892, and 3117 [disulfiram]) with anti-Leishmania activity at nanomolar concentrations. We further evaluated these compounds with the addition of divalent metal salts based on studies that indicated these salts could potentiate the action of disulfiram. In addition, clinical studies suggested that zinc has some efficacy in treating cutaneous leishmaniasis. Several divalent metal salts were evaluated at 1 μM, which is lower than the normal levels of copper and zinc in plasma of healthy individuals. The leishmanicidal activity of disulfiram and CID 7188 were enhanced by several divalent metal salts at 1 μM. The in vitro therapeutic index (IVTI) of disulfiram and CID 7188 increased 12- and 2.3-fold, respectively, against L. major when combined with ZnCl2. The combination of disulfiram with ZnSO4 resulted in a 1.8-fold increase in IVTI against L. donovani. This novel combination of thiuram disulfides and divalent metal ions salts could have application as topical and/or oral therapies for treatment of cutaneous and visceral leishmaniasis. PMID:26239994

  10. Bioavailability of Metal Ions and Evolutionary Adaptation

    PubMed Central

    Hong Enriquez, Rolando P.; Do, Trang N.

    2012-01-01

    The evolution of life on earth has been a long process that began nearly 3.5 × 109 years ago. In their initial moments, evolution was mainly influenced by anaerobic environments; with the rise of O2 and the corresponding change in bioavailability of metal ions, new mechanisms of survival were created. Here we review the relationships between ancient atmospheric conditions, metal ion bioavailability and adaptation of metals homeostasis during early evolution. A general picture linking geochemistry, biochemistry and homeostasis is supported by the reviewed literature and is further illustrated in this report using simple database searches. PMID:25371266

  11. Metal vapor arc ion plating

    DOEpatents

    Bertram, L.A.; Fisher, R.W.; Mattox, D.M.; Zanner, F.J.

    1986-09-09

    A method and apparatus for ion plating are described. The apparatus uses more negative than a first electrode voltage in a vacuum arc remelt system to attract low energy ions from the anode electrode to the article to be plated. 2 figs.

  12. The MEVVA ion source for high current metal ion implantation

    NASA Astrophysics Data System (ADS)

    Brown, Ian; Washburn, Jack

    The MEVVA (Metal Vapor Vacuum Arc) ion source is a new kind of source which can produce high current beams of metal ions. Beams of a wide range of elements have been produced, spanning the periodic table from lithium up to and including uranium. The source extraction voltage is up to 60 kV, and we are increasing this up to 120 kV. A total ion beam current of over 1 A has been extracted from the present embodiment of the concept, and this is not an inherent limit. The ion charge state distribution varies with cathode material and are current, and beams like Li +, Co +.2+.3+ and U 3+.4+.5+.6+ for example, are typical; thus the implantation energy can be up to several hundred kV without additional acceleration. The ion source has potential applications for ion implantation and ion beam mixing for achievement of improved corrosion resistance or wear resistance in metals or surface modification of ceramic materials and semiconductors. Here we outline the source and its performance, and describe some very preliminary implantation work using this source.

  13. Separation of metal ions in nitrate solution by ultrasonic atomization

    NASA Astrophysics Data System (ADS)

    Sato, Masanori; Ikeno, Masayuki; Fujii, Toshitaka

    2004-11-01

    In the ultrasonic atomization of metal nitrate solutions, the molar ratio of metal ions is changed between solution and mist. Small molar metal ions tend to be transferred to mist by ultrasonic wave acceleration, while large molar ions tend to remain in solution. As a result, metal ions can be separated by ultrasonic atomization. We show experimental data and propose a conceptual mechanism for the ultrasonic separation of metal ions.

  14. Separation of metal ions in nitrate solution by ultrasonic atomization.

    PubMed

    Sato, Masanori; Ikeno, Masayuki; Fujii, Toshitaka

    2004-11-15

    In the ultrasonic atomization of metal nitrate solutions, the molar ratio of metal ions is changed between solution and mist. Small molar metal ions tend to be transferred to mist by ultrasonic wave acceleration, while large molar ions tend to remain in solution. As a result, metal ions can be separated by ultrasonic atomization. We show experimental data and propose a conceptual mechanism for the ultrasonic separation of metal ions.

  15. Adsorbent for metal ions and method of making and using

    DOEpatents

    White, Lloyd R.; Lundquist, Susan H.

    1999-01-01

    A method comprises the step of spray-drying a solution or slurry comprising (alkali metal or ammonium) (metal) hexacyanoferrate particles in a liquid, to provide monodisperse, substantially spherical particles in a yield of at least 70 percent of theoretical yield and having a particle size in the range of 1 to 500 micrometers, said particles being active towards Cs ions. The particles, which can be of a single salt or a combination of salts, 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 Cs ions from aqueous solutions.

  16. Adsorbent for metal ions and method of making and using

    DOEpatents

    White, Lloyd R.; Lundquist, Susan H.

    2000-01-01

    A method comprises the step of spray-drying a solution or slurry comprising (alkali metal or ammonium) (metal) hexacyanoferrate particles in a liquid, to provide monodisperse, substantially spherical particles in a yield of at least 70 percent of theoretical yield and having a particle size in the range of 1 to 500 micrometers, said particles being active towards Cs ions. The particles, which can be of a single salt or a combination of salts, 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 Cs ions from aqueous solutions.

  17. Adsorbent for metal ions and method of making and using

    DOEpatents

    White, L.R.; Lundquist, S.H.

    1999-08-10

    A method comprises the step of spray-drying a solution or slurry comprising (alkali metal or ammonium) (metal) hexacyanoferrate particles in a liquid, to provide monodisperse, substantially spherical particles in a yield of at least 70 percent of theoretical yield and having a particle size in the range of 1 to 500 micrometers, said particles being active towards Cs ions. The particles, which can be of a single salt or a combination of salts, 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 Cs ions from aqueous solutions. 2 figs.

  18. An equilibrium model for ligand-modified micellar-enhanced ultrafiltration. Selective separation of metal ions using iminoacetic substituted polyamines and a theoretical model for the titration behavior of polyamines

    SciTech Connect

    Dharmawardana, Udeni Rajaratna

    1992-01-01

    This thesis consists of three chapters. Chapter 1, An equilibrium model for ligand-modified micellar-enhanced ultrafiltration, describes a theoretical model and experimental investigations which used the semi-equilibrium-dialysis method with N-n-dodecyl iminodiacetic acid as the ligand. In Chapter 2, Selective separation of metal ions using iminoacetic substituted polyamines, polyamines with a substituted ligand group are synthesized and used in investigating selective separation of copper ions from aqueous solution. In Chapter 3, A theoretical model for the titration behavior of polyamines, a novel approach to explain the titration behavior of polymeric amines based on the binding behavior of counterions is described. The application of this study is to the investigation of inexpensive and efficient methods of industrial waste water treatment.

  19. Identification of the N-terminal region of TjZNT2, a Zrt/Irt-like protein family metal transporter, as a novel functional region involved in metal ion selectivity.

    PubMed

    Nishida, Sho; Morinaga, Yasuhiro; Obata, Hitoshi; Mizuno, Takafumi

    2011-03-01

    The Zrt/Irt-like protein (ZIP) family of transporter proteins is involved in the uptake of essential metal elements in plants. Two homologous ZIP genes from Thlaspi japonicum, TjZNT1 and TjZNT2, encode products that share high amino acid sequence similarity except at the N-terminus and the cytoplasmic loop between transmembrane domains III and IV, and that have been shown to be Zn(2+) and Mn(2+) transporters, respectively. To identify the region that determines the ion selectivity of these transporters, we constructed a series of TjZNT1 and TjZNT2 chimeric genes and assayed for the Zn(2+) uptake of yeast cells expressing them. As a result, the extracellular N-terminal ends were identified as regions involved in Zn(2+) selectivity. TjZNT2 possesses a 36 amino acid hydrophilic extension at its N-terminus that is absent in native TjZNT1, and a mutant TjZNT2 lacking the N-terminal extension was shown to possess Zn(2+) uptake activity. This suggests that the extended N-terminal region inhibits Zn(2+) transport by TjZNT2. Further studies showed that it is the first 25 amino acid region of the N-terminus that is important for the inhibition of Zn(2+) transport. Furthermore, the N-terminal truncated TjZNT2 lacked Mn(2+) uptake activity. These findings suggest that the N-terminal region is a novel substrate selector in the ZIP family of transporters. © 2011 The Authors Journal compilation © 2011 FEBS.

  20. Critical evaluation and selection of standard state thermodynamic properties for chromium metal and its aqueous ions, hydrolysis species, oxides, and hydroxides

    USGS Publications Warehouse

    Ball, James W.; Nordstrom, D. Kirk

    1998-01-01

    This review critically evaluates the reported thermodynamic data on chromium metal, oxides, hydroxides, free aqueous ions, and hydrolysis species. Several discrepancies and inconsistencies have been uncovered and resolved to improve equilibrium calculations for chemical modeling and related engineering purposes. A revised set of data is derived from evaluation of electrochemical measurements, silver chromate solubility measurements, and auxiliary post-1980 data, reevaluation of earlier data, and reconsideration of the path for the thermodynamic network. The recommended thermodynamic values for Cr(cr), C , C , Cr , Cr2 , Cr2O3(cr), CrO3(cr), FeCr2O4(cr), CrCl2(cr), CrCl3(cr), and KFe3(CrO4)2(OH)6(cr)at 25 °C, 1 bar, and infinite dilution are given.

  1. Triboelectrification-Enabled Self-Powered Detection and Removal of Heavy Metal Ions in Wastewater.

    PubMed

    Li, Zhaoling; Chen, Jun; Guo, Hengyu; Fan, Xing; Wen, Zhen; Yeh, Min-Hsin; Yu, Chongwen; Cao, Xia; Wang, Zhong Lin

    2016-04-20

    A fundamentally new working principle into the field of self-powered heavy-metal-ion detection and removal using the triboelectrification effect is introduced. The as-developed tribo-nanosensors can selectively detect common heavy metal ions. The water-driven triboelectric nanogenerator is taken as a sustainable power source for heavy-metal-ion removal by recycling the kinetic energy from flowing wastewater. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Adsorption of Heavy Metal Ions from Aqueous Solutions by Bentonite Nanocomposites.

    PubMed

    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.

  3. Polymer filtration: An emerging technology for selective metals recovery

    SciTech Connect

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

    1997-12-31

    Polymer Filtration is a technology under development to selectively recover valuable or regulated metal ions from process or waste waters. The technology uses water-soluble polymers that are specially designed to selectively bind with metal ions in the aqueous solution. The polymers have a sufficiently large molecular weight that they can be separated and concentrated using available ultrafiltration technology. Water and smaller unbound components of the solution pass freely through the ultrafiltration membrane. The polymers can then be reused by changing the solution conditions to release the metal ions which are recovered in concentrated form for recycle or disposal. We are testing this technology to remove plutonium, americium, and other radionuclides from various process and waste streams found in nuclear facilities. Some advantages of polymer filtration relative to technology now in use are rapid binding kinetics, high selectivity, low energy and capital costs, and a small equipment footprint.

  4. Ion selective transistor modelling for behavioural simulations.

    PubMed

    Daniel, M; Janicki, M; Wroblewski, W; Dybko, A; Brzozka, Z; Napieralski, A

    2004-01-01

    Computer aided design and simulation of complex silicon microsystems oriented for environment monitoring requires efficient and accurate models of ion selective sensors, compatible with the existing behavioural simulators. This paper concerns sensors based on the back-side contact Ion Sensitive Field Effect Transistors (ISFETs). The ISFETs with silicon nitride gate are sensitive to hydrogen ion concentration. When the transistor gate is additionally covered with a special ion selective membrane, selectivity to other than hydrogen ions can be achieved. Such sensors are especially suitable for flow analysis of solutions containing various ions. The problem of ion selective sensor modelling is illustrated here on a practical example of an ammonium sensitive membrane. The membrane is investigated in the presence of some interfering ions and appropriate selectivity coefficients are determined. Then, the model of the whole sensor is created and used in subsequent electrical simulations. Providing that appropriate selectivity coefficients are known, the proposed model is applicable for any membrane, and can be straightforwardly implemented for behavioural simulation of water monitoring microsystems. The model has been already applied in a real on-line water pollution monitoring system for detection of various contaminants.

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

    PubMed

    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.

  6. IMMUNOASSAYS FOR METAL IONS. (R824029)

    EPA Science Inventory

    Abstract

    Antibodies that recognize chelated forms of metal ions have been used to construct immunoassays for Cd(II), Hg(II), Pb(II), and Ni(II). In this paper, the format of these immunoassays is described and the binding properties of three monoclonal antibodies direc...

  7. Chitosan Hydrogel Structure Modulated by Metal Ions

    NASA Astrophysics Data System (ADS)

    Nie, Jingyi; Wang, Zhengke; Hu, Qiaoling

    2016-10-01

    As one of the most important polysaccharide, chitosan (CS) has generated a great deal of interest for its desirable properties and wide applications. In the utilization of CS materials, hydrogel is a major and vital branch. CS has the ability to coordinate with many metal ions by a chelation mechanism. While most researchers focused on the applications of complexes between CS and metal ions, the complexes can also influence gelation process and structure of CS hydrogel. In the present work, such influence was studied with different metal ions, revealing two different kinds of mechanisms. Strong affinity between CS and metal ions leads to structural transition from orientation to multi-layers, while weak affinity leads to composite gel with in-situ formed inorganic particles. The study gave a better understanding of the gelation mechanism and provided strategies for the modulation of hydrogel morphology, which benefited the design of new CS-based materials with hierarchical structure and facilitated the utilization of polysaccharide resources.

  8. IMMUNOASSAYS FOR METAL IONS. (R824029)

    EPA Science Inventory

    Abstract

    Antibodies that recognize chelated forms of metal ions have been used to construct immunoassays for Cd(II), Hg(II), Pb(II), and Ni(II). In this paper, the format of these immunoassays is described and the binding properties of three monoclonal antibodies direc...

  9. Chitosan Hydrogel Structure Modulated by Metal Ions

    PubMed Central

    Nie, Jingyi; Wang, Zhengke; Hu, Qiaoling

    2016-01-01

    As one of the most important polysaccharide, chitosan (CS) has generated a great deal of interest for its desirable properties and wide applications. In the utilization of CS materials, hydrogel is a major and vital branch. CS has the ability to coordinate with many metal ions by a chelation mechanism. While most researchers focused on the applications of complexes between CS and metal ions, the complexes can also influence gelation process and structure of CS hydrogel. In the present work, such influence was studied with different metal ions, revealing two different kinds of mechanisms. Strong affinity between CS and metal ions leads to structural transition from orientation to multi-layers, while weak affinity leads to composite gel with in-situ formed inorganic particles. The study gave a better understanding of the gelation mechanism and provided strategies for the modulation of hydrogel morphology, which benefited the design of new CS-based materials with hierarchical structure and facilitated the utilization of polysaccharide resources. PMID:27777398

  10. Selective Recovery of Metals from Geothermal Brines

    SciTech Connect

    Ventura, Susanna; Bhamidi, Srinivas; Hornbostel, Marc; Nagar, Anoop; Perea, Elisabeth

    2016-12-16

    The objective of this project was to determine the feasibility of developing a new generation of highly selective low-cost ion-exchange resins based on metal-ion imprinted polymers for the separation of metals from geothermal fluids. Expansion of geothermal energy production over the entire U.S. will involve exploitation of low-to-medium temperature thermal waters. Creating value streams from the recovery of critical and near-critical metals from these thermal waters will encourage geothermal expansion. Selective extraction of metals from geothermal fluids is needed to design a cost-effective process for the recovery of lithium and manganese-two near-critical metals with well-known application in the growing lithium battery industry. We have prepared new lithium- and manganese-imprinted polymers in the form of beads by crosslinking polymerization of a metal polymerizable chelate, where the metal acts as a template. Upon leaching out the metal template, the crosslinked polymer is expected to leave cavities defined by the ligand functional group with enhanced selectivity for binding the template metal. We have demonstrated that lithium- and manganese-imprinted polymer beads can be used as selective solid sorbents for the extraction of lithium and manganese from brines. The polymers were tested both in batch extractions and packed bed lab-scale columns at temperatures of 45-100°C. Lithium-imprinted polymers were found to have Li+ adsorption capacity as high as 2.8 mg Li+/g polymer at 45°C. Manganese-imprinted polymers were found to have a Mn2+ adsorption capacity of more than 23 mg Mn2+/g polymer at 75°C. The Li+ extraction efficiency of the Li-imprinted polymer was found to be more that 95% when a brine containing 390 ppm Li+, 410 ppm Na+, and 390 ppm K+ was passed through a packed bed of the polymer in a lab-scale column at 45°C. In brines containing 360 ppm Li

  11. New Catalytic DNA Biosensors for Radionuclides and Metal ion

    SciTech Connect

    Yi Lu

    2008-03-01

    We aim to develop new DNA biosensors for simultaneous detection and quantification of bioavailable radionuclides, such as uranium, technetium, and plutonium, and metal contaminants, such as lead, chromium, and mercury. The sensors will be highly sensitive and selective. They will be applied to on-site, real-time assessment of concentration, speciation, and stability of the individual contaminants before and during bioremediation, and for long-term monitoring of DOE contaminated sites. To achieve this goal, we have employed a combinatorial method called “in vitro selection” to search from a large DNA library (~ 1015 different molecules) for catalytic DNA molecules that are highly specific for radionuclides or other metal ions through intricate 3-dimensional interactions as in metalloproteins. Comprehensive biochemical and biophysical studies have been performed on the selected DNA molecules. The findings from these studies have helped to elucidate fundamental principles for designing effective sensors for radionuclides and metal ions. Based on the study, the DNA have been converted to fluorescent or colorimetric sensors by attaching to it fluorescent donor/acceptor pairs or gold nanoparticles, with 11 part-per-trillion detection limit (for uranium) and over million fold selectivity (over other radionuclides and metal ions tested). Practical application of the biosensors for samples from the Environmental Remediation Sciences Program (ERSP) Field Research Center (FRC) at Oak Ridge has also been demonstrated.

  12. Microwave-assisted synthesis of HKUST-1 and functionalized HKUST-1-@H3PW12O40: selective adsorption of heavy metal ions in water analyzed with synchrotron radiation.

    PubMed

    Zou, Fang; Yu, Runhan; Li, Rongguan; Li, Wei

    2013-08-26

    A simple, rapid and efficient synthesis of the metal-organic framework (MOF) HKUST-1 [Cu3(1,3,5-benzene-tri-carboxilic-acid)2] by microwave irradiation is described, which afforded a homogeneous and highly selective material. The unusually short time to complete the synthesis by microwave irradiation is mainly attributable to rapid nucleation rather than to crystal growth rate. Using this method, HKUST-1-MW (MW=microwave) could be prepared within 20 min, whereas by hydrothermal synthesis, involving conventional heating, the preparation time is 8 h. Work efficiency was improved by the good performance of the obtained HKUST-1-MW which exhibited good selective adsorption of heavy metal ions, as well as a remarkably high adsorption affinity and adsorption capacity, but no adsorption of Hg(2+) under the same experimental conditions. Of particular importance is the preservation of the structure after metal-ion adsorption, which remained virtually intact, with only a few changes in X-ray diffraction intensity and a moderate decline in surface area. Synthesis of the polyoxometalate-containing HKUST-1-MW@H3PW12O40 afforded a MOF with enhanced stability in water, due to the introduced Keggin-type phosphotungstate, which systematically occluded in the cavities constituting the walls between the mesopores. Different Cu/W ratios were investigated according to the extrusion rate of cooper ions concentration, without significant structural changes after adsorption. The MOFs obtained feature particle sizes between 10-20 μm and their structures were determined using synchrotron-based X-ray diffraction. The results of this study can be considered important for potentially wider future applications of MOFs, especially to attend environmental issues. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Metalloregulatory Proteins: Metal Selectivity and Allosteric Switching

    PubMed Central

    Caballero, Hermes Reyes; Campanello, Gregory C.; Giedroc, David P.

    2011-01-01

    Prokaryotic organisms have evolved an impressive capacity to quickly adapt to a changing and challenging microenvironment in which the availability of both biologically required and non-essential transition metal ions can vary dramatically. In all bacteria, a panel of metalloregulatory proteins control the expression of genes encoding membrane transporters and metal trafficking proteins, that collectively manage metal homeostasis and resistance. These “metal sensors” are specialized allosteric proteins, in which the direct binding of a specific or small number of “cognate” metal ion(s) drives a conformational change in the regulator that allosterically activates or inhibits operator DNA binding, or alternatively, distorts the promoter structure thereby converting a poor promoter to a strong one. In this review, we discuss our current understanding of the features that control metal specificity of the allosteric response in these systems, and the role that structure, thermodynamics and conformational dynamics play in mediating allosteric activation or inhibition of DNA binding. PMID:21511390

  14. Material Removes Heavy Metal Ions From Water

    NASA Technical Reports Server (NTRS)

    Philipp, Warren H., Jr.; Street, Kenneth W.; Hill, Carol; Savino, Joseph M.

    1995-01-01

    New high capacity ion-exchange polymer material removes toxic metal cations from contaminated water. Offers several advantages. High sensitivities for such heavy metals as lead, cadmium, and copper and capable of reducing concentrations in aqueous solutions to parts-per-billion range. Removes cations even when calcium present. Material made into variety of forms, such as thin films, coatings, pellets, and fibers. As result, adapted to many applications to purify contaminated water, usually hard wherever found, whether in wastewater-treatment systems, lakes, ponds, industrial plants, or homes. Another important feature that adsorbed metals easily reclaimed by either destructive or nondestructive process. Other tests show ion-exchange polymer made inexpensively; easy to use; strong, flexible, not easily torn; and chemically stable in storage, in aqueous solutions, and in acidic or basic solution.

  15. Material Removes Heavy Metal Ions From Water

    NASA Technical Reports Server (NTRS)

    Philipp, Warren H., Jr.; Street, Kenneth W.; Hill, Carol; Savino, Joseph M.

    1995-01-01

    New high capacity ion-exchange polymer material removes toxic metal cations from contaminated water. Offers several advantages. High sensitivities for such heavy metals as lead, cadmium, and copper and capable of reducing concentrations in aqueous solutions to parts-per-billion range. Removes cations even when calcium present. Material made into variety of forms, such as thin films, coatings, pellets, and fibers. As result, adapted to many applications to purify contaminated water, usually hard wherever found, whether in wastewater-treatment systems, lakes, ponds, industrial plants, or homes. Another important feature that adsorbed metals easily reclaimed by either destructive or nondestructive process. Other tests show ion-exchange polymer made inexpensively; easy to use; strong, flexible, not easily torn; and chemically stable in storage, in aqueous solutions, and in acidic or basic solution.

  16. Hydrophilic Nb⁵⁺-immobilized magnetic core-shell microsphere--A novel immobilized metal ion affinity chromatography material for highly selective enrichment of phosphopeptides.

    PubMed

    Sun, Xueni; Liu, Xiaodan; Feng, Jianan; Li, Yan; Deng, Chunhui; Duan, Gengli

    2015-06-23

    Rapid and selective enrichment of phosphopeptides from complex biological samples is essential and challenging in phosphorylated proteomics. In this work, for the first time, niobium ions were directly immobilized on the surface of polydopamine-coated magnetic microspheres through a facile and effective synthetic route. The Fe3O4@polydopamine-Nb(5+) (denoted as Fe3O4@PD-Nb(5+)) microspheres possess merits of high hydrophilicity and good biological compatibility, and demonstrated low limit of detection (2 fmol). The selectivity was also basically satisfactory (β-casein:BSA=1:500) to capture phosphopeptides. They were also successfully applied for enrichment of phosphopeptides from real biological samples such as human serum and nonfat milk. Compared with Fe3O4@PD-Ti(4+) microspheres, the Fe3O4@PD-Nb(5+) microspheres exhibit superior selectivity to multi-phosphorylated peptides, and thus may be complementary to the conventional IMAC materials. Copyright © 2015 Elsevier B.V. All rights reserved.

  17. Speeding the Recovery from Ultraslow Inactivation of Voltage-Gated Na+ Channels by Metal Ion Binding to the Selectivity Filter: A Foot-on-the-Door?

    PubMed Central

    Szendroedi, Julia; Sandtner, Walter; Zarrabi, Touran; Zebedin, Eva; Hilber, Karlheinz; Dudley, Samuel C.; Fozzard, Harry A.; Todt, Hannes

    2007-01-01

    Slow inactivated states in voltage-gated ion channels can be modulated by binding molecules both to the outside and to the inside of the pore. Thus, external K+ inhibits C-type inactivation in Shaker K+ channels by a “foot-in-the-door” mechanism. Here, we explore the modulation of a very long-lived inactivated state, ultraslow inactivation (IUS), by ligand binding to the outer vestibule in voltage-gated Na+ channels. Blocking the outer vestibule by a mutant μ-conotoxin GIIIA substantially accelerated recovery from IUS. A similar effect was observed if Cd2+ was bound to a cysteine engineered to the selectivity filter (K1237C). In K1237C channels, exposed to 30 μM Cd2+, the time constant of recovery from IUS was decreased from 145.0 ± 10.2 s to 32.5 ± 3.3 s (P < 0.001). Recovery from IUS was only accelerated if Cd2+ was added to the bath solution during recovery (V = −120 mV) from IUS, but not when the channels were selectively exposed to Cd2+ during the development of IUS (−20 mV). These data could be explained by a kinetic model in which Cd2+ binds with high affinity to a slow inactivated state (IS), which is transiently occupied during recovery from IUS. A total of 50 μM Cd2+ produced an ∼8 mV hyperpolarizing shift of the steady-state inactivation curve of IS, supporting this kinetic model. Binding of lidocaine to the internal vestibule significantly reduced the number of channels entering IUS, suggesting that IUS is associated with a conformational change of the internal vestibule of the channel. We propose a molecular model in which slow inactivation (IS) occurs by a closure of the outer vestibule, whereas IUS arises from a constriction of the internal vestibule produced by a widening of the selectivity filter region. Binding of Cd2+ to C1237 promotes the closure of the selectivity filter region, thereby hastening recovery from IUS. Thus, Cd2+ ions may act like a foot-on-the-door, kicking the IS gate to close. PMID:17720727

  18. Method for removing metal ions from solution with titanate sorbents

    DOEpatents

    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.

  19. Improving cycle life of layered lithium transition metal oxide (LiMO2) based positive electrodes for Li ion batteries by smart selection of the electrochemical charge conditions

    NASA Astrophysics Data System (ADS)

    Kasnatscheew, Johannes; Evertz, Marco; Streipert, Benjamin; Wagner, Ralf; Nowak, Sascha; Cekic Laskovic, Isidora; Winter, Martin

    2017-08-01

    Increasing the specific energy of a lithium ion battery and maintaining its cycle life is a predominant goal and major challenge for electrochemical energy storage applications. Focusing on the positive electrode as the specific energy bottleneck, cycle life characteristics of promising layered oxide type active materials (LiMO2) has been thoroughly investigated. Comparing the variety of LiMO2 compositions, it could be shown that the ;Ni-rich; (Ni ≥ 60% for M in LiMO2) electrodes expectably revealed best performance compromises between specific energy and cycle life at 20 °C, but only LiNi0.6Mn0.2Co0.2O2 (NMC622) could also maintain sufficient cycle performance at elevated temperatures. Focusing on NMC622, it could be demonstrated that the applied electrochemical conditions (charge capacity, delithiation amount) in the formation cycles significantly influence the subsequent cycling performance. Moreover, the insignificant transition metal dissolution, demonstrated by means of total X-ray fluorescence (TXRF) technique, and unchanged lithiation degree in the discharged state, determined by the measurement of the Li+ content by means of the inductively coupled plasma optical emission spectroscopy (ICP-OES) technique, pointed to a delithiation (charge) hindrance capacity fade mechanism. Considering these insights, thoughtful modifications of the electrochemical charge conditions could significantly prolong the cycle life.

  20. Laboratory Evaluation of Ion-Selective Electrodes for Simultaneous Analysis of Macronutrients in Hydroponic Solution

    USDA-ARS?s Scientific Manuscript database

    Automated sensing of macronutrients in hydroponic solution would allow more efficient management of nutrients for crop growth in closed hydroponic systems. Ion-selective microelectrode technology requires an ion-selective membrane or a solid metal material that responds selectively to one analyte in...

  1. Headgroup interactions and ion flotation efficiency in mixtures of a chelating surfactant, different foaming agents, and divalent metal ions.

    PubMed

    Svanedal, Ida; Boija, Susanne; Norgren, Magnus; Edlund, Håkan

    2014-06-10

    The correlation between interaction parameters and ion flotation efficiency in mixtures of chelating surfactant metal complexes and different foaming agents was investigated. We have recently shown that chelating surfactant 2-dodecyldiethylenetriaminepentaacetic acid (4-C12-DTPA) forms strong coordination complexes with divalent metal ions, and this can be utilized in ion flotation. Interaction parameters for mixed micelles and mixed monolayer formation for Mg(2+) and Ni(2+) complexes with the chelating surfactant 4-C12-DTPA and different foaming agents were calculated by Rubingh's regular solution theory. Parameters for the calculations were extracted from surface tension measurements and NMR diffusometry. The effects of metal ion coordination on the interactions between 4-C12-DTPA and the foaming agents could be linked to a previously established difference in coordination chemistry between the examined metal ions. As can be expected from mixtures of amphoteric surfactants, the interactions were strongly pH-dependent. Strong correlation was found between interaction parameter β(σ) for mixed monolayer formation and the phase-transfer efficiency of Ni(2+) complexes with 4-C12-DTPA during flotation in a customized flotation cell. In a mixture of Cu(2+) and Zn(2+), the significant difference in conditional stability constants (log K) between the metal complexes was utilized to selectively recover the metal complex with the highest log K (Cu(2+)) by ion flotation. Flotation experiments in an excess concentration of metal ions confirmed the coordination of more than one metal ion to the headgroup of 4-C12-DTPA.

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

    PubMed

    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.

  3. Removal of metal ions from aqueous solution

    DOEpatents

    Jackson, Paul J.; Delhaize, Emmanuel; Robinson, Nigel J.; Unkefer, Clifford J.; Furlong, Clement

    1990-11-13

    A method of removing heavy metals from aqueous solution, a composition of matter used in effecting said removal, and apparatus used in effecting said removal. One or more of the polypeptides, poly (.gamma.-glutamylcysteinyl)glycines, is immobilized on an inert material in particulate form. Upon contact with an aqueous solution containing heavy metals, the polypeptides sequester the metals, removing them from the solution. There is selectivity of poly (.gamma.-glutamylcysteinyl)glycines having a particular number of monomer repeat unit for particular metals. The polypeptides are easily regenerated by contact with a small amount of an organic acid, so that they can be used again to remove heayv metals from solution. This also results in the removal of the metals from the column in a concentrated form.

  4. Removal of metal ions from aqueous solution

    DOEpatents

    Jackson, Paul J.; Delhaize, Emmanuel; Robinson, Nigel J.; Unkefer, Clifford J.; Furlong, Clement

    1990-01-01

    A method of removing heavy metals from aqueous solution, a composition of matter used in effecting said removal, and apparatus used in effecting said removal. One or more of the polypeptides, poly (.gamma.-glutamylcysteinyl)glycines, is immobilized on an inert material in particulate form. Upon contact with an aqueous solution containing heavy metals, the polypeptides sequester the metals, removing them from the solution. There is selectivity of poly (.gamma.-glutamylcysteinyl)glycines having a particular number of monomer repeat units for particular metals. The polypeptides are easily regenerated by contact with a small amount of an organic acid, so that they can be used again to remove heavy metals from solution. This also results in the removal of the metals from the column in a concentrated form.

  5. Ion irradiation effects on metallic nanocrystals

    SciTech Connect

    Kluth, P.; Johannessen, B.; Giulian, R.; Schnohr, C.S.; Foran, G.J.; Cookson, D.J.; Byrne, A.P.; Ridgway, M.C.

    2008-04-02

    We have investigated structural and morphological properties of metallic nanocrystals (NCs) exposed to ion irradiation. NCs were characterized by transmission electron microscopy in combination with advanced synchrotron-based analytical techniques, in particular X-ray absorption spectroscopy and small-angle X-ray scattering. A number of different effects were observed depending on the irradiation conditions. At energies where nuclear stopping is predominant, structural disorder/amorphization followed by inverse Ostwald ripening/dissolution due to ion beam mixing was observed for Au and Cu NCs embedded in SiO{sub 2}. The ion-irradiation-induced crystalline to amorphous transition in the NCs, which cannot be achieved in the corresponding bulk metals, was attributed to their initially higher structural energy as compared to bulk material and possibly preferential nucleation of the amorphous phase at the NC/SiO{sub 2} interface. At very high irradiation energies (swift heavy ion irradiation), where the energy loss is nearly entirely due to electronic stopping, a size-dependent shape transformation of the NCs from spheres to rod like shapes was apparent in Au NCs. Our preliminary results are in good agreement with considerations on melting of the NCs in the ion track as one mechanism involved in the shape transformation.

  6. New developments in metal ion implantation by vacuum arc ion sources and metal plasma immersion

    SciTech Connect

    Brown, I.G.; Anders, A.; Anders, S.

    1996-12-31

    Ion implantation by intense beams of metal ions can be accomplished using the dense metal plasma formed in a vacuum arc discharge embodied either in a vacuum arc ion source or in a metal plasma immersion configuration. In the former case high energy metal ion beams are formed and implantation is done in a more-or-less conventional way, and in the latter case the substrate is immersed in the plasma and repetitively pulse-biased so as to accelerate the ions at the high voltage plasma sheath formed at the substrate. A number of advances have been made in the last few years, both in plasma technology and in the surface modification procedures, that enhance the effectiveness and versatility of the methods, including for example: controlled increase of the in charge states produced; operation in a dual metal-gaseous ion species mode; very large area beam formation; macroparticle filtering; and the development of processing regimes for optimizing adhesion, morphology and structure. These complementary ion processing techniques provide the plasma tools for doing ion surface modification over a very wide parameter regime, from pure ion implantation at energies approaching the MeV level, through ion mixing at energies in the {approximately}1 to {approximately}100 keV range, to IBAD-like processing at energies from a few tens of eV to a few keV. Here the authors review the methods, describe a number of recent developments, and outline some of the surface modification applications to which the methods have been put. 54 refs., 9 figs.

  7. Mechanical property measurements on ion-irradiated metals

    SciTech Connect

    Zinkle, S.J.; Oliver, W.C.

    1986-08-01

    A recently developed mechanical properties microprobe (MPM) has been used to investigate strength and elastic modulus changes in ion-irradiated metals. The indenter load and its displacement are simultaneously monitored while the indentation is being made and also during unloading. Microindentation hardness measurements have been performed on ion-irradiated copper and Cu-0.15% Zr (AMZIRC). The depth dependence of the ion damage has been investigated in selected specimens which were prepared using a cross-section technique. This procedure allows a direct comparison to be made of hardness data from different irradiation depths while the indent size is held constant. The displacement damage associated with ion irradiation caused either hardening or softening, depending on the irradiation conditions and the material.

  8. Fluorescence enhancement of photoswitchable metal ion sensors

    NASA Astrophysics Data System (ADS)

    Sylvia, Georgina; Heng, Sabrina; Abell, Andrew D.

    2016-12-01

    Spiropyran-based fluorescence sensors are an ideal target for intracellular metal ion sensing, due to their biocompatibility, red emission frequency and photo-controlled reversible analyte binding for continuous signal monitoring. However, increasing the brightness of spiropyran-based sensors would extend their sensing capability for live-cell imaging. In this work we look to enhance the fluorescence of spiropyran-based sensors, by incorporating an additional fluorophore into the sensor design. We report a 5-membered monoazacrown bearing spiropyran with metal ion specificity, modified to incorporate the pyrene fluorophore. The effect of N-indole pyrene modification on the behavior of the spiropyran molecule is explored, with absorbance and fluorescence emission characterization. This first generation sensor provides an insight into fluorescence-enhancement of spiropyran molecules.

  9. Interplay of metal ions and urease

    PubMed Central

    Carter, Eric L.; Flugga, Nicholas; Boer, Jodi L.; Mulrooney, Scott B.; Hausinger, Robert P.

    2009-01-01

    Summary Urease, the first enzyme to be crystallized, contains a dinuclear nickel metallocenter that catalyzes the decomposition of urea to produce ammonia, a reaction of great agricultural and medical importance. Several mechanisms of urease catalysis have been proposed on the basis of enzyme crystal structures, model complexes, and computational efforts, but the precise steps in catalysis and the requirement of nickel versus other metals remain unclear. Purified bacterial urease is partially activated via incubation with carbon dioxide plus nickel ions; however, in vitro activation also has been achieved with manganese and cobalt. In vivo activation of most ureases requires accessory proteins that function as nickel metallochaperones and GTP-dependent molecular chaperones or play other roles in the maturation process. In addition, some microorganisms control their levels of urease by metal ion-dependent regulatory mechanisms. PMID:20046957

  10. Effects of metal ion adduction on the gas-phase conformations of protein ions.

    PubMed

    Flick, Tawnya G; Merenbloom, Samuel I; Williams, Evan R

    2013-11-01

    Changes in protein ion conformation as a result of nonspecific adduction of metal ions to the protein during electrospray ionization (ESI) from aqueous solutions were investigated using traveling wave ion mobility spectrometry (TWIMS). For all proteins examined, protein cations (and in most cases anions) with nonspecific metal ion adducts are more compact than the fully protonated (or deprotonated) ions with the same charge state. Compaction of protein cations upon nonspecific metal ion binding is most significant for intermediate charge state ions, and there is a greater reduction in collisional cross section with increasing number of metal ion adducts and increasing ion valency, consistent with an electrostatic interaction between the ions and the protein. Protein cations with the greatest number of adducted metal ions are no more compact than the lowest protonated ions formed from aqueous solutions. These results show that smaller collisional cross sections for metal-attached protein ions are not a good indicator of a specific metal-protein interaction in solution because nonspecific metal ion adduction also results in smaller gaseous protein cation cross sections. In contrast, the collisional cross section of α-lactalbumin, which specifically binds one Ca(2+), is larger for the holo-form compared with the apo-form, in agreement with solution-phase measurements. Because compaction of protein cations occurs when metal ion adduction is nonspecific, elongation of a protein cation may be a more reliable indicator that a specific metal ion-protein interaction occurs in solution.

  11. Effects of Metal Ion Adduction on the Gas-Phase Conformations of Protein Ions

    PubMed Central

    Flick, Tawnya G.; Merenbloom, Samuel I.; Williams, Evan R.

    2013-01-01

    Changes in protein ion conformation as a result of nonspecific adduction of metal ions to the protein during electrospray ionization (ESI) from aqueous solutions were investigated using traveling wave ion mobility spectrometry (TWIMS). For all proteins examined, protein cations (and in most cases anions) with nonspecific metal ion adducts are more compact than the fully protonated (or deprotonated) ions with the same charge state. Compaction of protein cations upon nonspecific metal ion binding is most significant for intermediate charge state ions, and there is a greater reduction in collisional cross section with increasing number of metal ion adducts and increasing ion valency, consistent with an electrostatic interaction between the ions and the protein. Protein cations with the greatest number of adducted metal ions are no more compact than the lowest protonated ions formed from aqueous solutions. These results show that smaller collisional cross sections for metal-attached protein ions are not a good indicator of a specific metal-protein interaction in solution, because nonspecific metal ion adduction also results in smaller gaseous protein cation cross sections. In contrast, the collisional cross section of α-lactalbumin, which specifically binds one Ca2+, is larger for the holo-form compared to the apo-form, in agreement with solution-phase measurements. Because compaction of protein cations occurs when metal ion adduction is nonspecific, elongation of a protein cation may be a more reliable indicator that a specific metal ion-protein interaction occurs in solution. PMID:23733259

  12. High current metal ion implantation facility

    SciTech Connect

    Oztarhan, A.; Brown, I.G.; Evans, P.; Watt, G.; Bakkaloglu, C.; Eltas, A.S.; Oks, E.

    1998-12-31

    A vacuum arc ion source based metal ion implantation facility has been established at Dokuz Eylul University, Izmir, Turkey and a surface modification research and development program is underway. The system is similar to the one in Lawrence Berkeley Laboratory which was first built and developed by Brown et al. The broad-beam ion source is repetitively pulsed at rates up to {approximately}10 pulses per second (can be increased to 50 pulses per second) and the extracted ion beam current can be up to {approximately}1 Amp. peak or {approximately}10 mA time averaged. The ion source extraction voltage was increased to 60 kV corresponding to mean beam energies of up to 150 keV or more because of the ion charge state multiplicity (extraction voltage can be increased to 100 kV if desired). Commissioning of the facility is in progress. Initial emphasis of the R and D programs that will be carried out will be in forming tribologically enhanced materials for industrial applications. In this paper they describe the design and operation of the implanter, summarize the preliminary performance parameters that have been obtained, and outline some of the programs they anticipate doing.

  13. Ion-Induced Electron Emission from Metals

    NASA Astrophysics Data System (ADS)

    Kirchhoff, Joseph Francis

    1992-01-01

    Ion-induced electron emission (IIEE) from several metals under 100 keV proton bombardment has been investigated. Room temperature (RT) yields, i.e., the number of electrons emitted per incident ion, were measured for gold, copper, and indium after sputter cleaning and agreed with published values. New experimental results indicate a lowering of the RT yield after ultra-high vacuum anneals and very light sputtering. Previously published RT yields, gamma _{rm sputtered}, were measured only after extensive sputter cleaning. Copper, after an anneal near 390^circC, had a room temperature gamma_{rm anneal} = 1.58 +/- 0.02 e^-/ion with gamma _{rm sputtered} = 1.77 +/- 0.02 e^-/ion. The yield for solid indium after melting and resolidification was measured as gamma_{rm anneal} = 1.69 +/- 0.02 e^-/ion with gamma _{rm sputtered} = 1.95 +/- 0.03 e^-/ion. It is believed that annealing orders the surface, while gamma_{rm sputtered} yield values are from disordered surfaces. Yield data as a function of target temperature were also measured. For copper and indium, yields were found to vary linearly with temperature up to at least 330^circC for Cu and 195 ^circC for In. The dgamma/ dT values found were 2.7 +/- 0.2 times 10^{ -4} and 3.3 +/- 0.3 times 10^{-4} e^-/ion/K, respectively. Yields for liquid indium and through the melting transition were also measured. UHV yields for liquid metals have not been reported before. After melting, no change was found in the yield (|Deltagamma/gamma |<0.2%). A semi-empirical model for the yields in nearly free electron metals has been developed and is based on the formalism of Sigmund and Tougaard. It suggests a strong dependence of yield on the surface potential barrier, U, which must be overcome for emission. The dependence of gamma on U^{ -2.5} has not been previously realized. The model explains yields measured by others, as well as the temperature dependent yield phenomena observed in this study. It also predicts relatively large yields

  14. Ion-selective self-referencing probes for measuring specific ion flux

    PubMed Central

    Reid, Brian

    2011-01-01

    The metal vibrating probe developed in the 1970s to measure electric current is sensitive down to the micro-Amp range, but detects only net current due to flow of multiple ions and is too large to measure from single cells. Electrophysiological techniques which use glass microelectrodes such as voltage clamping can be used on single cells but are also non-specific. Ion-selective probes are glass microelectrodes containing at their tip a small amount of ionophore permeable to a particular ion. The electrode is therefore sensitive to changes in concentration of this ion. If the probe tip is moved at low frequency between two points in a concentration gradient of this ion then the electrochemical potential of the solution inside the electrode fluctuates in proportion to the size of the ion gradient. This fluctuation is amplified and recorded and is used to calculate the actual ion flux using Fick's law of diffusion. In this mini-review we describe the technique of ion-selective self-referencing microelectrodes to measure specific ion fluxes. We discuss the development of the technique and describe in detail the methodology and present some representative results. PMID:22046453

  15. Interaction of metal ions with biomolecular ligands: how accurate are calculated free energies associated with metal ion complexation?

    PubMed

    Gutten, Ondrej; Beššeová, Ivana; Rulíšek, Lubomír

    2011-10-20

    To address fundamental questions in bioinorganic chemistry, such as metal ion selectivity, accurate computational protocols for both the gas-phase association of metal-ligand complexes and solvation/desolvation energies of the species involved are needed. In this work, we attempt to critically evaluate the performance of the ab initio and DFT electronic structure methods available and recent solvation models in calculations of the energetics associated with metal ion complexation. On the example of five model complexes ([M(II)(CH(3)S)(H(2)O)](+), [M(II)(H(2)O)(2)(H(2)S)(NH(3))](2+), [M(II)(CH(3)S)(NH(3))(H(2)O)(CH(3)COO)], [M(II)(H(2)O)(3)(SH)(CH(3)COO)(Im)], [M(II)(H(2)S)(H(2)O)(CH(3)COO)(PhOH)(Im)](+) in typical coordination geometries) and four metal ions (Fe(2+), Cu(2+), Zn(2+), and Cd(2+); representing open- and closed-shell and the first- and second-row transition metal elements), we provide reference values for the gas-phase complexation energies, as presumably obtained using the CCSD(T)/aug-cc-pVTZ method, and compare them with cheaper methods, such as DFT and RI-MP2, that can be used for large-scale calculations. We also discuss two possible definitions of interaction energies underlying the theoretically predicted metal-ion selectivity and the effect of geometry optimization on these values. Finally, popular solvation models, such as COSMO-RS and SMD, are used to demonstrate whether quantum chemical calculations can provide the overall free enthalpy (ΔG) changes in the range of the expected experimental values for the model complexes or match the experimental stability constants in the case of three complexes for which the experimental data exist. The data presented highlight several intricacies in the theoretical predictions of the experimental stability constants: the covalent character of some metal-ligand bonds (e.g., Cu(II)-thiolate) causing larger errors in the gas-phase complexation energies, inaccuracies in the treatment of solvation of the

  16. Metal hydrides for lithium-ion batteries.

    PubMed

    Oumellal, Y; Rougier, A; Nazri, G A; Tarascon, J-M; Aymard, L

    2008-11-01

    Classical electrodes for Li-ion technology operate via an insertion/de-insertion process. Recently, conversion electrodes have shown the capability of greater capacity, but have so far suffered from a marked hysteresis in voltage between charge and discharge, leading to poor energy efficiency and voltages. Here, we present the electrochemical reactivity of MgH(2) with Li that constitutes the first use of a metal-hydride electrode for Li-ion batteries. The MgH(2) electrode shows a large, reversible capacity of 1,480 mAh g(-1) at an average voltage of 0.5 V versus Li(+)/Li(o) which is suitable for the negative electrode. In addition, it shows the lowest polarization for conversion electrodes. The electrochemical reaction results in formation of a composite containing Mg embedded in a LiH matrix, which on charging converts back to MgH(2). Furthermore, the reaction is not specific to MgH(2), as other metal or intermetallic hydrides show similar reactivity towards Li. Equally promising, the reaction produces nanosized Mg and MgH(2), which show enhanced hydrogen sorption/desorption kinetics. We hope that such findings can pave the way for designing nanoscale active metal elements with applications in hydrogen storage and lithium-ion batteries.

  17. Biomimetic ion nanochannels as a highly selective sequential sensor for zinc ions followed by phosphate anions.

    PubMed

    Han, Cuiping; Su, Haiyan; Sun, Zhongyue; Wen, Long; Tian, Demei; Xu, Kai; Hu, Junfeng; Wang, Aming; Li, Haibing; Jiang, Lei

    2013-07-08

    A novel biomimetic ion-responsive multi-nanochannel system is constructed by covalently immobilizing a metal-chelating ligand, 2,2'-dipicolylamine (DPA), in polyporous nanochannels prepared in a polymeric membrane. The DPA-modified multi-nanochannels show specific recognition of zinc ions over other common metal ions, and the zinc-ion-chelated nanochannels can be used as secondary sensors for HPO4(2-) anions. The immobilized DPA molecules act as specific-receptor binding sites for zinc ions, which leads to the highly selective zinc-ion response through monitoring of ionic current signatures. The chelated zinc ions can be used as secondary recognition elements for the capture of HPO4(2-) anions, thereby fabricating a sensing nanodevice for HPO4(2-) anions. The success of the DPA immobilization and ion-responsive events is confirmed by measurement of the X-ray photoelectron spectroscopy (XPS), contact angle (CA), and current-voltage (I-V) characteristics of the systems. The proposed nanochannel sensing devices display remarkable specificity, high sensitivity, and wide dynamic range. In addition, control experiments performed in complex matrices suggest that this sensing system has great potential applications in chemical sensing, biotechnology, and many other fields.

  18. Metal assisted focused-ion beam nanopatterning

    NASA Astrophysics Data System (ADS)

    Kannegulla, Akash; Cheng, Li-Jing

    2016-09-01

    Focused-ion beam milling is a versatile technique for maskless nanofabrication. However, the nonuniform ion beam profile and material redeposition tend to disfigure the surface morphology near the milling areas and degrade the fidelity of nanoscale pattern transfer, limiting the applicability of the technique. The ion-beam induced damage can deteriorate the performance of photonic devices and hinders the precision of template fabrication for nanoimprint lithography. To solve the issue, we present a metal assisted focused-ion beam (MAFIB) process in which a removable sacrificial aluminum layer is utilized to protect the working material. The new technique ensures smooth surfaces and fine milling edges; in addition, it permits direct formation of v-shaped grooves with tunable angles on dielectric substrates or metal films, silver for instance, which are rarely achieved by using traditional nanolithography followed by anisotropic etching processes. MAFIB was successfully demonstrated to directly create nanopatterns on different types of substrates with high fidelity and reproducibility. The technique provides the capability and flexibility necessary to fabricate nanophotonic devices and nanoimprint templates.

  19. Liquid metal ion source assembly for external ion injection into an electron string ion source (ESIS)

    SciTech Connect

    Segal, M. J.; Bark, R. A.; Thomae, R.; Donets, E. E.; Donets, E. D.; Boytsov, A.; Ponkin, D.; Ramsdorf, A.

    2016-02-15

    An assembly for a commercial Ga{sup +} liquid metal ion source in combination with an ion transportation and focusing system, a pulse high-voltage quadrupole deflector, and a beam diagnostics system has been constructed in the framework of the iThemba LABS (Cape Town, South Africa)—JINR (Dubna, Russia) collaboration. First, results on Ga{sup +} ion beam commissioning will be presented. Outlook of further experiments for measurements of charge breeding efficiency in the electron string ion source with the use of external injection of Ga{sup +} and Au{sup +} ion beams will be reported as well.

  20. Liquid metal ion source assembly for external ion injection into an electron string ion source (ESIS)

    NASA Astrophysics Data System (ADS)

    Segal, M. J.; Bark, R. A.; Thomae, R.; Donets, E. E.; Donets, E. D.; Boytsov, A.; Ponkin, D.; Ramsdorf, A.

    2016-02-01

    An assembly for a commercial Ga+ liquid metal ion source in combination with an ion transportation and focusing system, a pulse high-voltage quadrupole deflector, and a beam diagnostics system has been constructed in the framework of the iThemba LABS (Cape Town, South Africa)—JINR (Dubna, Russia) collaboration. First, results on Ga+ ion beam commissioning will be presented. Outlook of further experiments for measurements of charge breeding efficiency in the electron string ion source with the use of external injection of Ga+ and Au+ ion beams will be reported as well.

  1. Transparent monolithic metal ion containing nanophase aerogels

    SciTech Connect

    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.

  2. Controlled Segmentation of Metal Nanowire Array by Block Copolymer Lithography and Reversible Ion Loading.

    PubMed

    Mun, Jeong Ho; Cha, Seung Keun; Kim, Ye Chan; Yun, Taeyeong; Choi, Young Joo; Jin, Hyeong Min; Lee, Jae Eun; Jeon, Hyun Uk; Kim, So Youn; Kim, Sang Ouk

    2017-02-20

    Spatial arrangement of 1D nanomaterials may offer enormous opportunities for advanced electronics and photonics. Moreover, morphological complexity and chemical diversity in the nanoscale components may lead to unique properties that are hardly anticipated in randomly distributed homogeneous nanostructures. Here, controlled chemical segmentation of metal nanowire arrays using block copolymer lithography and subsequent reversible metal ion loading are demonstrated. To impose chemical heterogeneity in the nanowires generated by block copolymer lithography, reversible ion loading method highly specific for one particular polymer block is introduced. Reversibility of the metal ion loading enables area-selective localized replacement of metal ions in the self-assembled patterns and creates segmented metal nanowire arrays with different metallic components. Further integration of this method with shear aligning process produces high aligned segmented metal nanowire array with desired local chemical compositions.

  3. Selective coulometric release of ions from ion selective polymeric membranes for calibration-free titrations.

    PubMed

    Bhakthavatsalam, Vishnupriya; Shvarev, Alexey; Bakker, Eric

    2006-08-01

    Coulometry belongs to one of the few known calibration-free techniques and is therefore highly attractive for chemical analysis. Titrations performed by the coulometric generation of reactants is a well-known approach in electrochemistry, but suffers from limited selectivity and is therefore not generally suited for samples of varying or unknown composition. Here, the selective coulometric release of ionic reagents from ion-selective polymeric membrane materials ordinarily used for the fabrication of ion-selective electrodes is described. The selectivity of such membranes can be tuned to a significant extent by the type and concentration of ionophore and lipophilic ion-exchanger and is today well understood. An anodic current of fixed magnitude and duration may be imposed across such a membrane to release a defined quantity of ions with high selectivity and precision. Since the applied current relates to a defined ion flux, a variety of non-redox active ions may be accurately released with this technique. In this work, the released titrant's activity was measured with a second ionophore-based ion-selective electrode and corresponded well with expected dosage levels on the basis of Faraday's law of electrolysis. Initial examples of coulometric titrations explored here include the release of calcium ions for complexometric titrations, including back titrations, and the release of barium ions to determine sulfate.

  4. Metal ion binding to iron oxides

    NASA Astrophysics Data System (ADS)

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

    2006-06-01

    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 show that it is possible to model the adsorption of protons and TE on a crystallized oxide (i.e., goethite) and on an amorphous oxide (HFO) in an identical way. Here, we use the CD-MUSIC approach in combination with valuable and reliable surface spectroscopy information about the nature of surface complexes of the TE. The other objective of this work is to obtain generic parameters to describe the binding of the following elements (Cd, Co, Cu, Ni, Pb, and Zn) onto both iron oxides for the CD-MUSIC approach. The results show that a consistent description of proton and metal ion binding is possible for goethite and HFO with the same set of model parameters. In general a good prediction of almost all the collected experimental data sets corresponding to metal ion binding to HFO is obtained. Moreover, dominant surface species are in agreement with the recently published surface complexes derived from X-ray absorption spectroscopy (XAS) data. Until more detailed information on the structure of the two iron oxides is available, the present option seems a reasonable approximation and can be used to describe complex geochemical systems. To improve our understanding and modeling of multi-component systems we need more data obtained at much lower metal ion to iron oxide ratios in order to be able to account eventually for sites that are not always characterized in spectroscopic studies.

  5. Metal-organic frameworks with 1,4-di(1H-imidazol-4-yl)benzene and varied carboxylate ligands for selectively sensing Fe(iii) ions and ketone molecules.

    PubMed

    Liu, Zhi-Qiang; Zhao, Yue; Zhang, Xiu-Du; Kang, Yan-Shang; Lu, Qing-Yi; Azam, Mohammad; Al-Resayes, Saud I; Sun, Wei-Yin

    2017-10-03

    Four new metal-organic frameworks (MOFs) [Zn(L)(bpdc)]·1.6H2O (1), [Co(L)(bpdc)]·H2O (2), [Ni3(L)2(bptc)2(H2O)10]·2H2O (3) and [Cd2(L)(Hbptc)2] (4) were achieved by reactions of the corresponding metal salt with mixed organic ligands of 1,4-di(1H-imidazol-4-yl)benzene (L) and 4,4'-benzophenonedicarboxylic acid (H2bpdc) or biphenyl-2,4',5-tricarboxylic acid (H3bptc). They exhibit varied structures: MOFs 1 and 4 are porous three-dimensional (3D) frameworks, while 2 is an infinite one-dimensional (1D) chain and 3 is a two-dimensional (2D) network. Remarkably, 1 and 4 can act as potential fluorescent materials for sensing Fe(iii) ions and different ketone molecules with high selectivity and sensitivity. In addition, MOF 1 shows selective adsorption of CO2 over N2.

  6. Rational Design of Metal Ion Sequestering Agents

    SciTech Connect

    Raymond, Kenneth N.

    2000-09-30

    The discriminate bonding of metal ions is a challenge to the synthetic chemist and a phenomenon of considerable practical importance.1 An important feature of many technical applications is the specific or preferential binding of a single metal ion in the presence of many metals. Examples range from large-volume uses (e.g. ferric EDTA as a plant food, calcium complexing agents as water softeners or anticaking formulations) to very high technology applications (technetium complexation in radiopharmaceuticals, synthetic metalloenzymes). We are interested in efficient and discriminate binding of actinides for waste stream remediation. Actinides represent a major and long-lived contaminant in nuclear waste. While the separation of actinides from other radioactive components of waste, such as Sr and Cs, is relatively well established, the separation of actinides from each other and in complex solutions (e.g. those found in tank wastes) is not as well resolved. The challenge of designing metal-specific (actinide) ligands is facilitated by examples from nature. Bacteria synthesize Fe(III)-specific ligands, called siderophores, to sequester Fe(III) from the environment and return it to the cell. The similarities between Fe(III) and Pu(IV) (their charge-to-size ratios and acidity), make the siderophores prototypical for designing actinide-specific ligands. The chelating groups present in siderophores are usually hydroxamic acids and catecholamides. We have developed derivatives of these natural products which have improved properties. The catechol derivatives are the 2,3-dihydroxyterephthalamides (TAMs), and 3,4-dihydroxysulfonamides (SFAMs), and the hydroxamic acid derivatives are three isomers of hydroxypyridinones, 1,2- HOPO, 3,2-HOPO, and 3,4-HOPO. All of these ligands are attached to molecular backbones by amides and a very important feature of HOPO and CAM ligands is a strong hydrogen bonds formed between the amide proton and the adjacent phenolic oxygen in the metal

  7. How do metal ions direct ribozyme folding?

    NASA Astrophysics Data System (ADS)

    Denesyuk, Natalia A.; Thirumalai, D.

    2015-10-01

    Ribozymes, which carry out phosphoryl-transfer reactions, often require Mg2+ ions for catalytic activity. The correct folding of the active site and ribozyme tertiary structure is also regulated by metal ions in a manner that is not fully understood. Here we employ coarse-grained molecular simulations to show that individual structural elements of the group I ribozyme from the bacterium Azoarcus form spontaneously in the unfolded ribozyme even at very low Mg2+ concentrations, and are transiently stabilized by the coordination of Mg2+ ions to specific nucleotides. However, competition for scarce Mg2+ and topological constraints that arise from chain connectivity prevent the complete folding of the ribozyme. A much higher Mg2+ concentration is required for complete folding of the ribozyme and stabilization of the active site. When Mg2+ is replaced by Ca2+ the ribozyme folds, but the active site remains unstable. Our results suggest that group I ribozymes utilize the same interactions with specific metal ligands for both structural stability and chemical activity.

  8. Laser materials based on transition metal ions

    NASA Astrophysics Data System (ADS)

    Moncorgé, Richard

    2017-01-01

    The purpose of this presentation is to review the spectroscopic properties of the main laser materials based on transition metal ions which lead to noticeable laser performance at room temperature and, for very few cases, because of unique properties, when they are operated at cryogenic temperatures. The description also includes the materials which are currently being used as saturable absorbers for passive-Q-switching of a variety of other near- and mid-infrared solid state lasers. A substantial part of the article is devoted first to the description of the energy levels and of the absorption and emission transitions of the transition metal ions in various types of environments by using the well-known Tanabe-Sugano diagrams. It is shown in particular how these diagrams can be used along with other theoretical considerations to understand and describe the spectroscopic properties of ions sitting in crystal field environments of near-octahedral or near-tetrahedral symmetry. The second part is then dedicated to the description (positions and intensities) of the main absorption and emission features which characterize the different types of materials.

  9. Site-selective hydrolysis of tRNA by lanthanide metal complexes

    SciTech Connect

    Hayashi, Nobuhiro ); Takeda, Naoya; Yashiro, Morio; Watanabe, Kimitsuna; Komiyama, Makoto ); Shiiba, Tetsuro )

    1993-12-22

    tRNA[sup Phe] is site-selectively hydrolyzed by lanthanide metal complexes (Ce(III), Eu(III), La(III)) of hexaimine macrocyclic ligands. The selectivities of the complexes are much higher than those of the metal ions and are strongly dependent on the ligand structure. The tertiary structure of tRNA is essential for the site-selective scission.

  10. New Catalytic DNA Biosensors for Radionuclides and Metal ions

    SciTech Connect

    Lu, Yi

    2003-06-01

    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.

  11. New Catalytic DNA Biosensors for Radionuclides and Metal ions

    SciTech Connect

    Lu, Yi

    2002-06-01

    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.

  12. Functional nucleic acid-based sensors for heavy metal ion assays.

    PubMed

    Zhu, Guichi; Zhang, Chun-yang

    2014-12-21

    Heavy metal contaminants such as lead ions (Pb(2+)), mercury ions (Hg(2+)) and silver ions (Ag(+)) can cause significant harm to humans and generate enduring bioaccumulation in ecological systems. Even though a variety of methods have been developed for Pb(2+), Hg(2+) and Ag(+) assays, most of them are usually laborious and time-consuming with poor sensitivity. Due to their unique advantages of excellent catalytic properties and high affinity for heavy metal ions, functional nucleic acids such as DNAzymes and aptamers show great promise in the development of novel sensors for heavy metal ion assays. In this review, we summarize the development of functional nucleic acid-based sensors for the detection of Pb(2+), Hg(2+) and Ag(+), and especially focus on two categories including the direct assay and the amplification-based assay. We highlight the emerging trends in the development of sensitive and selective sensors for heavy metal ion assays as well.

  13. Antifungal Properties of Electrically Generated Metallic Ions

    PubMed Central

    Berger, T. J.; Spadaro, J. A.; Bierman, Richard; Chapin, S. E.; Becker, R. O.

    1976-01-01

    A qualitative and quantitative investigation was undertaken to study the susceptibility of unicellular eucaryotic organisms (yeasts) to metallic cations generated by low levels of direct current. Results were characteristic of effects obtained previously using clinical and standard bacteria test organisms. The present study demonstrated that anodic silver (Ag+) at low direct currents had inhibitory and fungicidal properties. Broth dilution susceptibility tests were made on several species of Candida and one species of Torulopsis. Growth in all isolates was inhibited by concentrations of electrically generated silver ions between 0.5 and 4.7 μg/ml, and silver exhibited fungicidal properties at concentrations as low as 1.9 μg/ml. The inhibitory and fungicidal concentrations of electrically generated silver ions are lower than those reported for other silver compounds. Images PMID:1034467

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

    DOEpatents

    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.

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

    DOEpatents

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

    2017-01-24

    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.

  16. New Metal Niobate and Silicotitanate Ion Exchangers: Development and Characterization

    SciTech Connect

    Alexandra Navrotsky; Mary Lou Balmer; Tina M. Nenoff; Yali Su

    2003-12-05

    This renewal proposal outlines our current progress and future research plans for ion exchangers: novel metal niobate and silicotitanate ion exchangers and their ultimate deployment in the DOE complex. In our original study several forms (including Cs exchanged) of the heat treated Crystalline Silicotitanates (CSTs) were fully characterized by a combination of high temperature synthesis and phase identification, low temperature synthesis and phase identification, and thermodynamics. This renewal proposal is predicated on work completed in our current EMSP program: we have shown preliminary data of a novel class of niobate-based molecular sieves (Na/Nb/M/O, M = transition metals), which show exceptionally high selectivity for divalent cations under extreme conditions (acid solutions, competing cations), in addition to novel silicotitanate phases which are also selective for divalent cations. Furthermore, these materials are easily converted by a high temperature in-situ heat treatment into a refractory ceramic waste form with low cation leachability. The new waste form is a perovskite phase, which is also a major component of Synroc, a titanate ceramic waste form used for sequestration of HLW wastes from reprocessed, spent nuclear fuel. These new niobate ion exchangers also shown orders of magnitude better selectivity for Sr2+ under acid conditions than any other material. The goal of the program is to reduce the costs associated with divalent cation waste removal and disposal, to minimize the risk of contamination to the environment during ion exchanger processing, and to provide DOE with materials for near-term lab-bench stimulant testing, and eventual deployment. The proposed work will provide information on the structure/property relationship between ion exchanger frameworks and selectivity for specific ions, allowing for the eventual ''tuning'' of framework for specific ion exchange needs. To date, DOE sites have become interested in on-site testing of these

  17. Structural aspects of rubidium ion selectivity by tribenzo-21-crown-7

    SciTech Connect

    Bryan, J.C.; Sachleben, R.A.; Lavis, J.M.; Davis, M.C.; Burns, J.H.; Hay, B.P.

    1998-06-01

    The structural origins of the selectivity of rubidium ion over other alkali metal ions (Cs, Rb, Na, Re) by tribenzo-21-crown-7 is investigated from single-crystal X-ray diffraction. The structures reported here are the first reported for a tribenzo-21-crown-7, and the alkali metal ion complexes are the first reported structures of these ions with any 21-crown-7 ether. Different crown conformations are observed for each structure. Molecular mechanics calculations were performed on all conformers, and the results are related to the observed extraction selectivity for rubidium.

  18. Yeast metallothionein function in metal ion detoxification.

    PubMed

    Ecker, D J; Butt, T R; Sternberg, E J; Neeper, M P; Debouck, C; Gorman, J A; Crooke, S T

    1986-12-25

    A genetic approach was taken to test the function of yeast metallothionein in metal ion detoxification. A yeast strain was constructed in which the metallothionein locus was deleted (cup1 delta). The cup1 delta strain was complemented with normal or mutant metallothionein genes under normal or constitutive regulatory control on high copy episomal plasmids. Metal resistance of the cup1 delta strain with and without the metallothionein-expressing vectors was analyzed. The normally regulated metallothionein gene conferred resistance only to copper (1000-fold); constitutively expressed metallothionein conferred resistance to both copper (500-fold) and cadmium (1000-fold), but not to mercury, zinc, silver, cobalt, nickel, gold, platinum, lanthanum, uranium, or tin. Two mutant versions of the metallothionein gene were constructed and tested for their ability to confer metal resistance in the cup1 delta background. The first had a deletion of a highly conserved amino acid sequence (Lys-Lys-Ser-Cys-Cys-Ser). The second was a hybrid gene consisting of the sequences coding for the first 20 amino acids of the yeast protein fused to the monkey metallothionein gene. Expression of these genes under the CUP1 promoter provided significant protection from copper, but none of the other metals tested. These results demonstrate that there is significant flexibility in the structural requirements for metallothionein to function in copper detoxification and that yeast metallothionein is also capable of detoxifying cadmium under conditions of constitutive expression.

  19. Microfluidic Systems with Ion-Selective Membranes

    NASA Astrophysics Data System (ADS)

    Slouka, Zdenek; Senapati, Satyajyoti; Chang, Hsueh-Chia

    2014-06-01

    When integrated into microfluidic chips, ion-selective nanoporous polymer and solid-state membranes can be used for on-chip pumping, pH actuation, analyte concentration, molecular separation, reactive mixing, and molecular sensing. They offer numerous functionalities and are hence superior to paper-based devices for point-of-care biochips, with only slightly more investment in fabrication and material costs required. In this review, we first discuss the fundamentals of several nonequilibrium ion current phenomena associated with ion-selective membranes, many of them revealed by studies with fabricated single nanochannels/nanopores. We then focus on how the plethora of phenomena has been applied for transport, separation, concentration, and detection of biomolecules on biochips.

  20. Radioactive Ion Beam Purification by Selective Adsorption

    NASA Astrophysics Data System (ADS)

    Jost, C.; Carter, H. K.; Griffith, B. O.; Reed, C. A.; Kratz, K.-L.; Stora, T.; Stracener, D. W.

    2008-10-01

    Isobaric contaminations in ISOL beams are a recurrent problem in nuclear physics experiments. Surface effects in the transfer line between target and ion source can be employed to achieve additional selectivity. Since interactions of the atoms' outer electrons with the surface determine adsorption behavior it can change drastically within an isobaric chain, introducing a chemical selectivity. Quartz transfer lines are currently applied at ISOLDE to reduce alkali contaminations [1]. We will conduct an on-line study of the adsorption behavior of fission products on a range of materials stable at high temperatures. Therefore a special target--ion source unit with a variable-temperature transfer line and interchangeable liner has been constructed in collaboration with the ISOLDE technical group. Results of first tests using new adsorption materials at the on-line separator test facility at Holifield Radioactive Ion Beam Facility, ORNL, will be presented. [1] Bouquerel et al., Europ. Phys. J. -- Spec. Top. 150, 277 (2006)

  1. Ion imprinted polymeric nanoparticles for selective separation and sensitive determination of zinc ions in different matrices.

    PubMed

    Shamsipur, Mojtaba; Rajabi, Hamid Reza; Pourmortazavi, Seied Mahdi; Roushani, Mahmoud

    2014-01-03

    Preparation of Zn(2+) ion-imprinted polymer (Zn-IIP) nanoparticles is presented in this report. The Zn-IIP nanoparticles are prepared by dissolving stoichiometric amounts of zinc nitrate and selected chelating ligand, 3,5,7,20,40-pentahydroxyflavone, in 15 mL ethanol-acetonitrile (2:1; v/v) mixture as a porogen solvent in the presence of ethylene glycol-dimethacrylate (EGDMA) as cross-linking, methacrylic acid (MAA) as functional monomer, and 2,2-azobisisobutyronitrile (AIBN) as initiator. After polymerization, Cavities in the polymer particles corresponding to the Zn(2+) ions were created by leaching the polymer in HCl aqueous solution. The synthesized IIPs were characterized by scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, fluorescence spectroscopy and thermal analysis techniques. Also, the pH range for rebinding of Zn(2+) ion on the IIP and equilibrium binding time were optimized, using flame atomic absorption spectrometry. In selectivity study, it was found that imprinting results increased affinity of the material toward Zn(2+) ion over other competitor metal ions with the same charge and close ionic radius. The prepared IIPs were repeatedly used and regenerated for six times without any significant decrease in polymer binding affinities. Finally, the prepared sorbent was successfully applied to the selective recognition and determination of zinc ion in different real samples.

  2. Metal-ion rescue revisited: biochemical detection of site-bound metal ions important for RNA folding.

    PubMed

    Frederiksen, John K; Li, Nan-Sheng; Das, Rhiju; Herschlag, Daniel; Piccirilli, Joseph A

    2012-06-01

    Within the three-dimensional architectures of RNA molecules, divalent metal ions populate specific locations, shedding their water molecules to form chelates. These interactions help the RNA adopt and maintain specific conformations and frequently make essential contributions to function. Defining the locations of these site-bound metal ions remains challenging despite the growing database of RNA structures. Metal-ion rescue experiments have provided a powerful approach to identify and distinguish catalytic metal ions within RNA active sites, but the ability of such experiments to identify metal ions that contribute to tertiary structure acquisition and structural stability is less developed and has been challenged. Herein, we use the well-defined P4-P6 RNA domain of the Tetrahymena group I intron to reevaluate prior evidence against the discriminatory power of metal-ion rescue experiments and to advance thermodynamic descriptions necessary for interpreting these experiments. The approach successfully identifies ligands within the RNA that occupy the inner coordination sphere of divalent metal ions and distinguishes them from ligands that occupy the outer coordination sphere. Our results underscore the importance of obtaining complete folding isotherms and establishing and evaluating thermodynamic models in order to draw conclusions from metal-ion rescue experiments. These results establish metal-ion rescue as a rigorous tool for identifying and dissecting energetically important metal-ion interactions in RNAs that are noncatalytic but critical for RNA tertiary structure.

  3. Polymer-Supported Reagents: The Role of Bifunctionality in the Design of Ion-Selective Complexants

    SciTech Connect

    Alexandratos, S. D.

    2001-06-01

    The importance of multi-functionality in the preparation of ion-selective polymers is evident from the structure of enzymes where specific metal ions are bound through cooperative interactions among different amino acids. In synthetic polymers, ionic selectivity is enhanced when a chemical reaction is superimposed on an ion-exchange process. The concept of reactive ion exchange has been extended through the synthesis of crosslinked polymers whose metal ion selectivity is a function of reduction, coordination or precipitation reactions as determined by various covalently bound ligands. Development of three classes of dual mechanism bifunctional polymers, a new series of bifunctional diphosphonate polymers, and novel bifunctional ion-selective polymers with enhanced ionic accessibility has been accomplished.

  4. Predicting relative toxicity of metal ions to bacteria (Microtox{reg_sign}) using ion characteristics

    SciTech Connect

    McCloskey, J.T.; Newman, M.C.; Clark, S.B.

    1995-12-31

    The use of predictive effects models with metals has received little attention in toxicology. The purpose of this study was to predict the relative toxicity of individual metal ions and metal mixtures using ion characteristics. The concentration of metal resulting in a 50% reduction in light output (EC50) in marine bacteria (Vibrio fischeri) was determined for several metals using the Microtox{reg_sign} Toxicity Analyzer. Trends in metal toxicity were predicted by combining metal speciation calculations with empirical models based on metal ion characteristics. These trends were consistent for nine divalent metals (Ca{prime} Cd, Cu, Hg, Mg, Mn, Ni, Pb and Zn) whether the media mimicked salt water (NaC, medium) or freshwater (NaNO{sub 3} medium). When expanding the study to include an additional 14 mono-, di-, and trivalent metal ions, ion characteristics were still useful for predicting the relative toxicity of metal ions to bacteria. The prediction of nonadditive toxic effects using metal mixtures was also possible based on ion characteristics. Overall, models based on ion characteristics show much promise for predicting the relative toxicity of metal ions using the Microtox{reg_sign} assay.

  5. Behavior of metal ions in bioelectrochemical systems: A review

    NASA Astrophysics Data System (ADS)

    Lu, Zhihao; Chang, Dingming; Ma, Jingxing; Huang, Guangtuan; Cai, Lankun; Zhang, Lehua

    2015-02-01

    Bioelectrochemical systems (BESs) have been focused on by many researchers to treat wastewater and recover energy or valuable chemicals from wastes. In BESs, metal ions play an important role in the conductivity of solution, reactors' internal resistance, power generation, chemical production and activity of microorganisms. Additionally, the metal ions are also involved in anodic or cathodic reaction processes directly or indirectly in BESs. This paper reviews the behavior of metal ions in BESs, including (1) increase of the conductivity of electrolyte and decrease of internal resistance, (2) transfer for desalination, (3) enhancement or inhibition of the biocatalysis in anode, (4) improvement of cathodic performance by metal ions through electron acceptance or catalysis in cathodic process and (5) behavior of metal ions on membranes. Moreover, the perspectives of BESs removing heavy metal ions in wastewater or solid waste are discussed to realize recovery, reduction and detoxification simultaneously.

  6. Metalloregulatory proteins: metal selectivity and allosteric switching.

    PubMed

    Reyes-Caballero, Hermes; Campanello, Gregory C; Giedroc, David P

    2011-07-01

    Prokaryotic organisms have evolved the capacity to quickly adapt to a changing and challenging microenvironment in which the availability of both biologically required and non-essential transition metal ions can vary dramatically. In all bacteria, a panel of metalloregulatory proteins controls the expression of genes encoding membrane transporters and metal trafficking proteins that collectively manage metal homeostasis and resistance. These "metal sensors" are specialized allosteric proteins, in which the direct binding of a specific or small number of "cognate" metal ion(s) drives a conformational change in the regulator that allosterically activates or inhibits operator DNA binding, or alternatively, distorts the promoter structure thereby converting a poor promoter to a strong one. In this review, we discuss our current understanding of the features that control metal specificity of the allosteric response in these systems, and the role that structure, thermodynamics and conformational dynamics play in mediating allosteric activation or inhibition of DNA binding. Copyright © 2011 Elsevier B.V. All rights reserved.

  7. Measuring quaternary ammonium cleaning agents with ion selective electrodes.

    PubMed

    Plesha, Michael A; Van Wie, Bernard J; Mullin, James M; Kidwell, David A

    2006-06-16

    Data for coated-wire, ion selective electrodes (ISEs) are presented for cationic surfactant ions found in common cleaners including benzyldimethyltetradecylammonium, benzyldimethyldodecylammonium, and benzyldimethylhexadecylammonium. The ion exchangers dinonylnaphthalene sulfonic acid, tetraphenyborate, and tetrakis(4-chlorophenyl)borate are examined, showing dinonylnaphthalene sulfonic acid to be the favored species. The ISEs exhibit approximately Nernstian behavior down to the 10(-6) M limit of detection with lifetimes in excess of 50 days when used continuously, and a shelf life of over 100 days. Reaching the upper detection limit at the critical micelle concentration requires use of polymeric-membrane reference electrodes including a new membrane cocktail, which allow response measurements of an order of magnitude higher than the traditional fritted-glass reference electrode. The surfactant ISEs show excellent selectivity over the common metal ions Na+, K+, Mg2+, Ca2+, and Cu2+ with selectivity coefficients less than 10(-5.3). The ISEs are also selective over the lower molecular weight quaternary ammonium ions tetradecyltrimethylammonium, dodecyltrimethylammonium, benzyldimethyl(2-hydroxyethyl)ammonium, and tetrabutylammonium with selectivity coefficients ranging from 10(-1.7) to 10(-5.5). Use of a single electrode to determine accurately the total cationic surfactant concentration in common cleaning solutions is accomplished with information about concentration dependent interferences and a modified Nikolsky-Eisenman model. Finally, quaternary ammonium surfactants have a deleterious effect on the measurements of pH and common ions like K+, Mg2+ and Ca2+ with polymeric ISEs. This makes it critical to include surfactant electrodes in a detector array when cleaning agents are present.

  8. Template-directed synthesis of oligoguanylic acids - Metal ion catalysis

    NASA Technical Reports Server (NTRS)

    Bridson, P. K.; Fakhrai, H.; Lohrmann, R.; Orgel, L. E.; Van Roode, M.

    1981-01-01

    The effects of Zn(2+), Pb(2+) and other metal ions on the efficiency and stereo-selectivity of the template-directed oligomerization of guanosine 5'-phosphorimidazolide are investigated. Reactions were run in the presence of a polyC template in a 2,6-lutidine buffer, and products analyzed by high-performance liquid chromatography on an RPC-5 column. The presence of the Pb(2+) ion is found to lead to the formation of 2'-5' linked oligomers up to the 40-mer, while Zn(2+) favors the formation of predominantly 3'-5' linked oligomers up to the 35-mer. When amounts of uracil, cytidine or adenosine 5'-phosphorimidazole equal to those of the guanosine derivative are included in the reaction mixture, the incorrect base is incorporated into the oligomer about 10% of the time with a Pb(2+) catalyst, but less than 0.5% of the time with Zn(2+). The Sn(2+), Sb(3+) and Bi(3+) ions are also found to promote the formation of 2'-5' oligomers, although not as effectively as Pb(2+), while no metal ions other than Zn(2+) promote the formation of the 3'-5' oligomers. The results may be important for the understanding of the evolution of nucleic acid replication in the absence of enzymes.

  9. Template-directed synthesis of oligoguanylic acids - Metal ion catalysis

    NASA Technical Reports Server (NTRS)

    Bridson, P. K.; Fakhrai, H.; Lohrmann, R.; Orgel, L. E.; Van Roode, M.

    1981-01-01

    The effects of Zn(2+), Pb(2+) and other metal ions on the efficiency and stereo-selectivity of the template-directed oligomerization of guanosine 5'-phosphorimidazolide are investigated. Reactions were run in the presence of a polyC template in a 2,6-lutidine buffer, and products analyzed by high-performance liquid chromatography on an RPC-5 column. The presence of the Pb(2+) ion is found to lead to the formation of 2'-5' linked oligomers up to the 40-mer, while Zn(2+) favors the formation of predominantly 3'-5' linked oligomers up to the 35-mer. When amounts of uracil, cytidine or adenosine 5'-phosphorimidazole equal to those of the guanosine derivative are included in the reaction mixture, the incorrect base is incorporated into the oligomer about 10% of the time with a Pb(2+) catalyst, but less than 0.5% of the time with Zn(2+). The Sn(2+), Sb(3+) and Bi(3+) ions are also found to promote the formation of 2'-5' oligomers, although not as effectively as Pb(2+), while no metal ions other than Zn(2+) promote the formation of the 3'-5' oligomers. The results may be important for the understanding of the evolution of nucleic acid replication in the absence of enzymes.

  10. Separation of traces of metal ions from sodium matrices

    NASA Technical Reports Server (NTRS)

    Korkisch, J.; Orlandini, K. A.

    1969-01-01

    Method for isolating metal ion traces from sodium matrices consists of two extractions and an ion exchange step. Extraction is accomplished by using 2-thenoyltrifluoracetone and dithizone followed by cation exchange.

  11. Predictivity and fate of metal ion release from metal-on-metal total hip prostheses.

    PubMed

    Nicolli, Annamaria; Bisinella, Gianluca; Padovani, Giovanni; Vitella, Antonio; Chiara, Federica; Trevisan, Andrea

    2014-09-01

    Blood metal ion levels in 72 patients with large head metal-on-metal hip arthroplasty were studied to determine the correlation between the values measured in whole blood and urine. Urinary cobalt and chromium levels of 30μg and 21μg, respectively, adjusted to creatinine were found to correspond to the 7μg/l cut-off value that has been accepted in whole blood. Cobalt and chromium levels in whole blood and urine both significantly correlated with increased acetabular component inclination angle over 50 degrees and pain scores. There was no correlation with socket anteversion angle or femoral head diameter. The data support the use of urinary measurement of metal ions adjusted to creatinine to monitor patients with large head metal-on-metal total hip arthroplasty. Copyright © 2014 Elsevier Inc. All rights reserved.

  12. The spliceosome and its metal ions.

    PubMed

    Butcher, Samuel E

    2011-01-01

    The spliceosome is a massive complex of 5 RNAs and many proteins that associate to catalyze precursor messenger RNA splicing. The process of splicing involves two phosphoryl transfer reactions that result in intron excision and ligation of the flanking exons. Since it is required for normal protein production in eukaryotic cells, pre-mRNA splicing is an essential step in gene expression. Although high resolution structural views of the spliceosome do not yet exist, a growing body of evidence indicates that the spliceosome is a magnesium-dependent enzyme that utilizes catalytic metal ions to stabilize both transition states during the two phosphoryl transfer steps of splicing. A wealth of data also indicate that the core of the spliceosome is comprised of RNA, and suggest that the spliceosome may be a ribozyme. This chapter presents the evidence for metal ion catalysis by the spliceosome, draws comparisons to similar RNA enzymes, and discusses the future directions for research into the mechanism of pre-mRNA splicing.

  13. Optical methods for the detection of heavy metal ions

    NASA Astrophysics Data System (ADS)

    Uglov, A. N.; Bessmertnykh-Lemeune, A.; Guilard, R.; Averin, A. D.; Beletskaya, I. P.

    2014-03-01

    The review covers an important area of the modern chemistry, namely, the detection of heavy metal ions using optical molecular detectors. The role of this method in metal ion detection and the physicochemical grounds of operation of chemosensors are discussed, and examples of detection of most abundant heavy metal ions and synthetic approaches to molecular detectors are presented. The immobilization of molecular detectors on solid substrates for the design of analytical sensor devices is described. The bibliography includes 178 references.

  14. THE ROLES OF METAL IONS IN REGULATION BY RIBOSWITCHES

    PubMed Central

    2012-01-01

    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 metalloregulatory 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. PMID:22010271

  15. Eigen kinetics in surface complexation of aqueous metal ions.

    PubMed

    van Leeuwen, Herman P

    2008-10-21

    The mechanism of chemisorption of aqueous metal ions at surfaces has long been a topical issue in such fields as soil chemistry and bioenvironmental science. Here it is quantitatively demonstrated for the first time that release of water from the inner hydration shell is the rate-limiting step in inner-sphere surface complexation. The reactive intermediate is an outer-sphere complex between metal ion and surface site, with an electrostatically controlled stability defined by Boltzmann statistics. Using tabulated dehydration rate constants for metal ions, the resulting scheme allows for prediction of rates of sorption of aqueous metal ions at any type of complexing surface.

  16. Characteristics of a direct metal ion beam deposition source

    NASA Astrophysics Data System (ADS)

    Kim, Daeil; Kim, Steven

    2002-07-01

    In this study, we examine the performance of a direct metal ion beam deposition (DMIBD) system which uses a Cs-mordenite pellet as the ion source. We describe design aspects of DMIBD and process parameters such as secondary ion yields, secondary ion energy distributions, secondary ion to atom arrival ratios and deposition rates for C, Al, Si, Ni, Cu, Ta, and W targets. During deposition, the secondary negative metal ion yield strongly depends on the primary Cs+ ion does and bombarding energy. Also, the deposition rate and ion to atom arrival ratios for various targets can be controlled by adjusting the primary Cs+ ion dose, Cs+ ion bombarding energy, and ion beam energy to fit the desired application. copyright 2002 American Vacuum Society.

  17. Plasma immersion ion implantation for reducing metal ion release

    NASA Astrophysics Data System (ADS)

    Díaz, C.; García, J. A.; Mändl, S.; Pereiro, R.; Fernández, B.; Rodríguez, R. J.

    2012-11-01

    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.

  18. Plasma immersion ion implantation for reducing metal ion release

    SciTech Connect

    Diaz, C.; Garcia, J. A.; Maendl, S.; Pereiro, R.; Fernandez, B.; Rodriguez, R. J.

    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.

  19. The nature of ion exchange selectivity of phenol-formaldehyde sorbents with respect to cesium and rubidium ions

    NASA Astrophysics Data System (ADS)

    Kargov, S. I.; Shelkovnikova, L. A.; Ivanov, V. A.

    2012-05-01

    The structure of aqua complexes of alkali metal ions Me+(H2O) n , n = 1-6, where Me is Li, Na, K, Rb, and Cs, and complexes of 2,6-dimethylphenolate anion (CH3)2PhO- selected as a model of the elementary unit of phenol-formaldehyde ion exchanger with hydrated alkali metal cations Me+(H2O) n , n = 0-5, was studied by the density functional method. The energies of successive hydration of the cations and the energies of binding of alkali metal hydrated cations with (CH3)2PhO- depending on the number of water molecules n were calculated. It was shown that the dimethylphenolate ion did not have specific selectivity with respect to cesium and rubidium ions. The energies of hydration and the energies of binding of alkali metal cations with (CH3)2PhO- decreased in the series Li+ > Na+ > K+ > Rb+ > Cs+ as n increased. The conclusion was drawn that the reason for selectivity of phenol-formaldehyde and other phenol compounds with respect to cesium and rubidium ions was the predomination of the ion dehydration stage in the transfer from an aqueous solution to the phenol phase compared with the stage of binding with ion exchange groups.

  20. Facile preparation of ion-imprinted composite film for selective electrochemical removal of nickel(II) ions.

    PubMed

    Du, Xiao; Zhang, Hao; Hao, Xiaogang; Guan, Guoqing; Abudula, Abuliti

    2014-06-25

    A facile unipolar pulse electropolymerization (UPEP) technique is successfully applied for the preparation of ion-imprinted composite film composed of ferricyanide-embedded conductive polypyrrole (FCN/PPy) for the selective electrochemical removal of heavy metal ions from wastewater. The imprinted heavy metal ions are found to be easily removed in situ from the growing film only by tactfully applying potential oscillation due to the unstable coordination of FCN to the imprinted ions. The obtained Ni(2+) ion-imprinted FCN/PPy composite film shows fast uptake/release ability for the removal of Ni(2+) ions from aqueous solution, and the adsorption equilibrium time is less than 50 s. The ion exchange capacity reaches 1.298 mmol g(-1) and retains 93.5% of its initial value even after 1000 uptake/release cycles. Separation factors of 6.3, 5.6, and 6.2 for Ni(2+)/Ca(2+), Ni(2+)/K(+), and Ni(2+)/Na(+), respectively, are obtained. These characteristics are attributed to the high identification capability of the ion-imprinted composite film for the target ions and the dual driving forces resulting from both PPy and FCN during the redox process. It is expected that the present method can be used for simple preparation of other ion-imprinted composite films for the separation and recovery of target heavy metal ions as well.

  1. Three luminescent d{sup 10} metal coordination polymers assembled from a semirigid V-shaped ligand with high selective detecting of Cu{sup 2+} ion and nitrobenzene

    SciTech Connect

    Wu, Wei-Ping; Liu, Ping; Liang, Yu-Tong; Cui, Lin; Xi, Zheng-Ping; Wang, Yao-Yu

    2015-08-15

    Three 2D luminescent coordination polymers with helical frameworks, [ZnL{sub 2}]{sub n} (1) and ([ML{sub 2}]·(H{sub 2}O)){sub n} (M=Zn (2), Cd (3)) (HL=4-((2-methyl-1 H-imidazol-1-yl)methyl)benzoic acid), have been assembled under hydro(solvo)thermal conditions. Complex 1 is in chiral space group and displays a rare 2D→2D 2-fold parallel interpenetrated layer network with two types of chiral double helixes. Interestingly, the single crystal structure analyses indicate the coexistence of enantiomers la and 1b in one pot, while the bulk crystallization of 1 are racemic mixtures based on the CD measurement. 2 and 3 are isostructural, in the structure, there are two kinds of 2D chiral helical-layers which stack in an -ABAB- sequence leading to the overall structure are mesomer and achiral. All compounds display intense luminescence in solid state at room temperature with high chemical and thermal stability. More importantly, 1 has been successfully applied in the detection of Cu{sup 2+} ions in aqueous media and nitrobenzene and the probable detecting mechanism was also discussed. - Graphical abstract: Three luminescent d{sup 10} metal coordination polymers with helical-layer based on 4-((2-methyl-1H-imidazol-1-yl)methyl)benzoic acid have been obtained. Compound 1 shows high selective detecting for Cu{sup 2+} ion in aqueous and nitrobenzene. - Highlights: • Three coordination polymers with chiral helical-layer have been obtained. • 1 Can luminescent detect Cu{sup 2+} ion in aqueous media and nitrobenzene. • Racemic mixture or mesomer compounds can be obtained by controlling the reaction conditions.

  2. Metal-ion exchange, small-molecule sensing, selective dye adsorption, and reversible iodine uptake of three coordination polymers constructed by a new resorcin[4]arene-based tetracarboxylate.

    PubMed

    Lv, Li Li; Yang, Jin; Zhang, Hong-Mei; Liu, Ying-Ying; Ma, Jian-Fang

    2015-02-16

    By using a new resorcin[4]arene-based tetracarboxylate, three functional coordination polymers (CPs)--namely, [(CH3)2NH2][Cd2NaL(HCOO)2(HCOOH)(H2O)]·H2O (1), [(CH3)2NH2]2[CdL]·CH3OH·4H2O (2), and [(CH3)2NH2][Zn2Na3L2(H2O)2]·H2O (3)--have been synthesized under solvothermal conditions (H4L = 2,8,14,20-tetra-pentyl-4,10,16,22-tetrakis((4-carboxybenzyl)oxy)-6,12,18,24-tetra-methoxy-resorcin[4]arene and DMF = N,N'-dimethylformamide). The structures of 1-3 have been confirmed by single-crystal X-ray diffraction analyses and further physically characterized. In 1, L and HCOO(-) link Cd(II) and Na(I) ions to yield an unusual three-dimensional (3D) 4-connected heterometallic framework with (4(2)·6(4))(4·8(3)·10·12) topology. In 2, L anions link Cd(II) ions to give a 3D binodal 4-connected framework with (4(2)·6(3)·8)2 topology. In 3, adjacent dodecanuclear heterometallic clusters are joined together by L anions, yielding a two-dimensional (2D) (3,8)-connected (3·4(2))(3(4)·4(6)·5(6)·6(8)·7(3)·8) network. Most strikingly, CPs 1 and 2 display unusual metal-ion exchange characters. CP 2 shows remarkable reversible adsoption of I2 molecules. In addition, CPs 1-3 can selectively adsorb organic dyes and exhibit highly luminescent sensing properties for small molecules.

  3. Metal ion induced FRET OFF-ON in tren/dansyl-appended rhodamine.

    PubMed

    Lee, Min Hee; Kim, Hyun Jung; Yoon, Sangwoon; Park, Noejung; Kim, Jong Seung

    2008-01-17

    A series of new fluorescent probes bearing tren-spaced rhodamine B and dansyl groups have been synthesized. Compound 1 exhibits selective changes in the absorption and the emission spectra toward Cu2+ ion over miscellaneous metal cations. Among 1-3, 1 shows the best FRET efficiency through dansyl emission to rhodamine absorption for the Cu2+ ion.

  4. Adsorption of some bivalent heavy metal ions from aqueous solutions by manganese nodule leached residues.

    PubMed

    Das, Nigamananda; Jana, Ranajit Kumar

    2006-01-15

    The leached residue, generated after selective extraction of Cu, Ni, and Co in sulfur dioxide-ammonia leaching of manganese nodules, was characterized and batch isothermal adsorption experiments were conducted at ambient temperature to evaluate the effectiveness of the water-washed leached residue for removal of different bivalent metal ions from aqueous synthetic solutions. The effects of pH, initial metal ion concentrations, amount of adsorbent, interfering ions, and heat treatment were also investigated. The uptake of metal ions increased with increasing pH. Under identical conditions the adsorption capacity increased in the order Cd(2+)metal ions present in the leached residue were found to be released during adsorption of heavy metals, which decreased with increased pH and were practically negligible at pH approximately 6.0. Desorption of adsorbed metal ions from metal-loaded leached residue and its regeneration ability were also studied. The results obtained could be useful for considering the leached manganese nodules residue as adsorbent for removal of heavy metal ions from contaminated water bodies.

  5. Ion-selective electrodes based on L-tryptophan and L-tyrosine.

    PubMed

    Moriuchi-Kawakami, Takayo; Tokunaga, Yu; Yamamoto, Hiroyuki; Shibutani, Yasuhiko

    2012-05-30

    Novel ion-selective electrodes (ISEs) based on amino acids have been developed. L-Tryptophan and L-tyrosine, which are amino acids, are employed as ionophores for solvent polymeric membrane electrodes. The proposed ISEs show rapid Nernstian responses for the Cu(2+) ion over the concentration ranges of 3.0×10(-4)-1.0×10(-1) M. These ISEs exhibit comparatively good selectivity with respect to alkaline, alkaline earth, and some transition and heavy metal ions and the ammonium ion. The ISE based on tryptophan also indicates the Nernstian response for the benzylammonium ion. Copyright © 2012 Elsevier B.V. All rights reserved.

  6. A biosystem for removal of metal ions from water

    SciTech Connect

    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.

  7. High current metal ion implantation to synthesize some conducting metal-silicides

    SciTech Connect

    Liu, B. X.; Gao, K. Y.

    1999-06-10

    High current metal-ion implantation by a metal vapor vacuum arc ion source was conducted to synthesize some conducting metal-silicides. It was found that C54-TiSi{sub 2}, ZrSi{sub 2}, NiSi{sub 2}, CoSi{sub 2}, {beta}-FeSi{sub 2}, NbSi{sub 2} and TaSi{sub 2} layers on Si wafers with good electric properties could be obtained directly after implantation. In comparison, the formation of some other silicides like {alpha}-FeSi{sub 2}, NbSi{sub 2}, TaSi{sub 2}, tetragonal-WSi{sub 2} and tetragonal-MoSi{sub 2} required an additional post-annealing to improve their crystallinity and thus their electric properties. Interestingly, the NiSi{sub 2} layers of superior electric properties were obtained at a selected Ni-ion current density of 35 {mu}A/cm{sup 2}. At this current, a beam heating raised the Si wafer to a specific temperature of 380 deg. C, at which the size difference between NiSi{sub 2} and Si lattices was nil. The resistivity of the NiSi{sub 2} layers so obtained was much lower than that of the Ni-disilicide formed by solid-state reaction at >750 deg. C. The formation mechanism of the above metal-silicides and the associated electric properties will also be discussed.

  8. Synthesis, characterization, structural analysis of metal(II) complexes of N‧-[(E)-3-Bromo-5-Chloro-2-hydroxybenzidene]-4-hydroxybenzohydrazide-Multisubstituted Schiff base as a F- and Cu2+ ions selective chemosensor

    NASA Astrophysics Data System (ADS)

    Sundar, A.; Prabhu, M.; Indra Gandhi, N.; Marappan, M.; Rajagopal, G.

    2014-08-01

    New colorimetric chemosensor, N‧-[(E)-3-Bromo-5-Chloro-2-hydroxybenzidene]-4-hydroxybenzohydrazide, containing OH and NH groups as binding sites have been synthesized and characterized by spectral UV, IR, NMR and ESR. The molecular structure of ligand is determined by X-ray crystallography and it has the monoclinic space group P21/c with cell parameters a = 15.1058(6), b = 14.3433(6), c = 17.5800(8) Å and Z = 8. The electronic spectral measurements show that Co2+, Ni2+ and Zn2+ complexes have tetrahedral geometry, while Cu2+ complex has square planar geometry. Magnetic measurements show that Cu2+, Co2+ and Ni2+ complexes have paramagnetic behavior and Zn2+ complex has diamagnetic behavior. Anion binding studies carried out using 1H NMR and UV-visible spectrophotometric titrations revealed that these receptors exhibit selective recognition towards F- over other halide anions. The selectivity for F- among the halides is attributed mainly to the hydrogen-bond interaction of the receptor with F-. Receptor (5 × 10-5 M) shows color change from colorless to yellow in the presence of tetrabutylammonium fluoride (TBAF, 1.5 × 10-3 M). Moreover, F--induced color changes remain the same even in the presence of large excess of Cl-, Br- and I-. The binding constant is found to be higher towards F- ion and this may be due to presence of OH group, which offers extra binding site. Chromogenic receptor undergoes distinct color changes from colorless to green on gradual addition of Cu2+ can be used as colorimetric probes for spectrophotometric and visual analysis of Cu2+ in the presence of other transition metal ions such as Co2+, Ni2+ and Zn2+.

  9. Synthesis, characterization, structural analysis of metal(II) complexes of N'-[(E)-3-Bromo-5-Chloro-2-hydroxybenzidene]-4-hydroxybenzohydrazide-Multisubstituted Schiff base as a F(-) and Cu(2+) ions selective chemosensor.

    PubMed

    Sundar, A; Prabhu, M; Indra Gandhi, N; Marappan, M; Rajagopal, G

    2014-08-14

    New colorimetric chemosensor, N'-[(E)-3-Bromo-5-Chloro-2-hydroxybenzidene]-4-hydroxybenzohydrazide, containing OH and NH groups as binding sites have been synthesized and characterized by spectral UV, IR, NMR and ESR. The molecular structure of ligand is determined by X-ray crystallography and it has the monoclinic space group P21/c with cell parameters a=15.1058(6), b=14.3433(6), c=17.5800(8)Å and Z=8. The electronic spectral measurements show that Co(2+), Ni(2+) and Zn(2+) complexes have tetrahedral geometry, while Cu(2+) complex has square planar geometry. Magnetic measurements show that Cu(2+), Co(2+) and Ni(2+) complexes have paramagnetic behavior and Zn(2+) complex has diamagnetic behavior. Anion binding studies carried out using (1)H NMR and UV-visible spectrophotometric titrations revealed that these receptors exhibit selective recognition towards F(-) over other halide anions. The selectivity for F(-) among the halides is attributed mainly to the hydrogen-bond interaction of the receptor with F(-). Receptor (5 × 10(-5)M) shows color change from colorless to yellow in the presence of tetrabutylammonium fluoride (TBAF, 1.5 × 10(-3)M). Moreover, F(-)-induced color changes remain the same even in the presence of large excess of Cl(-), Br(-) and I(-). The binding constant is found to be higher towards F(-) ion and this may be due to presence of OH group, which offers extra binding site. Chromogenic receptor undergoes distinct color changes from colorless to green on gradual addition of Cu(2+) can be used as colorimetric probes for spectrophotometric and visual analysis of Cu(2+) in the presence of other transition metal ions such as Co(2+), Ni(2+) and Zn(2+).

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

    PubMed

    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.

  11. Structure-based differences between the metal ion selectivity of two siderophores desferrioxamine B (DFB) and desferricoprogen (DFC): why DFC is much better Pb(II) sequestering agent than DFB?

    PubMed

    Farkas, Etelka; Bátka, Dávid; Kremper, Georgina; Pócsi, István

    2008-08-01

    Complexation of desferrioxamine B (DFB) and desferricoprogen (DFC) with Cd(II) and Pb(II) toxic ions as well as complexation of DFC with Ca(II) and Mg(II) essential metals have been investigated and the results have been compared to those with other metal ions. The two siderophores have moderate Cd(II)-binding ability, but both, and especially DFC, bind Pb(II) in high stability complexes. Surprisingly, significant differences exist between Pb(II)-complexation of DFB and DFC. Namely, a maximum of two hydroxamate groups of a DFB coordinate to a Pb(II) ion, the third one binds to another metal ion with high preference and the formation of a trinuclear species, [Pb(3)(DFBH)(2)](2+), is predominant even at 1:1 metal to ligand ratio in this system. On the contrary, DFC forms mononuclear complex, [ML], with much higher stability and the formation of the trinuclear complex is negligible compared to DFB. The 6s(2) electron-pair of Pb(II), which remains always inert during complexation with hydroxamic acids and also with DFB, seems to become active in the DFC complexes (due to the effect of the double bonds in beta-position to each hydroxamate), what, at least in some extent, allows the coordination of all the three hydroxamates of DFC to the same Pb(II) ion. This way of interaction (unique with a hydroxamate-based compound) results in significant stability increase, and, as a consequence, DFC is much better Pb(II)-chelating agent than DFB. Although DFC forms unexpectedly high stability complexes with Mg(II) compared to Ca(II), but even Mg(II), compared to many other metals, is not an efficient DFC-binding metal. Therefore, any sequestration of this biologically very important metal is not likely from a living organism by DFC.

  12. Highly charged Arq+ ions interacting with metals

    NASA Astrophysics Data System (ADS)

    Wang, Jijin; Zhang, Jian; Gu, Jiangang; Luo, Xianwen; Hu, Bitao

    2009-12-01

    Using computer simulation, alternative methods of the interaction of highly charged ions Arq+ with metals (Au, Ag) are used and verified in the present work. Based on the classical over-barrier model, we discussed the promotion loss and peeling off processes. The simulated total potential electron yields agree well with the experiment data in incident energy ranging from 100 eV to 5 keV and all charge states of Arq+ . Based on the TRIM code, we obtain the side-feeding rate as well as the motion and charge transfer of HCI below the surface. Some results, including the array of KLx x-ray satellite lines, the respective contribution of autoionization, and side-feeding to inner shells, and the filling rates and lifetime of inner shells for Ar agree well with experiment or theory.

  13. Method and apparatus for providing negative ions of actinide-metal hexafluorides

    DOEpatents

    Compton, Robert N.; Reinhardt, Paul W.; Garrett, William R.

    1978-01-01

    This invention relates to a novel method and a novel generator, or source, for providing gaseous negative ions of selected metal hexafluorides. The method is summarized as follows: in an evacuated zone, reacting gaseous fluorine with an actinide-metal body selected from the group consisting of uranium, plutonium, neptunium, and americium to convert at least part of the metal to the hexafluoride state, thus producing gaseous negatively charged metal-hexafluoride ions in the evacuated zone, and applying an electric field to the zone to remove the ions therefrom. The ion source comprises a chamber defining a reaction zone; means for evacuating the zone; an actinide-metal body in the zone, the metal being uranium, plutonium, neptunium, or americium; means for contacting the body with gaseous fluorine to convert at least a part thereof to the hexafluoride state; and means for applying an electric field to the evacuated zone to extract gaseous, negatively charged metal-hexafluoride ions therefrom. The invention provides unique advantages over conventional surface-ionization techniques for producing such ions.

  14. A divalent cation-dependent variant of the glmS ribozyme with stringent Ca(2+) selectivity co-opts a preexisting nonspecific metal ion-binding site.

    PubMed

    Lau, Matthew W L; Trachman, Robert J; Ferré-D'Amaré, Adrian R

    2017-03-01

    Ribozymes use divalent cations for structural stabilization, as catalytic cofactors, or both. Because of the prominent role of Ca(2+) in intracellular signaling, engineered ribozymes with stringent Ca(2+) selectivity would be important in biotechnology. The wild-type glmS ribozyme (glmS(WT)) requires glucosamine-6-phosphate (GlcN6P) as a catalytic cofactor. Previously, a glmS ribozyme variant with three adenosine mutations (glmS(AAA)) was identified, which dispenses with GlcN6P and instead uses, with little selectivity, divalent cations as cofactors for site-specific RNA cleavage. We now report a Ca(2+)-specific ribozyme (glmS(Ca)) evolved from glmS(AAA) that is >10,000 times more active in Ca(2+) than Mg(2+), is inactive in even 100 mM Mg(2+), and is not responsive to GlcN6P. This stringent selectivity, reminiscent of the protein nuclease from Staphylococcus, allows rapid and selective ribozyme inactivation using a Ca(2+) chelator such as EGTA. Because glmS(Ca) functions in physiologically relevant Ca(2+) concentrations, it can form the basis for intracellular sensors that couple Ca(2+) levels to RNA cleavage. Biochemical analysis of glmS(Ca) reveals that it has co-opted for selective Ca(2+) binding a nonspecific cation-binding site responsible for structural stabilization in glmS(WT) and glmS(AAA) Fine-tuning of the selectivity of the cation site allows repurposing of this preexisting molecular feature.

  15. Theoretical study of transition-metal ions bound to benzene

    NASA Technical Reports Server (NTRS)

    Bauschlicher, Charles W., Jr.; Partridge, Harry; Langhoff, Stephen R.

    1992-01-01

    Theoretical binding energies are reported for all first-row and selected second-row transition metal ions (M+) bound to benzene. The calculations employ basis sets of at least double-zeta plus polarization quality and account for electron correlation using the modified coupled-pair functional method. While the bending is predominantly electrostatic, the binding energies are significantly increased by electron correlation, because the donation from the metal d orbitals to the benzene pi* orbitals is not well described at the self-consistent-field level. The uncertainties in the computed binding energies are estimated to be about 5 kcal/mol. Although the calculated and experimental binding energies generally agree to within their combined uncertainties, it is likely that the true binding energies lie in the lower portion of the experimental range. This is supported by the very good agreement between the theoretical and recent experimental binding energies for AgC6H6(+).

  16. Multiple metal ion exchange equilibria with humic acid

    NASA Astrophysics Data System (ADS)

    Gamble, Donald S.; Schnitzer, M.; Kerndorff, H.; Langford, C. H.

    1983-07-01

    A theoretical description is presented for multiple metal ion-humic acid cation exchange experiments. A law of mass action formalism and mole fraction relationships have been adapted to the simultaneous ion exchange equilibria of twelve cations with humic acid. The formal description relates the number of degrees of freedom of the system to the number of metal ions, identifies the independent variables, and accounts for cation interactions in the exchange equilibrium. A recalculation of experimental results reveals an Irving-Williams type of series for divalent metal ions. The implications of this for agriculture and add rain problems are discussed.

  17. Post-synthesis addition of transition metal ions and lanthanide ions to the surface of anatase titanium (IV) dioxide nanorods

    NASA Astrophysics Data System (ADS)

    Balasanthiran, Choumini

    Solar energy utilization is an attractive option for new energy technology and economic development. Our research is the formulation of catalyst materials for solar production of hydrogen from water. Titanium(IV) oxide has been explored for water splitting; however, a major challenge is that titanium(IV) oxide can only absorb UV light. Visible light absorption can be increased by metal ion or anion doping by creating interband states. Most dopant protocols lead to deposition of dopant ions throughout the solid, and interfacial deposition has received very little attention. We have developed a method to selectively attach transition metal ions and lanthanide ions on the surface of titanium(IV) oxide nanorods using metal chlorides as precursors. The present study demonstrates that Cr(III), Mn(II), Fe(II), Co(II), Ni(II), Cu (II), Eu(III), Ce(III), Pr(III) and Er(III) were coordinated to the surface of oleic acid capped TiO2 nanorods (NRs) by post-synthesis method without any phase or morphology transformation. Metal ion loading could be carefully controlled, and we show a titration curve for addition of transition metal ions and Eu(III) to the nanorod surface. The materials were characterized with UV-visible spectroscopy, transmission electron microscopy, elemental analysis, XPS and powder X-ray diffraction. X-ray photoelectron spectra were obtained for a series of M-TiO2 samples in which transition metal (M = Cr, Mn, Fe, Co, Ni, Cu) ions are directly attached to the surface of anatase TiO2 nanocrystals. Further, we report sequential, quantitative loading of transition metal ions (Cr, Mn, Fe, Co, Ni, Cu) to the surface of rod-shape anatase TiO2 nanocrystals in bimetallic combinations (6C2 = 15). TEM, PXRD, UV-Vis, XPS and elemental analysis characterization show that bimetallic combinations were synthesized successfully.

  18. Altered selectivity in an Arabidopsis metal transporter.

    PubMed

    Rogers, E E; Eide, D J; Guerinot, M L

    2000-10-24

    Plants require metals for essential functions ranging from respiration to photosynthesis. These metals also contribute to the nutritional value of plants for both humans and livestock. Additionally, plants have the ability to accumulate nonessential metals such as cadmium and lead, and this ability could be harnessed to remove pollutant metals from the environment. Designing a transporter that specifically accumulates certain cations while excluding others has exciting applications in all of these areas. The Arabidopsis root membrane protein IRT1 is likely to be responsible for uptake of iron from the soil. Like other Fe(II) transporters identified to date, IRT1 transports a variety of other cations, including the essential metals zinc and manganese as well as the toxic metal cadmium. By heterologous expression in yeast, we show here that the replacement of a glutamic acid residue at position 103 in wild-type IRT1 with alanine increases the substrate specificity of the transporter by selectively eliminating its ability to transport zinc. Two other mutations, replacing the aspartic acid residues at either positions 100 or 136 with alanine, also increase IRT1 metal selectivity by eliminating transport of both iron and manganese. A number of other conserved residues in or near transmembrane domains appear to be essential for all transport function. Therefore, this study identifies at least some of the residues important for substrate selection and transport in a protein belonging to the ZIP gene family, a large transporter family found in a wide variety of organisms.

  19. A Novel Methodology for Metal Ion Separation Based on Molecularly Imprinting

    SciTech Connect

    Zuo, Xiaobin; Mosha, Donnati; Hassan, Mansour M.; Givens, Richard S.; Busch, Daryle H.

    2004-03-31

    The siderophore-based extraction of iron from the soil by bacteria is proposed as a model for a new separation methodology labeled the soil poutice, a molecular device that would selectively retrieve the complex of a targeted metal ion. In this report we described the synthesis and characterization of molecularly imprinted polymers and their application in the specific recognition of macrocyclic metal complexes. The imprinting is based on non-covalent interactions such as hydrogen bonding, electrostatic attractions and minor metal-ligand coordination. Good rebinding capacity for the imprinting metal complex was observed in acetonitrile as well as in water. The polymers are resistant to strong acids and oxidizing agents and showed an increase of rebinding capacity during cycles of reuse. The imprinting procedure, combined with the previously known selective chelation of macrocyclic ligands, supports the feasibility of a new methodology that can be used to extract waste metal ions effectively and selectively from soils and ground water.

  20. Interactions between metal ions and carbohydrates: the coordination behavior of neutral erythritol to transition metal ions.

    PubMed

    Yang, Limin; Tian, Wen; Xu, Yizhuang; Su, Yunlan; Gao, Song; Wang, Zheming; Weng, Shifu; Yan, Chunhua; Wu, Jinguang

    2004-08-01

    The single crystals of coordinated complexes of neutral erythritol (C4H10O4) with various transition metal ions were synthesized and studied using FT-IR and single crystal X-ray diffraction analysis. Two CuCl2-erythritol complexes (denoted as CuE(I) and CuE(II)) were obtained. In CuE(I), Cu2+ coordinates with two chloride ions and four OH groups from two erythritol molecules. Two copper centers are linked by one erythritol molecule to form a zigzag chain. For CuE(II), each Cu2+ coordinates with two OH groups from an erythritol molecule and two chloride ions. The crystal of CuE(II) contains complexed and free erythritol, the dimers of [Cu2Cl4(C4H10O4)] further form a [Cu2Cl4(C4H10O4)]infinity chain via secondary Cu...Cl bonds, both the dimer unit of [Cu2Cl4.(C4H10O4)] and non-coordinated C4H10O4 unit exist side by side in the crystal. MnCl2-erythritol complex whose structure is similar to CuE(I) is also acquired. The OH groups of erythritol act as ligand to coordinate to metal ions on one hand, one the other hand, OH groups form hydrogen bonds network that link chain and layer together to build three-dimensional structures.

  1. Three luminescent d10 metal coordination polymers assembled from a semirigid V-shaped ligand with high selective detecting of Cu2+ ion and nitrobenzene

    NASA Astrophysics Data System (ADS)

    Wu, Wei-Ping; Liu, Ping; Liang, Yu-Tong; Cui, Lin; Xi, Zheng-Ping; Wang, Yao-Yu

    2015-08-01

    Three 2D luminescent coordination polymers with helical frameworks, [ZnL2]n (1) and {[ML2]·(H2O)}n (M=Zn (2), Cd (3)) (HL=4-((2-methyl-1 H-imidazol-1-yl)methyl)benzoic acid), have been assembled under hydro(solvo)thermal conditions. Complex 1 is in chiral space group and displays a rare 2D→2D 2-fold parallel interpenetrated layer network with two types of chiral double helixes. Interestingly, the single crystal structure analyses indicate the coexistence of enantiomers la and 1b in one pot, while the bulk crystallization of 1 are racemic mixtures based on the CD measurement. 2 and 3 are isostructural, in the structure, there are two kinds of 2D chiral helical-layers which stack in an -ABAB- sequence leading to the overall structure are mesomer and achiral. All compounds display intense luminescence in solid state at room temperature with high chemical and thermal stability. More importantly, 1 has been successfully applied in the detection of Cu2+ ions in aqueous media and nitrobenzene and the probable detecting mechanism was also discussed.

  2. A self-sputtering ion source: A new approach to quiescent metal ion beams

    SciTech Connect

    Oks, Efim M.; Anders, Andre

    2009-09-03

    A new metal ion source is presented based on sustained self-sputtering plasma in a magnetron discharge. Metals exhibiting high self-sputtering yield like Cu, Ag, Zn, and Bi can be used in a high-power impulse magnetron sputtering (HIPIMS) discharge such that the plasma almost exclusively contains singly charged metal ions of the target material. The plasma and extracted ion beam are quiescent. The ion beams consist mostly of singly charged ions with a space-charge limited current density which reached about 10 mA/cm2 at an extraction voltage of 45 kV and a first gap spacing of 12 mm.

  3. Development of a lithium liquid metal ion source for MeV ion beam analysis

    SciTech Connect

    Read, P.M.; Maskrey, J.T.; Alton, G.D.

    1988-01-01

    Lithium liquid metal ion sources are an attractive complement to the existing gaseous ion sources that are extensively used for ion beam analysis. This is due in part to the high brightness of the liquid metal ion source and in part to the availability of a lithium ion beam. High brightness is of particular importance to MeV ion microprobes which are now approaching current density limitations on targets determined by the ion source. The availability of a lithium beam provides increased capabilities for hydrogen profiling and high resolution Rutherford backscattering spectrometry. This paper describes the design and performance of a lithium liquid metal ion source suitable for use on a 5MV Laddertron accelerator. Operational experience with the source and some of its uses for ion beam analysis are discussed. 8 refs., 2 figs.

  4. Metal-clad optical waveguide fluorescence device for the detection of heavy metal ions

    NASA Astrophysics Data System (ADS)

    Margheri, Giancarlo; Giorgetti, Emilia; Marsili, Paolo; Zoppi, Angela; Lascialfari, Luisa; Cicchi, Stefano

    2014-07-01

    We developed Hg-sensing chips by decorating the external surface of metal-clad optical waveguides with a monolayer of Hg-sensitive fluorescent molecular probes. The emission properties of the original water-soluble form of the molecule were previously found to be selectively quenched in the presence of Hg ions. The fabricated samples were tested with optical waveguide fluorescence spectroscopy by putting them in contact with a 5-μM water solution of Hg ions and recording the emission spectra versus incubation time. The estimate of the limit of detection was 150 nM. A preliminary evaluation of the selectivity of the structure was also performed by using Cd as possible interfering analytes.

  5. Metal ion adsorption at the ionic liquid-mica interface

    NASA Astrophysics Data System (ADS)

    McDonald, Samila; Elbourne, Aaron; Warr, Gregory G.; Atkin, Rob

    2015-12-01

    Mica has been employed in many studies of ionic liquid (IL) interfaces on account of its atomic smoothness and well defined surface properties. However, until now it has been unclear whether ions dissolved in ILs can compete with the IL cation and adsorb to mica charge sites. In this work amplitude modulated atomic force microscopy (AM-AFM) has been used to probe metal ion adsorption at the interface of mica with propylammonium nitrate (PAN), a room temperature IL. Lithium, sodium, potassium, magnesium and calcium nitrate salts were added to PAN at a concentration of ~60 mM. Aluminum nitrate was also investigated, but only at 5 mM because its solubility in PAN is much lower. The AM-AFM images obtained when the metal ions were present are strikingly different to that of pure PAN, indicating that the ions compete effectively with the propylammonium cation and adsorb to negatively charged sites on the mica surface despite their much lower concentration. This is a consequence of electrostatic attractions between the mica charge sites and the metal ions being significantly stronger than for the propylammonium cation; compared to the metal ions the propylammonium charged group is relatively constrained sterically. A distinct honeycomb pattern is noted for the PAN + Al3+ system, less obviously for the divalent ions and not at all for monovalent ions. This difference is attributed to the strength of electrostatic interactions between metal ions and mica charge sites increasing with the ion charge, which means that divalent and (particularly) trivalent ions are located more precisely above the charged sites of the mica lattice. The images obtained allow important distinctions between metal ion adsorption at mica-water and mica-PAN interfaces to be made.Mica has been employed in many studies of ionic liquid (IL) interfaces on account of its atomic smoothness and well defined surface properties. However, until now it has been unclear whether ions dissolved in ILs can compete

  6. Alkali metal ion battery with bimetallic electrode

    DOEpatents

    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.

  7. New polymer-supported ion-complexing agents: design, preparation and metal ion affinities of immobilized ligands.

    PubMed

    Alexandratos, Spiro D

    2007-01-31

    Polymer-supported reagents are comprised of crosslinked polymer networks that have been modified with ligands capable of selective metal ion complexation. Applications of these polymers are in environmental remediation, ion chromatography, sensor technology, and hydrometallurgy. Bifunctional polymers with diphosphonate/sulfonate ligands have a high selectivity for actinide ions. The distribution coefficient for the uranyl ion from 1 M nitric acid is 70,000, compared to 900 for the monophosphonate/sulfonate polymer and 200 for the sulfonic acid ion-exchange resin. A bifunctional trihexyl/triethylammonium polymer has a high affinity and selectivity for pertechnetate and perchlorate anions from groundwater. In one example, its distribution coefficient for perchlorate ions in the presence of competing anions is 3,300,000, compared to 203,180 for a commercially available anion-exchange resin. Polystyrene modified with N-methyl-D-glucamine ligands is capable of selectively complexing arsenate from groundwater. It complexes 99% of the arsenate present in a solution of 100 mg/L arsenate with 560 mg/L sulfate ions. Its selectivity is retained even in the presence of 400 mg/L phosphate. There is no affinity for arsenate above pH 9, allowing for the polymer to be regenerated with moderate alkali solution. In studies aimed at developing a Hg(II)-selective resin, simple amine resins were found to have a high Hg(II) affinity and that affinity is dependent upon the solution pH and the counterion.

  8. Equilibrium selectivity alone does not create K+-selective ion conduction in K+ channels

    NASA Astrophysics Data System (ADS)

    Liu, Shian; Lockless, Steve W.

    2013-11-01

    Potassium (K+) channels are selective for K+ over Na+ ions during their transport across membranes. We and others have previously shown that tetrameric K+ channels are primarily occupied by K+ ions in their selectivity filters under physiological conditions, demonstrating the channel’s intrinsic equilibrium preference for K+ ions. Based on this observation, we hypothesize that the preference for K+ ions over Na+ ions in the filter determines its selectivity during ion conduction. Here, we ask whether non-selective cation channels, which share an overall structure and similar individual ion-binding sites with K+ channels, have an ion preference at equilibrium. The variants of the non-selective Bacillus cereus NaK cation channel we examine are all selective for K+ over Na+ ions at equilibrium. Thus, the detailed architecture of the K+ channel selectivity filter, and not only its equilibrium ion preference, is fundamental to the generation of selectivity during ion conduction.

  9. A 1-dodecanethiol-based phase transfer protocol for the highly efficient extraction of noble metal ions from aqueous phase.

    PubMed

    Chen, Dong; Cui, Penglei; Cao, Hongbin; Yang, Jun

    2015-03-01

    A 1-dodecanethiol-based phase-transfer protocol is developed for the extraction of noble metal ions from aqueous solution to a hydrocarbon phase, which calls for first mixing the aqueous metal ion solution with an ethanolic solution of 1-dodecanethiol, and then extracting the coordination compounds formed between noble metal ions and 1-dodecanethiol into a non-polar organic solvent. A number of characterization techniques, including inductively coupled plasma atomic emission spectroscopy, Fourier transform infrared spectroscopy, and thermogravimetric analysis demonstrate that this protocol could be applied to extract a wide variety of noble metal ions from water to dichloromethane with an efficiency of >96%, and has high selectivity for the separation of the noble metal ions from other transition metals. It is therefore an attractive alternative for the extraction of noble metals from water, soil, or waste printed circuit boards. Copyright © 2015. Published by Elsevier B.V.

  10. Structural resolution of 4-substituted proline diastereomers with ion mobility spectrometry via alkali metal ion cationization.

    PubMed

    Flick, Tawnya G; Campuzano, Iain D G; Bartberger, Michael D

    2015-03-17

    The chirality of substituents on an amino acid can significantly change its mode of binding to a metal ion, as shown here experimentally by traveling wave ion mobility spectrometry-mass spectrometry (TWIMS-MS) of different proline isomeric molecules complexed with alkali metal ions. Baseline separation of the cis- and trans- forms of both hydroxyproline and fluoroproline was achieved using TWIMS-MS via metal ion cationization (Li(+), Na(+), K(+), and Cs(+)). Density functional theory calculations indicate that differentiation of these diastereomers is a result of the stabilization of differing metal-complexed forms adopted by the diastereomers when cationized by an alkali metal cation, [M + X](+) where X = Li, Na, K, and Cs, versus the topologically similar structures of the protonated molecules, [M + H](+). Metal-cationized trans-proline variants exist in a linear salt-bridge form where the metal ion interacts with a deprotonated carboxylic acid and the proton is displaced onto the nitrogen atom of the pyrrolidine ring. In contrast, metal-cationized cis-proline variants adopt a compact structure where the carbonyl of the carboxylic acid, nitrogen atom, and if available, the hydroxyl and fluorine substituent solvate the metal ion. Experimentally, it was observed that the resolution between alkali metal-cationized cis- and trans-proline variants decreases as the size of the metal ion increases. Density functional theory demonstrates that this is due to the decreasing stability of the compact charge-solvated cis-proline structure with increased metal ion radius, likely a result of steric hindrance and/or weaker binding to the larger metal ion. Furthermore, the unique structures adopted by the alkali metal-cationized cis- and trans-proline variants results in these molecules having significantly different quantum mechanically calculated dipole moments, a factor that can be further exploited to improve the diastereomeric resolution when utilizing a drift gas with a

  11. Application of immobilized metal ion chelate complexes as pseudocation exchange adsorbents for protein separation.

    PubMed

    Zachariou, M; Hearn, M T

    1996-01-09

    The interactions of horse muscle myoglobin (MYO), tuna heart cytochrome c (CYT), and hen egg white lysozyme (LYS) with three different immobilized metal ion affinity (IMAC) adsorbents involving the chelated complexes of the hard Lewis metal ions Al3+, Ca2+, Fe3+, and Yb3+ and the borderline Lewis metal ion Cu2+ have been investigated in the presence of low- and high-ionic strength buffers and at two different pH values. In contrast to the selectivity behavior noted with buffers of high ionic strength, with low-ionic strength buffers, these three proteins interact with the hard metal ion IMAC adsorbents in a manner more characteristic of cation exchange behavior, although in contrast to the cation exchange chromatography of these proteins, as the pH value of the elution buffer was increased, the retention also increased. The selectivity differences observed under these conditions appear to be due to the formation of hydrolytic complexes of these immobilized metal ion chelate systems involving a change in the coordination geometry of the im-M(n+)-chelate at higher pH values. The experimental observations have been evaluated in terms of the effective charge on the immobilized metal ion chelate complex and the charge characteristics of the specific proteins.

  12. Silicon Quantum Dot-Based Fluorescence Turn-On Metal Ion Sensors in Live Cells.

    PubMed

    Dhenadhayalan, Namasivayam; Lee, Hsin-Lung; Yadav, Kanchan; Lin, King-Chuen; Lin, Yih-Tyng; Chang, A H H

    2016-09-14

    Multiple sensor systems are designed by varying aza-crown ether moiety in silicon quantum dots (SiQDs) for detecting individual Mg(2+), Ca(2+), and Mn(2+) metal ions with significant selectivity and sensitivity. The detection limit of Mg(2+), Ca(2+), and Mn(2+) can reach 1.81, 3.15, and 0.47 μM, respectively. Upon excitation of the SiQDs which are coordinated with aza-crown ethers, the photoinduced electron transfer (PET) takes place from aza-crown ether moiety to the valence band of SiQDs core such that the reduced probability of electron-hole recombination may diminish the subsequent fluorescence. The fluorescence suppression caused by such PET effect will be relieved after selective metal ion is added. The charge-electron binding force between the metal ion and aza-crown ether hinders the PET and thereby restores the fluorescence of SiQDs. The design of sensor system is based on the fluorescence "turn-on" of SiQDs while in search of the appropriate metal ion. For practical application, the sensing capabilities of metal ions in the live cells are performed and the confocal image results reveal their promising applicability as an effective and nontoxic metal ion sensor.

  13. Determination of metal ions by high-performance liquid chromatographic separation of their hydroxamic acid chelates

    SciTech Connect

    Palmieri, M.D.; Fritz, J.S.

    1987-09-15

    Metal ions are determined by adding N-methylfurohydroxamic acid to an aqueous sample and then separating the metal chelates by direct injection onto a liquid chromatographic column. Separations on a C/sub 8/ silica column and a polystyrene-divinylbenzene column are compared, with better separations seen on the polymeric column. The complexes formed at low pH values are cationic and are separated by an ion pairing mechanism. Retention times and selectivity of the metal complexes can be varied by changing the pH. Several metal ions can be separated and quantified; separation conditions, linear calibration curve ranges, and detection limits are presented for Zr(IV), Hf(IV), Fe(III), Nb(V), Al(III), and Sb(III). Interferences due to the presence of other ions in solution are investigated. Finally, an antiperspirant sample is analyzed for zirconium by high-performance liquid chromatography.

  14. Impregnated-electrode-type liquid metal ion source

    NASA Astrophysics Data System (ADS)

    Ishikawa, J.; Gotoh, Y.; Tsuji, H.; Takagi, T.

    We have developed an impregnated-electrode-type liquid metal ion source whose tip is a sintered-porous structure made of a refractory metal such as tungsten. By this structure the ratio of the liquid metal surface area facing the vacuum to the volume is low, which decreases useless metal evaporation from the surface. The maximum vapour pressure of the metal in operation for this ion source is 10 -1-10 0 Torr, which is 2-3 orders of magnitude higher than that for the needle type. Therefore, useful metal ions such as Ga +, Au +, Ag +, In +, Si 2+, Ge 2+, and Sb 2+ can be extracted from single element metals or alloys. The porous structure of the tip has also an effect on the positive control of the liquid metal flow rate to the tip head. Thus, a stable operation with a high current of a few hundreds of μA can be obtained together with a low current high brightness ion beam. Therefore, this ion source is suitable not only for microfocusing but also for a general use as a metal ion source.

  15. Reusable chelating resins concentrate metal ions from highly dilute solutions

    NASA Technical Reports Server (NTRS)

    Bauman, A. J.; Weetal, H. H.; Weliky, N.

    1966-01-01

    Column chromatographic method uses new metal chelating resins for recovering heavy-metal ions from highly dilute solutions. The absorbed heavy-metal cations may be removed from the chelating resins by acid or base washes. The resins are reusable after the washes are completed.

  16. Selective covalent bond formation in polypeptide ions via gas-phase ion/ion reaction chemistry.

    PubMed

    Han, Hongling; McLuckey, Scott A

    2009-09-16

    Primary amines present in protonated polypeptides can be covalently modified via gas-phase ion/ion reactions using bifunctional reagent ions. The use of reagent anions with a charge-bearing site that leads to strong interactions with the polypeptide, such as sulfonic acid, gives rise to the formation of a long-lived adduct. A distinct reactive functional group, an aldehyde in the present case, can then undergo reaction with the peptide. Collisional activation of the adduct ion formed from a reagent with an aldehyde group and a peptide ion with a primary amine gives rise to water loss in conjunction with imine (Schiff base) formation. The covalently bound modification is retained upon subsequent collisional activation. This work demonstrates the ability to selectively modify polypeptide ions in the gas phase within the context of a multistage mass spectrometry experiment.

  17. {sup 1}H and {sup 23}Na MAS NMR spectroscopy of cationic species in CO{sub 2} selective alkaline earth metal porous silicoaluminophosphates prepared via liquid and solid state ion exchange

    SciTech Connect

    Arevalo-Hidalgo, Ana G.; Dugar, Sneha; Fu, Riqiang; Hernandez-Maldonado, Arturo J.

    2012-07-15

    The location of extraframework cations in Sr{sup 2+} and Ba{sup 2+} ion-exchanged SAPO-34 was estimated by means of {sup 1}H and {sup 23}Na MAS NMR spectroscopy and spectral deconvolution. Incorporation of the alkaline earth metal cations onto the SAPO framework was achieved via liquid state ion exchange, coupled partial detemplation/solid-state ion exchange, and combination of both techniques. MAS NMR revealed that the level of ion exchange was limited by the presence of protons and sodium cations near hexagonal prisms (site SI), which are relatively difficult to exchange with the alkaline earth metal due to steric and charge repulsion criteria. In addition, the presence of ammonium cations in the supercages facilitated the exchange of otherwise tenacious hydrogen as corroborated by unit cell compositional data as well as enhanced CO{sub 2} adsorption at low partial pressures. The extraframework ammonium species were produced from partial detemplation of the structure-directing agent employed for the SAPO-34 synthesis, tetraethylammonium. - Graphical abstract: MAS NMR was used to elucidate the position the cationic species in alkaline earth metal exchanged silicoaluminophosphates. These species played a significant role during the ion exchange process and, therefore, the materials ultimate CO{sub 2} adsorption performance. Highlights: Black-Right-Pointing-Pointer Location of extraframework Sr{sup 2+} or Ba{sup 2+} cations was estimated by means of {sup 1}H and {sup 23}Na MAS NMR. Black-Right-Pointing-Pointer Level of Sr{sup 2+} or Ba{sup 2+} ion exchange was limited by the presence of protons and sodium cations. Black-Right-Pointing-Pointer Presence of ammonium cations in the supercages facilitated the exchange. Black-Right-Pointing-Pointer Sr{sup 2+} and Ba{sup 2+} ion exchanged SAPOs are outstanding CO{sub 2} adsorbents.

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

    PubMed

    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.

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

    PubMed

    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.

  20. Metal ion sensing solution containing double crossover DNA

    NASA Astrophysics Data System (ADS)

    Park, Byeongho; Dugasani, Sreekantha R.; Cho, Youngho; Oh, Juyeong; Kim, Chulki; Seo, Min Ah; Lee, Taikjin; Jhon, Young Miin; Woo, Deok Ha; Lee, Seok; Jun, Seong Chan; Park, Sung Ha; Kim, Jae Hun

    2015-07-01

    The current study describes metal ion sensing with double crossover DNAs (DX1 and DX2), artificially designed as a platform of doping. The sample for sensing is prepared by a facile annealing method to grow the DXs lattice on a silicon/silicon oxide. Adding and incubating metal ion solution with the sensor substrate into the micro-tube lead the optical property change. Photoluminescence (PL) is employed for detecting the concentration of metal ion in the specimen. We investigated PL emission for sensor application with the divalent copper. In the range from 400 to 650 nm, the PL features of samples provide significantly different peak positions with excitation and emission detection. Metal ions contribute to modify the optical characteristics of DX with structural and functional change, which results from the intercalation of them into hydrogen bonding positioned at the center of double helix. The PL intensity is decreased gradually after doping copper ion in the DX tile on the substrate.

  1. Ion Beam Synthesis Of Metal - Silicon Carbide - Si Multilayer Structures

    NASA Astrophysics Data System (ADS)

    Lindner, J. K. N.; Tsang, W. M.; Stritzker, B.; Wong, S. P.

    2003-08-01

    High doses of Ti, Ni, Mo, or W ions were implanted at elevated temperatures either conventionally or using a MEVVA ion source into ion beam synthesized Si/SiC/Si or SiC/Si layer structures in order to create metallic layers contacting the SiC. The depth distribution of metal atoms and the formation of silicide and carbide phases as well as the formation of cavities at the lower SiC/Si interface are studied by Rutherford backscattering spectroscopy (RBS) and cross-sectional transmission electron microscopy (XTEM). A brief survey of the effects ocurring in the ion beam metallization of SiC films is given and the benefit of using ion beams for metallization of thin films is elucidated.

  2. Catalysis using hydrous metal oxide ion exchangers

    DOEpatents

    Dosch, R.G.; Stephens, H.P.; Stohl, F.V.

    1983-07-21

    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.

  3. Catalysis using hydrous metal oxide ion exchanges

    DOEpatents

    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.

  4. Metal ion-exchange on the muscovite mica surface

    NASA Astrophysics Data System (ADS)

    de Poel, Wester; Vaessen, Sarah L.; Drnec, Jakub; Engwerda, Anthonius H. J.; Townsend, Eleanor R.; Pintea, Stelian; de Jong, Aryan E. F.; Jankowski, Maciej; Carlà, Francesco; Felici, Roberto; Elemans, Johannes A. A. W.; van Enckevort, Willem J. P.; Rowan, Alan E.; Vlieg, Elias

    2017-11-01

    The surface potassium ions of muscovite mica were exchanged for several different metal ions from aqueous solution (Ag, Ca, V, Mn, Fe, Ni, Cu, Zn, Co, and Cd). The surfaces were rinsed in water, dried under nitrogen atmosphere, and subsequently analysed using atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and, for half the systems, surface X-ray diffraction (SXRD). XPS and SXRD confirmed the presence of the different metal ions at the muscovite mica surface, with a partial monolayer of the monovalent and divalent ions present on the surface. No counter ions from the used salts were detected. AFM revealed that Ni-, and Fe-terminated muscovite mica surfaces were partially covered by nanoparticles, most likely consisting of metal (hydr)oxide. The exchanged ions remained on the surface after rinsing with ultra pure water three times. SXRD showed that Cd and Ag have a lower affinity for the muscovite mica surface than Cu, Ca, and Mn.

  5. Bioinorganic Chemistry of the Alkali Metal Ions.

    PubMed

    Kim, Youngsam; Nguyen, Thuy-Tien T; Churchill, David G

    2016-01-01

    The common Group 1 alkali metals are indeed ubiquitous on earth, in the oceans and in biological systems. In this introductory chapter, concepts involving aqueous chemistry and aspects of general coordination chemistry and oxygen atom donor chemistry are introduced. Also, there are nuclear isotopes of importance. A general discussion of Group 1 begins from the prevalence of the ions, and from a comparison of their ionic radii and ionization energies. While oxygen and water molecule binding have the most relevance to biology and in forming a detailed understanding between the elements, there is a wide range of basic chemistry that is potentially important, especially with respect to biological chelation and synthetic multi-dentate ligand design. The elements are widely distributed in life forms, in the terrestrial environment and in the oceans. The details about the workings in animal, as well as plant life are presented in this volume. Important biometallic aspects of human health and medicine are introduced as well. Seeing as the elements are widely present in biology, various particular endogenous molecules and enzymatic systems can be studied. Sodium and potassium are by far the most important and central elements for consideration. Aspects of lithium, rubidium, cesium and francium chemistry are also included; they help in making important comparisons related to the coordination chemistry of Na(+) and K(+). Physical methods are also introduced.

  6. Structure and selectivity in bestrophin ion channels

    SciTech Connect

    Yang, Tingting; Liu, Qun; Kloss, Brian; Bruni, Renato; Kalathur, Ravi C.; Guo, Youzhong; Kloppmann, Edda; Rost, Burkhard; Colecraft, Henry M.; Hendrickson, Wayne A.

    2014-09-25

    Human bestrophin 1 (hBest1) is a calcium-activated chloride channel from the retinal pigment epithelium, where it can suffer mutations associated with vitelliform macular degeneration, or Best disease. We describe the structure of a bacterial homolog (KpBest) of hBest1 and functional characterizations of both channels. KpBest is a pentamer that forms a five-helix transmembrane pore, closed by three rings of conserved hydrophobic residues, and has a cytoplasmic cavern with a restricted exit. From electrophysiological analysis of structure-inspired mutations in KpBest and hBest1, we find a subtle control of ion selectivity in the bestrophins, including reversal of anion/cation selectivity, and dramatic activation by mutations at the exit restriction. Lastly, a homology model of hBest1 shows the locations of disease-causing mutations and suggests possible roles in regulation.

  7. Structure and selectivity in bestrophin ion channels

    DOE PAGES

    Yang, Tingting; Liu, Qun; Kloss, Brian; ...

    2014-09-25

    Human bestrophin 1 (hBest1) is a calcium-activated chloride channel from the retinal pigment epithelium, where it can suffer mutations associated with vitelliform macular degeneration, or Best disease. We describe the structure of a bacterial homolog (KpBest) of hBest1 and functional characterizations of both channels. KpBest is a pentamer that forms a five-helix transmembrane pore, closed by three rings of conserved hydrophobic residues, and has a cytoplasmic cavern with a restricted exit. From electrophysiological analysis of structure-inspired mutations in KpBest and hBest1, we find a subtle control of ion selectivity in the bestrophins, including reversal of anion/cation selectivity, and dramatic activationmore » by mutations at the exit restriction. Lastly, a homology model of hBest1 shows the locations of disease-causing mutations and suggests possible roles in regulation.« less

  8. Nuclear quantum effects on adsorption of H2 and isotopologues on metal ions

    NASA Astrophysics Data System (ADS)

    Savchenko, Ievgeniia; Gu, Bing; Heine, Thomas; Jakowski, Jacek; Garashchuk, Sophya

    2017-02-01

    The nuclear quantum effects on the zero-point energy (ZPE), influencing adsorption of H2 and isotopologues on metal ions, are examined using normal mode analysis of ab initio electronic structure results for complexes with 17 metal cations. The lightest metallic nuclei, Li and Be, are found to be the most 'quantum'. The largest selectivity in adsorption is predicted for Cu, Ni and Co ions. Analysis of the nuclear wavepacket dynamics on the ground state electronic potential energy surfaces (PES) performed for complexes of Li+ and Cu+2 with H2/D2/HD shows that the PES anharmonicity changes the ZPE by up to 9%.

  9. Ion-selective electrodes for determination of organic ammonium ions: Ways for selectivity control.

    PubMed

    Egorov, Vladimir V; Bolotin, Alexander A

    2006-12-15

    The influence of the ISE membrane composition on the selectivity for primary, secondary, tertiary, and quaternary alkylammonium cations, as well as for cations of physiologically active amines, has been investigated. Factors studied include the effect of plasticizer (2-nitrophenyl octyl ether, o-NPOE; dibutyl phthalate, DBP; dinonyl adipate, DNA; tris(2-ethylhexyl) phosphate, TEHP) and ion exchanger (potassium tetrakis(4-chlorophenyl)borate, K(TpClPB); potassium tris(nonyloxy)benzenesulfonate, K(TNOBS)), as well as that of the lipophilic cationic additive (tetradecylammonium nitrate, (TDA)NO(3)) and neutral carrier (dibenzo-18-crown-6) presence in membrane. It has been established that plasticizer nature affects K(i,j)(pot) values both when the target and/or foreign ions have non-ionic polar groups capable of specific interaction with plasticizer, and when the only difference consists in the substitution degree of their ionic groups. K(i,j)(pot) values for quaternary alkylammonium cations over primary-tertiary ones change in the following order: TEHP>DBP approximately DNA>o-NPOE. The highest K(i,j)(pot) value change is achieved for the primary-quaternary alkylammonium cation pair, amounting to 3 and 4.7 orders for membranes containing K(TNOBS) and K(TpClPB) as ion exchangers, respectively. In its turn, the ion exchanger influence on the selectivity depends on plasticizer nature, it being maximal for o-NPOE (about 2 orders) and practically non-existent for TEHP. On the whole, as compared to K(TpClPB)-based ISEs, those based on K(TNOBS) show higher selectivity for primary-tertiary alkylammonium cations over quaternary ones. Incorporation of (TDA)NO(3) into membrane causes further improvement of selectivity for primary-tertiary alkylammonium cations in the case of K(TNOBS) only. The maximal total effect of the ion exchanger and lipophilic ionic additive is observed for ISEs with DNA-plasticized membranes and is over 3 orders. The influence of crown ether on the

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

    SciTech Connect

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

    PubMed

    Ramírez-Sandoval, Roxana; Luévano-Rodríguez, Nayeli; Rodríguez-Rodríguez, Mayra; Pérez-Pérez, María Elena; Saldívar-Elias, Sergio; Gurrola-Carlos, Reinaldo; Avalos-Díaz, Esperanza; Bollain-y-Goytia, Juan José; Herrera-Esparza, Rafael

    2015-01-01

    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(NO3)2. 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.

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

    PubMed Central

    Ramírez-Sandoval, Roxana; Luévano-Rodríguez, Nayeli; Rodríguez-Rodríguez, Mayra; Pérez-Pérez, María Elena; Saldívar-Elias, Sergio; Gurrola-Carlos, Reinaldo; Avalos-Díaz, Esperanza; Bollain-y-Goytia, Juan José

    2015-01-01

    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(NO3)2. 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. PMID:26064998

  13. Effect of template ion-ligand complex stoichiometry on selectivity of ion-imprinted polymers.

    PubMed

    Laatikainen, Katri; Udomsap, Dutduan; Siren, Heli; Brisset, Hugues; Sainio, Tuomo; Branger, Catherine

    2015-03-01

    In order to highlight the importance of the complex stoichiometry during ion imprinted polymer (IIP) synthesis, we investigated the effect of the complex structure on IIPs selectivity by adjusting the complex stoichiometry before polymerization. 2-(aminomethyl)pyridine monomer (amp) was chosen as a functionalized ligand for nickel(II) ions and a polymerizable vinylbenzyl derivative (Vbamp) was prepared. Complex formation was studied by varying the nickel/Vbamp ratio and recording absorption spectra of the complexes at the polymerization conditions. Using a least-squares minimization scheme, the complex species distribution was successfully established. From these results, it was possible to choose the metal/ligand stoichiometry in the complex (1:1; 1:2 or 1:3) by adjusting the initial metal/ligand ratio. IIPs were then prepared by inverse suspension copolymerization of Vbamp with ethyleneglycol dimethacrylate (EDMA). Highly porous particles with good nickel binding capacity and good Ni/Zn selectivity even at acidic conditions were obtained. Equilibrium uptake of Ni(II) at pH 7 ranged from 0.12 to 0.2 mmol g(-1) and relative selective coefficient was as high as 260 for the IIP prepared using the Ni(Vbamp)2 complex. Copyright © 2014 Elsevier B.V. All rights reserved.

  14. Uranium Metal Analysis via Selective Dissolution

    SciTech Connect

    Delegard, Calvin H.; Sinkov, Sergey I.; Schmidt, Andrew J.; Chenault, Jeffrey W.

    2008-09-10

    Uranium metal, which is present in sludge held in the Hanford Site K West Basin, can create hazardous hydrogen atmospheres during sludge handling, immobilization, or subsequent transport and storage operations by its oxidation/corrosion in water. A thorough knowledge of the uranium metal concentration in sludge therefore is essential to successful sludge management and waste process design. The goal of this work was to establish a rapid routine analytical method to determine uranium metal concentrations as low as 0.03 wt% in sludge even in the presence of up to 1000-fold higher total uranium concentrations (i.e., up to 30 wt% and more uranium) for samples to be taken during the upcoming sludge characterization campaign and in future analyses for sludge handling and processing. This report describes the experiments and results obtained in developing the selective dissolution technique to determine uranium metal concentration in K Basin sludge.

  15. Rechargeable dual-metal-ion batteries for advanced energy storage.

    PubMed

    Yao, Hu-Rong; You, Ya; Yin, Ya-Xia; Wan, Li-Jun; Guo, Yu-Guo

    2016-04-14

    Energy storage devices are more important today than any time before in human history due to the increasing demand for clean and sustainable energy. Rechargeable batteries are emerging as the most efficient energy storage technology for a wide range of portable devices, grids and electronic vehicles. Future generations of batteries are required to have high gravimetric and volumetric energy, high power density, low price, long cycle life, high safety and low self-discharge properties. However, it is quite challenging to achieve the above properties simultaneously in state-of-the-art single metal ion batteries (e.g. Li-ion batteries, Na-ion batteries and Mg-ion batteries). In this contribution, hybrid-ion batteries in which various metal ions simultaneously engage to store energy are shown to provide a new perspective towards advanced energy storage: by connecting the respective advantages of different metal ion batteries they have recently attracted widespread attention due to their novel performances. The properties of hybrid-ion batteries are not simply the superposition of the performances of single ion batteries. To enable a distinct description, we only focus on dual-metal-ion batteries in this article, for which the design and the benefits are briefly discussed. We enumerate some new results about dual-metal-ion batteries and demonstrate the mechanism for improving performance based on knowledge from the literature and experiments. Although the search for hybrid-ion batteries is still at an early age, we believe that this strategy would be an excellent choice for breaking the inherent disadvantages of single ion batteries in the near future.

  16. Metal ion levels: how can they help us?

    PubMed

    Griffin, William L

    2014-04-01

    Ion levels have been shown to reliably predict abnormal function of the bearing surface with increased wear, but ion levels should not be used alone as a trigger for when to proceed with revision surgery with metal-metal articulations. Risk stratification strategies help determine which patients should be monitored more closely with serial ion levels, cross-sectional imaging with a MARS MRI, or proceed on to revision. Based on the current data available, an ion level greater than 4.5 ppb (Cr or Co) may serve as a threshold for when abnormal wear is occurring, and is suggested as a trigger for a MARS MRI scan.

  17. Selective extraction of uranyl ions using ion-imprinted chelating microspheres.

    PubMed

    Monier, M; Elsayed, Nadia H

    2014-06-01

    In this work, uranyl complex with Schiff base derived from condensation of p-aminostyrene and salicyaldehyde (HASS) was synthesized. Both ligand and uranyl complex were characterized using elemental analysis, FTIR, (1)H and (13)C NMR spectra. The complex was then copolymerized with styrene and divinylbenzene cross-linker using potassium persulfate free radical initiator through emulsion polymerization technique. The uranyl ions were then leached out from the cross-linked network to finally produce uranyl ion-imprinted microspheres (U-PASS), which were investigated using SEM and FTIR. The effect of various significant parameters such as pH, temperature, contact times and initial uranyl concentration on the removal of uranyl from aqueous solution was examined and the results indicated that the adsorption was exothermic in nature and the kinetics of adsorption fit with the second-order kinetic model. Also, Langmuir adsorption isotherm exhibited the best fit with the experimental results with maximum adsorption capacity 147.8 mg/g. Moreover, the selectivity studies revealed that the ion-imprinted microspheres resin exhibited an obvious affinity toward the uranyl ions in presence of other interfering metal ions compared to the non-imprinted resin.

  18. Electron beam selectively seals porous metal filters

    NASA Technical Reports Server (NTRS)

    Snyder, J. A.; Tulisiak, G.

    1968-01-01

    Electron beam welding selectively seals the outer surfaces of porous metal filters and impedances used in fluid flow systems. The outer surface can be sealed by melting a thin outer layer of the porous material with an electron beam so that the melted material fills all surface pores.

  19. Optimal selection of biochars for remediating metals ...

    EPA Pesticide Factsheets

    Approximately 500,000 abandoned mines across the U.S. pose a considerable, pervasive risk to human health and the environment due to possible exposure to the residuals of heavy metal extraction. Historically, a variety of chemical and biological methods have been used to reduce the bioavailability of the metals at mine sites. Biochar with its potential to complex and immobilize heavy metals, is an emerging alternative for reducing bioavailability. Furthermore, biochar has been reported to improve soil conditions for plant growth and can be used for promoting the establishment of a soil-stabilizing native plant community to reduce offsite movement of metal-laden waste materials. Because biochar properties depend upon feedstock selection, pyrolysis production conditions, and activation procedures used, they can be designed to meet specific remediation needs. As a result biochar with specific properties can be produced to correspond to specific soil remediation situations. However, techniques are needed to optimally match biochar characteristics with metals contaminated soils to effectively reduce metal bioavailability. Here we present experimental results used to develop a generalized method for evaluating the ability of biochar to reduce metals in mine spoil soil from an abandoned Cu and Zn mine. Thirty-eight biochars were produced from approximately 20 different feedstocks and produced via slow pyrolysis or gasification, and were allowed to react with a f

  20. Carbon Nanotube-Based Ion Selective Sensors for Wearable Applications.

    PubMed

    Roy, Soumyendu; David-Pur, Moshe; Hanein, Yael

    2017-10-11

    Wearable electronics offer new opportunities in a wide range of applications, especially sweat analysis using skin sensors. A fundamental challenge in these applications is the formation of sensitive and stable electrodes. In this article we report the development of a wearable sensor based on carbon nanotube (CNT) electrode arrays for sweat sensing. Solid-state ion selective electrodes (ISEs), sensitive to Na(+) ions, were prepared by drop coating plasticized poly(vinyl chloride) (PVC) doped with ionophore and ion exchanger on CNT electrodes. The ion selective membrane (ISM) filled the intertubular spaces of the highly porous CNT film and formed an attachment that was stronger than that achieved with flat Au, Pt, or carbon electrodes. Concentration of the ISM solution used influenced the attachment to the CNT film, the ISM surface morphology, and the overall performance of the sensor. Sensitivity of 56 ± 3 mV/decade to Na(+) ions was achieved. Optimized solid-state reference electrodes (REs), suitable for wearable applications, were prepared by coating CNT electrodes with colloidal dispersion of Ag/AgCl, agarose hydrogel with 0.5 M NaCl, and a passivation layer of PVC doped with NaCl. The CNT-based REs had low sensitivity (-1.7 ± 1.2 mV/decade) toward the NaCl solution and high repeatability and were superior to bare Ag/AgCl, metals, carbon, and CNT films, reported previously as REs. CNT-based ISEs were calibrated against CNT-based REs, and the short-term stability of the system was tested. We demonstrate that CNT-based devices implemented on a flexible support are a very attractive platform for future wearable technology devices.

  1. Energy-resolved depth profiling of metal-polymer interfaces using dynamic quadrupole secondary ion mass spectrometry.

    PubMed

    Téllez, Helena; Vadillo, José M; Laserna, J Javier

    2009-08-01

    Quadrupole secondary ion mass spectrometry (qSIMS) characterization of a metallized polypropylene film used in the manufacturing of capacitors has been performed. Ar(+) primary ions were used to preserve the oxidation state of the surface. The sample exhibits an incomplete metallization that made it difficult to determine the exact location of the metal-polymer interface due to the simultaneous contribution of ions with identical m/z values from the metallic and the polymer layers. Energy filtering by means of a 45 degrees electrostatic analyzer allowed resolution of the metal-polymer interface by selecting a suitable kinetic energy corresponding to the ions generated in the metallized layer but not from the polymer. Under these conditions, selective analyses of isobaric interferences such as (27)Al(+) and (27)C(2)H(3) (+) or (43)AlO(+) and (43)C(3)H(7) (+) have been successfully performed.

  2. Silica-polyamine composite materials for heavy metal ion removal, recovery, and recycling. 2. Metal ion separations from mine wastewater and soft metal ion extraction efficiency

    SciTech Connect

    Fischer, R.J.; Pang, D.; Beatty, S.T.; Rosenberg, E.

    1999-12-01

    Silica-polyamine composites have been synthesized which have metal ion capacities as high as 0.84 mmol/g for copper ions removed from aqueous solutions. In previous reports it has been demonstrated that these materials survive more than 3,000 cycles of metal ion extraction, elution, and regeneration with almost no loss of capacity (less than 10%). This paper describes two modified silica-polyamine composite materials and reveals the results of tests designed to determine the effectiveness of these materials for extracting and separating metal ions from actual mining wastewater samples. Using these materials, the concentration of copper, aluminum, and zinc in Berkeley Pit mine wastewater is reduced to below allowable discharge limits. The recovered copper and zinc solutions were greater than 90% pure, and metal ion concentration factors of over 20 for copper were realized. Further, the ability of one of these materials to decrease low levels of the soft metals cadmium, mercury, and lead from National Sanitation Foundation recommended challenge levels to below Environmental Protection Agency allowable limits is also reported.

  3. Aptamer selection for fishing of palladium ion using graphene oxide-adsorbed nanoparticles.

    PubMed

    Cho, Yea Seul; Lee, Eun Jeong; Lee, Gwan-Ho; Hah, Sang Soo

    2015-12-01

    A new aptamer selection method using graphene oxide (GO)-adsorbed nanoparticles (GO-adsorbed NPs) was employed for specific fishing of palladium ion. High affinity ssDNA aptamers were isolated through 13 rounds of selection and the capacity of the selected DNA aptamers for palladium ion uptake was measured, clarifying that DNA01 exhibits the highest affinity to palladium ion with a dissociation constant (Kd) of 4.60±1.17 μM. In addition, binding ability of DNA01 to palladium ion was verified against other metal ions, such as Li(+), Cs(+), Mg(2+), and Pt(2+). Results of the present study suggest that future modification of DNA01 may improve palladium ion-binding ability, leading to economic recovery of palladium from water solution.

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

    PubMed

    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.

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

    PubMed

    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

  6. Select metal adsorption by activated carbon made from peanut shells.

    PubMed

    Wilson, Kermit; Yang, Hong; Seo, Chung W; Marshall, Wayne E

    2006-12-01

    Agricultural by-products, such as peanut shells, contribute large quantities of lignocellulosic waste to the environment each growing season; but few, if any, value-added uses exist for their disposal. The objective of this study was to convert peanut shells to activated carbons for use in adsorption of select metal ions, namely, cadmium (Cd2+), copper (Cu2+), lead (Pb2+), nickel (Ni2+) and zinc (Zn2+). Milled peanut shells were pyrolyzed in an inert atmosphere of nitrogen gas, and then activated with steam at different activation times. Following pyrolysis and activation, the carbons underwent air oxidation. The prepared carbons were evaluated either for adsorption efficiency or adsorption capacity; and these parameters were compared to the same parameters obtained from three commercial carbons, namely, DARCO 12x20, NORIT C GRAN and MINOTAUR. One of the peanut shell-based carbons had metal ion adsorption efficiencies greater than two of the three commercial carbons but somewhat less than but close to Minotaur. This study demonstrates that peanut shells can serve as a source for activated carbons with metal ion-removing potential and may serve as a replacement for coal-based commercial carbons in applications that warrant their use.

  7. Selective disulfide bond cleavage in gold(I) cationized polypeptide ions formed via gas-phase ion/ion cation switching.

    PubMed

    Gunawardena, Harsha P; O'Hair, Richard A J; McLuckey, Scott A

    2006-09-01

    Gaseous multiply protonated disulfide-linked peptides have been subjected to reactions with AuCl2(-) ions to explore the possibility of effecting cation switching of Au+ for two protons and to determine whether cationization by Au+ ions affords selective dissociation of disulfide linkages. The incorporation of Au+ into several model disulfide-linked peptides proved to be straightforward. The primary ion/ion reaction channels were proton transfer, which does not lead to Au+ incorporation, and attachment of AuCl2(-) ions to the polypeptide cation, which does incorporate Au+. Fragmentation of the attachment product, the extent of which varied with peptide and charge state, led to losses of one or more molecules of HCl and, to some extent, cleavage of polypeptides at the disulfide linkage into its two constituent chains. Collisional activation of the intact metal-ion-incorporated peptides showed cleavage of the disulfide linkage to be a major, and in some cases exclusive, process. Cations with protons as the only cationizing agents showed only small contributions from cleavage of the disulfide linkage. These results indicate that Au+ incorporation into a disulfide-linked polypeptide ion is a promising way to effect selective dissociation of disulfide bonds. Cation switching via ion/ion reactions is a convenient means for incorporating gold and is attractive because it avoids the requirement of adding metal salts to the analyte solution.

  8. Selective separation of sodium ions from a mixture with phenylalanine by Donnan dialysis with a profiled sulfogroup cation exchange membrane

    NASA Astrophysics Data System (ADS)

    Vasil'eva, V. I.; Goleva, E. A.

    2013-11-01

    The possibility of separating ions of metal from a mixture with ampholyte (an amino acid) by Donnan dialysis with an MK-40 sulfogroup cation exchange membrane is demonstrated. Conditions ensuring the selectivity and intensity of the mass transfer of sodium ions from a mixture with bipolar phenylalanine ions into a diffusate containing hydrochloric acid through a cation exchange membrane are found.

  9. Nucleic acid-metal ion interactions in the solid state.

    PubMed

    Aoki, Katsuyuki; Murayama, Kazutaka

    2012-01-01

    Metal ions play a key role in nucleic acid structure and activity. Elucidation of the rules that govern the binding of metal ions is therefore an essential step for better understanding of the nucleic acid functions. This review is as an update to a preceding one (Metal Ions Biol. Syst., 1996, 32, 91-134), in which we offered a general view of metal ion interactions with mono-, di-, tri-, and oligonucleotides in the solid state, based on their crystal structures reported before 1994. In this chapter, we survey all the crystal structures of metal ion complexes with nucleotides involving oligonucleotides reported after 1994 and we have tried to uncover new characteristic metal bonding patterns for mononucleotides and oligonucleotides with A-RNA and A/B/Z-DNA fragments that form duplexes. We do not cover quadruplexes, duplexes with metal-mediated base-pairs, tRNAs, rRNAs in ribosome, ribozymes, and nucleic acid-drug and -protein complexes. Factors that affect metal binding to mononucleotides and oligonucleotide duplexes are also dealt with.

  10. Predicting the relative toxicity of metal ions using ion characteristics: Microtox{reg_sign} bioluminescence assay

    SciTech Connect

    McCloskey, J.T.; Newman, M.C.; Clark, S.B.

    1996-10-01

    Quantitative structure-activity relationships have been used to predict the relative toxicity of organic compounds. Although not as common, ion characteristics have also proven useful for predicting the relative toxicity of metal ions. The purpose of this study was to determine if the relative toxicity of metal ions using the Microtox{reg_sign} bioassay was predictable using ion characteristics. Median effect concentrations (EC50s) were determined for 20 metals in a NaNO{sub 3} medium, which reflected freshwater speciation conditions, using the Microtox bacterial assay. The log of EC50 values was modeled using several ion characteristics, and Akaike`s Information Criterion was calculated to determine which ion characteristics provided the best fit. Whether modeling total ion or free ion EC50 values, the one variable which best modeled EC50s was the softness index, while a combination of {chi}{sub m}{sup 2}r ({chi}{sub m} = electronegativity, r = Pauling ionic radius) and {vert_bar}log K{sub OH}{vert_bar} was the best two-variable model. Other variables, including {Delta}E{sub 0} and {chi}{sub m}{sup 2}r (one-variable models) and (AN/{Delta}IP, {Delta}E{sub 0}) and ({chi}{sub m}{sup 2}r, Z{sup 2}/r) (two-variable models), also gave adequate fits. Modeling with speciated (free ion) versus unspeciated (total ion) EC50 values did not improve fits. Modeling mono-, di-, and trivalent metal ions separately improved the models. The authors conclude that ion characteristics can be used to predict the relative toxicity of metal ions whether in freshwater (NaNO{sub 3} medium) or saltwater (NaCl medium) speciation conditions and that this approach can be applied to metal ions varying widely in both valence and binding tendencies.

  11. Metal ion sorption by untreated and chemically treated biomass

    SciTech Connect

    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.

  12. The catalytic role of the M2 metal ion in PP2Cα.

    PubMed

    Pan, Chang; Tang, Jun-yi; Xu, Yun-fei; Xiao, Peng; Liu, Hong-da; Wang, Hao-an; Wang, Wen-bo; Meng, Fan-guo; Yu, Xiao; Sun, Jin-peng

    2015-02-24

    PP2C family phosphatases (the type 2C family of protein phosphatases; or metal-dependent phosphatase, PPM) constitute an important class of signaling enzymes that regulate many fundamental life activities. All PP2C family members have a conserved binuclear metal ion active center that is essential for their catalysis. However, the catalytic role of each metal ion during catalysis remains elusive. In this study, we discovered that mutations in the structurally buried D38 residue of PP2Cα (PPM1A) redefined the water-mediated hydrogen network in the active site and selectively disrupted M2 metal ion binding. Using the D38A and D38K mutations of PP2Cα as specific tools in combination with enzymology analysis, our results demonstrated that the M2 metal ion determines the rate-limiting step of substrate hydrolysis, participates in dianion substrate binding and stabilizes the leaving group after P-O bond cleavage. The newly characterized catalytic role of the M2 metal ion in this family not only provides insight into how the binuclear metal centers of the PP2C phosphatases are organized for efficient catalysis but also helps increase our understanding of the function and substrate specificity of PP2C family members.

  13. The catalytic role of the M2 metal ion in PP2Cα

    NASA Astrophysics Data System (ADS)

    Pan, Chang; Tang, Jun-Yi; Xu, Yun-Fei; Xiao, Peng; Liu, Hong-Da; Wang, Hao-An; Wang, Wen-Bo; Meng, Fan-Guo; Yu, Xiao; Sun, Jin-Peng

    2015-02-01

    PP2C family phosphatases (the type 2C family of protein phosphatases; or metal-dependent phosphatase, PPM) constitute an important class of signaling enzymes that regulate many fundamental life activities. All PP2C family members have a conserved binuclear metal ion active center that is essential for their catalysis. However, the catalytic role of each metal ion during catalysis remains elusive. In this study, we discovered that mutations in the structurally buried D38 residue of PP2Cα (PPM1A) redefined the water-mediated hydrogen network in the active site and selectively disrupted M2 metal ion binding. Using the D38A and D38K mutations of PP2Cα as specific tools in combination with enzymology analysis, our results demonstrated that the M2 metal ion determines the rate-limiting step of substrate hydrolysis, participates in dianion substrate binding and stabilizes the leaving group after P-O bond cleavage. The newly characterized catalytic role of the M2 metal ion in this family not only provides insight into how the binuclear metal centers of the PP2C phosphatases are organized for efficient catalysis but also helps increase our understanding of the function and substrate specificity of PP2C family members.

  14. The catalytic role of the M2 metal ion in PP2Cα

    PubMed Central

    Pan, Chang; Tang, Jun-yi; Xu, Yun-fei; Xiao, Peng; Liu, Hong-da; Wang, Hao-an; Wang, Wen-bo; Meng, Fan-guo; Yu, Xiao; Sun, Jin-peng

    2015-01-01

    PP2C family phosphatases (the type 2C family of protein phosphatases; or metal-dependent phosphatase, PPM) constitute an important class of signaling enzymes that regulate many fundamental life activities. All PP2C family members have a conserved binuclear metal ion active center that is essential for their catalysis. However, the catalytic role of each metal ion during catalysis remains elusive. In this study, we discovered that mutations in the structurally buried D38 residue of PP2Cα (PPM1A) redefined the water-mediated hydrogen network in the active site and selectively disrupted M2 metal ion binding. Using the D38A and D38K mutations of PP2Cα as specific tools in combination with enzymology analysis, our results demonstrated that the M2 metal ion determines the rate-limiting step of substrate hydrolysis, participates in dianion substrate binding and stabilizes the leaving group after P-O bond cleavage. The newly characterized catalytic role of the M2 metal ion in this family not only provides insight into how the binuclear metal centers of the PP2C phosphatases are organized for efficient catalysis but also helps increase our understanding of the function and substrate specificity of PP2C family members. PMID:25708299

  15. Extracting metal ions with diphosphonic acid, or derivative thereof

    DOEpatents

    Horwitz, E.P.; Gatrone, R.C.; Nash, K.L.

    1994-07-26

    Thermodynamically-unstable complexing agents which are diphosphonic acids and diphosphonic acid derivatives (or sulfur containing analogs), like carboxyhydroxymethanediphosphonic acid and vinylidene-1,1-diphosphonic acid, are capable of complexing with metal ions, and especially metal ions in the II, III, IV, V and VI oxidation states, to form stable, water-soluble metal ion complexes in moderately alkaline to highly-acidic media. However, the complexing agents can be decomposed, under mild conditions, into non-organic compounds which, for many purposes are environmentally-nondamaging compounds thereby degrading the complex and releasing the metal ion for disposal or recovery. Uses for such complexing agents as well as methods for their manufacture are also described. 1 fig.

  16. Extracting metal ions with diphosphonic acid, or derivative thereof

    DOEpatents

    Horwitz, Earl P.; Gatrone, Ralph C.; Nash, Kenneth L.

    1994-01-01

    Thermodynamically-unstable complexing agents which are diphosphonic acids and diphosphonic acid derivatives (or sulphur containing analogs), like carboxyhydroxymethanediphosphonic acid and vinylidene-1,1-diphosphonic acid, are capable of complexing with metal ions, and especially metal ions in the II, III, IV, V and VI oxidation states, to form stable, water-soluble metal ion complexes in moderately alkaline to highly-acidic media. However, the complexing agents can be decomposed, under mild conditions, into non-organic compounds which, for many purposes are environmentally-nondamaging compounds thereby degrading the complex and releasing the metal ion for disposal or recovery. Uses for such complexing agents as well as methods for their manufacture are also described.

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

    PubMed

    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.

  18. Metal ion-catalyzed nucleic acid alkylation and fragmentation.

    PubMed

    Browne, Kenneth A

    2002-07-10

    Nucleic acid microarrays are a growing technology in which high densities of known sequences are attached to a substrate in known locations (addressed). Hybridization of complementary sequences leads to a detectable signal such as an electrical impulse or fluorescence. This combination of sequence addressing, hybridization, and detection increases the efficiency of a variety of genomic disciplines including those that profile genetic expression, search for single nucleotide polymorphisms (SNPs), or diagnose infectious diseases by sequencing portions of microbial or viral genomes. Incorporation of reporter molecules into nucleic acids is essential for the sensitive detection of minute amounts of nucleic acids on most types of microarrays. Furthermore, polynucleic acid size reduction increases hybridization because of increased diffusion rates and decreased competing secondary structure of the target nucleic acids. Typically, these reactions would be performed as two separate processes. An improvement to past techniques, termed labeling-during-cleavage (LDC), is presented in which DNA or RNA is alkylated with fluorescent tags and fragmented in the same reaction mixture. In model studies with 26 nucleotide-long RNA and DNA oligomers using ultraviolet/visible and fluorescence spectroscopies as well as high-pressure liquid chromatography and mass spectrometry, addition of both alkylating agents (5-(bromomethyl)fluorescein, 5- or 6-iodoacetamidofluorescein) and select metal ions (of 21 tested) to nucleic acids in aqueous solutions was critical for significant increases in both labeling and fragmentation, with >or=100-fold increases in alkylation possible relative to metal ion-free reactions. Lanthanide series metal ions, Pb(2+), and Zn(2+) were the most reactive ions in terms of catalyzing alkylation and fragmentation. While oligonucleotides were particularly susceptible to fragmentation at sites containing phosphorothioate moieties, labeling and cleavage reactions

  19. Metallic glass as a temperature sensor during ion plating

    NASA Technical Reports Server (NTRS)

    Miyoshi, K.; Spalvins, T.; Buckley, D. H.

    1985-01-01

    The temperature of the interface and/or a superficial layer of a substrate during ion plating was investigated using a metallic glass of the composition Fe67Co18B14Si1 as the substrate and as the temperature sensor. Transmission electron microscopy and diffraction studies determined the microstructure of the ion-plated gold film and the substrate. Results indicate that crystallization occurs not only in the film, but also in the substrate. The grain size of crystals formed during ion plating was 6 to 60 nm in the gold film and 8 to 100 nm in the substrate at a depth of 10 to 15 micrometers from the ion-plated interface. The temperature rise of the substrate during ion plating was approximately 500 C. Discontinuous changes in metallurgical microstructure, and physical, chemical, and mechanical properties during the amorphous to crystalline transition in metallic glasses make metallic glasses extremely useful materials for temperature sensor applications in coating processes.

  20. Metallic glass as a temperature sensor during ion plating

    NASA Technical Reports Server (NTRS)

    Miyoshi, K.; Spalvins, T.; Buckley, D. H.

    1984-01-01

    The temperature of the interface and/or a superficial layer of a substrate during ion plating was investigated using a metallic glass of the composition Fe67Co18B14Si1 as the substrate and as the temperature sensor. Transmission electron microscopy and diffraction studies determined the microstructure of the ion-plated gold film and the substrate. Results indicate that crystallization occurs not only in the film, but also in the substrate. The grain size of crystals formed during ion plating was 6 to 60 nm in the gold film and 8 to 100 nm in the substrate at a depth of 10 to 15 micrometers from the ion-plated interface. The temperature rise of the substrate during ion plating was approximately 500 C. Discontinuous changes in metallurgical microstructure, and physical, chemical, and mechanical properties during the amorphous to crystalline transition in metallic glasses make metallic glasses extremely useful materials for temperature sensor applications in coating processes.

  1. Metallic glass as a temperature sensor during ion plating

    NASA Technical Reports Server (NTRS)

    Miyoshi, K.; Spalvins, T.; Buckley, D. H.

    1985-01-01

    The temperature of the interface and/or a superficial layer of a substrate during ion plating was investigated using a metallic glass of the composition Fe67Co18B14Si1 as the substrate and as the temperature sensor. Transmission electron microscopy and diffraction studies determined the microstructure of the ion-plated gold film and the substrate. Results indicate that crystallization occurs not only in the film, but also in the substrate. The grain size of crystals formed during ion plating was 6 to 60 nm in the gold film and 8 to 100 nm in the substrate at a depth of 10 to 15 micrometers from the ion-plated interface. The temperature rise of the substrate during ion plating was approximately 500 C. Discontinuous changes in metallurgical microstructure, and physical, chemical, and mechanical properties during the amorphous to crystalline transition in metallic glasses make metallic glasses extremely useful materials for temperature sensor applications in coating processes.

  2. Systematic Design of a Metal Ion Biosensor: A Multi-Objective Optimization Approach.

    PubMed

    Hsu, Chih-Yuan; Chen, Bor-Sen

    2016-01-01

    With the recent industrial expansion, heavy metals and other pollutants have increasingly contaminated our living surroundings. Heavy metals, being non-degradable, tend to accumulate in the food chain, resulting in potentially damaging toxicity to organisms. Thus, techniques to detect metal ions have gradually begun to receive attention. Recent progress in research on synthetic biology offers an alternative means for metal ion detection via the help of promoter elements derived from microorganisms. To make the design easier, it is necessary to develop a systemic design method for evaluating and selecting adequate components to achieve a desired detection performance. A multi-objective (MO) H2/H∞ performance criterion is derived here for design specifications of a metal ion biosensor to achieve the H2 optimal matching of a desired input/output (I/O) response and simultaneous H∞ optimal filtering of intrinsic parameter fluctuations and external cellular noise. According to the two design specifications, a Takagi-Sugeno (T-S) fuzzy model is employed to interpolate several local linear stochastic systems to approximate the nonlinear stochastic metal ion biosensor system so that the multi-objective H2/H∞ design of the metal ion biosensor can be solved by an associated linear matrix inequality (LMI)-constrained multi-objective (MO) design problem. The analysis and design of a metal ion biosensor with optimal I/O response matching and optimal noise filtering ability then can be achieved by solving the multi-objective problem under a set of LMIs. Moreover, a multi-objective evolutionary algorithm (MOEA)-based library search method is employed to find adequate components from corresponding libraries to solve LMI-constrained MO H2/H∞ design problems. It is a useful tool for the design of metal ion biosensors, particularly regarding the tradeoffs between the design factors under consideration.

  3. Systematic Design of a Metal Ion Biosensor: A Multi-Objective Optimization Approach

    PubMed Central

    Hsu, Chih-Yuan

    2016-01-01

    With the recent industrial expansion, heavy metals and other pollutants have increasingly contaminated our living surroundings. Heavy metals, being non-degradable, tend to accumulate in the food chain, resulting in potentially damaging toxicity to organisms. Thus, techniques to detect metal ions have gradually begun to receive attention. Recent progress in research on synthetic biology offers an alternative means for metal ion detection via the help of promoter elements derived from microorganisms. To make the design easier, it is necessary to develop a systemic design method for evaluating and selecting adequate components to achieve a desired detection performance. A multi-objective (MO) H2/H∞ performance criterion is derived here for design specifications of a metal ion biosensor to achieve the H2 optimal matching of a desired input/output (I/O) response and simultaneous H∞ optimal filtering of intrinsic parameter fluctuations and external cellular noise. According to the two design specifications, a Takagi-Sugeno (T-S) fuzzy model is employed to interpolate several local linear stochastic systems to approximate the nonlinear stochastic metal ion biosensor system so that the multi-objective H2/H∞ design of the metal ion biosensor can be solved by an associated linear matrix inequality (LMI)-constrained multi-objective (MO) design problem. The analysis and design of a metal ion biosensor with optimal I/O response matching and optimal noise filtering ability then can be achieved by solving the multi-objective problem under a set of LMIs. Moreover, a multi-objective evolutionary algorithm (MOEA)-based library search method is employed to find adequate components from corresponding libraries to solve LMI-constrained MO H2/H∞ design problems. It is a useful tool for the design of metal ion biosensors, particularly regarding the tradeoffs between the design factors under consideration. PMID:27832110

  4. An Engineered Palette of Metal Ion Quenchable Fluorescent Proteins

    PubMed Central

    Yu, Xiaozhen; Strub, Marie-Paule; Barnard, Travis J.; Noinaj, Nicholas; Piszczek, Grzegorz; Buchanan, Susan K.; Taraska, Justin W.

    2014-01-01

    Many fluorescent proteins have been created to act as genetically encoded biosensors. With these sensors, changes in fluorescence report on chemical states in living cells. Transition metal ions such as copper, nickel, and zinc are crucial in many physiological and pathophysiological pathways. Here, we engineered a spectral series of optimized transition metal ion-binding fluorescent proteins that respond to metals with large changes in fluorescence intensity. These proteins can act as metal biosensors or imaging probes whose fluorescence can be tuned by metals. Each protein is uniquely modulated by four different metals (Cu2+, Ni2+, Co2+, and Zn2+). Crystallography revealed the geometry and location of metal binding to the engineered sites. When attached to the extracellular terminal of a membrane protein VAMP2, dimeric pairs of the sensors could be used in cells as ratiometric probes for transition metal ions. Thus, these engineered fluorescent proteins act as sensitive transition metal ion-responsive genetically encoded probes that span the visible spectrum. PMID:24752441

  5. Removal of heavy metal ions by biogenic hydroxyapatite: Morphology influence and mechanism study

    NASA Astrophysics Data System (ADS)

    Wang, Dandan; Guan, Xiaomei; Huang, Fangzhi; Li, Shikuo; Shen, Yuhua; Chen, Jun; Long, Haibo

    2016-08-01

    Based on the synthesis of hydroxyapatite (HA) with different morphologies, such as nanorod-like, flower-like and sphere-like assembled HA nanorods, a new strategy has been developed for the removal of heavy metal ions such as Pb2+, Cu2+, Mn2+, Zn2+. The dependence of removal efficiency on the morphology and the suspended concentration of trapping agent, the removal time and selectivity were evaluated and discussed. The experimental results proved that the removal capacity of flower-like assembled HA nanorods (NAFL-HA) was the best, and the maximum removal ratio for Pb2+ ion was 99.97%. The mechanism of Pb2+ removal was studied in detail, noting that some metal ions were completely incorporated into hydroxyapatitie to produce Pb-HA. It reveals that the metal ions capture by HA is mainly controlled by sample surface adsorption and co-precipitation, which are directly controlled by sample morphology.

  6. Frictional and morphological characteristics of ion plated soft, metallic films

    NASA Technical Reports Server (NTRS)

    Spalvins, T.; Buzek, B.

    1981-01-01

    Ion plated metallic films in contrast to films applied by other deposition techniques offer a lower friction coefficient, longer endurance lives and exhibit a gradual increase in friction coefficient after the film has been worn off. The friction coefficients of metallic films are affected by the degree of adherence, thickness and nucleation and growth characteristics during ion plating lead to a fine, continuous crystalline structure, which contributes to a lower friction coefficient.

  7. Smart textile device using ion polymer metal compound.

    PubMed

    Nakamura, Taro; Ihara, Tadashi

    2013-01-01

    We have developed a smart textile device that detects angular displacement of attached surface using ion polymer metal compound. The device was composed of ion polymer metal compound (IPMC) which was fabricated from Nafion resin by heat-press and chemical gold plating. The generated voltage from IPMC was measured as a function of bending angle. Fabricated IPMC device was weaved into a cotton cloth and multidirectional movements were detected.

  8. An optical dosimeter for monitoring heavy metal ions in water

    NASA Astrophysics Data System (ADS)

    Mignani, Anna G.; Regan, Fiona; Leamy, D.; Mencaglia, A. A.; Ciaccheri, L.

    2005-05-01

    This work presents an optochemical dosimeter for determining and discriminating nickel, copper, and cobalt ions in water that can be used as an early warning system for water pollution. An inexpensive fiber optic spectrophotometer monitors the sensor's spectral behavior under exposure to water solutions of heavy metal ions in the 1-10 mg/l concentration range. The Principal Component Analysis (PCA) method quantitatively determines the heavy metals and discriminates their type and combination.

  9. Isothermal Titration Calorimetry Measurements of Metal Ions Binding to Proteins.

    PubMed

    Quinn, Colette F; Carpenter, Margaret C; Croteau, Molly L; Wilcox, Dean E

    2016-01-01

    ITC measurements involving metal ions are susceptible to a number of competing reactions (oxidation, precipitation, and hydrolysis) and coupled reactions involving the buffer and protons. Stabilization and delivery of the metal ion as a well-defined and well-characterized complex with the buffer, or a specific ligand, can suppress undesired solution chemistry and, depending on the stability of the metal complex, allow accurate measurements of higher affinity protein-binding sites. This requires, however, knowledge of the thermodynamics of formation of the metal complex and accounting for its contribution to the experimentally measured values (KITC and ΔHITC) through a post hoc analysis that provides the condition-independent binding thermodynamics (K, ΔG(o), ΔH, ΔS, and ΔCP). This analysis also quantifies the number of protons that are displaced when the metal ion binds to the protein.

  10. Metal ion implantation for large scale surface modification

    SciTech Connect

    Brown, I.G.

    1992-10-01

    Intense energetic beams of metal ions can be produced by using a metal vapor vacuum arc as the plasma discharge from which the ion beam is formed. We have developed a number of ion sources of this kind and have built a metal ion implantation facility which can produce repetitively pulsed ion beams with mean ion energy up to several hundred key, pulsed beam current of more than an ampere, and time averaged current of several tens of milliamperes delivered onto a downstream target. We've also done some preliminary work on scaling up this technology to very large size. For example, a 50-cm diameter (2000 cm[sup 2]) set of beam formation electrodes was used to produce a pulsed titanium beam with ion current over 7 amperes at a mean ion energy of 100 key. Separately, a dc embodiment has been used to produce a dc titanium ion beam with current over 600 mA, power supply limited in this work, and up to 6 amperes of dc plasma ion current was maintained for over an hour. In a related program we've developed a plasma immersion method for applying thin metallic and compound films in which the added species is atomically mixed to the substrate. By adding a gas flow to the process, well-bonded compound films can also be formed; metallic films and multilayers as well as oxides and nitrides with mixed transition zones some hundreds of angstroms thick have been synthesized. Here we outline these parallel metal-plasma-based research programs and describe the hardware that we've developed and some of the surface modification research that we've done with it.

  11. Production of negative hydrogen ions on metal grids

    SciTech Connect

    Oohara, W.; Maetani, Y.; Takeda, Takashi; Takeda, Toshiaki; Yokoyama, H.; Kawata, K.

    2015-03-15

    Negative hydrogen ions are produced on a nickel grid with positive-ion irradiation. In order to investigate the production mechanism, a copper grid without the chemisorption of hydrogen atoms and positive helium ions without negative ionization are used for comparison. Positive hydrogen ions reflected on the metal surface obtain two electrons from the surface and become negatively ionized. It is found that the production yield of negative ions by desorption ionization of chemisorbed hydrogen atoms seems to be small, and the production is a minor mechanism.

  12. The effect of the adsorption of metal ions on the interfacial behavior of silicate minerals

    SciTech Connect

    Huang, P.; Fuerstenau, D.W.

    1997-08-01

    Because of its importance in the fields of environmental and mineral engineering, the adsorption mechanism of metal ions on oxides has been studied rather extensively using such techniques as titration, adsorption isotherm determination, flotation and spectroscopy. However, limited work has been done to compare the behavior of hydrophilic silicates with those that are naturally hydrophobic. This investigation was undertaken to provide a better understanding of the adsorption mechanism of selected metal ions at the solid/liquid interface through simultaneous measurements of zeta potentials, adsorption densities and turbidity on colloidal suspension of two silicate minerals, as a function of pH, to delineate the effect of hydrophobicity and surface heterogeneity on these processes. In present investigation, quartz and talc are selected as model minerals and lead and cadmium are chosen as the metal ions to investigate because of their importance in industry application.

  13. Scintillating 99Tc Selective Ion Exchange Resins

    SciTech Connect

    Mitchell Greenhalgh; Richard D. Tillotson

    2012-07-01

    Scintillating technetium (99Tc) selective ion exchange resins have been developed and evaluated for equilibrium capacities and detection efficiencies. These resins can be utilized for the in-situ concentration and detection of low levels of pertechnetate anions (99TcO4-) in natural waters. Three different polystyrene type resin support materials were impregnated with varying amounts of tricaprylmethylammonium chloride (Aliquat 336) extractant, several different scintillating fluors and wavelength shifters. The prepared resins were contacted batch-wise to equilibrium over a wide range of 99TcO4- concentrations in natural water. The measured capacities were used to develop Langmuir adsorption isotherms for each resin. 99Tc detection efficiencies were determined and up to 71.4 ± 2.6% was achieved with some resins. The results demonstrate that a low level detection limit for 99TcO4- in natural waters can be realized.

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

    PubMed

    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. Ion distribution and selectivity of ionic liquids in microporous electrodes

    NASA Astrophysics Data System (ADS)

    Neal, Justin N.; Wesolowski, David J.; Henderson, Douglas; Wu, Jianzhong

    2017-05-01

    The energy density of an electric double layer capacitor, also known as supercapacitor, depends on ion distributions in the micropores of its electrodes. Herein we study ion selectivity and partitioning of symmetric, asymmetric, and mixed ionic liquids among different pores using the classical density functional theory. We find that a charged micropore in contact with mixed ions of the same valence is always selective to the smaller ions, and the ion selectivity, which is strongest when the pore size is comparable to the ion diameters, drastically falls as the pore size increases. The partitioning behavior in ionic liquids is fundamentally different from those corresponding to ion distributions in aqueous systems whereby the ion selectivity is dominated by the surface energy and entropic effects insensitive to the degree of confinement.

  16. Implantation of nitrogen, carbon, and phosphorus ions into metals

    SciTech Connect

    Guseva, M.I.; Gordeeva, G.V.

    1987-01-01

    The application of ion implantation for alloying offers a unique opportunity to modify the chemical composition, phase constitution, and microstructure of the surface layers of metals. The authors studied ion implantation of nitrogen and carbon into the surface layers of metallic targets. The phase composition of the implanted layers obtained on the Kh18N10T stainless steel, the refractory molybdenum alloy TsM-6, niobium, and nickel was determined according to the conventional method of recording the x-ray diffraction pattern of the specimens using monochromatic FeK/sub alpha/-radiation on a DRON-2,0 diffractometer. The targets were bombarded at room temperature in an ILU-3 ion accelerator. The implantation of metalloid ions was also conducted with the targets being bombarded with 100-keV phosphorus ions and 40-keV carbon ions.

  17. Quantum ion-acoustic wave oscillations in metallic nanowires

    SciTech Connect

    Moradi, Afshin

    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.

  18. ION EXCHANGE IN FUSED SALTS. II. THE DISTRIBUTION OF ALKALI METAL AND ALKALINE EARTH IONS BETWEEN CHABAZITE AND FUSED LINO3, NANO3, AND KNO3,

    DTIC Science & Technology

    ION EXCHANGE, SALTS ), (*ALKALI METALS, ION EXCHANGE), (*ALKALINE EARTH METALS, ION EXCHANGE), (*NITRATES, ION EXCHANGE), SODIUM , CALCIUM, POTASSIUM...BARIUM, RUBIDIUM, CESIUM, LITHIUM COMPOUNDS, SODIUM COMPOUNDS, POTASSIUM COMPOUNDS, DISTRIBUTION, MINERALS, IONS

  19. A method for the determination of potentiometric selectivity coefficients of ion selective electrodes in the presence of several interfering ions.

    PubMed

    Deyhimi, F

    1999-12-06

    In this work a new method is reported for the determination of potentiometric selectivity coefficients of ion-selective electrode in which, similar to real samples, several interfering ions are simultaneously present in test solutions and where the electrode shows its practical behavior. In order to illustrate this method, the potentiometric selectivity coefficients of a commercial liquid membrane ammonium selective electrode is determined for biologically important interfering ions: Li(+), Na(+) and K(+).

  20. Apparatus for reduction of selected ion intensities in confined ion beams

    DOEpatents

    Eiden, Gregory C.; Barinaga, Charles J.; Koppenaal, David W.

    2001-01-01

    An apparatus for producing an ion beam having an increased proportion of analyte ions compared to carrier gas ions is disclosed. Specifically, the apparatus has an ion trap or a collision cell containing a reagent gas wherein the reagent gas accepts charge from the analyte ions thereby selectively neutralizing the carrier gas ions. Also disclosed is the collision cell as employed in various locations within analytical instruments including an inductively coupled plasma mass spectrometer.

  1. Method for reduction of selected ion intensities in confined ion beams

    DOEpatents

    Eiden, G.C.; Barinaga, C.J.; Koppenaal, D.W.

    1998-06-16

    A method for producing an ion beam having an increased proportion of analyte ions compared to carrier gas ions is disclosed. Specifically, the method has the step of addition of a charge transfer gas to the carrier analyte combination that accepts charge from the carrier gas ions yet minimally accepts charge from the analyte ions thereby selectively neutralizing the carrier gas ions. Also disclosed is the method as employed in various analytical instruments including an inductively coupled plasma mass spectrometer. 7 figs.

  2. Method for reduction of selected ion intensities in confined ion beams

    DOEpatents

    Eiden, Gregory C.; Barinaga, Charles J.; Koppenaal, David W.

    1998-01-01

    A method for producing an ion beam having an increased proportion of analyte ions compared to carrier gas ions is disclosed. Specifically, the method has the step of addition of a charge transfer gas to the carrier analyte combination that accepts charge from the carrier gas ions yet minimally accepts charge from the analyte ions thereby selectively neutralizing the carrier gas ions. Also disclosed is the method as employed in various analytical instruments including an inductively coupled plasma mass spectrometer.

  3. IRMPD Spectroscopy of Metalated Flavins: Structure and Bonding of Lumiflavin Complexes with Alkali and Coinage Metal Ions.

    PubMed

    Nieto, Pablo; Günther, Alan; Berden, Giel; Oomens, Jos; Dopfer, Otto

    2016-10-01

    Flavins are a fundamental class of biomolecules, whose photochemical properties strongly depend on their environment and their redox and metalation state. Infrared multiphoton dissociation (IRMPD) spectra of mass selected isolated metal-lumiflavin ionic complexes (M+LF) are analyzed in the fingerprint range (800-1830 cm-1) to determine the bonding of lumiflavin with alkali (M=Li, Na, K, Cs) and coinage (M=Cu, Ag) metal ions. The complexes are generated in an electrospray ionization source coupled to an ion cyclotron resonance mass spectrometer and the IR free electron laser FELIX. Vibrational and isomer assignments of the IRMPD spectra are accomplished by comparison to quantum chemical calculations at the B3LYP/cc-pVDZ level, yielding structure, binding energy, bonding mechanism, and spectral properties of the complexes. The most stable binding sites identified in the experiments involve metal bonding to the oxygen atoms of the two available CO groups of LF. Hence, CO stretching frequencies are a sensitive indicator of both the metal binding site and the metal bond strength. More than one isomer is observed for M=Li, Na, and K, and the preferred CO binding site changes with the size of the alkali ion. For Cs+LF only one isomer is identified although the energies of the two most stable structures differ by less than 7 kJ/mol. While the M+-LF bonds for alkali ions are mainly based on electrostatic forces, substantial covalent contributions lead to stronger bonds for the coinage metal ions. Comparison between lumiflavin and lumichrome reveals substantial differences in the metal binding motifs and interactions due to the different flavin structures.

  4. Bidentate and tridentate metal-ion coordination states within ternary complexes of RB69 DNA polymerase

    SciTech Connect

    Xia, Shuangluo; Eom, Soo Hyun; Konigsberg, William H.; Wang, Jimin

    2012-02-21

    Two divalent metal ions are required for primer-extension catalyzed by DNA polymerases. One metal ion brings the 3'-hydroxyl of the primer terminus and the {alpha}-phosphorus atom of incoming dNTP together for bond formation so that the catalytically relevant conformation of the triphosphate tail of the dNTP is in an {alpha},{beta},{gamma}-tridentate coordination complex with the second metal ion required for proper substrate alignment. A probable base selectivity mechanism derived from structural studies on Dpo4 suggests that the inability of mispaired dNTPs to form a substrate-aligned, tridentate coordination complex could effectively cause the mispaired dNTPs to be rejected before catalysis. Nevertheless, we found that mispaired dNTPs can actually form a properly aligned tridentate coordination complex. However, complementary dNTPs occasionally form misaligned complexes with mutant RB69 DNA polymerases (RB69pols) that are not in a tridentate coordination state. Here, we report finding a {beta},{gamma}-bidentate coordination complex that contained the complementary dUpNpp opposite dA in the structure of a ternary complex formed by the wild type RB69pol at 1.88 {angstrom} resolution. Our observations suggest that several distinct metal-ion coordination states can exist at the ground state in the polymerase active site and that base selectivity is unlikely to be based on metal-ion coordination alone.

  5. Metal ion adsorption to complexes of humic acid and metal oxides: Deviations from the additivity rule

    SciTech Connect

    Vermeer, A.W.P.; McCulloch, J.K.; Van Riemsdijk, W.H.; Koopal, L.K.

    1999-11-01

    The adsorption of cadmium ions to a mixture of Aldrich humic acid and hematite is investigated. The actual adsorption to the humic acid-hematite complex is compared with the sum of the cadmium ion adsorptivities to each of the isolated components. It is shown that the sum of the cadmium ion adsorptivities is not equal to the adsorption to the complex. In general, the adsorption of a specific metal ion to the complex can be understood and qualitatively predicted using the adsorptivities to each of the pure components and taking into account the effect of the pH on the interaction between humic acid and iron oxide on the metal ion adsorption. Due to the interaction between the negatively charged humic acid and the positively charged iron oxide, the adsorption of metal ions on the mineral oxide in the complex will increase as compared to that on the isolated oxide, whereas the adsorption to the humic acid will decrease as compared to that on the isolated humic acid. As a result, the overall adsorption of a specific metal ion to the complex will be smaller than predicted by the additivity rule when this metal ion has a more pronounced affinity for the humic acid than for the mineral oxide, whereas it will be larger than predicted by the additivity rule when the metal ion has a higher affinity for the oxide than for the humic acid.

  6. Polymer filtration: A new technology for selective metals recovery

    SciTech Connect

    Smith, B.F.; Robison, T.W.; Cournoyer, M.E.; Wilson, K.V.; Sauer, N.N.; Mullen, K.I.; Lu, M.T.; Jarvinen, J.J.

    1995-04-01

    Polymer Filtration (PF) was evaluated for the recovery of electroplating metal ions (zinc and nickel) from rinse waters. Polymer Filtration combines the use of water-soluble metal-binding polymers and ultrafiltration to concentrate metal ions from dilute rinse water solutions. The metal ions are retained by the polymers; the smaller, unbound species freely pass through the ultrafiltration membrane. By using this process the ultrafiltered permeate more than meets EPA discharge limits. The metal ions are recovered from the concentrated polymer solution by pH adjustment using diafiltration and can be recycled to the original electroplating baths with no deleterious effects on the test panels. Metal-ion recovery is accomplished without producing sludge.

  7. Continuous metal plasmonic frequency selective surfaces.

    PubMed

    Zhang, Jianfa; Ou, Jun-Yu; Papasimakis, Nikitas; Chen, Yifang; Macdonald, Kevin F; Zheludev, Nikolay I

    2011-11-07

    In the microwave part of the spectrum, where losses are minimal, metal films regularly patterned (perforated) on the sub-wavelength scale achieve spectral selectivity by balancing the transmission and reflection characteristics of the surface. Here we show for optical frequencies, where joule losses are important, that periodic structuring of a metal film without violation of continuity (i.e. without perforation) is sufficient to achieve substantial modification of reflectivity. By engineering the geometry of the structure imposed on a surface one can dramatically change the perceived color of the metal without employing any form of chemical modification, thin-film coating or diffraction effects. This novel frequency selective effect is underpinned by plasmonic Joule losses in the constituent elements of the patterns (dubbed 'intaglio' and 'bas relief' metamaterials to distinguish indented and raised structures respectively) and is specific to the optical part of the spectrum. It has the advantage of maintaining the integrity of metal surfaces and is well suited to high-throughput fabrication via techniques such as nano-imprint.

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

    SciTech Connect

    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.

  9. Selective anion exchange with nanogated isoreticular positive metal-organic frameworks.

    PubMed

    Zhao, Xiang; Bu, Xianhui; Wu, Tao; Zheng, Shou-Tian; Wang, Le; Feng, Pingyun

    2013-01-01

    Crystalline porous materials, especially inorganic porous solids such as zeolites, usually have negative frameworks with extra-framework mobile cations and are widely used for cation exchange. It is highly desirable to develop new materials with positive frameworks for selective anion exchange and separation or storage and delivery. Recent advances in metal-organic framework synthesis have created new opportunities in this direction. Here we report the synthesis of a series of positive indium metal-organic frameworks and their utilization as a platform for the anion exchange-based separation process. This process is capable of size- or charge-selective ion-exchange of organic dyes and may form the basis for size-selective ion chromatography. Ion-exchange dynamics of a series of organic dyes and their selective encapsulation and release are also studied, highlighting the advantages of metal-organic framework compositions for designing host materials tailored for applications in anion separation and purification.

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

    PubMed

    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.

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

    PubMed

    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.

  12. Property enchancement of polyimide films by way of the incorporation of lanthanide metal ions

    NASA Technical Reports Server (NTRS)

    Thompson, David W.

    1993-01-01

    selective gas permeability. Much more commonly than above, polyimide films are prepared by casting the film as the poly(amic acid) precursor which is then converted to the imidized form during the thermal cure cycle. Very limited success was achieved in the past in adding lanthanide metal ions to the amide precursors because of gellation and lack of solubility. With the use of the diketone ligands cited above, the solubility and gellation problems were overcome. However, the films after curing were clear but unacceptably brittle. Attempts to overcome this cure embrittlement problem are in progress.

  13. Property enchancement of polyimide films by way of the incorporation of lanthanide metal ions

    NASA Technical Reports Server (NTRS)

    Thompson, David W.

    1993-01-01

    selective gas permeability. Much more commonly than above, polyimide films are prepared by casting the film as the poly(amic acid) precursor which is then converted to the imidized form during the thermal cure cycle. Very limited success was achieved in the past in adding lanthanide metal ions to the amide precursors because of gellation and lack of solubility. With the use of the diketone ligands cited above, the solubility and gellation problems were overcome. However, the films after curing were clear but unacceptably brittle. Attempts to overcome this cure embrittlement problem are in progress.

  14. Means for obtaining a metal ion beam from a heavy-ion cyclotron source

    DOEpatents

    Hudson, E.D.; Mallory, M.L.

    1975-08-01

    A description is given of a modification to a cyclotron ion source used in producing a high intensity metal ion beam. A small amount of an inert support gas maintains the usual plasma arc, except that it is necessary for the support gas to have a heavy mass, e.g., xenon or krypton as opposed to neon. A plate, fabricated from the metal (or anything that can be sputtered) to be ionized, is mounted on the back wall of the ion source arc chamber and is bombarded by returning energetic low-charged gas ions that fail to cross the initial accelerating gap between the ion source and the accelerating electrode. Some of the atoms that are dislodged from the plate by the returning gas ions become ionized and are extracted as a useful beam of heavy ions. (auth)

  15. Neutralization by Metal Ions of the Toxicity of Sodium Selenide

    PubMed Central

    Dauplais, Marc; Lazard, Myriam; Blanquet, Sylvain; Plateau, Pierre

    2013-01-01

    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. PMID:23342137

  16. A mechanism for enhancing ionic accessibility into selective ion exchange resins

    SciTech Connect

    Alexandratos, S.D.; Shelley, C.A.; Horwitz, E.P.; Chiarizia, R.

    1998-07-01

    A bifunctional monophosphonic/sulfonic acid ion exchange resin with high capacity has been synthesized. Metal ion studies have been carried out with europium, americium, and ferric nitrate in solutions of varying acidity, with and without sodium nitrate added. The bifunctional resin complexes far higher levels of Eu(III) from 0.5 and 1 N nitric acid than the monofunctional phosphonic acid resin. It is postulated that the sulfonic acid ligand provides an access mechanism for the metal ions into the polymer matrix by hydrating the matrix and preventing its collapse in high ionic strength solutions thus allowing for rapid ionic complexation by the selective phosphonic acid ligands. The bifunctional monophosphonic/sulfonic acid resin has both ligands bound to a polystyrene support. It complexes higher levels of metal ions than a comparable resin differing only by having the monophosphonic acid ligand directly bound to the C-C backbone. Results are compared to a diphosphonic/sulfonic acid resin.

  17. Optical studies of ion-beam synthesized metal alloy nanoparticles

    NASA Astrophysics Data System (ADS)

    Magudapathy, P.; Srivatsava, S. K.; Gangopadhyay, P.; Amirthapandian, S.; Sairam, T. N.; Panigrahi, B. K.

    2015-06-01

    AuxAg1-x alloy nanoparticles with tunable surface plasmon resonance (SPR) have been synthesized on a silica glass substrate. A small Au foil on an Ag foil is irradiated as target substrates such that ion beam falls on both Ag foil and Au foils. Silica slides are kept at an angle ˜45° with respect to the metallic foils. While irradiating the metallic foils with 100 keV Ar+ ions, sputtered Au and Ag atoms get deposited on the silica-glass. In this configuration the foils have been irradiated by Ar+ ions to various fluences at room temperature and the sputtered species are collected on silica slides. Formation of AuxAg1-x nanoparticles has been confirmed from the optical absorption measurements. With respect to the exposure area of Au and Ag foils to the ion beam, the SPR peak position varies from 450 to 500 nm. Green photoluminescence has been observed from these alloy metal nanoparticles.

  18. Hall transport of divalent metal ion modified DNA lattices

    SciTech Connect

    Dugasani, Sreekantha Reddy; Lee, Keun Woo; Yoo, Sanghyun; Gnapareddy, Bramaramba; Bashar, Saima; Park, Sung Ha; Kim, Si Joon; Jung, Joohye; Jung, Tae Soo; Kim, Hyun Jae

    2015-06-29

    We investigate the Hall transport characteristics of double-crossover divalent metal ion (Cu{sup 2+}, Ni{sup 2+}, Zn{sup 2+}, and Co{sup 2+})-modified DNA (M-DNA) lattices grown on silica via substrate-assisted growth. The electronic characteristics of the M-DNA lattices are investigated by varying the concentration of the metal ions and then conducting Hall measurements, including resistivity, Hall mobility, carrier concentration, and magneto resistance. The tendency of the resistivity and Hall mobility was to initially decrease as the ion concentration increased, until reaching the saturation concentration (C{sub s}) of each metal ion, and then to increase as the ion concentration increased further. On the other hand, the carrier concentration revealed the opposite tendency as the resistivity and Hall mobility. The specific binding (≤C{sub s}) and the nonspecific aggregates (>C{sub s}) of the ions into the DNA lattices were significantly affected by the Hall characteristics. The numerical ranges of the Hall parameters revealed that the M-DNA lattices with metal ions had semiconductor-like characteristics. Consequently, the distinct characteristics of the electrical transport through M-DNA lattices will provide useful information on the practical use of such structures in physical devices and chemical sensors.

  19. A vacuum spark ion source: High charge state metal ion beams

    NASA Astrophysics Data System (ADS)

    Yushkov, G. Yu.; Nikolaev, A. G.; Oks, E. M.; Frolova, V. P.

    2016-02-01

    High ion charge state is often important in ion beam physics, among other reasons for the very practical purpose that it leads to proportionately higher ion beam energy for fixed accelerating voltage. The ion charge state of metal ion beams can be increased by replacing a vacuum arc ion source by a vacuum spark ion source. Since the voltage between anode and cathode remains high in a spark discharge compared to the vacuum arc, higher metal ion charge states are generated which can then be extracted as an ion beam. The use of a spark of pulse duration less than 10 μs and with current up to 10 kA allows the production of ion beams with current of several amperes at a pulse repetition rate of up to 5 pps. We have demonstrated the formation of high charge state heavy ions (bismuth) of up to 15 + and a mean ion charge state of more than 10 +. The physics and techniques of our vacuum spark ion source are described.

  20. A vacuum spark ion source: High charge state metal ion beams

    SciTech Connect

    Yushkov, G. Yu. Nikolaev, A. G.; Frolova, V. P.; Oks, E. M.

    2016-02-15

    High ion charge state is often important in ion beam physics, among other reasons for the very practical purpose that it leads to proportionately higher ion beam energy for fixed accelerating voltage. The ion charge state of metal ion beams can be increased by replacing a vacuum arc ion source by a vacuum spark ion source. Since the voltage between anode and cathode remains high in a spark discharge compared to the vacuum arc, higher metal ion charge states are generated which can then be extracted as an ion beam. The use of a spark of pulse duration less than 10 μs and with current up to 10 kA allows the production of ion beams with current of several amperes at a pulse repetition rate of up to 5 pps. We have demonstrated the formation of high charge state heavy ions (bismuth) of up to 15 + and a mean ion charge state of more than 10 +. The physics and techniques of our vacuum spark ion source are described.

  1. Search for selective ion diffusion through membranes

    NASA Technical Reports Server (NTRS)

    May, C. E.; Philipp, W. H.

    1983-01-01

    The diffusion rates of several ions through some membranes developed as battery separators were measured. The ions investigated were Li(+), Rb(+), Cl(-), and So4. The members were crosslinked polyvinyl alcohol, crosslinked polyacrylic acid, a copolymer of the two, crosslinked calcium polyacrylate, cellulose, and several microporous polyphenylene oxide based films. No true specificity for diffusion of any of these ions was found for any of the membranes. But the calcium polyacrylate membrane was found to exhibit ion exchange with the diffusing ions giving rise to the leaching of the calcium ion and low reproducibility. These findings contrast earlier work where the calcium polyacrylate membrane did show specificity to the diffusion of the copper ion. In general, Fick's law appeared to be obeyed. Except for the microporous membranes, the coefficients for ion diffusion through the membranes were comparable with their values in water. For the microporous membranes, the values found for the coefficients were much less, due to the tortuosity of the micropores.

  2. Development of a linear-type double reflectron for focused imaging of photofragment ions from mass-selected complex ions

    NASA Astrophysics Data System (ADS)

    Okutsu, Kenichi; Nakashima, Yuji; Yamazaki, Kenichiro; Fujimoto, Keita; Nakano, Motoyoshi; Ohshimo, Keijiro; Misaizu, Fuminori

    2017-05-01

    An ion imaging apparatus with a double linear reflectron mass spectrometer has been developed, in order to measure velocity and angular distributions of mass-analyzed fragment ions produced by photodissociation of mass-selected gas phase complex ions. The 1st and the 2nd linear reflectrons were placed facing each other and controlled by high-voltage pulses in order to perform the mass-separation of precursor ions in the 1st reflectron and to observe the focused image of the photofragment ions in the 2nd reflectron. For this purpose, metal meshes were attached on all electrodes in the 1st reflectron, whereas the mesh was attached only on the last electrode in the 2nd reflectron. The performance of this apparatus was evaluated using imaging measurement of Ca+ photofragment ions from photodissociation reaction of Ca+Ar complex ions at 355 nm photoexcitation. The focused ion images were obtained experimentally with the double linear reflectron at the voltages of the reflection electrodes close to the predictions by ion trajectory simulations. The velocity and angular distributions of the produced Ca+ ([Ar] 4p1, 2P3/2) ion were analyzed from the observed images. The binding energy D0 of Ca+Ar in the ground state deduced in the present measurement was consistent with those determined theoretically and by spectroscopic measurements. The anisotropy parameter β of the transition was evaluated for the first time by this instrument.

  3. Quantum Interference and Selectivity through Biological Ion Channels

    NASA Astrophysics Data System (ADS)

    Salari, Vahid; Naeij, Hamidreza; Shafiee, Afshin

    2017-01-01

    The mechanism of selectivity in ion channels is still an open question in biology for more than half a century. Here, we suggest that quantum interference can be a solution to explain the selectivity mechanism in ion channels since interference happens between similar ions through the same size of ion channels. In this paper, we simulate two neighboring ion channels on a cell membrane with the famous double-slit experiment in physics to investigate whether there is any possibility of matter-wave interference of ions via movement through ion channels. Our obtained decoherence timescales indicate that the quantum states of ions can only survive for short times, i.e. ≈100 picoseconds in each channel and ≈17–53 picoseconds outside the channels, giving the result that the quantum interference of ions seems unlikely due to environmental decoherence. However, we discuss our results and raise few points, which increase the possibility of interference.

  4. Quantum Interference and Selectivity through Biological Ion Channels

    PubMed Central

    Salari, Vahid; Naeij, Hamidreza; Shafiee, Afshin

    2017-01-01

    The mechanism of selectivity in ion channels is still an open question in biology for more than half a century. Here, we suggest that quantum interference can be a solution to explain the selectivity mechanism in ion channels since interference happens between similar ions through the same size of ion channels. In this paper, we simulate two neighboring ion channels on a cell membrane with the famous double-slit experiment in physics to investigate whether there is any possibility of matter-wave interference of ions via movement through ion channels. Our obtained decoherence timescales indicate that the quantum states of ions can only survive for short times, i.e. ≈100 picoseconds in each channel and ≈17–53 picoseconds outside the channels, giving the result that the quantum interference of ions seems unlikely due to environmental decoherence. However, we discuss our results and raise few points, which increase the possibility of interference. PMID:28134331

  5. Two mechanisms of ion selectivity in protein binding sites.

    PubMed

    Yu, Haibo; Noskov, Sergei Yu; Roux, Benoît

    2010-11-23

    A theoretical framework is presented to clarify the molecular determinants of ion selectivity in protein binding sites. The relative free energy of a bound ion is expressed in terms of the main coordinating ligands coupled to an effective potential of mean force representing the influence of the rest of the protein. The latter is separated into two main contributions. The first includes all the forces keeping the ion and the coordinating ligands confined to a microscopic subvolume but does not prevent the ligands from adapting to a smaller or larger ion. The second regroups all the remaining forces that control the precise geometry of the coordinating ligands best adapted to a given ion. The theoretical framework makes it possible to delineate two important limiting cases. In the limit where the geometric forces are dominant (rigid binding site), ion selectivity is controlled by the ion-ligand interactions within the matching cavity size according to the familiar "snug-fit" mechanism of host-guest chemistry. In the limit where the geometric forces are negligible, the ion and ligands behave as a "confined microdroplet" that is free to fluctuate and adapt to ions of different sizes. In this case, ion selectivity is set by the interplay between ion-ligand and ligand-ligand interactions and is controlled by the number and the chemical type of ion-coordinating ligands. The framework is illustrated by considering the ion-selective binding sites in the KcsA channel and the LeuT transporter.

  6. Luminescent microporous metal-organic framework with functional lewis basic sites on the pore surface: specific sensing and removal of metal ions.

    PubMed

    Jayaramulu, Kolleboyina; Narayanan, Raghu Pradeep; George, Subi J; Maji, Tapas Kumar

    2012-10-01

    A three-dimensional luminescent metal-organic framework, {Mg(DHT)(DMF)(2)}(n) (1), based on an excited-state intramolecular proton-transfer (ESIPT) responsive linker, 2,5-dihydroxyterephthalic acid (H(2)DHT), has been synthesized, and its desolvated microporous framework with pendent -OH groups on the pore surface was exploited for the binding and specific sensing of metal ions via Lewis acid-base interactions. The luminescence intensity significantly quenches with Cu(II) among various s- and d-block metal ions, and highly selective sensing of Cu(II) ions has been realized in both solid and solution states (up to nanomolar concentration). The immobilized Cu(II) metal ions can be selectively removed by chelating agents like ethylenediaminetetraacetic acid without any structural disintegration of the framework, as revealed by the luminescence and gas-adsorption studies.

  7. Types and concentrations of metal ions affect local structure and dynamics of RNA

    NASA Astrophysics Data System (ADS)

    Wang, Jun; Xiao, Yi

    2016-10-01

    The roles that metal ions play in the structure and dynamics of RNA molecules are long-standing problems that have been studied extensively but are still not well understood. Here we show that metal ions have distributions around RNA molecules that strongly depend on the types and concentrations of the metal ions and also the electrostatic surface of the molecule. In particular, the ion distributions may not balance all the local electronegativity of the molecule. These ion distributions do not only greatly affect local structures but also lead to different local dynamics of RNA. We studied the effects of different ion solutions on the structure and dynamics of RNA by taking the pre Q1 riboswitch aptamer domain as an illustrative example and using molecular dynamics simulations. Since the local structures and dynamics of RNAs are important to their functions, our results also indicate that the selection of proper ion conditions is necessary to model them correctly, in contrast to the use of diverse ion solutions in current molecular dynamics simulations.

  8. Metallic dental material biocompatibility in osteoblastlike cells: correlation with metal ion release.

    PubMed

    Cortizo, María C; De Mele, Mónica Fernández L; Cortizo, Ana M

    2004-08-01

    Ions released from metallic dental materials used in orthodontic appliances could induce undesirable effects on cells and tissues. This study evaluates the biocompatibility of two of the most labile components of metallic dental alloys on osteoblastlike cells. The influence of protein and ions on metal dissolution properties is also investigated using different electrolyte solutions. Morphological alterations, cell growth, and differentiation of osteoblasts were assessed after exposure to pure metals (Ag, Cu, Pd, Au) and Ni-Ti alloy and correlated with the kinetics of elements released into the culture media. Results showed that Cu and Ag were the most cytotoxic elements and the other metals were biocompatible with the osteoblasts. The parameters of biocompatibility were correlated with the levels of ions detected into the culture media. Metal ions induced cell death through early mitosis arrest, apoptotic phenomena, and necrotic processes. Voltammograms showed that anions and proteins interfered in the corrosion process. Fetal bovine serum (FBS) strongly affected the electrochemical process, decreasing the oxidation rate of the metals. In conclusion, copper and silver ions showed a time-dependent low biocompatibility, which correlated with the concentration of released ions. The dissolution of the metallic materials was dependent on the composition of the simulated biological media.

  9. Ion-Plated Soft Metallic Films Reduce Friction and Wear

    NASA Technical Reports Server (NTRS)

    Spalvins, T.

    1986-01-01

    Ion plating is ion-assisted or glow-discharge surface-deposition technique. In this process, ions or energetic atoms transfer energy, momentum, and charge to substrate and deposited surface film. Process controlled to modify physical characteristics of surface, subsurface chemical conditions, and surface and subsurface microstructures as well. Ion plating with such soft, thin metallic films as gold, silver, or lead has great potential for producing self-contained lubricating surfaces. Such films reduce friction, wear, and corrosion on sliding or rotating mechanical surfaces used in wide range of environments.

  10. Ion-Plated Soft Metallic Films Reduce Friction and Wear

    NASA Technical Reports Server (NTRS)

    Spalvins, T.

    1986-01-01

    Ion plating is ion-assisted or glow-discharge surface-deposition technique. In this process, ions or energetic atoms transfer energy, momentum, and charge to substrate and deposited surface film. Process controlled to modify physical characteristics of surface, subsurface chemical conditions, and surface and subsurface microstructures as well. Ion plating with such soft, thin metallic films as gold, silver, or lead has great potential for producing self-contained lubricating surfaces. Such films reduce friction, wear, and corrosion on sliding or rotating mechanical surfaces used in wide range of environments.

  11. Entropy driven insulator-metal crossover in ion channels and water filled nanopores

    NASA Astrophysics Data System (ADS)

    Zhang, Jingshan; Kamenev, Alex; Shklovskii, Boris; Larkin, Anatony

    2006-03-01

    We consider ion transport of an ion channel in a lipid membrane or a water filled nanopore in silicon films [1]. It is known that due to the large ratio of dielectric constants of water (80) and lipid (2), the electric lines of an ion in the channel are squeezed. This should lead to a large electrostatic self-energy barrier for Ohmic resistance [2]. Nevertheless biological channels are well transparent at least for some selected ions. To address this paradox, we study reduction of the electrostatic barrier by a finite concentration of salt in water and/or by immobile charges on the internal channel walls. We show that both types of charges reduce the barrier, leading to insulator-metal crossover resembling metal-insulator transition in excited gas or in doped semiconductors. But here entropy plays the role of quantum mechanics. Evolution of ion channels took into account biological concentration of monovalent salt, and more importantly, made some channels charged from inside to reduce electrostatic barrier for a given sign of ions (cation/anion selectivity). We also show that in the channel with negative wall charges fractionalization of divalent Ca ions into monovalent excitations leads to good Ca-Vs.-Na selectivity of Ca channels. [1] A. Kamenev, J. Zhang, A. I. Larkin, B. I. Shklovskii, Physica A 359, 129 (2006); J. Zhang, A. Kamenev, B. I. Shklovskii, Phys. Rev. Lett. 95, 148101 (2005); cond-mat/0510327. [2] A. Parsegian, Nature 221, 844 (1969).

  12. Study of Ion Dynamics by Electron Transfer Dissociation: Alkali Metals as Targets

    PubMed Central

    Hayakawa, Shigeo

    2017-01-01

    High energy collision processes for singly charged positive ions using an alkali metal target are confirmed, as a charge inversion mass spectrometry, to occur by electron transfers in successive collisions and the dissociation processes involve the formation of energy-selected neutral species from near-resonant neutralization with alkali metal targets. A doubly charged thermometer molecule was made to collide with alkali metal targets to give singly and doubly charged positive ions. The internal energy resulting from the electron transfer with the alkali metal target was very narrow and centered at a particular energy. This narrow internal energy distribution can be attributed to electron transfer by Landau–Zener potential crossing between the precursor ion and an alkali metal atom, and the coulombic repulsion between singly charged ions in the exit channel. A large cross section of more than 10−14 cm2 was estimated for high-energy electron transfer dissociation (HE-ETD). Doubly protonated phosphorylated peptides obtained by electrospray ionization were collided with Xe and Cs targets to give singly and doubly charged positive ions. Whereas doubly charged fragment ions resulting from CAD were dominant in the case of the Xe target, singly charged fragment ions resulting from ETD were dominant with the Cs target. HE-ETD using the Cs target provided all of the z-type ions by N–Cα bond cleavage without the loss of the phosphate groups. The results demonstrate that HE-ETD with an alkali metal target allowed the position of phosphorylation and the amino acid sequence of peptides with post translational modifications (PTM) to be determined. PMID:28966899

  13. Study of Ion Dynamics by Electron Transfer Dissociation: Alkali Metals as Targets.

    PubMed

    Hayakawa, Shigeo

    2017-01-01

    High energy collision processes for singly charged positive ions using an alkali metal target are confirmed, as a charge inversion mass spectrometry, to occur by electron transfers in successive collisions and the dissociation processes involve the formation of energy-selected neutral species from near-resonant neutralization with alkali metal targets. A doubly charged thermometer molecule was made to collide with alkali metal targets to give singly and doubly charged positive ions. The internal energy resulting from the electron transfer with the alkali metal target was very narrow and centered at a particular energy. This narrow internal energy distribution can be attributed to electron transfer by Landau-Zener potential crossing between the precursor ion and an alkali metal atom, and the coulombic repulsion between singly charged ions in the exit channel. A large cross section of more than 10(-14) cm(2) was estimated for high-energy electron transfer dissociation (HE-ETD). Doubly protonated phosphorylated peptides obtained by electrospray ionization were collided with Xe and Cs targets to give singly and doubly charged positive ions. Whereas doubly charged fragment ions resulting from CAD were dominant in the case of the Xe target, singly charged fragment ions resulting from ETD were dominant with the Cs target. HE-ETD using the Cs target provided all of the z-type ions by N-Cα bond cleavage without the loss of the phosphate groups. The results demonstrate that HE-ETD with an alkali metal target allowed the position of phosphorylation and the amino acid sequence of peptides with post translational modifications (PTM) to be determined.

  14. Removal of heavy metal ions from wastewaters: a review.

    PubMed

    Fu, Fenglian; Wang, Qi

    2011-03-01

    Heavy metal pollution has become one of the most serious environmental problems today. The treatment of heavy metals is of special concern due to their recalcitrance and persistence in the environment. In recent years, various methods for heavy metal removal from wastewater have been extensively studied. This paper reviews the current methods that have been used to treat heavy metal wastewater and evaluates these techniques. These technologies include chemical precipitation, ion-exchange, adsorption, membrane filtration, coagulation-flocculation, flotation and electrochemical methods. About 185 published studies (1988-2010) are reviewed in this paper. It is evident from the literature survey articles that ion-exchange, adsorption and membrane filtration are the most frequently studied for the treatment of heavy metal wastewater.

  15. The impact of immobilized metal affinity chromatography (IMAC) resins on DNA aptamer selection.

    PubMed

    Kowalska, E; Bartnicki, F; Pels, K; Strzalka, W

    2014-09-01

    DNA aptamers are single-stranded oligonucleotides which can form various secondary and tertiary structures. They can recognize a broad range of targets ranging from small molecules, such as ions, vitamins, antibiotics, to high molecular weight structures, including enzymes and antibodies. DNA aptamers are extensively studied as a potential source of new pharmaceutical drugs due to their inexpensive synthesis, low immunogenicity, and high specificity. The commonly used aptamer selection procedure is systematic evolution of ligands by exponential enrichment (SELEX) where the target molecule is immobilized on an appropriate chromatography resin. For peptide/protein targets, immobilized metal affinity chromatography (IMAC) resins are frequently used. There is a broad range of commercially available resins which can be used for IMAC. They are characterized by different metal ions, linker types, and bead materials. In this study, we tested the impact of different IMAC resins on the DNA aptamer selection process during eight SELEX cycles. A histidine-tagged 29 amino acid peptide corresponding to the interdomain connecting loop of human proliferating cell nuclear antigen was used as a selection target. Different resin materials containing the same metal ion (Co(2+)) were tested. Simultaneously, agarose resins containing identical linkers, but different metal ions (Co(2+), Cu(2+), Ni(2+), and Zn(2+)) were analyzed. The results of this study clearly demonstrated the impact of the metal ion and resin material on the DNA aptamer selection progress. The presented data indicate that for successful IMAC resin-based SELEX, the determination of the optimal resin might be crucial.

  16. Waste treatment by selective mineral ion exchanger

    SciTech Connect

    Polito, Aurelie

    2007-07-01

    STMI, subsidiary company of the AREVA Group with over 40 years in the D and D business, has been continuously innovating and developing new decontamination techniques, with the objectives of achieving more efficient decontaminations on a growing spectrum of media. In the field of liquid waste treatment, STMI manufactures uses and commercialises selective inorganic ion exchangers (RAN). These are hydrated synthetic inorganic compounds prepared from very pure raw materials. Different types of RANs (POLYAN, OXTAIN, Fe-Cu, Fe-CoK, Si-Fe-CoK) can be used to trap a large number of radioactive elements in contaminated effluents. Different implementations could be applied depending on technical conditions. STMI's offers consist in building global solution and preliminary design of installation either in dispersed form (batch) or in column (cartridge filtration). Those products are used all over the world not only in the nuclear business (Canada, US, Belgium, France...) but also in other fields. Indeed, it provides competitive solutions to many domains of application especially water pollution control, liquid waste treatment in the nuclear business by decreasing the activity level of waste. The following paper will focus on the theoretical principle of the mineral exchanger, its implementation and the feed back collected by STMI. (author)

  17. Catalytic mechanisms of metallohydrolases containing two metal ions.

    PubMed

    Mitić, Nataša; Miraula, Manfredi; Selleck, Christopher; Hadler, Kieran S; Uribe, Elena; Pedroso, Marcelo M; Schenk, Gerhard

    2014-01-01

    At least one-third of enzymes contain metal ions as cofactors necessary for a diverse range of catalytic activities. In the case of polymetallic enzymes (i.e., two or more metal ions involved in catalysis), the presence of two (or more) closely spaced metal ions gives an additional advantage in terms of (i) charge delocalisation, (ii) smaller activation barriers, (iii) the ability to bind larger substrates, (iv) enhanced electrostatic activation of substrates, and (v) decreased transition-state energies. Among this group of proteins, enzymes that catalyze the hydrolysis of ester and amide bonds form a very prominent family, the metallohydrolases. These enzymes are involved in a multitude of biological functions, and an increasing number of them gain attention for translational research in medicine and biotechnology. Their functional versatility and catalytic proficiency are largely due to the presence of metal ions in their active sites. In this chapter, we thus discuss and compare the reaction mechanisms of several closely related enzymes with a view to highlighting the functional diversity bestowed upon them by their metal ion cofactors. © 2014 Elsevier Inc. All rights reserved.

  18. Fluorescent carbon nanoparticles for the fluorescent detection of metal ions.

    PubMed

    Guo, Yongming; Zhang, Lianfeng; Zhang, Shushen; Yang, Yan; Chen, Xihan; Zhang, Mingchao

    2015-01-15

    Fluorescent carbon nanoparticles (F-CNPs) as a new kind of fluorescent nanoparticles, have recently attracted considerable research interest in a wide range of applications due to their low-cost and good biocompatibility. The fluorescent detection of metal ions is one of the most important applications. In this review, we first present the general detection mechanism of F-CNPs for the fluorescent detection of metal ions, including fluorescence turn-off, fluorescence turn-on, fluorescence resonance energy transfer (FRET) and ratiometric response. We then focus on the recent advances of F-CNPs in the fluorescent detection of metal ions, including Hg(2+), Cu(2+), Fe(3+), and other metal ions. Further, we discuss the research trends and future prospects of F-CNPs. We envision that more novel F-CNPs-based nanosensors with more accuracy and robustness will be widely used to assay and remove various metal ions, and there will be more practical applications in coming years. Copyright © 2014 Elsevier B.V. All rights reserved.

  19. Solvent effects and alkali metal ion catalysis in phosphodiester hydrolysis.

    PubMed

    Gomez-Tagle, Paola; Vargas-Zúñiga, Idania; Taran, Olga; Yatsimirsky, Anatoly K

    2006-12-22

    The kinetics of the alkaline hydrolysis of bis(p-nitrophenyl) phosphate (BNPP) have been studied in aqueous DMSO, dioxane, and MeCN. In all solvent mixtures the reaction rate steadily decreases to half of its value in pure water in the range of 0-70 vol % of organic cosolvent and sharply increases in mixtures with lower water content. Correlations based on different scales of solvent empirical parameters failed to describe the solvent effect in this system, but it can be satisfactorily treated in terms of a simplified stepwise solvent-exchange model. Alkali metal ions catalyze the BNPP hydrolysis but do not affect the rate of hydrolysis of neutral phosphotriester p-nitrophenyl diphenyl phosphate in DMSO-rich mixtures. The catalytic activity decreases in the order Li+ > Na+ > K+ > Rb+ > Cs+. For all cations except Na+, the reaction rate is first-order in metal ion. With Na+, both first- and second-order kinetics in metal ions are observed. Binding constants of cations to the dianionic transition state of BNPP alkaline hydrolysis are of the same order of magnitude and show a similar trend as their binding constants to p-nitrophenyl phosphate dianion employed as a transition-state model. The appearance of alkali metal ion catalysis in a medium, which solvates metal ions stronger than water, is attributed to the increased affinity of cations to dianions, which undergo a strong destabilization in the presence of an aprotic dipolar cosolvent.

  20. [Effect of heavy metal ions on triphenyltin enzymatic degradation].

    PubMed

    Tong, Yao; Ye, Jin-Shao; Yin, Hu; Peng, Hui; Chen, Shuo-Na; Qin, Hua-Ming; He, Bao-Yan

    2011-03-01

    The influence of different metal ions and different forms of addition on triphenyltin enzymatic degradation was investigated under conditions using enzyme obtained from Klebsiella pneumoniae. The objective of this study is to illuminate the mechanism of enzymatic degradation of triphenyltin (TPhT). The results demonstrated that the strain was able to tolerate K+, Mg2+, CU2+, Ca2+ and Fe3+ at high concentrations. High concentrations of Zn2+ and Fe2+ had some toxic effects on the strain, thus affecting its growth. The endoenzyme activity was enhanced by metal ions such as K+, Mg2+, Zn2+, Cu2+ and Fe2+ at certain concentrations. In the presence of 30 mg/L of Mg2+, the removal percentage of TPhT was up to 77.22%. Fe3+ restrained the enzyme activity at certain concentrations. Adding K+, Mg2+, Zn2+, Cu2+ into medium can promote the production of enzyme, among which Mg2+ demonstrated up to 85.66% of removal percentage of TPhT, suggesting some metal ions at the appropriate concentration range can be used as enzyme activator for the enzymatic degradation of triphenyltin. Metal ions showed no relevant impact on the cell growth and enzyme production. Certain metal ions can only serve as activators of endoenzyme and exhibited no similar effect towards exoenzyme.

  1. Acylpyrazolones: Synthesis, self-assembly and lanthanide metal ion separation

    NASA Astrophysics Data System (ADS)

    Yang, Jun

    The central hypothesis that nanoscale self-assemblies can provide excellent metal ion recognition has been substantiated by employing acylpyrazolones and trivalent lanthanide metal ions as model systems. Several novel acylpyrazolones and their amphiphilic analogs have been designed, synthesized, and characterized. Their lanthanide metal ion recognition efficacies have been demonstrated through baseline separations of a mixture of light, middle, and heavy lanthanide metal ions by employing them in the aqueous mobile phase of high performance liquid chromatography (HPLC) with octadecylsilanized silica (ODS) as the stationary phase. The complex separation mechanism is influenced by the structures of acylpyrazolone and amphiphilic moieties, and spontaneous self-assembly of the ligand in the aqueous and on the stationary phases. Transmission electron microscopy (TEM) studies of the ligand self-assemblies in the aqueous phase in the absence and presence of lanthanide metal ions reveal spherical, dendritic, and linear (nanofibers, nanorods, and nanotubes) nanoscale structures. Such structures have also been observed when chloromethylated acylpyrazolones are stimulated to self-assemble by a base in nonaqueous solvents and when silica nanoparticles derivatized with them spontaneously self-assemble in aqueous and nonaqueous solvents.

  2. Chelation ability of spironaphthoxazine with metal ions in silica gel.

    PubMed

    Nishikiori, Hiromasa; Teshima, Katsuya; Fujii, Tsuneo

    2012-07-01

    Spironaphthoxazine (SNO) and three metal ions, Mg(2+), Zn(2+), and Al(3+), were dispersed in silica gels by the sol-gel method. The chelation ability of SNO with the metal ions in silica gels was investigated by measuring the fluorescence spectra and was compared to that of 8-hydroxyquinoline (8-HQ) in ethanol and silica gels. A merocyanine-type isomer photoderived from SNO as well as 8-HQ easily formed complexes of the metal ions in the order of Al(3+), Zn(2+), and Mg(2+) because the coordination ability of the metal ions to such ligands depended on their electron affinity. The changes in the fluorescence spectra of the silica gel samples during light irradiation were also investigated. The relative band intensity due to the intermediate species between the original SNO and the merocyanine species decreased and that of the complex increased with the UV irradiation time. The reverse process was observed during visible irradiation. The UV irradiation effects on the chelation of SNO and its photochromic property also depended on the electron affinity of the metal ions.

  3. Chromosomal antioxidant genes have metal ion-specific roles as determinants of bacterial metal tolerance.

    PubMed

    Harrison, Joe J; Tremaroli, Valentina; Stan, Michelle A; Chan, Catherine S; Vacchi-Suzzi, Caterina; Heyne, Belinda J; Parsek, Matthew R; Ceri, Howard; Turner, Raymond J

    2009-10-01

    Microbiological metal toxicity involves redox reactions between metal species and cellular molecules, and therefore, we hypothesized that antioxidant systems might be chromosomal determinants affecting the susceptibility of bacteria to metal toxicity. Here, survival was quantified in metal ion-exposed planktonic cultures of several Escherichia coli strains, each bearing a mutation in a gene important for redox homeostasis. This characterized approximately 250 gene-metal combinations and identified that sodA, sodB, gor, trxA, gshA, grxA and marR have distinct roles in safeguarding or sensitizing cells to different toxic metal ions (Cr(2)O(7)(2-), Co(2+), Cu(2+), Ag(+), Zn(2+), AsO(2)(-), SeO(3)(2-) or TeO(3)(2-)). To shed light on these observations, fluorescent sensors for reactive oxygen species (ROS) and reduced thiol (RSH) quantification were used to ascertain that different metal ions exert oxidative toxicity through disparate modes-of-action. These oxidative mechanisms of metal toxicity were categorized as involving ROS and thiol-disulfide chemistry together (AsO(2)(-), SeO(3)(2-)), ROS predominantly (Cu(2+), Cr(2)O(7)(2-)) or thiol-disulfide chemistry predominantly (Ag(+), Co(2+), Zn(2+), TeO(3)(2-)). Corresponding to this, promoter-luxCDABE fusions showed that toxic doses of different metal ions up- or downregulate the transcription of gene sets marking distinct pathways of cellular oxidative stress. Altogether, our findings suggest that different metal ions are lethal to cells through discrete pathways of oxidative biochemistry, and moreover, indicate that chromosomally encoded antioxidant systems may have metal ion-specific physiological roles as determinants of bacterial metal tolerance.

  4. Ultrasensitive Quantum Dot Fluorescence quenching Assay for Selective Detection of Mercury Ions in Drinking Water

    NASA Astrophysics Data System (ADS)

    Ke, Jun; Li, Xinyong; Zhao, Qidong; Hou, Yang; Chen, Junhong

    2014-07-01

    Mercury is one of the most acutely toxic substances at trace level to human health and living thing. Developing a rapid, cheap and water soluble metal sensor for detecting mercury ions at ppb level remains a challenge. Herein, a metal sensor consisting of MPA coated Mn doped ZnSe/ZnS colloidal nanoparticles was utilized to ultrasensitively and selectively detect Hg2+ ions with a low detection limit (0.1 nM) over a dynamic range from 0 to 20 nM. According to strong interaction between thiol(s) and mercury ions, mercaptopropionic acid (MPA) was used as a highly unique acceptor for mercury ions in the as-obtained ultrasensitive sensor. In the presence of mercury ions, colloidal nanoparticles rapidly agglomerated due to changes of surface chemical properties, which results in severe quenching of fluorescent intensity. Meanwhile, we find that the original ligands are separated from the surface of colloidal nanoparticles involving strongly chelation between mercury ion and thiol(s) proved by controlled IR analysis. The result shows that the QD-based metal ions sensor possesses satisfactory precision, high sensitivity and selectivity, and could be applied for the quantification analysis of real samples.

  5. Ultrasensitive Quantum Dot Fluorescence quenching Assay for Selective Detection of Mercury Ions in Drinking Water

    PubMed Central

    Ke, Jun; Li, Xinyong; Zhao, Qidong; Hou, Yang; Chen, Junhong

    2014-01-01

    Mercury is one of the most acutely toxic substances at trace level to human health and living thing. Developing a rapid, cheap and water soluble metal sensor for detecting mercury ions at ppb level remains a challenge. Herein, a metal sensor consisting of MPA coated Mn doped ZnSe/ZnS colloidal nanoparticles was utilized to ultrasensitively and selectively detect Hg2+ ions with a low detection limit (0.1 nM) over a dynamic range from 0 to 20 nM. According to strong interaction between thiol(s) and mercury ions, mercaptopropionic acid (MPA) was used as a highly unique acceptor for mercury ions in the as-obtained ultrasensitive sensor. In the presence of mercury ions, colloidal nanoparticles rapidly agglomerated due to changes of surface chemical properties, which results in severe quenching of fluorescent intensity. Meanwhile, we find that the original ligands are separated from the surface of colloidal nanoparticles involving strongly chelation between mercury ion and thiol(s) proved by controlled IR analysis. The result shows that the QD-based metal ions sensor possesses satisfactory precision, high sensitivity and selectivity, and could be applied for the quantification analysis of real samples. PMID:25005836

  6. Ultrasensitive quantum dot fluorescence quenching assay for selective detection of mercury ions in drinking water.

    PubMed

    Ke, Jun; Li, Xinyong; Zhao, Qidong; Hou, Yang; Chen, Junhong

    2014-07-09

    Mercury is one of the most acutely toxic substances at trace level to human health and living thing. Developing a rapid, cheap and water soluble metal sensor for detecting mercury ions at ppb level remains a challenge. Herein, a metal sensor consisting of MPA coated Mn doped ZnSe/ZnS colloidal nanoparticles was utilized to ultrasensitively and selectively detect Hg(2+) ions with a low detection limit (0.1 nM) over a dynamic range from 0 to 20 nM. According to strong interaction between thiol(s) and mercury ions, mercaptopropionic acid (MPA) was used as a highly unique acceptor for mercury ions in the as-obtained ultrasensitive sensor. In the presence of mercury ions, colloidal nanoparticles rapidly agglomerated due to changes of surface chemical properties, which results in severe quenching of fluorescent intensity. Meanwhile, we find that the original ligands are separated from the surface of colloidal nanoparticles involving strongly chelation between mercury ion and thiol(s) proved by controlled IR analysis. The result shows that the QD-based metal ions sensor possesses satisfactory precision, high sensitivity and selectivity, and could be applied for the quantification analysis of real samples.

  7. Immunologic mechanisms in hypersensitivity reactions to metal ions: an overview.

    PubMed

    Büdinger, L; Hertl, M

    2000-02-01

    Metal ions such as Ni2+, Co2+, Cu2+, or Cr3+ are haptens with a high immunogenic potential, as contact dermatitis caused by ionic metals occurs in about 10-15% of the human population. Since alloys containing Ni2+, Co2+, and Cr3+ are components of implants in replacement surgery, dentures, orthodontic wires, and various other devices, adverse reactions to metal ions create serious problems in practical medicine as incompatibility reactions to metal-containing biomaterials. On the other hand, contact dermatitis to metal ions such as Ni2+ is a well-established model for studying the molecular mechanisms involved in the recognition of haptens by the immune system. Although many investigations have been performed to elucidate the molecular interactions causing contact hypersensitivity in man, many aspects remain to be clarified. This review will focus on the experimental data accumulated so far on the immunologic mechanisms responsible for the recognition of metal ions by T cells and eliciting adverse immune reactions causing contact dermatitis.

  8. On the abundance of metal ions in the lower ionosphere

    NASA Astrophysics Data System (ADS)

    Kopp, Ernest

    1997-05-01

    Height profiles of the metal ions Fe+, Mg+, Ca+, and Na+ in the lower ionosphere measured in situ in five rocket flights with a magnetic mass spectrometer are presented. The mean total column density of the ionized metals is within 4.4+/-1.2×109cm-2 in periods without special meteor shower activity. The column density increased by 1 order of magnitude during the Perseid meteor shower of August 12, 1976. The dominant metal ion in all five flights is Fe+. Its column density in the five flights is, in average, a factor 2.0+/-0.6 larger than Mg+. A comparison of the column densities of Ni+, Al+, Ca+, Mg+, K+, and Na+, which were normalized to Fe+, to the corresponding ratios in carbonaceous chondrites type I (CI) showed a depletion in the abundance of aluminium (80%), calcium (65%), magnesium (55%), and nickel (35%). At heights above 95 km all metals under consideration should predominantly occur as ions, and no distinct mass fractionation between the different ionized metals is expected from the main loss process, the downward movement of the metal ion layers. The reduced abundance of Al, Ca, Mg, and Ni is therefore most likely an effect of a fractionation originating from partially melted micrometeorites and an associated partial evaporation retaining elements having a relatively high condensation temperature as compared to Fe, which is the case for Ni, Al, Ca, and Mg.

  9. Modification of porous starch for the adsorption of heavy metal ions from aqueous solution.

    PubMed

    Ma, Xiaofei; Liu, Xueyuan; Anderson, Debbie P; Chang, Peter R

    2015-08-15

    Porous starch xanthate (PSX) and porous starch citrate (PSC) were prepared in anticipation of the attached xanthate and carboxylate groups respectively forming chelation and electrostatic interactions with heavy metal ions in the subsequent adsorption process. The lead(II) ion was selected as the model metal and its adsorption by PSX and PSC was characterized. The adsorption capacity was highly dependent on the carbon disulfide/starch and citric acid/starch mole ratios used during preparation. The adsorption behaviors of lead(II) ion on PSXs and PSCs fit both the pseudo-second-order kinetic model and the Langmuir isotherm model. The maximum adsorption capacity from the Langmuir isotherm equation reached 109.1 and 57.6 mg/g for PSX and PSC when preparation conditions were optimized, and the adsorption times were just 20 and 60 min, respectively. PSX and PSC may be used as effective adsorbents for removal of heavy metals from contaminated liquid.

  10. A cross-reactive sensor array for the fluorescence qualitative analysis of heavy metal ions.

    PubMed

    Kang, Huaizhi; Lin, Liping; Rong, Mingcong; Chen, Xi

    2014-11-01

    A cross-reactive sensor array using mercaptopropionic acid modified cadmium telluride (CdTe), glutathione modified CdTe, poly(methacrylic acid) modified silver nanoclusters, bovine serum albumin modified gold nanoclusters, rhodamine derivative and calcein blue as fluorescent indicators has been designed for the detection of seven heavy metal ions (Ag(+), Hg(2+), Pb(2+), Cu(2+), Cr(3+), Mn(2+) and Cd(2+)). The discriminatory capacity of the sensor array to different heavy metal ions in different pH solutions has been tested and the results have been analyzed with linear discriminant analysis. Results showed that the sensor array could be used to qualitatively analyze the selected heavy metal ions. The array performance was also evaluated in the identification of known and unknown samples and the preliminary results suggested the promising practicability of the designed sensor assay.

  11. Membranes Remove Metal Ions Fron Industrial Liquids

    NASA Technical Reports Server (NTRS)

    Hsu, W. P. L.; May, C.

    1983-01-01

    Use of membrane films affords convenient and economical alternative for removing and recovering metal cations present in low concentrations from large quantities of liquid solutions. Possible applications of membrane films include use in analytical chemistry for determination of small amounts of toxic metallic impurities in lakes, streams, and municipal effluents. Also suitable for use as absorber of certain pollutant gases and odors present in confined areas.

  12. Piezoelectric sensor for sensitive determination of metal ions based on the phosphate-modified dendrimer

    NASA Astrophysics Data System (ADS)

    Wang, S. H.; Shen, C. Y.; Lin, Y. M.; Du, J. C.

    2016-08-01

    Heavy metal ions arising from human activities are retained strongly in water; therefore public water supplies must be monitored regularly to ensure the timely detection of potential problems. A phosphate-modified dendrimer film was investigated on a quartz crystal microbalance (QCM) for sensing metal ions in water at room temperature in this study. The chemical structures and sensing properties were characterized by Fourier transform infrared spectroscopy and QCM measurement, respectively. This phosphate-modified dendrimer sensor can directly detect metal ions in aqueous solutions. This novel sensor was evaluated for its capacity to sense various metal ions. The sensor exhibited a higher sensitivity level and shorter response time to copper(II) ions than other sensors. The linear detection range of the prepared QCM based on the phosphate-modified dendrimer was 0.0001 ∼ 1 μM Cu(II) ions (R2 = 0.98). The detection properties, including sensitivity, response time, selectivity, reusability, maximum adsorption capacity, and adsorption equilibrium constants, were also investigated.

  13. Reducing hazardous heavy metal ions using mangium bark waste.

    PubMed

    Khabibi, Jauhar; Syafii, Wasrin; Sari, Rita Kartika

    2016-08-01

    The objective of this study was to evaluate the characteristics of mangium bark and its biosorbent ability to reduce heavy metal ions in standard solutions and wastewater and to assess changes in bark characteristics after heavy metal absorption. The experiments were conducted to determine heavy metal absorption from solutions of heavy metals alone and in mixtures as well as from wastewater. The results show that mangium bark can absorb heavy metals. Absorption percentages and capacities from single heavy metal solutions showed that Cu(2+) > Ni(2+) > Pb(2+) > Hg(2+), while those from mixture solutions showed that Hg(2+) > Cu(2+) > Pb(2+) > Ni(2+). Wastewater from gold mining only contained Cu, with an absorption percentage and capacity of 42.87 % and 0.75 mg/g, respectively. The highest absorption percentage and capacity of 92.77 % and 5.18 mg/g, respectively, were found for Hg(2+) in a mixture solution and Cu(2+) in single-metal solution. The Cu(2+) absorption process in a single-metal solution changed the biosorbent characteristics of the mangium bark, yielding a decreased crystalline fraction; changed transmittance on hydroxyl, carboxyl, and carbonyl groups; and increased the presence of Cu. In conclusion, mangium bark biosorbent can reduce hazardous heavy metal ions in both standard solutions and wastewater.

  14. Variable selectivity of the Hitachi chemistry analyzer chloride ion-selective electrode toward interfering ions.

    PubMed

    Wang, T; Diamandis, E P; Lane, A; Baines, A D

    1994-02-01

    Chloride measurements by ion-selective electrodes are vulnerable to interference by anions such as iodide, thiocyanate, nitrate, and bromide. We have found that the degree of interference of these anions on the Hitachi chemistry analyzer chloride electrode varies from electrode to electrode and this variation can even occur within the same lot of membrane. This variation is not dependent upon the length of time the cartridge has been in the analyzer because no correlation existed between the usage time and the electrode response to interfering ions. Neither is this variation due to the deterioration of the electrode because all electrodes tested had calibration slopes within the manufacturer's specification. Our study, however, showed that even after repeated exposure to a plasma sample containing 2 mM thiocyanate, the chloride electrode was still able to accurately measure the chloride in plasma without thiocyanate, thus confirming that a carryover effect does not exist from a previous thiocyanate-containing sample.

  15. Immobilized materials for removal of toxic metal ions from surface/groundwaters and aqueous waste streams.

    PubMed

    Zawierucha, Iwona; Kozlowski, Cezary; Malina, Grzegorz

    2016-04-01

    Heavy metals from industrial processes are of special concern because they produce chronic poisoning in the aquatic environment. More strict environmental regulations on the discharge of toxic metals require the development of various technologies for their removal from polluted streams (i.e. industrial wastewater, mine waters, landfill leachate, and groundwater). The separation of toxic metal ions using immobilized materials (novel sorbents and membranes with doped ligands), due to their high selectivity and removal efficiency, increased stability, and low energy requirements, is promising for improving the environmental quality. This critical review is aimed at studying immobilized materials as potential remediation agents for the elimination of numerous toxic metal (e.g. Pb, Cd, Hg, and As) ions from polluted streams. This study covers the general characteristics of immobilized materials and separation processes, understanding of the metal ion removal mechanisms, a review of the application of immobilized materials for the removal of toxic metal ions, as well as the impacts of various parameters on the removal efficiency. In addition, emerging trends and opportunities in the field of remediation technologies using these materials are addressed.

  16. Enhanced selective hydrogen desorption from metals

    SciTech Connect

    Knize, R.J.; Cecchi, J.L.

    1982-12-01

    The thermal desorption of hydrogen isotopes from a metal is usually a second order process, the rate for which becomes asymptotically slow. We present a method for enhancing the desorption rate of one particular isotope by maintaining a constant pressure of another molecular species. This results in an effective first order desorption and concomitant exponential decay of the concentration of the selected isotope. Data are presented for the enhanced desorption of deuterium from a Zr-Al getter. The results agree well with a theoretical model, which is discussed. This enhanced desorption method should be particularly useful for tritium operation in the Tokamak Fusion Test Reactor.

  17. Enhanced selective hydrogen desorption from metals

    SciTech Connect

    Knize, R.J.; Cecchi, J.L.

    1983-04-01

    The thermal desorption of hydrogen isotopes from a metal is usually a second order process the rate for which becomes asymptotically slow. We present a method for enhancing the desorption rate of one particular isotope by maintaining a constant pressure of another molecular species. This results in an effective first order desorption and concommitant exponential decay of the concentration of the selected isotope. Data is presented for the enhanced desorption of deuterium from a Zr--Al getter. The results agree well with a theoretical model, which is discussed. This enhanced desorption method should be particularly useful for tritium operation in the tokamak fusion test reactor.

  18. Low coefficient of thermal expansion polyimides containing metal ion additives

    NASA Technical Reports Server (NTRS)

    Stoakley, D. M.; St. Clair, A. K.

    1992-01-01

    Polyimides have become widely used as high performance polymers as a result of their excellent thermal stability and toughness. However, lowering their coefficient of thermal expansion (CTE) would increase their usefulness for aerospace and electronic applications where dimensional stability is a requirement. The incorporation of metal ion-containing additives into polyimides, resulting in significantly lowered CTE's, has been studied. Various metal ion additives have been added to both polyamic acid resins and soluble polyimide solutions in the concentration range of 4-23 weight percent. The incorporation of these metal ions has resulted in reductions in the CTE's of the control polyimides of 12 percent to over 100 percent depending on the choice of additive and its concentration.

  19. Low coefficient of thermal expansion polyimides containing metal ion additives

    NASA Technical Reports Server (NTRS)

    Stoakley, D. M.; St. Clair, A. K.

    1992-01-01

    Polyimides have become widely used as high performance polymers as a result of their excellent thermal stability and toughness. However, lowering their coefficient of thermal expansion (CTE) would increase their usefulness for aerospace and electronic applications where dimensional stability is a requirement. The incorporation of metal ion-containing additives into polyimides, resulting in significantly lowered CTE's, has been studied. Various metal ion additives have been added to both polyamic acid resins and soluble polyimide solutions in the concentration range of 4-23 weight percent. The incorporation of these metal ions has resulted in reductions in the CTE's of the control polyimides of 12 percent to over 100 percent depending on the choice of additive and its concentration.

  20. Metal ion modulated electron transfer in photosynthetic proteins.

    SciTech Connect

    Utschig, L. M.; Thurnauer, M. C.; Chemistry

    2004-07-01

    Photosynthetic purple bacterial reaction center (RC) proteins are ideal native systems for addressing basic questions regarding the nature of biological electron transfer because both the protein structure and the electron-transfer reactions are well-characterized. Metal ion binding to the RC can affect primary photochemistry and provides a probe for understanding the involvement of local protein environments in electron transfer. The RC has two distinct transition metal ion binding sites, the well-known non-heme Fe{sup 2+} site buried in the protein interior and a recently discovered Zn{sup 2+} site located on the surface of the protein. Fe{sup 2+} removal and Zn{sup 2+} binding systematically affect different electron-transfer steps in the RC. Factors involved in the metal ion alteration of RC electron transfer may provide a paradigm for other biological systems involved in electron transfer.

  1. Ion exchange properties of novel hydrous metal oxide materials

    SciTech Connect

    Gardner, T.J.; McLaughlin, L.I.

    1996-12-31

    Hydrous metal oxide (HMO) materials are inorganic ion exchangers which have many desirable characteristics for catalyst support applications, including high cation exchange capacity, anion exchange capability, high surface area, ease of adjustment of acidity and basicity, bulk or thin film preparation, and similar chemistry for preparation of various transition metal oxides. Cation exchange capacity is engineered into these materials through the uniform incorporation of alkali cations via manipulation of alkoxide chemistry. Specific examples of the effects of Na stoichiometry and the addition of SiO{sub 2} to hydrous titanium oxide (HTO) on ion exchange behavior will be given. Acid titration and cationic metal precursor complex exchange will be used to characterize the ion exchange behavior of these novel materials.

  2. Selective and low temperature transition metal intercalation in layered tellurides

    PubMed Central

    Yajima, Takeshi; Koshiko, Masaki; Zhang, Yaoqing; Oguchi, Tamio; Yu, Wen; Kato, Daichi; Kobayashi, Yoji; Orikasa, Yuki; Yamamoto, Takafumi; Uchimoto, Yoshiharu; Green, Mark A.; Kageyama, Hiroshi

    2016-01-01

    Layered materials embrace rich intercalation reactions to accommodate high concentrations of foreign species within their structures, and find many applications spanning from energy storage, ion exchange to secondary batteries. Light alkali metals are generally most easily intercalated due to their light mass, high charge/volume ratio and in many cases strong reducing properties. An evolving area of materials chemistry, however, is to capture metals selectively, which is of technological and environmental significance but rather unexplored. Here we show that the layered telluride T2PTe2 (T=Ti, Zr) displays exclusive insertion of transition metals (for example, Cd, Zn) as opposed to alkali cations, with tetrahedral coordination preference to tellurium. Interestingly, the intercalation reactions proceed in solid state and at surprisingly low temperatures (for example, 80 °C for cadmium in Ti2PTe2). The current method of controlling selectivity provides opportunities in the search for new materials for various applications that used to be possible only in a liquid. PMID:27966540

  3. Selective and low temperature transition metal intercalation in layered tellurides

    NASA Astrophysics Data System (ADS)

    Yajima, Takeshi; Koshiko, Masaki; Zhang, Yaoqing; Oguchi, Tamio; Yu, Wen; Kato, Daichi; Kobayashi, Yoji; Orikasa, Yuki; Yamamoto, Takafumi; Uchimoto, Yoshiharu; Green, Mark A.; Kageyama, Hiroshi

    2016-12-01

    Layered materials embrace rich intercalation reactions to accommodate high concentrations of foreign species within their structures, and find many applications spanning from energy storage, ion exchange to secondary batteries. Light alkali metals are generally most easily intercalated due to their light mass, high charge/volume ratio and in many cases strong reducing properties. An evolving area of materials chemistry, however, is to capture metals selectively, which is of technological and environmental significance but rather unexplored. Here we show that the layered telluride T2PTe2 (T=Ti, Zr) displays exclusive insertion of transition metals (for example, Cd, Zn) as opposed to alkali cations, with tetrahedral coordination preference to tellurium. Interestingly, the intercalation reactions proceed in solid state and at surprisingly low temperatures (for example, 80 °C for cadmium in Ti2PTe2). The current method of controlling selectivity provides opportunities in the search for new materials for various applications that used to be possible only in a liquid.

  4. Detection of heavy metal ions in drinking water using a high-resolution differential surface plasmon resonance sensor.

    PubMed

    Forzani, Erica S; Zhang, Haiqian; Chen, Wilfred; Tao, Nongjian

    2005-03-01

    We have built a high-resolution differential surface plasmon resonance (SPR) sensor for heavy metal ion detection. The sensor surface is divided into a reference and sensing areas, and the difference in the SPR angles from the two areas is detected with a quadrant cell photodetector as a differential signal. In the presence of metal ions, the differential signal changes due to specific binding of the metal ions onto the sensing area coated with properly selected peptides, which provides an accurate real-time measurement and quantification of the metal ions. Selective detection of Cu2+ and Ni2+ in the ppt-ppb range was achieved by coating the sensing surface with peptides NH2-Gly-Gly-His-COOH and NH2-(His)6-COOH. Cu2+ in drinking water was tested using this sensor.

  5. Binding of alkali metal ions by cyclic polyethers: significance in ion transport processes.

    PubMed

    Izatt, R M; Rytting, J H; Nelson, D P; Haymore, B L; Christensen, J J

    1969-04-25

    Values for the formation constant (log K), the change in enthalpy (triangle upH degrees ), and the change in entropy (triangle upS degrees ) have been determined for the interaction of lithium, sodium, potassium, rubidium, and cesium ions with the two isomers of the cyclic polyether, 2,5,8,15,18,21-hexaoxatricyclo[20.4.0.0(9,14)] hexacosane. The stability order of these metal ions with either isomer is identical to the permeability order for these same metal ions with the structurally related antibiotics, valinomycin and monactin.

  6. Assembly of nanoions via electrostatic interactions: ion-like behavior of charged noble metal nanoclusters.

    PubMed

    Yao, Qiaofeng; Luo, Zhentao; Yuan, Xun; Yu, Yue; Zhang, Chao; Xie, Jianping; Lee, Jim Yang

    2014-01-24

    The assembly of ultrasmall metal nanoclusters (NCs) is of interest to both basic and applied research as it facilitates the determination of cluster structures and the customization of cluster physicochemical properties. Here we present a facile and general approach to assemble noble metal NCs by selectively inducing electrostatic interactions between negatively-charged metal NCs and divalent cations. The charged metal NCs, which have well-defined sizes, charges and structures; and behave similarly to multivalent anions, can be considered as nanoions. These nanoions exhibit step-like assembly behavior when interacting with the counter cations - assembly only occurs when the solubility product (Ksp) between the carboxylate ions on the NC surface and the divalent cations is exceeded. The assembly here is distinctively different from the random aggregation of colloidal particles by counter ions. The nanoions would assemble into fractal-like monodisperse spherical particles with a high order of regularity that mimic the assembly of ionic crystals.

  7. Biosurfactant Mediated Biosynthesis of Selected Metallic Nanoparticles

    PubMed Central

    Płaza, Grażyna A.; Chojniak, Joanna; Banat, Ibrahim M.

    2014-01-01

    Developing a reliable experimental protocol for the synthesis of nanomaterials is one of the challenging topics in current nanotechnology particularly in the context of the recent drive to promote green technologies in their synthesis. The increasing need to develop clean, nontoxic and environmentally safe production processes for nanoparticles to reduce environmental impact, minimize waste and increase energy efficiency has become essential in this field. Consequently, recent studies on the use of microorganisms in the synthesis of selected nanoparticles are gaining increased interest as they represent an exciting area of research with considerable development potential. Microorganisms are known to be capable of synthesizing inorganic molecules that are deposited either intra- or extracellularly. This review presents a brief overview of current research on the use of biosurfactants in the biosynthesis of selected metallic nanoparticles and their potential importance. PMID:25110864

  8. Reactions of fourth-period metal ions (Ca + - Zn + ) with O2: Metal-oxide ion bond energies

    NASA Astrophysics Data System (ADS)

    Fisher, Ellen R.; Elkind, J. L.; Clemmer, D. E.; Georgiadis, R.; Loh, S. K.; Aristov, N.; Sunderlin, L. S.; Armentrout, P. B.

    1990-08-01

    Reactions of Ca+, Zn+ and all first-row atomic transition metal ions with O2 are studied using guided ion beam techniques. While reactions of the ground states of Sc+, Ti+, and V+ are exothermic, the remaining metal ions react with O2 in endothermic processes. Analyses of these endothermic reactions provide new determinations of the M+-O bond energies for these eight elements. Source conditions are varied such that the contributions of excited states of the metal ions can be explicitly considered for Mn+, Co+, Ni+, and Cu+. Results (in eV) at 0 K are D0(Ca+-O)= 3.57±0.05, D0(Cr+-O)=3.72±0.12, D0(Mn+-O)=2.95±0.13, D0(Fe+-O)=3.53±0.06 (reported previously), D0(Co+-O)=3.32±0.06, D0(Ni+-O) =2.74±0.07, D0(Cu+-O)=1.62±0.15, and D0(Zn+-O)=1.65±0.12. These values along with literature data for neutral metal oxide bond energies and ionization energies are critically evaluated. Periodic trends in the ionic metal oxide bond energies are compared with those of the neutral metal oxides and those of other related molecules.

  9. Comet encke: meteor metallic ion identification by mass spectrometer.

    PubMed

    Goldberg, R A; Aikin, A C

    1973-04-20

    Metal ions including 23(+) (Na(+)), 24(+) (Mg(+)) 28(+) (Si(+)), 39(+) (K(+)), 40(+) (Ca(+)), 45(+) (Sc(+)), 52(+) Cr(+)). 56(+) (Fe(+)), and 58(+) (Ni(+)) have been detected in the upper atmosphere during the period of the Beta Taurids meteor shower. The abundances of these ions relative to Si(+) show, agreement in most instances with abundances in chondrites. A notable exception is 45(+), which, if it is Sc(+), is 100 times more abundant than neutral scandium found in chondrites.

  10. Comet Encke: Meteor metallic ion identification by mass spectrometer

    NASA Technical Reports Server (NTRS)

    Goldberg, R. A.; Aikin, A. C.

    1972-01-01

    Metal ions including Na-40(+), Mg-24(+), Si-28(+), K-39(+), Ca-40(+), Sc-45(+), Cr-52(+), Fe-56(+), and Ni-58(+) were detected in the upper atmosphere during the beta Taurids meteor shower. Abundances of these ions relative to Si(+) show agreement in most instances with chondrites. A notable exception is 45(+), which is Sc(+), is 100 times more abundant than neutral scandium found in chondrites.

  11. Surface ion-imprinted amino-functionalized cellulosic cotton fibers for selective extraction of Cu(II) ions.

    PubMed

    Monier, M; Ibrahim, Amr A; Metwally, M M; Badawy, D S

    2015-11-01

    Surface ion-imprinted amino-functionalized cellulosic fibers (Cu-ABZ) were manufactured for efficient selective adsorption of Cu(2+) ions. The chemical modification steps had been characterized utilizing elemental analysis; Fourier transforms infrared (FTIR) along with wide angle X-ray diffraction (XRD) spectroscopy. Also, the morphological structure of the ion-imprinted and the non-imprinted (NI-ABZ) fibers were visualized and compared with that of the native cotton fibers using scanning electron microscope (SEM). In addition, the coordination mode by which the Cu(2+) ions bonded to the active sites were examined by both FTIR and X-ray photo electron spectra (XPS). Both Cu-ABZ and NI-ABZ were implemented in batch experiments for optimizing the conditions by which the Cu(2+) ions can be selectively removal from aqueous medium and pH 5 was the optimum for the metal ion extraction. Moreover, the kinetics and isotherm studies revealed that the adsorption data fitted with pseudo-second-order kinetic and Langmuir models with estimated maximum adsorption capacity 93.6mg/g. Also, the reusability studies indicated that the prepared ion-imprinted adsorbent maintains more than 95% of its original activity after fifth generation cycle.

  12. Structural aspects of group I metal ion-nucleoside interactions

    NASA Astrophysics Data System (ADS)

    Theophanides, T.; Bariyanga, J.

    1989-12-01

    Lithium, sodium and potassium complexes of guanosine and inosine have been synthesized and characterized. The structures of the complexes have been studied by fast atom bombardment mass spectrometry (FAB-MS). The molecular structures of some defined complexes have been studied from spectral analysis. Detailed interpretation of the spectra suggests that the metal cation is linked to purine's N7 site. In addition, several ion clusters containing the matrix glycerol and the metal ions have been detected among the fragments of the mass spectra.

  13. Determination of metal ions in biological purification of waste waters

    SciTech Connect

    Tikhomirova, L.N.; Spiridonova, N.N.; Mandzhgaladze, I.D.

    1994-12-01

    Chromium, nickel, copper, zinc, and manganese were determined in active sludge extracted for utilization from sewage purification works in biological purification of waste waters. The measurements were carried out by the atomic absorption method and with Merck colorimetric kits for rapid determination of metal ions. The results obtained by the rapid colorimetric method agree fairly well with those obtained by the atomic absorption method, which makes it possible to recommend rapid colorimetric methods for routine analysis of biological objects for the content of ions of heavy metals.

  14. Existence of efficient divalent metal ion-catalyzed and inefficient divalent metal ion-independent channels in reactions catalyzed by a hammerhead ribozyme

    PubMed Central

    Zhou, Jing-Min; Zhou, De-Min; Takagi, Yasuomi; Kasai, Yasuhiro; Inoue, Atsushi; Baba, Tadashi; Taira, Kazunari

    2002-01-01

    The hammerhead ribozyme is generally accepted as a well characterized metalloenzyme. However, the precise nature of the interactions of the RNA with metal ions remains to be fully defined. Examination of metal ion-catalyzed hammerhead reactions at limited concentrations of metal ions is useful for evaluation of the role of metal ions, as demonstrated in this study. At concentrations of Mn2+ ions from 0.3 to 3 mM, addition of the ribozyme to the reaction mixture under single-turnover conditions enhances the reaction with the product reaching a fixed maximum level. Further addition of the ribozyme inhibits the reaction, demonstrating that a certain number of divalent metal ions is required for proper folding and also for catalysis. At extremely high concentrations, monovalent ions, such as Na+ ions, can also serve as cofactors in hammerhead ribozyme-catalyzed reactions. However, the catalytic efficiency of monovalent ions is extremely low and, thus, high concentrations are required. Furthermore, addition of monovalent ions to divalent metal ion-catalyzed hammerhead reactions inhibits the divalent metal ion-catalyzed reactions, suggesting that the more desirable divalent metal ion–ribozyme complexes are converted to less desirable monovalent metal ion–ribozyme complexes via removal of divalent metal ions, which serve as a structural support in the ribozyme complex. Even though two channels appear to exist, namely an efficient divalent metal ion-catalyzed channel and an inefficient monovalent metal ion-catalyzed channel, it is clear that, under physiological conditions, hammerhead ribozymes are metalloenzymes that act via the significantly more efficient divalent metal ion-dependent channel. Moreover, the observed kinetic data are consistent with Lilley’s and DeRose’s two-phase folding model that was based on ground state structure analyses. PMID:12034824

  15. DUHOCAMIS: a dual hollow cathode ion source for metal ion beams.

    PubMed

    Zhao, W J; Müller, M W O; Janik, J; Liu, K X; Ren, X T

    2008-02-01

    In this paper we describe a novel ion source named DUHOCAMIS for multiply charged metal ion beams. This ion source is derived from the hot cathode Penning ion gauge ion source (JINR, Dubna, 1957). A notable characteristic is the modified Penning geometry in the form of a hollow sputter electrode, coaxially positioned in a compact bottle-magnetic field along the central magnetic line of force. The interaction of the discharge geometry with the inhomogeneous but symmetrical magnetic field enables this device to be operated as hollow cathode discharge and Penning discharge as well. The main features of the ion source are the very high metal ion efficiency (up to 25%), good operational reproducibility, flexible and efficient operations for low charged as well as highly charged ions, compact setup, and easy maintenance. For light ions, e.g., up to titanium, well-collimated beams in the range of several tens of milliamperes of pulsed ion current (1 ms, 10/s) have been reliably performed in long time runs.

  16. Metal-Ion Additives Reduce Thermal Expansion Of Polyimides

    NASA Technical Reports Server (NTRS)

    Stoakley, Diane M.; St. Clair, Anne K.; Emerson, Burt R., Jr.; Willis, George L.

    1994-01-01

    Polyimides widely used as high-performance polymers because of their excellent thermal stability and toughness. However, their coefficients of thermal expansion (CTE's) greater than those of metals, ceramics, and glasses. Decreasing CTE's of polyimides increase usefulness for aerospace and electronics applications in which dimensional stability required. Additives containing metal ions reduce coefficients of thermal expansion of polyimides. Reductions range from 11 to over 100 percent.

  17. Substrate and Metal Ion Promiscuity in Mannosylglycerate Synthase*

    PubMed Central

    Nielsen, Morten M.; Suits, Michael D. L.; Yang, Min; Barry, Conor S.; Martinez-Fleites, Carlos; Tailford, Louise E.; Flint, James E.; Dumon, Claire; Davis, Benjamin G.; Gilbert, Harry J.; Davies, Gideon J.

    2011-01-01

    The enzymatic transfer of the sugar mannose from activated sugar donors is central to the synthesis of a wide range of biologically significant polysaccharides and glycoconjugates. In addition to their importance in cellular biology, mannosyltransferases also provide model systems with which to study catalytic mechanisms of glycosyl transfer. Mannosylglycerate synthase (MGS) catalyzes the synthesis of α-mannosyl-d-glycerate using GDP-mannose as the preferred donor species, a reaction that occurs with a net retention of anomeric configuration. Past work has shown that the Rhodothermus marinus MGS, classified as a GT78 glycosyltransferase, displays a GT-A fold and performs catalysis in a metal ion-dependent manner. MGS shows very unusual metal ion dependences with Mg2+ and Ca2+ and, to a lesser extent, Mn2+, Ni2+, and Co2+, thus facilitating catalysis. Here, we probe these dependences through kinetic and calorimetric analyses of wild-type and site-directed variants of the enzyme. Mutation of residues that interact with the guanine base of GDP are correlated with a higher kcat value, whereas substitution of His-217, a key component of the metal coordination site, results in a change in metal specificity to Mn2+. Structural analyses of MGS complexes not only provide insight into metal coordination but also how lactate can function as an alternative acceptor to glycerate. These studies highlight the role of flexible loops in the active center and the subsequent coordination of the divalent metal ion as key factors in MGS catalysis and metal ion dependence. Furthermore, Tyr-220, located on a flexible loop whose conformation is likely influenced by metal binding, also plays a critical role in substrate binding. PMID:21288903

  18. Metal ions and RNA folding: a highly charged topic with a dynamic future.

    PubMed

    Woodson, Sarah A

    2005-04-01

    Metal ions are required to stabilize RNA tertiary structure and to begin the folding process. How different metal ions enable RNAs to fold depends on the electrostatic potential of the RNA and correlated fluctuations in the positions of the ions themselves. Theoretical models, fluorescence spectroscopy, small angle scattering and structural biology reveal that metal ions alter the RNA dynamics and folding transition states. Specifically coordinated divalent metal ions mediate conformational rearrangements within ribozyme active sites.

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

    PubMed Central

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

    2010-01-01

    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 – 2.5 Å) 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. PMID:18614239

  20. An Entropic Mechanism of Generating Selective Ion Binding in Macromolecules

    PubMed Central

    Thomas, Michael; Jayatilaka, Dylan; Corry, Ben

    2013-01-01

    Several mechanisms have been proposed to explain how ion channels and transporters distinguish between similar ions, a process crucial for maintaining proper cell function. Of these, three can be broadly classed as mechanisms involving specific positional constraints on the ion coordinating ligands which arise through: a “rigid cavity”, a ‘strained cavity’ and ‘reduced ligand fluctuations’. Each operates in subtly different ways yet can produce markedly different influences on ion selectivity. Here we expand upon preliminary investigations into the reduced ligand fluctuation mechanism of ion selectivity by simulating how a series of model systems respond to a decrease in ligand thermal fluctuations while simultaneously maintaining optimal ion-ligand binding distances. Simple abstract-ligand models, as well as simple models based upon the ion binding sites in two amino acid transporters, show that limiting ligand fluctuations can create ion selectivity between Li+, Na+ and K+ even when there is no strain associated with the molecular framework accommodating the different ions. Reducing the fluctuations in the position of the coordinating ligands contributes to selectivity toward the smaller of two ions as a consequence of entropic differences. PMID:23468604

  1. Reactions of Ions with Ionic Liquid Vapors by Selected-Ion Flow Tube Mass Spectrometry.

    PubMed

    Chambreau, Steven D; Boatz, Jerry A; Vaghjiani, Ghanshyam L; Friedman, Jeffrey F; Eyet, Nicole; Viggiano, A A

    2011-04-21

    Room-temperature ionic liquids exert vanishingly small vapor pressures under ambient conditions. Under reduced pressure, certain ionic liquids have demonstrated volatility, and they are thought to vaporize as intact cation-anion ion pairs. However, ion pair vapors are difficult to detect because their concentration is extremely low under these conditions. In this Letter, we report the products of reacting ions such as NO(+), NH4(+), NO3(-), and O2(-) with vaporized aprotic ionic liquids in their intact ion pair form. Ion pair fragmentation to the cation or anion as well as ion exchange and ion addition processes are observed by selected-ion flow tube mass spectrometry. Free energies of the reactions involving 1-ethyl-3-methylimidazolium bis-trifluoromethylsulfonylimide determined by ab initio quantum mechanical calculations indicate that ion exchange or ion addition are energetically more favorable than charge-transfer processes, whereas charge-transfer processes can be important in reactions involving 1-butyl-3-methylimidazolium dicyanamide.

  2. Heavy metal ions are potent inhibitors of protein folding

    SciTech Connect

    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. Cd{sup 2+}, Hg{sup 2+} and Pb{sup 2+} 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{sub 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.

  3. Selective adsorption of silver(I) ions over copper(II) ions on a sulfoethyl derivative of chitosan.

    PubMed

    Petrova, Yulia S; Pestov, Alexandr V; Usoltseva, Maria K; Neudachina, Ludmila K

    2015-12-15

    This study presents a simple and effective method of preparation of N-(2-sulfoethyl) chitosan (NSE-chitosan) that allows obtaining a product with a degree of modification up to 1.0. The chemical structure of the obtained polymers was confirmed by FT-IR and 1H NMR spectroscopies. Cross-linking of N-(2-sulfoethyl) chitosans by glutaraldehyde allows preparation of sorbents for removal and concentration of metal ions. Capacity of sorbents towards hydroxide ions was determined depending on the degree of sulfoethylation under static and dynamic conditions. Dissociation constants of functional amino groups of the analyzed sorbents were determined by potentiometric titration. It was shown that basicity of the amino groups decreased (wherein pKa decreased from 6.53 to 5.67) with increase in degree of sulfoethylation. It explains the significant influence of sulfo groups on selectivity of sorption of metal ions on N-(2-sulfoethyl) chitosan-based sorbents. The investigated substances selectively remove copper(II) and silver(I) ions from solutions of complex composition. Wherein the selectivity coefficient KAg/Cu increased to 20 (pH 6.5, ammonium acetate buffer solution) with increase in degree of sulfoethylation of the sorbent up to 1.0.

  4. How do energetic ions damage metallic surfaces?

    DOE PAGES

    Osetskiy, Yury N.; Calder, Andrew F.; Stoller, Roger E.

    2015-02-20

    Surface modification under bombardment by energetic ions observed under different conditions in structural and functional materials and can be either unavoidable effect of the conditions or targeted modification to enhance materials properties. Understanding basic mechanisms is necessary for predicting properties changes. The mechanisms activated during ion irradiation are of atomic scale and atomic scale modeling is the most suitable tool to study these processes. In this paper we present results of an extensive simulation program aimed at developing an understanding of primary surface damage in iron by energetic particles. We simulated 25 keV self-ion bombardment of Fe thin films withmore » (100) and (110) surfaces at room temperature. A large number of simulations, ~400, were carried out allow a statistically significant treatment of the results. The particular mechanism of surface damage depends on how the destructive supersonic shock wave generated by the displacement cascade interacts with the free surface. Three basic scenarios were observed, with the limiting cases being damage created far below the surface with little or no impact on the surface itself, and extensive direct surface damage on the timescale of a few picoseconds. In some instances, formation of large <100> vacancy loops beneath the free surface was observed, which may explain some earlier experimental observations.« less

  5. How do energetic ions damage metallic surfaces?

    SciTech Connect

    Osetskiy, Yury N.; Calder, Andrew F.; Stoller, Roger E.

    2015-02-20

    Surface modification under bombardment by energetic ions observed under different conditions in structural and functional materials and can be either unavoidable effect of the conditions or targeted modification to enhance materials properties. Understanding basic mechanisms is necessary for predicting properties changes. The mechanisms activated during ion irradiation are of atomic scale and atomic scale modeling is the most suitable tool to study these processes. In this paper we present results of an extensive simulation program aimed at developing an understanding of primary surface damage in iron by energetic particles. We simulated 25 keV self-ion bombardment of Fe thin films with (100) and (110) surfaces at room temperature. A large number of simulations, ~400, were carried out allow a statistically significant treatment of the results. The particular mechanism of surface damage depends on how the destructive supersonic shock wave generated by the displacement cascade interacts with the free surface. Three basic scenarios were observed, with the limiting cases being damage created far below the surface with little or no impact on the surface itself, and extensive direct surface damage on the timescale of a few picoseconds. In some instances, formation of large <100> vacancy loops beneath the free surface was observed, which may explain some earlier experimental observations.

  6. Measurement of Extracellular Ion Fluxes Using the Ion-selective Self-referencing Microelectrode Technique

    PubMed Central

    Luxardi, Guillaume; Reid, Brian; Ferreira, Fernando; Maillard, Pauline; Zhao, Min

    2015-01-01

    Cells from animals, plants and single cells are enclosed by a barrier called the cell membrane that separates the cytoplasm from the outside. Cell layers such as epithelia also form a barrier that separates the inside from the outside or different compartments of multicellular organisms. A key feature of these barriers is the differential distribution of ions across cell membranes or cell layers. Two properties allow this distribution: 1) membranes and epithelia display selective permeability to specific ions; 2) ions are transported through pumps across cell membranes and cell layers. These properties play crucial roles in maintaining tissue physiology and act as signaling cues after damage, during repair, or under pathological condition. The ion-selective self-referencing microelectrode allows measurements of specific fluxes of ions such as calcium, potassium or sodium at single cell and tissue levels. The microelectrode contains an ionophore cocktail which is selectively permeable to a specific ion. The internal filling solution contains a set concentration of the ion of interest. The electric potential of the microelectrode is determined by the outside concentration of the ion. As the ion concentration varies, the potential of the microelectrode changes as a function of the log of the ion activity. When moved back and forth near a source or sink of the ion (i.e. in a concentration gradient due to ion flux) the microelectrode potential fluctuates at an amplitude proportional to the ion flux/gradient. The amplifier amplifies the microelectrode signal and the output is recorded on computer. The ion flux can then be calculated by Fick’s law of diffusion using the electrode potential fluctuation, the excursion of microelectrode, and other parameters such as the specific ion mobility. In this paper, we describe in detail the methodology to measure extracellular ion fluxes using the ion-selective self-referencing microelectrode and present some representative

  7. Adsorption characteristics of metal ions on chitosan chemically modified by D-galactose

    SciTech Connect

    Kondo, Kazuo; Sumi, Hisaharu; Matsumoto, Michiaki

    1996-07-01

    The adsorption characteristics of metal ions on chitosan chemically modified by D-galactose were examined. The pH dependency on the distribution ratio was found to be affected by the valency of the metal ion, and the apparent adsorption equilibrium constants of the metal ions were determined. The order of adsorption of the metal ions is Ga > In > Nd > Eu for the trivalent metal ions and Cu > Ni > Co for the divalent metal ions. It is believed that amino and hydroxyl groups in the chitosan act as a chelating ligand.

  8. Sensing metal ions with DNA building blocks: fluorescent pyridobenzimidazole nucleosides.

    PubMed

    Kim, Su Jeong; Kool, Eric T

    2006-05-10

    We describe novel fluorescent N-deoxyribosides (1 and 2) having 2-pyrido-2-benzimidazole and 2-quino-2-benzimidazole as aglycones. The compounds were prepared from the previously unknown heterocyclic precursors and Hoffer's chlorosugar, yielding alpha anomers as the chief products. X-ray crystal structures confirmed the geometry and showed that the pyridine and benzimidazole ring systems deviated from coplanarity in the solid state by 154 degrees and 140 degrees , respectively. In methanol compounds 1 and 2 had absorption maxima at 360 and 370 nm, respectively, and emission maxima at 494 and 539 nm. Experiments revealed varied fluorescence responses of the nucleosides to a panel of 17 monovalent, divalent, and trivalent metal ions in methanol. One or both of the nucleosides showed significant changes with 10 of the metal ions. The most pronounced spectral changes for ligand-nucleoside 1 included red shifts in fluorescence (Au(+), Au(3+)), strong quenching (Cu(2+), Ni(2+), Pt(2+)), and substantial enhancements in emission intensity coupled with red shifts (Ag(+), Cd(2+), Zn(2+)). The greatest spectral changes for ligand-nucleoside 2 included a red shift in fluorescence (Ag(+)), a blue shift (Cd(2+)), strong quenching (Pd(2+), Pt(2+)), and substantial enhancements in emission intensity coupled with a blue shift (Zn(2+)). The compounds could be readily incorporated into oligodeoxynucleotides, where an initial study revealed that they retained sensitivity to metal ions in aqueous solution and demonstrated possible cooperative sensing behavior with several ions. The two free nucleosides alone can act as differential sensors for multiple metal ions, and they are potentially useful monomers for contributing metal ion sensing capability to DNAs.

  9. Sensing Metal Ions with DNA Building Blocks: Fluorescent Pyridobenzimidazole Nucleosides

    PubMed Central

    Kim, Su Jeong; Kool, Eric T.

    2008-01-01

    We describe novel fluorescent N-deoxyribosides (1 and 2) having 2-pyrido-2-benzimidazole and 2-quino-2-benzimidazole as aglycones. The compounds were prepared from the previously unknown heterocyclic precursors and Hoffer’s chlorosugar, yielding alpha anomers as the chief products. X-ray crystal structures confirmed the geometry, and showed that the pyridine and benzimidazole ring systems deviated from coplanarity in the solid state by 154° and 140°, respectively. In methanol the compounds 1 and 2 had absorption maxima at 360 and 370 nm respectively, and emission maxima at 494 and 539 nm. Experiments revealed varied fluorescence responses of the nucleosides to a panel of seventeen monovalent, divalent and trivalent metal ions in methanol. One or both of the nucleosides showed significant changes with ten of the metal ions. The most pronounced spectral changes for ligand-nucleoside 1 included red shifts in fluorescence (Au+, Au3+), strong quenching (Cu2+, Ni2+, Pt2+), and in substantial enhancements in emission intensity coupled with redshifts (Ag+, Cd2+, Zn2+). The greatest spectral changes for ligand-nucleoside 2 included a redshift in fluorescence (Ag+), a blueshift (Cd2+), strong quenching (Pd2+, Pt2+), and in substantial enhancements in emission intensity coupled with a blueshift (Zn2+). The compounds could be readily incorporated into oligodeoxynucleotides, where an initial study revealed that they retained sensitivity to metal ions in aqueous solution, and demonstrated possible cooperative sensing behavior with several ions. The two free nucleosides alone can act as differential sensors for at multiple metal ions, and they are potentially useful monomers for contributing metal ion sensing capability to DNAs. PMID:16669686

  10. Effects of metal ions and cosolutes on G-quadruplex topology.

    PubMed

    Fujii, Taiga; Podbevšek, Peter; Plavec, Janez; Sugimoto, Naoki

    2017-01-01

    Topologies of G-quadruplexes depend on oligonucleotide sequences and on environmental factors, and the diversity of G-quadruplex topologies complicates investigation of functions of these nucleic acid structures. To investigate how metal ions and cosolutes regulate topologies of G-quadruplexes, we stabilized the antiparallel conformation by insertion of 2'-deoxyxanthosine and 8-oxo-2'-deoxyguanosine into selected positions of an oligonucleotide. Thermodynamic analyses of the oligonucleotide revealed that Na(+) stabilized the antiparallel G-quadruplex, whereas K(+) destabilized this topology. This result suggests that metal ions selectively stabilize G-quadruplex topologies with cavities between G-quartet planes of certain sizes. In the presence of KCl in 20wt% poly(ethylene glycol) with average molecular weight of 200, the antiparallel basket-type G-quadruplex conformation was not stabilized compared with the dilute condition. In the presence of NaCl, the cosolute did stabilize the G-quadruplex with respect to the dilute condition. The presented data show that metal ions and cosolutes regulate topologies of G-quadruplexes through mechanisms that depend on sizes of metal ion cavities and hydration states.

  11. Metal ion bombardment of onion skin cell wall

    SciTech Connect

    Sangyuenyongpipat, S.; Vilaithong, T.; Yu, L.D.; Verdaguer, A.; Ratera, I.; Ogletree, D.F.; Monteiro, O.R.; Brown, I.G.

    2004-05-10

    Ion bombardment of living cellular material is a novel subfield of ion beam surface modification that is receiving growing attention from the ion beam and biological communities. Although it has been demonstrated that the technique is sound, in that an adequate fraction of the living cells can survive both the vacuum environment and energetic ion bombardment, there remains much uncertainty about the process details. Here we report on our observations of onion skin cells that were subjected to ion implantation, and propose some possible physical models that tend to support the experimental results. The ion beams used were metallic (Mg, Ti, Fe, Ni, Cu), mean ion energy was typically 30keV, and the implantation fluence was in the range 1014 1016 ions/cm2. The cells were viewed using Atomic Force Microscopy, revealing the formation of microcrater-like structures due to ion bombardment. The implantation depth profile was measured with Rutherford backscattering spectrometry and compared to the results of the TRIM, T-DYN and PROFILE computer codes.

  12. Metal ion bombardment of onion skin cell wall

    NASA Astrophysics Data System (ADS)

    Sangyuenyongpipat, S.; Vilaithong, T.; Yu, L. D.; Verdaguer, A.; Ratera, I.; Ogletree, D. F.; Monteiro, O. R.; Brown, I. G.

    2005-01-01

    Ion bombardment of living cellular material is a novel subfield of ion beam surface modification that is receiving growing attention from the ion beam and biological communities. Although it has been demonstrated that the technique is sound, in that an adequate fraction of the living cells can survive both the vacuum environment and energetic ion bombardment, there remains much uncertainty about the process details. Here we report on our observations of onion skin cells that were subjected to ion implantation, and propose some possible physical models that tend to support the experimental results. The ion beams used were metallic (Mg, Ti, Fe, Ni, Cu), mean ion energy was typically 30 keV, and the implantation fluence was in the range 1014-1016 ions/cm2. The cells were viewed using Atomic Force Microscopy, revealing the formation of microcrater-like structures due to ion bombardment. The implantation depth profile was measured with Rutherford backscattering spectrometry and compared to the results of the TRIM, T-DYN and PROFILE computer codes.

  13. Metal ions affecting the immune system.

    PubMed

    Lehmann, Irina; Sack, Ulrich; Lehmann, Jörg

    2011-01-01

    Certain heavy metals have been reported to seriously affect the immune system potentially resulting in a broad range of harmful health effects. Reported alterations in immune cell function include a variety of affected mechanisms. Thereby, depending on the particular metal, its concentration, route and duration of exposure, and biologic availability, the net outcome may be either immunosuppression or stimulation of immune cell activity. Since the key importance of the immune system is protection of the host against pathogenic agents, an impaired immune competence inevitably increases the susceptibility to invading pathogens. However, being aware that the immune system represents a sensitively regulated network of different cells, tissues, and soluble mediators it has to be stated that any form of dys-regulation may result in adverse health effects with overstimulation being as harmful as inhibition of functional activity. Chronic-inflammatory reactions, cancer development, hypersensitivity, allergic and autoimmune diseases are known consequences of persisting overstimulation. All these manifestations were already found to be related with heavy metal exposure.

  14. Selective Metallization Induced by Laser Activation: Fabricating Metallized Patterns on Polymer via Metal Oxide Composite.

    PubMed

    Zhang, Jihai; Zhou, Tao; Wen, Liang

    2017-02-28

    Recently, metallization on polymer substrates has been given more attention due to its outstanding properties of both plastics and metals. In this study, the metal oxide composite of copper-chromium oxide (CuO·Cr2O3) was incorporated into the polymer matrix to design a good laser direct structuring (LDS) material, and the well-defined copper pattern (thickness =10 μm) was successfully fabricated through selective metallization based on 1064 nm near-infrared pulsed laser activation and electroless copper plating. We also prepared polymer composites incorporated with CuO and Cr2O3; however, these two polymer composites both had very poor capacity of selective metallization, which has no practical value for LDS technology. In our work, the key reasons causing the above results were systematically studied and elucidated using XPS, UV-vis-IR, optical microscopy, SEM, contact angle, ATR FTIR, and so on. The results showed that 54.0% Cu(2+) in the polymer composite of CuO·Cr2O3 (the amount =5 wt %) is reduced to Cu(0) (elemental copper) after laser activation (irradiation); however, this value is only 26.8% for the polymer composite of CuO (the amount =5 wt %). It was confirmed that to achieve a successful selective metallization after laser activation, not only was the new formed Cu(0) (the catalytic seeds) the crucial factor, but the number of generated Cu(0) catalytic seeds was also important. These two factors codetermined the final results of the selective metallization. The CuO·Cr2O3 is very suitable for applications of fabricating metallic patterns (e.g., metal decoration, circuit) on the inherent pure black or bright black polymer materials via LDS technology, which has a prospect of large-scale industrial applications.

  15. Highly selective fluorescent and colorimetric chemosensor for detection of Hg2 + ion in aqueous media

    NASA Astrophysics Data System (ADS)

    Zareh Jonaghani, Mohammad; Zali-Boeini, Hassan

    2017-05-01

    A highly efficient and selective fluorescent and colorimetric chemosensor based on naphthothiazole skeleton was synthesized and its colorimetric and fluorescent properties were investigated. The sensor displays a rapid and highly selective colorimetric and fluorescence response toward Hg2 + without interference with other metal ions in CH3CN/H2O mixture (50/50, v/v). The detection limit for the fluorescent chemosensor S1 toward Hg2 + was 3.42 × 10- 8 M.

  16. Current and prospective applications of metal ion-protein binding.

    PubMed

    Ueda, E K M; Gout, P W; Morganti, L

    2003-02-21

    Since immobilized metal ion affinity chromatography (IMAC) was first introduced, several variants of this method and many other metal affinity-based techniques have been devised. IMAC quickly established itself as a highly reliable purification procedure, showing rapid expansion in the number of preparative and analytical applications while not remaining confined to protein separation. It was soon applied to protein refolding (matrix-assisted refolding), evaluation of protein folding status, protein surface topography studies and biosensor development. In this review, applications in protein processing are described of IMAC as well as other metal affinity-based technologies.

  17. Uptake of Metal Ions by Rhizopus arrhizus Biomass

    PubMed Central

    Tobin, J. M.; Cooper, D. G.; Neufeld, R. J.

    1984-01-01

    Rhizopus arrhizus biomass was found to absorb a variety of different metal cations and anions but did not absorb alkali metal ions. The amount of uptake of the cations was directly related to ionic radii of La3+, Mn2+, Cu2+, Zn2+, Cd2+, Ba2+, Hg2+, Pb2+, UO22+, and Ag+. The uptake of all the cations is consistent with absorption of the metals by sites in the biomass containing phosphate, carboxylate, and other functional groups. The uptake of the molybdate and vanadate anions was strongly pH dependent, and it is proposed that the uptake mechanism involves electrostatic attraction to positively charged functional groups. PMID:16346521

  18. Longan shell as novel biomacromolecular sorbent for highly selective removal of lead and mercury ions.

    PubMed

    Huang, Mei-Rong; Li, Shu; Li, Xin-Gui

    2010-03-18

    Strongly selective adsorbability of natural longan (Euphoria longan) shell as a biomacromolecular sorbent toward heavy metal ions from aqueous solutions has been discovered and successfully optimized by facilely controlling the shell dosage, sorption time, pH value, and ion concentration. The sorption well-fits the Langmuir isotherm and obeys the pseudo-second-order kinetics. The maximum adsorptivity of Pb(II) and Hg(II) is 99.3 and 99.1%, respectively, with short equilibrium sorption time. The redox sorption mechanism of Pb(II) and Hg(II) ions onto longan shell was proposed on the basis of IR and X-ray diffraction analyses. In particular, a slow but durative redox interaction between Pb(II) ions and longan shell was revealed even at a solid state, resulting in the formation of Pb(syn) crystals onto longan shell. Competitive sorption suggested that the shell demonstrated a preferential sorption to Pb(II) over Hg(II) in their mixture solution, despite higher adsorptivity of Hg(II) than Pb(II) in corresponding pure solutions. The shell displayed highly selective sorption to Pb(II) over light metal ions with an adsorbability order of Pb(II) > Hg(II) > Zn(II) > Cu(II) > Ca(II) > Mg(II) > Fe(III,II), indicating that the shell could efficiently purify drinking water and nutritious liquids by just eliminating the harmful metal ions and still retaining the nutritious metal ions. The printery sewage and polluted river water both meet the discharge standard after being treated once with longan shell, and even satisfy the standards for irrigation/fishery and drinking water, respectively, after being treated twice. A large amount of functional groups like hydroxyl, ether, and carbonyl in the longan shell, as well as its intrinsic hydrophilicity, are responsible for the strong adsorbability toward the heavy metal ions. Not only does the longan shell have low cost and have inherent environmental friendliness in contrast to all synthetic and even seminatural sorbents but it also

  19. Pesticides Curbing Soil Fertility: Effect of Complexation of Free Metal Ions.

    PubMed

    Kaur, Sukhmanpreet; Kumar, Vijay; Chawla, Mohit; Cavallo, Luigi; Poater, Albert; Upadhyay, Niraj

    2017-01-01

    Researchers have suggested that the reason behind infertility is pernicious effect of broad spectrum pesticides on non target, beneficial microorganism of soil. Here, studying the chelating effect of selective organophosphate and carbamate pesticides with essential metal ions, at all possible combinations of three different pH (4 ± 0.05, 7 ± 0.05 and 9 ± 0.05) and three different temperatures (15 ± 0.5°C, 30 ± 0.5°C and 45 ± 0.5°C), shows very fast rate of reaction which further increases with increase of pH and temperature. Carbonyl oxygen of carbamate and phosphate oxygen of organophosphate were found to be common ligating sites among all the complexes. Formed metal complexes were found to be highly stable and water insoluble on interaction with essential metal ions in solvent medium as well as over silica. Density functional theory (DFT) calculations not only reinforced the experimental observations, but, after a wide computational conformational analysis, unraveled the nature of the high stable undesired species that consist of pesticides complexed by metal ions from the soil. All in all, apart from the direct toxicity of pesticides, the indirect effect by means of complexation of free metal ions impoverishes the soil.

  20. Quadrupole ion trap studies of the structure and reactivity of transition metal ion pair complexes

    PubMed

    Vachet; Callahan

    2000-03-01

    Ion pairs are common species observed in the electrospray mass spectra of transition metal coordination complexes. To understand the nature of these ion pairs, a systematic study of the gas-phase chemistry of these species using ion-molecule reactions and collision-induced dissociation (CID) was carried out. Ion pair complexes of the type MLnX+ (where M is Mn(II), Fe(II), Co(II), Ni(II), Cu(II) or Zn(II), L is 1,10-phenanthroline, 2,2'-bipyridine, ethylenediamine, diethylenetriamine or 1,4,8,11-tetraazacyclotetradecane and X is Cl-, NO3-, acetylacetonate, ClO4-, acetate or SCN-) were studied. Ion-molecule reactions can distinguish whether the counterion in an ion pair is an inner- or outer-sphere ligand and can determine the coordination mode of the counterion. In addition, CID and ion-molecule reactions reveal some interesting chemistry of these complexes and unique coordination modes for some of the anions studied here were inferred from the ion-molecule reactions. For example, the thiocyanate ion is found to coordinate in a bidentate fashion in Zn(II) and Ni(II) complexes, contrasting behavior typically observed in solution. Also, certain Co(II) and Fe(II) ion pair complexes undergo oxidation reactions in which species such as dioxygen and nitric oxide from the counterions ClO4- and NO3- are transferred to the Co(II) and Fe(II) complexes, showing the inherent affinity of these metals for these molecules. These complexes were also studied by ion-molecule reactions and CID. Dioxygen in complexes formed by CID is demonstrated to be bidentate, suggesting the formation of a peroxo ligand with concurrent oxidation of the metal.

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

    PubMed

    Dauplais, Marc; Lazard, Myriam; Blanquet, Sylvain; Plateau, Pierre

    2013-01-01

    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.

  2. Peptide platforms for metal ion sensing

    NASA Astrophysics Data System (ADS)

    Imperiali, Barbara; Pearce, Dierdre A.; Sohna Sohna, Jean-Ernest; Walkup, Grant; Torrado, Alicia

    1999-12-01

    Naturally occurring motifs have been redesigned to product fluorescent peptidyl-chemosensors that sensitively and selectively recognize Cu(II) or Fe(III). The modular nature of peptide architecture allows preparation and evaluation of potential sensors on solid supports.

  3. Precipitation of alkylbenzene sulfonates with metal ions

    SciTech Connect

    Peacock, J.M.; Matijevic, E.

    1980-10-01

    The precipitation domains of P-(1-methylnonyl)benzene sulfonate ions with Li/sup +/, Na/sup +/, K/sup +/, Ca/sup 2 +/, Mg/sup 2 +/, Al/sup 3 +/, and La/sup 3 +/ and of Ca/sup 2 +/-P-(hexyloctyl)benzene sulfonate have been determined at constant pH and 25 C. The linear solubility boundaries reverse their slope at the critical micellar concentration of the surfactant. A semiquantitative interpretation of the data is offered. The properties of the solids formed also are described. 18 references.

  4. Host Materials for Transition-Metal Ions

    DTIC Science & Technology

    1989-09-01

    BeA1204 (Chrysoberyl, Cr:BeA204 - Alexandrite ) ..................... 90 15.1 Crystallographic Data on BeA 204 ............................ 9 0 15.2 X...Chrysoberyl, Cr:BeA1 2 04 = Alexandrite ) 15.1 Crystallographic Data on BeA204 Orthorhombic D 16 (Pnma), 62, Z = 4 Orthorhomb__ D2h Ion Site Symmetry x...Stimulated Emission from Alexandrite (BeAl 1204 :Cr 3 +) Sov. J. Quantum Electron. 8 (1978), 671. 2. C. F. Cline, R. C. Morris, M. Dutoit, and P. J

  5. Microspheres aided introduction of ionophore and ion-exchanger to the ion-selective membrane.

    PubMed

    Wojciechowski, Marcin; Kisiel, Anna; Bulska, Ewa; Michalska, Agata

    2012-01-15

    In this work a novel method for introduction of ionophore and ion-exchanger to the ion-selective polyacrylate based membrane is proposed. These compounds (and optionally primary ions) are introduced to polyacrylate microspheres, used to prepare ion-selective membrane. The approach proposed here can be used to prepare membranes containing primary ions equally distributed through the receptor phase, i.e. membranes that do not require conditioning in primary ions solution and are free from problems related to slow diffusion of primary ions. Thus obtained sensors were characterized with linear responses (also at relatively high activities) and high selectivities, despite considerable reduction of ionophore and ion-exchanger amount introduced to the membrane. To be able to prepare ion-selective membranes using this approach, a method for quantification of ionophore and ion-exchanger introduced into microspheres is required. In this work a novel method utilizing high performance liquid chromatography (HPLC) with DAD or FLD detection is proposed. Incorporation of ionophore and ion-exchanger into the microspheres was achieved either by absorption into ready spheres or in course of photopolymerization of polymeric beads. The obtained results have proven that both procedures led to incorporation of ionophore/ion-exchanger into polymeric spheres, however, the content of the compounds in the spheres post process is different from their ratio in solution from which they had been introduced. These effects need to be considered/compensated while preparing microspheres containing ion-selective membranes. As a model system poly(n-butyl acrylate) spheres, silver selective ionophore and sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate were chosen, resulting ultimately in silver-selective electrodes. Copyright © 2011 Elsevier B.V. All rights reserved.

  6. Molecular design of the microbial cell surface toward the recovery of metal ions.

    PubMed

    Kuroda, Kouichi; Ueda, Mitsuyoshi

    2011-06-01

    The genetic engineering of microorganisms to adsorb metal ions is an attractive method to facilitate the environmental cleanup of metal pollution and to enrich the recovery of metal ions such as rare metal ions. For the recovery of metal ions by microorganisms, cell surface design is an effective strategy for the molecular breeding of bioadsorbents as an alternative to intracellular accumulation. The cell surface display of known metal-binding proteins/peptides and the molecular design of novel metal-binding proteins/peptides have been performed using a cell surface engineering approach. The adsorption of specific metal ions is the important challenge for the practical recovery of metal ions. In this paper, we discuss the recent progress in surface-engineered bioadsorbents for the recovery of metal ions. Copyright © 2011 Elsevier Ltd. All rights reserved.

  7. Electropositive bivalent metallic ion unsaturated polyester complexed polymer concrete

    DOEpatents

    Sugama, T.; Kukacka, L.E.; Horn, W.H.

    1981-11-04

    Quick setting polymer concrete compositions which are mixtures of unsaturated polyesters and crosslinking monomers together with appropriate initiators and promoters in association with aggregate which may be wet and a source of bivalent metallic ions which will set to polymer concrete with excellent structural properties.

  8. Electropositive bivalent metallic ion unsaturated polyester complexed polymer concrete

    DOEpatents

    Sugama, T.; Kukacka, L.E.; Horn, W.H.

    1983-05-13

    Quick setting polymer concrete compositions are described which are mixtures of unsaturated polyesters and crosslinking monomers together with appropriate initiators and promoters in association with aggregate which may be wet and a source of bivalent metallic ions which will set to polymer concrete with excellent structural properties.

  9. Electropositive bivalent metallic ion unsaturated polyester complexed polymer concrete

    DOEpatents

    Sugama, Toshifumi; Kukacka, Lawrence E.; Horn, William H.

    1985-01-01

    Quick setting polymer concrete compositions with excellent structural properties are disclosed; these polymer concrete compositions are mixtures of unsaturated polyesters and crosslinking monomers together with appropriate initiators and promoters in association with aggregate, which may be wet, and with a source of bivalent metallic ions.

  10. Dislocation loop formation by swift heavy ion irradiation of metals

    NASA Astrophysics Data System (ADS)

    Khara, Galvin S.; Murphy, Samuel T.; Duffy, Dorothy M.

    2017-07-01

    A coupled two-temperature, molecular dynamics methodology is used to simulate the structural evolution of bcc metals (Fe and W) and fcc metals (Cu and Ni) following irradiation by swift heavy ions. Electronic temperature dependent electronic specific heat capacities and electron-phonon coupling strengths are used to capture the full effects of the variation in the electronic density of states. Tungsten is found to be significantly more resistant to damage than iron, due both to the higher melting temperature and the higher thermal conductivity. Very interesting defect structures, quite different from defects formed in cascades, are found to be created by swift heavy ion irradiation in the bcc metals. Isolated vacancies form a halo around elongated interstitial dislocation loops that are oriented along the ion path. Such configurations are formed by rapid recrystallization of the molten cylindrical region that is created by the energetic ion. Vacancies are created at the recrystallization front, resulting in excess atoms at the core which form interstitial dislocation loops on completion of crystallization. These unique defect structures could, potentially, be used to create metal films with superior mechanical properties and interesting nanostructures.

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

    PubMed

    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

  12. Growth of metal phthalocyanine on deactivated semiconducting surfaces steered by selective orbital coupling

    DOE PAGES

    Wagner, Sean R.; Feng, Jiagui; Yoon, Mina; ...

    2015-08-25

    Using scanning tunneling microscopy and density functional theory, we show that the molecular ordering and orientation of metal phthalocyanine molecules on the deactivated Si surface display a strong dependency on the central transition-metal ion, driven by the degree of orbital hybridization at the heterointerface via selective p – d orbital coupling. As a result, this Letter identifies a selective mechanism for modifying the molecule-substrate interaction which impacts the growth behavior of transition-metal-incorporated organic molecules on a technologically relevant substrate for silicon-based devices.

  13. Growth of metal phthalocyanine on deactivated semiconducting surfaces steered by selective orbital coupling

    SciTech Connect

    Wagner, Sean R.; Feng, Jiagui; Yoon, Mina; Zhang, Pengpeng; Huang, Bing; Park, Changwon

    2015-08-25

    Using scanning tunneling microscopy and density functional theory, we show that the molecular ordering and orientation of metal phthalocyanine molecules on the deactivated Si surface display a strong dependency on the central transition-metal ion, driven by the degree of orbital hybridization at the heterointerface via selective p – d orbital coupling. As a result, this Letter identifies a selective mechanism for modifying the molecule-substrate interaction which impacts the growth behavior of transition-metal-incorporated organic molecules on a technologically relevant substrate for silicon-based devices.

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

    PubMed

    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.

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

    SciTech Connect

    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.

  16. A stability concept for metal ion coordination to single-stranded nucleic acids and affinities of individual sites.

    PubMed

    Sigel, Roland K O; Sigel, Helmut

    2010-07-20

    The three-dimensional architecture and function of nucleic acids strongly depend on the presence of metal ions, among other factors. Given the negative charge of the phosphate-sugar backbone, positively charged species, mostly metal ions, are necessary for compensation. However, these ions also allow and induce folding of complicated RNA structures. Furthermore, metal ions bind to specific sites, stabilizing local motifs and positioning themselves correctly to aid (or even enable) a catalytic mechanism, as, for example, in ribozymes. Many nucleic acids thereby exhibit large differences in folding and activity depending not only on the concentration but also on the kind of metal ion involved. As a consequence, understanding the role of metal ions in nucleic acids requires knowing not only the exact positioning and coordination sphere of each specifically bound metal ion but also its intrinsic site affinity. However, the quantification of metal ion affinities toward certain sites in a single-stranded (though folded) nucleic acid is a demanding task, and few experimental data exist. In this Account, we present a new tool for estimating the binding affinity of a given metal ion, based on its ligating sites within the nucleic acid. To this end, we have summarized the available affinity constants of Mg(2+), Ca(2+), Mn(2+), Cu(2+), Zn(2+), Cd(2+), and Pb(2+) for binding to nucleobase residues, as well as to mono- and dinucleotides. We have also estimated for these ions the stability constants for coordinating the phosphodiester bridge. In this way, stability increments for each ligand site are obtained, and a clear selectivity of the ligating atoms, as well as their discrimination by different metal ions, can thus be recognized. On the basis of these data, we propose a concept that allows one to estimate the intrinsic stabilities of nucleic acid-binding pockets for these metal ions. For example, the presence of a phosphate group has a much larger influence on the overall

  17. [Spectroscopic studies on transition metal ions in colored diamonds].

    PubMed

    Meng, Yu-Fei; Peng, Ming-Sheng

    2004-07-01

    Transition metals like nickel, cobalt and iron have been often used as solvent catalysts in high pressure high temperature (HPHT) synthesis of diamond, and nickel and cobalt ions have been found in diamond lattice. Available studies indicated that nickel and cobalt ions could enter the lattice as interstitial or substitutional impurities and form complexes with nitrogen. Polarized microscopy, SEM-EDS, EPR, PL and FTIR have been used in this study to investigate six fancy color natural and synthetic diamonds in order to determine the spectroscopic characteristics and the existing forms of transition metal ions in colored diamond lattice. Cobalt-related optical centers were first found in natural chameleon diamonds, and some new nickel and cobalt-related optical and EPR centers have also been detected in these diamond samples.

  18. Metal negative ion beam extraction from a radio frequency ion source

    SciTech Connect

    Kanda, S.; Yamada, N.; Kasuya, T.; Romero, C. F. P.; Wada, M.

    2015-04-08

    A metal ion source of magnetron magnetic field geometry has been designed and operated with a Cu hollow target. Radio frequency power at 13.56 MHz is directly supplied to the hollow target to maintain plasma discharge and induce self-bias to the target for sputtering. The extraction of positive and negative Cu ion beams have been tested. The ion beam current ratio of Cu{sup +} to Ar{sup +} has reached up to 140% when Ar was used as the discharge support gas. Cu{sup −} ion beam was observed at 50 W RF discharge power and at a higher Ar gas pressure in the ion source. Improvement of poor RF power matching and suppression of electron current is indispensable for a stable Cu{sup −} ion beam production from the source.

  19. Liquid metal ion source and alloy for ion emission of multiple ionic species

    DOEpatents

    Clark, Jr., William M.; Utlaut, Mark W.; Wysocki, Joseph A.; Storms, Edmund K.; Szklarz, Eugene G.; Behrens, Robert G.; Swanson, Lynwood W.; Bell, Anthony E.

    1987-06-02

    A liquid metal ion source and alloy for the simultaneous ion evaporation of arsenic and boron, arsenic and phosphorus, or arsenic, boron and phosphorus. The ionic species to be evaporated are contained in palladium-arsenic-boron and palladium-arsenic-boron-phosphorus alloys. The ion source, including an emitter means such as a needle emitter and a source means such as U-shaped heater element, is preferably constructed of rhenium and tungsten, both of which are readily fabricated. The ion sources emit continuous beams of ions having sufficiently high currents of the desired species to be useful in ion implantation of semiconductor wafers for preparing integrated circuit devices. The sources are stable in operation, experience little corrosion during operation, and have long operating lifetimes.

  20. Effect of heavy metals ions on enzyme activity in the Mediterranean mussel, Donax trunculus

    SciTech Connect

    Mizrahi, L.; Achituv, Y. )

    1989-06-01

    Heavy metal ions strongly are bound by sulfhydryl groups of proteins. Sulfhydryl binding changes the structure and enzymatic activities of proteins and causes toxic effects evident at the whole organism level. Heavy metal ions like Cd, Cu, Hg, Zn, and Pb in sufficiently high concentrations might kill organisms or cause other adverse effects that changing aquatic community structures. Bivalves are known to be heavy metal accumulators. The aim of the present study was to examine the effects of different concentrations of each of five heavy metal ions on the activity of four enzymes in D. trunculus. As it is known that heavy metals inhibit the activity of a wide range of enzymes, the authors chose representative examples of dehydrogenases (lactate and malate dehydrogenases), respiratory enzyme (cytochrome oxidase) and digestive enzyme ({alpha}-amylase). The acute effects of different concentrations of selected metals were examined. These concentrations were higher than those found usually in the locality where the animals occur, but might be encountered during a given event of pollution.

  1. Changes in blood ion levels after removal of metal-on-metal hip replacements

    PubMed Central

    Durrani, Salim K; Sampson, Barry; Panetta, Therese; Liddle, Alexander D; Sabah, Shiraz A; Chan, Newton K; Skinner, John A; Hart, Alister J

    2014-01-01

    Background and purpose In patients with metal-on-metal (MoM) hip prostheses, pain and joint effusions may be associated with elevated blood levels of cobalt and chromium ions. Since little is known about the kinetics of metal ion clearance from the body and the rate of resolution of elevated blood ion levels, we examined the time course of cobalt and chromium ion levels after revision of MoM hip replacements. Patients and methods We included 16 patients (13 female) who underwent revision of a painful MoM hip (large diameter, modern bearing) without fracture or infection, and who had a minimum of 4 blood metal ion measurements over an average period of 6.1 (0–12) months after revision. Results Average blood ion concentrations at the time of revision were 22 ppb for chromium and 43 ppb for cobalt. The change in ion levels after revision surgery varied extensively between patients. In many cases, over the second and third months after revision surgery ion levels decreased to 50% of the values measured at revision. Decay of chromium levels occurred more slowly than decay of cobalt levels, with a 9% lag in return to normal levels. The rate of decay of both metals followed second-order (exponential) kinetics more closely than first-order (linear) kinetics. Interpretation The elimination of cobalt and chromium from the blood of patients who have undergone revision of painful MoM hip arthroplasties follows an exponential decay curve with a half-life of approximately 50 days. Elevated blood levels of cobalt and chromium ions can persist for at least 1 year after revision, especially in patients with high levels of exposure. PMID:24758321

  2. Stable alkali metal ion intercalation compounds as optimized metal oxide nanowire cathodes for lithium batteries.

    PubMed

    Zhao, Yunlong; Han, Chunhua; Yang, Junwei; Su, Jie; Xu, Xiaoming; Li, Shuo; Xu, Lin; Fang, Ruopian; Jiang, Hong; Zou, Xiaodong; Song, Bo; Mai, Liqiang; Zhang, Qingjie

    2015-03-11

    Intercalation of ions in electrode materials has been explored to improve the rate capability in lithium batteries and supercapacitors, due to the enhanced diffusion of Li(+) or electrolyte cations. Here, we describe a synergistic effect between crystal structure and intercalated ion by experimental characterization and ab initio calculations, based on more than 20 nanomaterials: five typical cathode materials together with their alkali metal ion intercalation compounds A-M-O (A = Li, Na, K, Rb; M = V, Mo, Co, Mn, Fe-P). Our focus on nanowires is motivated by general enhancements afforded by nanoscale structures that better sustain lattice distortions associated with charge/discharge cycles. We show that preintercalation of alkali metal ions in V-O and Mo-O yields substantial improvement in the Li ion charge/discharge cycling and rate, compared to A-Co-O, A-Mn-O, and A-Fe-P-O. Diffraction and modeling studies reveal that preintercalation with K and Rb ions yields a more stable interlayer expansion, which prevents destructive collapse of layers and allow Li ions to diffuse more freely. This study demonstrates that appropriate alkali metal ion intercalation in admissible structure can overcome the limitation of cyclability as well as rate capability of cathode materials, besides, the preintercalation strategy provides an effective method to enlarge diffusion channel at the technical level, and more generally, it suggests that the optimized design of stable intercalation compounds could lead to substantial improvements for applications in energy storage.

  3. Electrochemical selective ion separation in capacitive deionization with sodium manganese oxide.

    PubMed

    Kim, Seonghwan; Yoon, Hansun; Shin, Dongyoon; Lee, Jaehan; Yoon, Jeyong

    2017-11-15

    Electrochemical selective ion separation via capacitive deionization, for example, separation of lithium resource from brine, using lithium ion batteries is proposed and demonstrated to have the potential for separating specific ions selectively from a solution containing diverse ions. This separation method is of great industrial concern because of applicability in various fields such as deionization, water softening, purification, heavy metal removal, and resource recovery. Nevertheless, besides the selectivity of materials for lithium ion batteries toward Li(+), there is very little investigation on the selectivity of the materials for sodium ion batteries toward Na(+). Here, the electrochemical selectivity of sodium manganese oxide (Na0.44MnO2), one of the most widely used material in sodium ion batteries, for Na(+) and other cations (K(+), Mg(2+), and Ca(2+)) is investigated. Selective Na(+) separation using the system consisting of Na0.44MnO2 and a Ag/AgCl electrode is successfully demonstrated from a solution containing diverse cations (Na(+), K(+), Mg(2+), and Ca(2+)) via a two-step process that involves a capturing step (charging process) and a releasing step (discharging process). The results showed that Na0.44-xMnO2 has over 13 times higher selectivity for Na(+) than for K(+) and 6-8times higher selectivity for Na(+) than for Mg(2+) and Ca(2+) in the electrolyte containing equal concentrations of the respective ions. Additionally, as a practical demonstration, Na(+) was successfully separated from an industrial raw material used for pure KOH production (estimated ratio of Na(+):K(+)=1:200). Copyright © 2017 Elsevier Inc. All rights reserved.

  4. Conversion and displacement reaction types of transition metal compounds for sodium ion battery

    NASA Astrophysics Data System (ADS)

    Chen, Guo-Ying; Sun, Qian; Yue, Ji-Li; Shadike, Zulipiya; Yang, Yin; Ding, Fei; Sang, Lin; Fu, Zheng-Wen

    2015-06-01

    Transition metal compounds of FeSe and CuWO4 thin films have been successfully fabricated by using R.F. sputtering method. Although two kinds of transition metal compounds of FeSe and CuWO4 thin films can react with sodium electrochemically, they exhibit different electrochemical features. The nanosized metal Fe is highly dispersed into Na2Se matrix and metal Cu is extruded from Na2WO4 mixture after the FeSe/Na and CuWO4/Na cells are discharged, respectively. The conversion reaction mechanism between FeSe and Na2Se is proposed for the FeSe/Na cell. While the displacement reaction mechanism for CuWO4/Na cell is proposed for the first time based on the transmission electron microscopy (TEM) and selected area electron diffraction (SAED) data. These various mechanisms make transition metal compounds interesting materials for rechargeable sodium ion batteries.

  5. Chitosan removes toxic heavy metal ions from cigarette mainstream smoke

    NASA Astrophysics Data System (ADS)

    Zhou, Wen; Xu, Ying; Wang, Dongfeng; Zhou, Shilu

    2013-09-01

    This study investigated the removal of heavy metal ions from cigarette mainstream smoke using chitosan. Chitosan of various deacetylation degrees and molecular weights were manually added to cigarette filters in different dosages. The mainstream smoke particulate matter was collected by a Cambridge filter pad, digested by a microwave digestor, and then analyzed for contents of heavy metal ions, including As(III/V), Pb(II), Cd(II), Cr(III/VI) and Ni(II), by graphite furnace atomic absorption spectrometry (GFAAS). The results showed that chitosan had a removal effect on Pb(II), Cd(II), Cr(III/VI) and Ni(II). Of these, the percent removal of Ni(II) was elevated with an increasing dosage of chitosan. Chitosan of a high deace tylation degree exhibited good binding performance toward Cd(II), Cr(III/VI) and Ni(II), though with poor efficiency for Pb(II). Except As(III/V), all the tested metal ions showed similar tendencies in the growing contents with an increasing chitosan molecular weight. Nonetheless, the percent removal of Cr(III/VI) peaked with a chitosan molecular weight of 200 kDa, followed by a dramatic decrease with an increasing chitosan molecular weight. Generally, chitosan had different removal effects on four out of five tested metal ions, and the percent removal of Cd(II), Pb(II), Cr(III/VI) and Ni(II) was approximately 55%, 45%, 50%, and 16%, respectively. In a word, chitosan used in cigarette filter can remove toxic heavy metal ions in the mainstream smoke, improve cigarette safety, and reduce the harm to smokers.

  6. Metal ion influence on eumelanin fluorescence and structure

    NASA Astrophysics Data System (ADS)

    Sutter, Jens-Uwe; Birch, David J. S.

    2014-06-01

    Melanin has long been thought to have an unworkably weak and complex fluorescence, but here we study its intrinsic fluorescence in order to demonstrate how metal ions can be used to control the rate of formation, constituents and structure of eumelanin formed from the well-known laboratory auto-oxidation of 3,4-dihydroxy-L-phenylalanine (L-DOPA). The effect on eumelanin absorption and fluorescence of a range of solvated metal ions is reported including Cu, Zn, Ni, Na and K. Monovalent cations and Zn have little effect, but the effect of transition metal cations can be considerable. For example, at pH 10, copper ions are shown to accelerate the onset of eumelanin formation, but not the rate of formation once it commences, and simplify the usual complex structure and intrinsic fluorescence of eumelanin in a way that is consistent with an increased abundance of 5,5-dihydroxyindole-2-carboxylic acid (DHICA). The presence of a dominant 6 ns fluorescence decay time at 480 nm, when excited at 450 nm describes a distinct photophysical species, which we tentatively assign to small oligomers. Copper is well-known to normally quench fluorescence, but increasing amounts of copper surprisingly leads to an increase in the fluorescence decay time of eumelanin, while reducing the fluorescence intensity, suggesting copper modification of the excited state. Such results have bearing on diverse areas. The most accepted morphology for melanin is that of a graphite-like sheet structure, and one which readily binds metal ions, an interaction that is thought to have an important, though as yet unclear bearing on several areas of medicine including neurology. There is also increasing interest in bio-mimicry by preparing and labelling sheet structures with metal ions for new electronic and photonic materials.

  7. ‘Pseudotumour’ invading the proximal femur with normal metal ions following metal on metal hip resurfacing

    PubMed Central

    Krishnan, Harry; Sugand, Kapil; Ali, Ibrahim; Smith, Jay

    2015-01-01

    A 75-year-old woman who had undergone hybrid metal-on-metal hip resurfacing 8 years earlier underwent revision arthroplasty because of hip, groin and lateral thigh pain. The main differential was aseptic loosening; however, serum cobalt and chromium levels were normal. Multiple imaging modalities revealed a periprosthetic, cystic soft tissue mass adjacent to the proximal femur. A large ‘pseudotumour’ with proximal femoral invasion was found at revision arthroplasty. We report the first finding of a ‘pseudotumour’ invading the proximal femur with normal metal ions following metal on metal hip resurfacing. PMID:25670783

  8. High adsorptive γ-AlOOH(boehmite)@SiO2/Fe3O4 porous magnetic microspheres for detection of toxic metal ions in drinking water.

    PubMed

    Wei, Yan; Yang, Ran; Zhang, Yong-Xing; Wang, Lun; Liu, Jin-Huai; Huang, Xing-Jiu

    2011-10-21

    γ-AlOOH(boehmite)@SiO(2)/Fe(3)O(4) porous magnetic microspheres with high adsorption capacity toward heavy metal ions were found to be useful for the simultaneous and selective electrochemical detection of five metal ions, such as ultratrace zinc(II), cadmium(II), lead(II), copper(II), and mercury(II), in drinking water.

  9. A modular platform to develop peptoid-based selective fluorescent metal sensors.

    PubMed

    Knight, Abigail S; Kulkarni, Rishikesh U; Zhou, Effie Y; Franke, Jenna M; Miller, Evan W; Francis, Matthew B

    2017-03-25

    Despite the reduction in industrial use of toxic heavy metals, there remain contaminated natural water sources across the world. Herein we present a modular platform for developing selective sensors for toxic metal ions using N-substituted glycine, or peptoid, oligomers coupled to a fluorophore. As a preliminary evaluation of this strategy, structures based on previously identified metal-binding peptoids were synthesized with terminal pyrene moieties. Both derivatives of this initial design demonstrated a turn-off response in the presence of various metal ions. A colorimetric screen was designed to identify a peptoid ligand that chelates Hg(ii). Multiple ligands were identified that were able to deplete Hg(ii) from a solution selectively in the presence of an excess of competing ions. The C-terminal fluoropeptoid derivatives demonstrated similar selectivity to their label-free counterparts. This strategy could be applied to develop sensors for many different metal ions of interest using a variety of fluorophores, leading to a panel of sensors for identifying various water source contaminants.

  10. Solution NMR refinement of a metal ion bound protein using metal ion inclusive restrained molecular dynamics methods.

    PubMed

    Chakravorty, Dhruva K; Wang, Bing; Lee, Chul Won; Guerra, Alfredo J; Giedroc, David P; Merz, Kenneth M

    2013-06-01

    Correctly calculating the structure of metal coordination sites in a protein during the process of nuclear magnetic resonance (NMR) structure determination and refinement continues to be a challenging task. In this study, we present an accurate and convenient means by which to include metal ions in the NMR structure determination process using molecular dynamics (MD) simulations constrained by NMR-derived data to obtain a realistic and physically viable description of the metal binding site(s). This method provides the framework to accurately portray the metal ions and its binding residues in a pseudo-bond or dummy-cation like approach, and is validated by quantum mechanical/molecular mechanical (QM/MM) MD calculations constrained by NMR-derived data. To illustrate this approach, we refine the zinc coordination complex structure of the zinc sensing transcriptional repressor protein Staphylococcus aureus CzrA, generating over 130 ns of MD and QM/MM MD NMR-data compliant sampling. In addition to refining the first coordination shell structure of the Zn(II)